Welding and brazing of nickel and nickel-base alloys

NASA Technical Reports Server (NTRS)

Mortland, J. E.; Evans, R. M.; Monroe, R. E.

1972-01-01

The joining of four types of nickel-base materials is described: (1) high-nickel, nonheat-treatable alloys, (2) solid-solution-hardening nickel-base alloys, (3) precipitation-hardening nickel-base alloys, and (4) dispersion-hardening nickel-base alloys. The high-nickel and solid-solution-hardening alloys are widely used in chemical containers and piping. These materials have excellent resistance to corrosion and oxidation, and retain useful strength at elevated temperatures. The precipitation-hardening alloys have good properties at elevated temperature. They are important in many aerospace applications. Dispersion-hardening nickel also is used for elevated-temperature service.

Atomistic simulation of the influence of Cr on the mobility of the edge dislocation in Fe(Cr) alloys

NASA Astrophysics Data System (ADS)

Hafez Haghighat, S. M.; Terentyev, D.; Schäublin, R.

2011-10-01

In this work Fe-Cr compounds, as model alloys for the ferritic base steels that are considered as main candidates for the structural materials of the future fusion reactors, are studied using molecular dynamics simulations. The Cr or so-called α' precipitates, which are obstacles to dislocations, affect mechanical properties, leading to hardening and loss of ductility. The flow stress to move an edge dislocation in a Cr solid solution in pure Fe is studied as a function of Cr content. The strength of a nanometric Cr precipitate as obstacle to an edge dislocation in pure Fe is investigated as a function of its Cr content. Results show that with increasing Cr content the precipitate obstacle strength increases, with a strong sensitivity to the local atomic order. Temperature induces a monotonic decrease of the flow stress of the Cr solid solution and of the Cr precipitate obstacle strength.

Investigation of Plutonium and Uranium Precipitation Behavior with Gadolinium as a Neutron Poison

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

Visser, A.E.

2003-10-17

The caustic precipitation of plutonium (Pu)-containing solutions has been investigated to determine whether the presence of 3:1 uranium (U):Pu in solutions stored in the H-Canyon Facility at the U.S. Department of Energy's (DOE) Savannah River Site (SRS) would adversely impact the use of gadolinium nitrate (Gd(NO3)3) as a neutron poison. In the past, this disposition strategy has been successfully used to discard solutions containing approximately 100 kg of Pu to the SRS high level waste (HLW) system. In the current experiments, gadolinium (as Gd(NO3)3) was added to samples of a 3:1 U:Pu solution, a surrogate 3 g/L U solution, andmore » a surrogate 3 g/L U with 1 g/L Pu solution. A series of experiments was then performed to observe and characterize the precipitate at selected pH values. Solids formed at pH 4.5 and were found to contain at least 50 percent of the U and 94 percent of the Pu, but only 6 percent of the Gd. As the pH of the solution increased (e.g., pH greater than 14 with 1.2 or 3.6 M sodium hydroxide (NaOH) excess), the precipitate contained greater than 99 percent of the Pu, U, and Gd. After the pH greater than 14 systems were undisturbed for one week, no significant changes were found in the composition of the solid or supernate for each sample. The solids were characterized by X-ray diffraction (XRD) which found sodium diuranate (Na2U2O7) and gadolinium hydroxide (Gd(OH)3) at pH 14. Thermal gravimetric analysis (TGA) indicated sufficient water molecules were present in the solids to thermalize the neutrons, a requirement for the use of Gd as a neutron poison. Scanning electron microscopy (SEM) was also performed and the accompanying back-scattering electron analysis (BSE) found Pu, U, and Gd compounds in all pH greater than 14 precipitate samples. The rheological properties of the slurries at pH greater than 14 were also investigated by performing precipitate settling rate studies and measuring the viscosity and density of the materials. Based on the results of these experiments, poisoning the Pu-U solutions with Gd and subsequent neutralization is a viable process for discarding the Pu to the SRS HLW system.« less

Solid-State Characterization of Novel Propylene Glycol Ester Solvates Isolated from Lipid Formulations.

PubMed

Chakravarty, Paroma; Kothari, Sanjeev; Deese, Alan; Lubach, Joseph W

2015-07-06

The purpose of this study was to identify and characterize precipitates obtained from a liquid formulation of GNE068.HCl, a Genentech developmental compound, and lipophilic excipients, such as propylene glycol monocaprylate, and monolaurate. Precipitates were characterized using powder X-ray diffractometry (PXRD), differential scanning calorimetry, thermogravimetry, microscopy, nuclear magnetic resonance spectroscopy (NMR; solution and solid-state) and water sorption analysis. PXRD and NMR revealed the precipitates to be crystalline solvates of propylene glycol esters. The solvates (capryolate and lauroglycolate) were isomorphic and stable up to 70 °C, beyond which melting of the lattice occurred with subsequent dissolution of the active ingredient in the melt (microscopy and variable temperature PXRD). They were found to be mechanically stable (no change in PXRD pattern upon compression) and were nonhygroscopic up to ∼70% RH (25 °C). Our results highlight the outcome of inadvertent drug-excipient interactions in two separate lipid solution formulations with good solid-state properties and, thus, potential for further development.

Geochemical Modeling of Reactions and Partitioning of Trace Metals and Radionuclides during Titration of Contaminated Acidic Sediments

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

Zhang, Fan; Parker, Jack C.; Luo, Wensui

2008-01-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This study was undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cationmore » exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO{sub 4}{sup 2-} for contaminated sediments indicated close agreement, suggesting that the model could potentially be used to predict the acid-base behavior of the sediment-solution system under variable pH conditions.« less

Large-scale fluctuations in the diffusive decomposition of solid solutions

NASA Astrophysics Data System (ADS)

Karpov, V. G.; Grimsditch, M.

1995-04-01

The concept of an instability in the classic Ostwald ripening theory with respect to compositional fluctuations is suggested. We show that small statistical fluctuations in the precipitate phase lead to gigantic Coulomb-like fluctuations in the solute concentration which in turn affect the ripening. As a result large-scale fluctuations in both the precipitate and solute concentrations appear. These fluctuations are characterized by amplitudes of the order of the average values of the corresponding quantities and by a space scale L~(na)-1/2 which is considerably greater than both the average nuclear radius and internuclear distance. The Lifshitz-Slyozov theory of ripening is shown to remain locally applicable, over length scales much less than L. The implications of these findings for elastic light scattering in solid solutions that have undergone Ostwald ripening are considered.

Nano Precipitation and Hardening of Die-Quenched 6061 Aluminum Alloy.

PubMed

Utsunomiya, Hiroshi; Tada, Koki; Matsumoto, Ryo; Watanabe, Katsumi; Matsuda, Kenji

2018-03-01

Die quenching is applied to an age-hardenable aluminium alloys to obtain super-saturated solid solution. The application is advantageous because it can reduce number of manufacturing processes, and may increase strength by strain aging. If die quenching is realized in forging as well as sheet forming, it may widen industrial applicability further. In this study, Al-Mg-Si alloy AA6061 8 mm-thick billets were reduced 50% in height without cracks by die-quench forging. Supersaturated solid solution was successfully obtained. The die-quenched specimen shows higher hardness with nano precipitates at shorter aging time than the conventional water-quenched specimen.

Effects of hydrogen on thermal creep behaviour of Zircaloy fuel cladding

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Interfacial Microstructure and Its Influence on Resistivity of Thin Layers Copper Cladding Steel Wires

NASA Astrophysics Data System (ADS)

Li, Hongjuan; Ding, Zhimin; Zhao, Ruirong

2018-04-01

The interfacial microstructure and resistivity of cold-drawn and annealed thin layers copper cladding steel (CCS) wires have been systematically investigated by the methods of scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and resistivity testing. The results showed that the Cu and Fe atoms near interface diffused into each other matrixes. The Fe atoms diffused into Cu matrixes and formed a solid solution. The mechanism of solid solution is of substitution type. When the quantity of Fe atoms exceeds the maximum solubility, the supersaturated solid solution would form Fe clusters and decompose into base Cu and α-Fe precipitated phases under certain conditions. A few of α-Fe precipitates was observed in the copper near Cu/Fe interfaces of cold-drawn CCS wires, with 1-5 nm in size. A number of α-Fe precipitates of 1-20 nm in size can be detected in copper near Cu/Fe interfaces of CCS wires annealed at 850°C. When annealing temperature was less than 750°C, the resistivity of CCS wires annealed was lower than that of cold-drawn CCS wires. However, when annealing temperature was above 750°C, the resistivity of CCS wires was greater than that of cold-drawn CCS wires and increased with rising the annealing temperature. The relationship between nanoscale α-Fe precipitation and resistivity of CCS wires has been well discussed.

Composition of steam in the system NaCl-KCl-H2O-quartz at 600°C

USGS Publications Warehouse

Fournier, Robert O.; Thompson, J. Michael

1993-01-01

In the system NaCl-KCl-H2O, with and without ??-quartz present, steam was equilibrated in a large-volume reaction vessel with brine and/or precipitated salt at 600??C and pressures ranging from about 100 to 0.4 MPa. Episodically, steam was extracted for chemical analysis, accompanied by a decrease in pressure within the reaction vessel. In the absence of precipitated salt, within the analytical uncertainty stoichiometric quantities of Cl and total alkali, metals (Na + K) dissolve in steam coexisting with chloriderich brine. In contrast, in the presence of precipitated salt (in our experiments halite with some KCl in solid solution), significant excess chloride as associated hydrogen chloride (HCl0??) dissolves in steam. The HCl0 is generated by the reaction of steam with solid NaCl(s), producing solid NaOH(s) that diffuses into halite, forming a solid solution. In our quasistatic experiments, compared to dynamic flow-through experiments of others, higher initial ratios of H2O/NaCl have apparently resulted in higher model fractions of NaOH(s) in solid solution in halite. This, in turn, resulted in incrementally higher concentrations of associated NaOHo dissolved in steam. Addition of quartz to the system NaCl + KC1 + H2O resulted in an order of magnitude increase in the concentration of HCl0 dissolved in steam, apparently as a consequence of the formation of sodium disilicate by reaction of silica with NaOH(s). The measured dissolved silica in steam saturated with alkali halides at 600??C in the pressure range 7-70 MPa agrees nicely with calculated values of the solubility of ??-quartz obtained using the equation of Fournier and Potter (1982), corrected for dissolved salt by the method of fournier (1983). Na K ratios in steam at 600??C tend to be slightly greater than in coexisting brine. When precipitated halite is present, larger mole fractions of NaOH(s) in solid solution in that halite apparently result in even larger Na K ratios in coexisting steam. Precipitation of more halite as a consequence of repeated depressurization episodes results in decreased Na K ratios in both the brine and coexisting steam phases, indicating that the lower pressures begin to favor K over Na in the vapor. When steam is in contact with precipitated salts in the absence of brine, the Na K ratio in the steam is less than that of the bulk composition of the salt-H2O system. ?? 1993.

Nanocrystalline Ce 1- xY xO 2- x/2 (0≤ x≤0.35) Oxides via Carbonate Precipitation: Synthesis and Characterization

NASA Astrophysics Data System (ADS)

Li, Ji-Guang; Ikegami, Takayasu; Wang, Yarong; Mori, Toshiyuki

2002-10-01

A novel carbonate (co)precipitation method, employing nitrates as the starting salts and ammonium carbonate as the precipitant, has been used to synthesize nanocrystalline CeO 2 and Ce 1- xY xO 2- x/2 ( x≤0.35) solid-solutions. The resultant powders are characterized by elemental analysis, differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffractometry (XRD), Brunauer-Emmett-Teller (BET) analysis, and high-resolution scanning electron microscopy (HRSEM). Due to the direct formation of carbonate solid-solutions during precipitation, Ce 1- xY xO 2- x/2 solid-solution oxides are formed directly during calcination at a very low temperature of ˜300°C for 2 h. The thus-produced oxide nanopowders are essentially non-agglomerated, as revealed by BET in conjunction with XRD analysis. The solubility of YO 1.5 in CeO 2 is determined via XRD to be somewhere in the range from 27 to 35 mol%, from which a Y 2O 3-related type-C phase appears in the final product. Y 3+-doping promotes the formation of spherical nanoparticles, retards thermal decomposition of the precursors, and suppresses significantly crystallite coarsening of the oxides during calcination. The activation energy for crystallite coarsening increases gradually from 68.7 kJ mol -1 for pure CeO 2 to 138.6 kJ mol -1 for CeO 2 doped with 35 mol% YO 1.5. The dopant effects on crystallite coarsening is elaborated from the view point of solid-state chemistry.

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

Wu, Zeen; Hu, Rui; Zhang, Tiebang, E-mail: tiebang

The microstructure and solidification behavior of high Nb containing TiAl alloys with the composition of Ti-46Al-8Nb-xC (x = 0.1, 0.7, 1.4, 2.5 at.%) prepared by arc-melting method have been investigated in this work. The results give evidence that the addition of carbon changes the solidification behavior from solidification via the β phase to the peritectic solidification. And carbon in solid solution enriches in the α{sub 2} phase and increases the microhardness. As the carbon content increases to 1.4 at.%, plate-shape morphology carbides Ti{sub 2}AlC (H phase) precipitate from the TiAl matrix which leads to the refinement microstructure. By aging atmore » 1173 K for 24 h after quenching treatment, fine needle-like and granular shape Ti{sub 3}AlC (P phase) carbides are observed in the matrix of Ti-46Al-8Nb-2.5C alloy, which distribute along the lamellar structure or around the plate-shape Ti{sub 2}AlC. Transmission electron microscope observation shows that the Ti{sub 3}AlC carbides precipitate at dislocations. The phase transformation in-situ observations indicate that the Ti{sub 2}AlC carbides partly precipitate during the solid state phase transformation process. - Highlights: •Carbon changes the solidification behavior from β phase to peritectic solidification. •Dislocations in solution treated γ phase act as nucleation sites of Ti{sub 3}AlC precipitations. •Ti{sub 3}AlC precipitates as fine needle-like or granular shape in the solution treated matrix. •Ti{sub 2}AlC carbides precipitate during the solid state phase transformation process.« less

Recovery of iron oxide from coal fly ash

DOEpatents

Dobbins, Michael S.; Murtha, Marlyn J.

1983-05-31

A high quality iron oxide concentrate, suitable as a feed for blast and electric reduction furnaces is recovered from pulverized coal fly ash. The magnetic portion of the fly ash is separated and treated with a hot strong alkali solution which dissolves most of the silica and alumina in the fly ash, leaving a solid residue and forming a precipitate which is an acid soluble salt of aluminosilicate hydrate. The residue and precipitate are then treated with a strong mineral acid to dissolve the precipitate leaving a solid residue containing at least 90 weight percent iron oxide.

Reactive solute transport in an acidic stream: Experimental pH increase and simulation of controls on pH, aluminum, and iron

USGS Publications Warehouse

Broshears, R.E.; Runkel, R.L.; Kimball, B.A.; McKnight, Diane M.; Bencala, K.E.

1996-01-01

Solute transport simulations quantitatively constrained hydrologic and geochemical hypotheses about field observations of a pH modification in an acid mine drainage stream. Carbonate chemistry, the formation of solid phases, and buffering interactions with the stream bed were important factors in explaining the behavior of pH, aluminum, and iron. The precipitation of microcrystalline gibbsite accounted for the behavior of aluminum; precipitation of Fe(OH)3 explained the general pattern of iron solubility. The dynamic experiment revealed limitations on assumptions that reactions were controlled only by equilibrium chemistry. Temporal variation in relative rates of photoreduction and oxidation influenced iron behavior. Kinetic limitations on ferrous iron oxidation and hydrous oxide precipitation and the effects of these limitations on field filtration were evident. Kinetic restraints also characterized interaction between the water column and the stream bed, including sorption and desorption of protons from iron oxides at the sediment-water interface and post-injection dissolution of the precipitated aluminum solid phase.

Effect of scandium on the phase composition and mechanical properties of ABM alloys

NASA Astrophysics Data System (ADS)

Molchanova, L. V.

2010-09-01

The effect of scandium on the composition and mechanical properties of ABM-1 alloys (Al-30% Be-5% Mg) is studied. The scandium content is varied from 0.1 to 0.5 wt %. It is established that, in the studied part of the Al-Be-Mg-Sc system, an aluminum solid solution (Al) and the ScBe13 compound are in equilibrium with a beryllium solid solution (Be). Magnesium dissolves in both the aluminum component and the ScBe13 compound. The strengthening effect related to the decomposition of the solid solution and the precipitation of Al3Sc cannot be extended to the strengthening of ABM-type alloys. Additions of 0.1-0.15 wt % Sc only weakly improve the mechanical properties of the alloys due to the refinement of beryllium-component grains. At high scandium contents, the strength increases insignificantly due to primary precipitation of ScBe13 and the plasticity decreases simultaneously.

Method for removing metals from a cleaning solution

DOEpatents

Deacon, Lewis E.

2002-01-01

A method for removing accumulated metals from a cleaning solution is provided. After removal of the metals, the cleaning solution can be discharged or recycled. The process manipulates the pH levels of the solution as a means of precipitating solids. Preferably a dual phase separation at two different pH levels is utilized.

Calculation of the solvus temperature of metastable phases in the Al-Mg-Si alloys

NASA Astrophysics Data System (ADS)

Vasilyev, A. A.; Gruzdev, A. S.; Kuz'min, N. L.

2011-09-01

A procedure has been proposed for the self-consistent calculation of the solvus temperatures of metastable phase precipitates in Al-Mg-Si alloys and the specific energy of their interface with the aluminum matrix. The procedure is based on the results of experimental studies on the kinetics of formation of these precipitates during decomposition of supersaturated solid solutions of quenched Al-Mg-Si alloys, which were carried out by measuring the Young's modulus and electrical resistivity. On the basis of the obtained set of solvus temperatures of the β″-phase, an empirical formula has been proposed for calculating this temperature as a function of the chemical composition of the initial solid solution.

Capillary-Driven Solute Transport and Precipitation in Porous Media during Dry-Out

NASA Astrophysics Data System (ADS)

Ott, Holger; Andrew, Matthew; Blunt, Martin; Snippe, Jeroen

2014-05-01

The injection of dry or under-saturated gases or supercritical (SC) fluids into water bearing formations might lead to a formation dry-out in the vicinity of the injection well. The dry-out is caused by the evaporation/dissolution of formation water into the injected fluid and the subsequent transport of dissolved water in the injected fluid away from the injection well. Dry-out results in precipitation from solutes of the formation brine and consequently leads to a reduction of the rock's pore space (porosity) and eventually to a reduction of permeability near the injection well, or even to the loss of injectivity. Recently evidence has been found that the complexity of the pore space and the respective capillary driven solute transport plays a key role. While no effective-permeability (Keff) reduction was observed in a single-porosity sandstone, multi porosity carbonate rocks responded to precipitation with a strong reduction of Keff. The reason for the different response of Keff to salt precipitation is suspected to be in the exact location of the precipitate (solid salt) in the pore space. In this study, we investigate dry-out and salt precipitation due to supercritical CO2 injection in single and multi-porosity systems under near well-bore conditions. We image fluid saturation changes by means of μCT scanning during desaturation. We are able to observe capillary driven transport of the brine phase and the respective transport of solutes on the rock's pore scale. Finally we have access to the precipitated solid-salt phase and their distribution. The results can proof the thought models behind permeability porosity relationships K(φ) for injectivity modeling. The topic and the mechanisms we show are of general interest for drying processes in porous material such as soils and paper.

Specific solubilization of impurities in culture media: Arg solution improves purification of pH-responsive tag CspB50 with Teriparatide.

PubMed

Oki, Shogo; Nonaka, Takahiro; Shiraki, Kentaro

2018-06-01

Protein purification using non-chromatographic methods is a simple technique that avoids costly resin. Recently, a cell surface protein B (CspB) tag has been developed for a pH-responsive tag for protein purification by solid-liquid separation. Proteins fused with the CspB tag show reversible insolubilization at acidic pH that can be used in solid-liquid separation for protein purification. However, brown-color impurities from co-precipitation hamper further analysis of the target proteins. In this study, we investigated the effect of additives on the co-precipitation of CspB-tagged Teriparatide (CspB50TEV-Teriparatide) expressed in Corynebacterium glutamicum and associated impurities. Arginine (Arg) at 1.0 M was found to be the most effective additive for removing impurities, particularly carotenoids and nucleic acids. Furthermore, all impurities detected in the fluorescence and absorbance spectra were successfully removed by the repetition of precipitation-redissolution in the Arg solution. The precipitation yield of the CspB50TEV-Teriparatide did not change with the addition of Arg and the repetition of the precipitation-redissolution process. Collectively, our findings indicate that the specific desorption of π-electron rich compounds by Arg may be useful in conjunction with the pH-responsive CspB tag for solid-liquid protein purification. Copyright © 2018 Elsevier Inc. All rights reserved.

Analysis of thermoelectric properties of high-temperature complex alloys of nickel-base, iron-base and cobalt-base groups

NASA Technical Reports Server (NTRS)

Holanda, R.

1984-01-01

The thermoelectric properties alloys of the nickel-base, iron-base, and cobalt-base groups containing from 1% to 25% 106 chromium were compared and correlated with the following material characteristics: atomic percent of the principle alloy constituent; ratio of concentration of two constituents; alloy physical property (electrical resistivity); alloy phase structure (percent precipitate or percent hardener content); alloy electronic structure (electron concentration). For solid-solution-type alloys the most consistent correlation was obtained with electron concentration, for precipitation-hardenable alloys of the nickel-base superalloy group, the thermoelectric potential correlated with hardener content in the alloy structure. For solid-solution-type alloys, no problems were found with thermoelectric stability to 1000; for precipitation-hardenable alloys, thermoelectric stability was dependent on phase stability. The effects of the compositional range of alloy constituents on temperature measurement uncertainty are discussed.

Method of repressing the precipitation of calcium fluozirconate

DOEpatents

Newby, B.J.; Rhodes, D.W.

1973-12-25

Boric acid or a borate salt is added to aqueous solutions of fluoride containing radioactive wastes generated during the reprocessing of zirconium alloy nuclear fuels which are to be converted to solid form by calcining in a fluidized bed. The addition of calcium nitrate to the aqueous waste solutions to prevent fluoride volatility during calcination, causes the precipitation of calcium fluozirconate, which tends to form a gel at fluoride concentrations of 3.0 M or greater. The boron containing species introduced into the solution by the addition of the boric acid or borate salt retard the formation of the calcium fluozirconate precipitate and prevent formation of the gel. These boron containing species can be introduced into the solution by the addition of a borate salt but preferably are introduced by the addition of an aqueous solution of boric acid. (Official Gazette)

Process for purification of waste water produced by a Kraft process pulp and paper mill

NASA Technical Reports Server (NTRS)

Humphrey, M. F. (Inventor)

1979-01-01

The water from paper and pulp wastes obtained from a mill using the Kraft process is purified by precipitating lignins and lignin derivatives from the waste stream with quaternary ammonium compounds, removing other impurities by activated carbon produced from the cellulosic components of the water, and then separating the water from the precipitate and solids. The activated carbon also acts as an aid to the separation of the water and solids. If recovery of lignins is also desired, then the precipitate containing the lignins and quaternary ammonium compounds is dissolved in methanol. Upon acidification, the lignin is precipitated from the solution. The methanol and quaternary ammonium compound are recovered for reuse from the remainder.

Precipitation of silicon from splat-cooled Al-Si alloys

NASA Technical Reports Server (NTRS)

Matyja, H.; Russell, K. C.; Grant, N. J.; Giessen, B. C.

1975-01-01

Splat cooled Al-Si solid solutions with 1 to 11 at.% Si were prepared and their precipitation kinetics were studied by transmission electron microscopy. The time required for appearance of particles visible at a magnification of 35,000 times was determined at temperatures between 248 K and 573 K. The resulting Arrhenius plots yielded activation energies ranging from 55 to 40 plus or minus 2kJ/mol over the composition range. Precipitate densities were higher and denuded zones of 100 to 150 nm were narrower than in comparable solid quenched samples. The activation energies are explained in terms of excess point defect concentrations.

PHOTOSENSITIVE 2,5-DISTYRYLPYRAZINE PARTICLES PRODUCED FROM RAPID EXPANSION OF SUPERCRITICAL SOLUTIONS. (R826648)

EPA Science Inventory

Solvent-free, photoreactive particles of 2,5-distyrylpyrazine (DSP) monomer were developed by rapid precipitation from an expanding supercritical chlorodifluoromethane solution. DSP polymer particles were produced by solid-state photopolymerization. DSP particles below a criti...

Nucleation of the diamond phase in aluminium-solid solutions

NASA Technical Reports Server (NTRS)

Hornbogen, E.; Mukhopadhyay, A. K.; Starke, E. A., Jr.

1993-01-01

Precipitation was studied from fcc solid solutions with silicon, germanium, copper and magnesium. Of all these elements only silicon and germanium form diamond cubic (DC) precipitates in fcc Al. Nucleation of the DC structure is enhanced if both types of atom are dissolved in the fcc lattice. This is interpreted as due to atomic size effects in the prenucleation stage. There are two modes of interference of fourth elements with nucleation of the DC phase in Al + Si, Ge. The formation of the DC phase is hardly affected if the atoms (for example, copper) are rejected from the (Si, Ge)-rich clusters. If additional types of atom are attracted by silicon and/or germanium, DC nuclei are replaced by intermetallic compounds (for example Mg2Si).

PROCESS OF RECOVERING URANIUM

DOEpatents

Kilner, S.B.

1959-12-29

A method is presented for separating and recovering uranium from a complex mixure of impurities. The uranium is dissolved to produce an aqueous acidic solution including various impurities. In accordance with one method, with the uranium in the uranyl state, hydrogen cyanide is introduced into the solution to complex the impurities. Subsequently, ammonia is added to the solution to precipitate the uraniunn as ammonium diuranate away from the impurities in the solution. Alternatively, the uranium is precipitated by adding an alkaline metal hydroxide. In accordance with the second method, the uranium is reduced to the uranous state in the solution. The reduced solution is then treated with solid alkali metal cyanide sufficient to render the solution about 0.1 to 1.0 N in cyanide ions whereat cyanide complex ions of the metal impurities are produced and the uranium is simultaneously precipituted as uranous hydroxide. Alternatively, hydrogen cyanide may be added to the reduced solution and the uranium precipitated subsequently by adding ammonium hydroxide or an alkali metal hydroxide. Other refinements of the method are also disclosed.

One-Dimensional Transport with Equilibrium Chemistry (OTEQ) - A Reactive Transport Model for Streams and Rivers

USGS Publications Warehouse

Runkel, Robert L.

2010-01-01

OTEQ is a mathematical simulation model used to characterize the fate and transport of waterborne solutes in streams and rivers. The model is formed by coupling a solute transport model with a chemical equilibrium submodel. The solute transport model is based on OTIS, a model that considers the physical processes of advection, dispersion, lateral inflow, and transient storage. The equilibrium submodel is based on MINTEQ, a model that considers the speciation and complexation of aqueous species, acid-base reactions, precipitation/dissolution, and sorption. Within OTEQ, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (waterborne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach. The model's ability to simulate pH, precipitation/dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between instream chemistry and hydrologic transport at the field scale. This report details the development and application of OTEQ. Sections of the report describe model theory, input/output specifications, model applications, and installation instructions. OTEQ may be obtained over the Internet at http://water.usgs.gov/software/OTEQ.

Yielding Unexpected Results: Precipitation of Ba[subscript3](PO[subscript4])[subscript2] and Implications for Teaching Solubility Principles in the General Chemistry Curriculum

ERIC Educational Resources Information Center

Hazen, Jeffery L.; Cleary, David A.

2014-01-01

Precipitation of barium phosphate from aqueous solutions of a barium salt and a phosphate salt forms the basis for a number of conclusions drawn in general chemistry. For example, the formation of a solid white precipitate is offered as evidence that barium phosphate is insoluble. Furthermore, analysis of the supernatant is used to illustrate the…

Effect of Heat Treatment on Borides Precipitation and Mechanical Properties of CoCrFeNiAl1.8Cu0.7B0.3Si0.1 High-Entropy Alloy Prepared by Arc-Melting and Laser-Cladding

NASA Astrophysics Data System (ADS)

Zhang, H.; Tang, H.; He, Y. Z.; Zhang, J. L.; Li, W. H.; Guo, S.

2017-11-01

Effects of heat treatment on borides precipitation and mechanical properties of arc-melted and laser-cladded CoCrNiFeAl1.8Cu0.7B0.3Si0.1 high-entropy alloys were comparatively studied. The arc-melted alloy contains lots of long strip borides distributed in the body-centered cubic phase, with a hardness about 643 HV0.5. Laser-cladding can effectively inhibit the boride precipitation and the laser-cladded alloy is mainly composed of a simple bcc solid solution, with a high hardness about 769 HV0.5, indicating the strengthening effect by interstitial boron atoms is greater than the strengthening by borides precipitation. Heat treatments between 800°C and 1200°C can simultaneously improve the hardness and fracture toughness of arc-melted alloys, owing to the boride spheroidization, dissolution, re-precipitation, and hence the increased boron solubility and nano-precipitation in the bcc solid solution. By contrast, the hardness of laser-cladded alloys reduce after heat treatments in the same temperature range, due to the decreased boron solubility in the matrix.

Phosphate recovery through struvite precipitation by CO2 removal: effect of magnesium, phosphate and ammonium concentrations.

PubMed

Korchef, Atef; Saidou, Hassidou; Ben Amor, Mohamed

2011-02-15

In the present study, the precipitation of struvite (MgNH(4)PO(4)·6H(2)O) using the CO(2) degasification technique is investigated. The precipitation of struvite was done from supersaturated solutions in which precipitation was induced by the increase of the solution supersaturation concomitant with the removal of dissolved carbon dioxide. The effect of magnesium, phosphate and ammonium concentrations on the kinetics and the efficiency of struvite precipitation was measured monitoring the respective concentrations in solution. In all cases struvite precipitated exclusively and the solid was characterized by powder XRD and FTIR. The morphology of the precipitated crystals was examined by scanning electronic microscopy and it was found that it exhibited the typical prismatic pattern of the struvite crystals with sizes in the range between 100 and 300 μm. The increase of magnesium concentration in the supersaturated solutions, resulted for all phosphate concentration tested, in significantly higher phosphate removal efficiency. Moreover, it is interesting to note that in this case the adhesion of the suspended struvite crystals to the reactor walls was reduced suggesting changes in the particle characteristics. The increase of phosphate concentration in the supersaturated solutions, for the magnesium concentrations tested resulted to the reduction of struvite suppression which reached complete suppression of the precipitate formation. Excess of ammonium in solution was found favour struvite precipitation. Contrary to the results found with increasing the magnesium concentration in solution, higher ammonium concentrations resulted to higher adhesion of the precipitated crystallites to the reactor walls. The results of the present work showed that it is possible to recover phosphorus in the form of struvite from wastewater reducing water pollution and at the same time saving valuable resources. Copyright © 2010 Elsevier B.V. All rights reserved.

UV-vis Imaging of Piroxicam Supersaturation, Precipitation, and Dissolution in a Flow-Through Setup.

PubMed

Sun, Yu; Chapman, Alex; Larsen, Susan W; Jensen, Henrik; Petersen, Nickolaj J; Goodall, David M; Østergaard, Jesper

2018-06-05

Evaluation of drug precipitation is important in order to address challenges regarding low and variable bioavailability of poorly water-soluble drugs, to assess potential risk of patient safety with infusion therapy, and to explore injectable in situ suspension-forming drug delivery systems. Generally, drug precipitation is assessed in vitro through solution concentration analysis methods. Dual-wavelength UV-vis imaging is a novel imaging technique that may provide an opportunity for simultaneously monitoring changes in both solution and solid phases during precipitation. In the present study, a multimodal approach integrating UV-vis imaging, light microscopy, and Raman spectroscopy was developed for characterization of piroxicam supersaturation, precipitation, and dissolution in a flow-through setup. A solution of piroxicam dissolved in 1-methyl-2-pyrrolidinone was injected into a flowing aqueous environment (pH 7.4), causing piroxicam to precipitate. Imaging at 405 and 280 nm monitored piroxicam concentration distributions during precipitation and revealed different supersaturation levels dependent on the initial concentration of the piroxicam solution. The combination with imaging at 525 nm, light microscopy, and Raman spectroscopy measurements demonstrated concentration-dependent precipitation and the formation, growth, and dissolution of individual particles. Results emphasize the importance of the specific hydrodynamic conditions on the piroxicam precipitation. The approach used may facilitate comprehensive understanding of drug precipitation and dissolution processes and may be developed further into a basic tool for formulation screening and development.

Quantitative analysis of Bordeaux red wine precipitates by solid-state NMR: Role of tartrates and polyphenols.

PubMed

Prakash, Shipra; Iturmendi, Nerea; Grelard, Axelle; Moine, Virginie; Dufourc, Erick

2016-05-15

Stability of wines is of great importance in oenology matters. Quantitative estimation of dark red precipitates formed in Merlot and Cabernet Sauvignon wine from Bordeaux region for vintages 2012 and 2013 was performed during the oak barrel ageing process. Precipitates were obtained by placing wine at -4°C or 4°C for 2-6 days and monitored by periodic sampling during a one-year period. Spectroscopic identification of the main families of components present in the precipitate powder was performed with (13)C solid-state CPMAS NMR and 1D and 2D solution NMR of partially water re-solubilized precipitates. The study revealed that the amount of precipitate obtained is dependent on vintage, temperature and grape variety. Major components identified include potassium bitartrate, polyphenols, polysaccharides, organic acids and free amino acids. No evidence was found for the presence of proteins. The influence of main compounds found in the precipitates is discussed in relation to wine stability. Copyright © 2016. Published by Elsevier Ltd.

Process for removing metals from water

DOEpatents

Napier, John M.; Hancher, Charles M.; Hackett, Gail D.

1989-01-01

A process for removing metals from water including the steps of prefiltering solids from the water, adjusting the pH to between about 2 and 3, reducing the amount of dissolved oxygen in the water, increasing the pH to between about 6 and 8, adding water-soluble sulfide to precipitate insoluble sulfide- and hydroxide-forming metals, adding a flocculating agent, separating precipitate-containing floc, and postfiltering the resultant solution. The postfiltered solution may optionally be eluted through an ion exchange resin to remove residual metal ions.

Precipitation of Co(2+) carbonates from aqueous solution: insights on the amorphous to crystalline transformation.

NASA Astrophysics Data System (ADS)

González-López, Jorge; Fernández-González, Ángeles; Jiménez, Amalia

2016-04-01

Cobalt is toxic metal that is present only as a trace in the Earth crust. However, Co might concentrate on specific areas due to both natural and anthropogenic factors and thus, soils and groundwater can be contaminated. It is from this perspective that we are interested in the precipitation of cobalt carbonates, since co-precipitation with minerals phases is a well-known method for metal immobilization in the environment. In particular, the carbonates are widely used due to its reactivity and natural abundance. In order to evaluate the cobalt carbonate precipitation at room temperature, a simple experimental work was carried out in this work. The precipitation occurred via reaction of two common salts: 0.05M of CoCl2 and 0.05M of Na2CO3 in aqueous solution. After reaction, the precipitated solid was kept in the remaining water at 25 oC and under constant stirring for different aging times of 5 min, 1 and 5 hours, 1, 2, 4, 7, 30 and 60 days. In addition to the aging and precipitation experiments, we carried out experiments to determine the solubility of the solids. In these experiments each precipitate was dissolved in Milli-Q water until equilibrium was reached and then the aqueous solution was analyzed regarding Co2+ and total alkalinity. Furthermore, acid solution calorimetry of the products were attained. Finally, we modeled the results using the PHREEQC code. Solid and aqueous phase identification and characterization have been extensively reported in a previous work (González-López et al., 2015). The main results of our investigation were the initial precipitation of an amorphous cobalt carbonate that evolve towards a poorly crystalline cobalt hydroxide carbonate with aging treatment. Solubility of both phases have been calculated under two different approaches: precipitation and dissolution. Values of solubility from each approach were obtained with a general error due to differences in experiment conditions, for instance, ionic strength, temperature and water content. It was surprising the low solubility product (Ksp) of the new phase Co2CO3(OH)2 in the order of 10-30 and this could explain its appearance only after 7 days of aging. On the other hand, the high solubility product of amorphous is consistent with its instantaneous precipitation at the beginning of the reaction. Solution calorimetry shows a higher value of exothermic solution enthalpy for crystalline cobalt hydroxide carbonate and hence, the solubility result are confirmed. Although geochemical models indicated that aqueous solution was supersaturated with respect both phases, the sequence of obtained phases (first amorphous and next crystalline) indicate that the evolution of the saturation index has to be dropped with respect to amorphous phase with time. These results points towards a simultaneous dissolution of the amorphous and the precipitation of crystalline phase Co2CO3(OH)2 at the first stages of the reaction. González-López, J. ; Fernández-González, Á. ; Jiménez, A. (2015) Prepublication: Crystallization of nanostructured cobalt hydroxide carbonate at ambient conditions: a key precursor of Co3O4. DOI: http://dx.doi.org/10.1180/minmag.2015.079.7.02

Catalysis and chemical mechanisms of calcite dissolution in seawater.

PubMed

Subhas, Adam V; Adkins, Jess F; Rollins, Nick E; Naviaux, John; Erez, Jonathan; Berelson, William M

2017-07-18

Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric [Formula: see text] on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve 13 C-labeled calcites in natural seawater. We show that the time-evolving enrichment of [Formula: see text] in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the 13 C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution-precipitation shifts significantly toward a dissolution-dominated mechanism below about [Formula: see text] Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of [Formula: see text] is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid-solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at [Formula: see text], which we interpret as the onset of homogeneous etch pit nucleation.

Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.; Reardon, E.J.; Plummer, Niel; Busenberg, E.

1990-01-01

Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO4 and (Sr, Ca)C??O3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H2O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation GE = ??KBr??KClRT[a0 + a1(2??KBr-1)], where a0 is 1.40 ?? 0.02, a1, is -0.08 ?? 0.03 at 25??C, and ??KBr and ??KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at ??KBr = 0.676 and at a total solubility product, ???? = [K+]([Cl-] + [Br-]) = 15.35. ?? 1990.

Sample Results from MCU Solids Outage

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

Peters, T.; Washington, A.; Oji, L.

2014-09-22

Savannah River National Laboratory (SRNL) has received several solid and liquid samples from MCU in an effort to understand and recover from the system outage starting on April 6, 2014. SRNL concludes that the presence of solids in the Salt Solution Feed Tank (SSFT) is the likely root cause for the outage, based upon the following discoveries: A solids sample from the extraction contactor #1 proved to be mostly sodium oxalate; A solids sample from the scrub contactor#1 proved to be mostly sodium oxalate; A solids sample from the Salt Solution Feed Tank (SSFT) proved to be mostly sodium oxalate;more » An archived sample from Tank 49H taken last year was shown to contain a fine precipitate of sodium oxalate; A solids sample from ; A liquid sample from the SSFT was shown to have elevated levels of oxalate anion compared to the expected concentration in the feed. Visual inspection of the SSFT indicated the presence of precipitated or transferred solids, which were likely also in the Salt Solution Receipt Tank (SSRT). The presence of the solids coupled with agitation performed to maintain feed temperature resulted in oxalate solids migration through the MCU system and caused hydraulic issues that resulted in unplanned phase carryover from the extraction into the scrub, and ultimately the strip contactors. Not only did this carryover result in the Strip Effluent (SE) being pushed out of waste acceptance specification, but it resulted in the deposition of solids into several of the contactors. At the same time, extensive deposits of aluminosilicates were found in the drain tube in the extraction contactor #1. However it is not known at this time how the aluminosilicate solids are related to the oxalate solids. The solids were successfully cleaned out of the MCU system. However, future consideration must be given to the exclusion of oxalate solids into the MCU system. There were 53 recommendations for improving operations recently identified. Some additional considerations or additional details are provided below as recommendations. From this point on, IC-Anions analyses of the DSSHT should be part of the monthly routine analysis in order to spot negative trends in the oxalate leaving the MCU system. Care must be taken to monitor the oxalate content to watch for sudden precipitation of oxalate salts in the system; Conduct a study to optimize the cleaning strategy at ARP-MCU through decreasing the concentration or entirely eliminating the oxalic acid; The contents of the SSFT should remain unagitated. Routine visual observation should be maintained to ensure there is not a large buildup of solids. As water with agitation provided sufficient removal of the solids in the feed tank, it should be considered as a good means for dissolving oxalate solids if they are found in the future; Conduct a study to improve prediction of oxalate solubility in salt batch feed materials. As titanium and mercury have been found in various solids in this report, evaluate if either element plays a role in oxalate solubility during processing; Salt batch characterization focuses primarily on characterization and testing of unaltered Tank 21H material; however, non-typical feeds are developed through cleaning, washing, and/or sump transfers. As these solutions are processed through MCU, they may precipitate solids or reduce performance. Salt batch characterization and testing should be expanded to encompass a broader range of feeds that may be processed through ARPMCU.« less

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

Yasukawa, Akemi, E-mail: yasukawa@cc.hirosaki-u.ac.jp; Kandori, Kazuhiko; Tanaka, Hidekazu

Highlights: Black-Right-Pointing-Pointer LnCaHap solid solution particles were prepared using five types of heavy rare earth ions by a precipitation method. Black-Right-Pointing-Pointer The length and the crystallinity of the LnCaHap particles first increased and then decreased with increasing Ln{sup 3+} contents. Black-Right-Pointing-Pointer A series of YCaHap solid solution particles formed with Y/(Y + Ca) = 0-0.10 were investigated using various methods in detail. -- Abstract: Calcium hydroxyapatite (CaHap) particles substituted five types of heavy rare earth ions (Ln: Y{sup 3+}, Gd{sup 3+}, Dy{sup 3+}, Er{sup 3+} and Yb{sup 3+}) were synthesized using a precipitation method and characterized using various means. Thesemore » Ln ions strongly affected the crystal phases and the structures of the products. With increasing Ln/(Ln + Ca) in the starting solution ([X{sub Ln}]), the length and the crystallinity of the particles first increased and then decreased. The rare earth metal-calcium hydroxyapatite (LnCaHap) solid solution particles were obtained at [X{sub Y}] {<=} 0.10 for substituting Y system and at [X{sub Ln}] {<=} 0.01-0.03 for substituting the other Ln systems. LnPO{sub 4} was mixed with LnCaHap at higher [X{sub Ln}] for all Ln systems. A series of yttrium-calcium hydroxyapatite (YCaHap) solid solutions with [X{sub Y}] = 0-0.10 were investigated using XRD, TEM, ICP-AES, IR and TG-DTA in detail.« less

Determination of solute site occupancies within γ' precipitates in nickel-base superalloys via orientation-specific atom probe tomography

DOE PAGES

Meher, Subhashish; Rojhirunsakool, Tanaporn; Nandwana, Peeyush; ...

2015-04-28

In this study, the analytical limitations in atom probe tomography such as resolving a desired set of atomic planes, for solving complex materials science problems, have been overcome by employing a well-developed unique and reproducible crystallographic technique, involving synergetic coupling of orientation microscopy with atom probe tomography. The crystallographic information in atom probe reconstructions has been utilized to determine the solute site occupancies in Ni-Al-Cr based superalloys accurately. The structural information in atom probe reveals that both Al and Cr occupy the same sub-lattice within the L1 2-ordered g precipitates to form Ni 3(Al,Cr) precipitates in a Ni-14Al-7Cr(at.%) alloy. Interestingly,more » the addition of Co, which is a solid solution strengthener, to a Ni-14Al-7Cr alloy results in the partial reversal of Al site occupancy within g precipitates to form (Ni,Al) 3(Al,Cr,Co) precipitates. This unique evidence of reversal of Al site occupancy, resulting from the introduction of other solutes within the ordered structures, gives insights into the relative energetics of different sub-lattice sites when occupied by different solutes.« less

Solid solution partitioning of Sr2+, Ba2+, and Cd2+ to calcite

USGS Publications Warehouse

Tesoriero, A.J.; Pankow, J.F.

1996-01-01

Although solid solutions play important roles in controlling the concentrations of minor metal ions in natural waters, uncertainties regarding their compositions, thermodynamics, and kinetics usually prevent them from being considered. A range of precipitation rates was used here to study the nonequilibrium and equilibrium partitioning behaviors of Sr2+, Ba2+, and Cd2+ to calcite (CaCO3(s)). The distribution coefficient of a divalent metal ion Me2+ for partitioning from an aqueous solution into calcite is given by DMe = (XMeCO3(s)/[Me2+])/(XCaCO3(s)/[Ca 2+]). The X values are solid-phase mole fractions; the bracketed values are the aqueous molal concentrations. In agreement with prior work, at intermediate to high precipitation rates R (nmol/mg-min), DSr, DBa, and DCd were found to depend strongly on R. At low R, the values of DSr, DBa, and DCd became constant with R. At 25??C, the equilibrium values for DSr, DBa, and DCd for dilute solid solutions were estimated to be 0.021 ?? 0.003, 0.012 ?? 0.005, and 1240 ?? 300, respectively. Calculations using these values were made to illustrate the likely importance of partitioning of these ions to calcite in groundwater systems. Due to its large equilibrium DMe value, movement of Cd2+ will be strongly retarded in aquifers containing calcite; Sr2+ and Ba2+ will not be retarded nearly as much.

Heat exchanger life extension via in-situ reconditioning

DOEpatents

Holcomb, David E.; Muralidharan, Govindarajan

2016-06-28

A method of in-situ reconditioning a heat exchanger includes the steps of: providing an in-service heat exchanger comprising a precipitate-strengthened alloy wherein at least one mechanical property of the heat exchanger is degraded by coarsening of the precipitate, the in-service heat exchanger containing a molten salt working heat exchange fluid; deactivating the heat exchanger from service in-situ; in a solution-annealing step, in-situ heating the heat exchanger and molten salt working heat exchange fluid contained therein to a temperature and for a time period sufficient to dissolve the coarsened precipitate; in a quenching step, flowing the molten salt working heat-exchange fluid through the heat exchanger in-situ to cool the alloy and retain a supersaturated solid solution while preventing formation of large precipitates; and in an aging step, further varying the temperature of the flowing molten salt working heat-exchange fluid to re-precipitate the dissolved precipitate.

Extraction of Li and Co from Li-ion Batteries by Chemical Methods

NASA Astrophysics Data System (ADS)

Guzolu, Jafar Sharrivar; Gharabaghi, Mahdi; Mobin, Mohammad; Alilo, Hojat

2017-04-01

In this work a process involving ultrasonic washing and leaching and precipitation was used to recover Li and Co from spent Li-ion batteries. Ultrasonic washing was used to reduce energy consumption and pollution whereas hydrochloric acid was used as leaching reagent. 98 % of Li and nearly 99 % of Co were obtained under optimum condition of 5 M hydrochloric acid solution, temperature of 95 °C, reaction time of 70 min, and solid-liquid ratio of 10 g/L. In this process at first nickel, copper, iron, aluminum, cobalt, and manganese were precipitated from leaching solution using sodium hydroxide at pH f 12.5 and reaction time of 1 h and temperature was 55 °C and all metal recoveries were more than 99 %. In the precipitation experiments, lithium loss was only 18.34 %. In the next stage, white lithium carbonate was precipitated by addition of saturated sodium carbonate solution to the left filtrate from first precipitation step. The purity of the recovered powder of lithium was 95 %.

Abiotic transformation of high explosives by freshly precipitated iron minerals in aqueous Fe¹¹ solutions

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

Boparai, Hardiljeet K.; Comfort, Steve; Satapanajaru, Tunlawit

Zerovalent iron barriers have become a viable treatment for field-scale cleanup of various ground water contaminants. While contact with the iron surface is important for contaminant destruction, the interstitial pore water within and near the iron barrier will be laden with aqueous, adsorbed and precipitated FeII phases. These freshly precipitated iron minerals could play an important role in transforming high explosives (HE). Our objective was to determine the transformation of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and TNT (2,4,6-trinitrotoluene) by freshly precipitated iron FeII/FeIII minerals. This was accomplished by quantifying the effects of initial FeII concentration, pH, and the presence of aquifermore » solids (FeIII phases) on HE transformation rates. Results showed that at pH 8.2, freshly precipitated iron minerals transformed RDX, HMX, and TNT with reaction rates increasing with increasing FeII concentrations. RDX and HMX transformations in these solutions also increased with increasing pH (5.8-8.55). By contrast, TNT transformation was not influenced by pH (6.85-8.55) except at pH values <6.35. Transformations observed via LC/MS included a variety of nitroso products (RDX, HMX) and amino degradation products (TNT). XRD analysis identified green rust and magnetite as the dominant iron solid phases that precipitated from the aqueous FeII during HE treatment under anaerobic conditions. Geochemical modeling also predicted FeII activity would likely be controlled by green rust and magnetite. These results illustrate the important role freshly precipitated FeII/FeIII minerals in aqueous FeII solutions play in the transformation of high explosives.« less

Alkali metal nitrate purification

DOEpatents

Fiorucci, Louis C.; Morgan, Michael J.

1986-02-04

A process is disclosed for removing contaminants from impure alkali metal nitrates containing them. The process comprises heating the impure alkali metal nitrates in solution form or molten form at a temperature and for a time sufficient to effect precipitation of solid impurities and separating the solid impurities from the resulting purified alkali metal nitrates. The resulting purified alkali metal nitrates in solution form may be heated to evaporate water therefrom to produce purified molten alkali metal nitrates suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of purified alkali metal nitrates.

Process for separating dissolved solids from a liquid using an anti-solvent and multiple effect evaporators

DOEpatents

Daniels, Edward J.; Jody, Bassam J.; Bonsignore, Patrick V.

1994-01-01

A process and system for treating aluminum salt cake containing water soluble halide salts by contacting the salt cake with water to dissolve water soluble halide salts forming a saturated brine solution. Transporting a portion of about 25% of the saturated brine solution to a reactor and introducing into the saturated brine solution at least an equal volume of a water-miscible low-boiling organic material such as acetone to precipitate a portion of the dissolved halide salts forming a three-phase mixture of an aqueous-organic-salt solution phase and a precipitated salt phase and an organic rich phase. The precipitated salt phase is separated from the other phases and the organic rich phase is recycled to the reactor. The remainder of the saturated brine solution is sent to a multiple effect evaporator having a plurality of stages with the last stage thereof producing low grade steam which is used to boil off the organic portion of the solution which is recycled.

Process for separating dissolved solids from a liquid using an anti-solvent and multiple effect evaporators

DOEpatents

Daniels, E.J.; Jody, B.J.; Bonsignore, P.V.

1994-07-19

A process and system are disclosed for treating aluminum salt cake containing water soluble halide salts by contacting the salt cake with water to dissolve water soluble halide salts forming a saturated brine solution. Transporting a portion of about 25% of the saturated brine solution to a reactor and introducing into the saturated brine solution at least an equal volume of a water-miscible low-boiling organic material such as acetone to precipitate a portion of the dissolved halide salts forming a three-phase mixture of an aqueous-organic-salt solution phase and a precipitated salt phase and an organic rich phase. The precipitated salt phase is separated from the other phases and the organic rich phase is recycled to the reactor. The remainder of the saturated brine solution is sent to a multiple effect evaporator having a plurality of stages with the last stage thereof producing low grade steam which is used to boil off the organic portion of the solution which is recycled. 3 figs.

Separation and Precipitation of Nickel from Acidic Sulfate Leaching Solution of Molybdenum-Nickel Black Shale by Potassium Nickel Sulfate Hexahydrate Crystallization

NASA Astrophysics Data System (ADS)

Deng, Zhigan; Wei, Chang; Fan, Gang; Li, Xingbin; Li, Minting; Li, Cunxiong

2018-02-01

Nickel was separated and precipitated with potassium nickel sulfate hexahydrate [K2Ni(SO4)2·6H2O] from acidic sulfate solution, a leach solution from molybdenum-nickel black shale. The effects of the potassium sulfate (K2SO4) concentration, crystallization temperature, solution pH, and crystallization time on nickel(II) recovery and iron(III) precipitation were investigated, revealing that nickel and iron were separated effectively. The optimum parameters were K2SO4 concentration of 200 g/L, crystallization temperature of 10°C, solution pH of 0.5, and crystallization time of 24 h. Under these conditions, 97.6% nickel(II) was recovered as K2Ni(SO4)2·6H2O crystals while only 2.0% of the total iron(III) was precipitated. After recrystallization, 98.4% pure K2Ni(SO4)2·6H2O crystals were obtained in the solids. The mother liquor was purified by hydrolysis-precipitation followed by cooling, and more than 99.0% K2SO4 could be crystallized. A process flowsheet was developed to separate iron(III) and nickel(II) from acidic-sulfate solution.

Effect of Arsenic on the Formation and Adsorption Property of Ferric Hydroxide Precipitates in ZVI Treatment

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

Peng, Xing; Xi, Beidou; Zhao, Ying

Treatment of arsenic by zerovalent iron (ZVI) has been studied extensively. However, the effect of arsenic on the formation of ferric hydroxide precipitates in the ZVI treatment has not been investigated. We discovered that the specific surface area (ca. 187 m2/g) and arsenic content (ca. 67 mg/g) of the suspended solids (As-containing solids) generated in the ZVI treatment of arsenic solutions were much higher than the specific surface area (ca. 37 m2/g) and adsorption capacity (ca.12 mg/g) of the suspended solids (As-free solids) generated in the arsenic-free solutions. Arsenic in the As-containing solids was much more stable than the adsorbedmore » arsenic in As-free solids. XRD, SEM, TEM, and selected area electron diffraction (SAED) analyses showed that the As-containing solids consisted of amorphous nanoparticles, while the As-free solids were composed of micron particles with weak crystallinity. Extended X-ray absorption fine structure (EXAFS) analysis determined that As(V) was adsorbed on the As-containing suspended solids and magnetic solid surfaces through bidentate binuclear complexation; and As(V) formed a mononuclear complex on the As-free suspended solids. The formation of the surface As(V) complexes retarded the bonding of free FeO6 octahedra to the oxygen sites on FeO6 octahedral clusters and prevented the growth of the clusters and their development into 3-dimensional crystalline phases.« less

Determination of filter pore size for use in HB line phase II production of plutonium oxide

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

Shehee, T.; Crowder, M.; Rudisill, T.

2014-08-01

H-Canyon and HB-Line are tasked with the production of plutonium oxide (PuO 2) from a feed of plutonium (Pu) metal. The PuO 2 will provide feed material for the Mixed Oxide (MOX) Fuel Fabrication Facility. After dissolution of the Pu metal in H-Canyon, plans are to transfer the solution to HB-Line for purification by anion exchange. Anion exchange will be followed by plutonium(IV) oxalate precipitation, filtration, and calcination to form PuO 2. The filtrate solutions, remaining after precipitation, contain low levels of Pu ions, oxalate ions, and may include solids. These solutions are transferred to H-Canyon for disposition. To mitigatemore » the criticality concern of Pu solids in a Canyon tank, past processes have used oxalate destruction or have pre-filled the Canyon tank with a neutron poison. The installation of a filter on the process lines from the HB-Line filtrate tanks to H-Canyon Tank 9.6 is proposed to remove plutonium oxalate solids. This report describes SRNL’s efforts to determine the appropriate pore size for the filters needed to perform this function. Information provided in this report aids in developing the control strategies for solids in the process.« less

Chemical weathering rates of a soil chronosequence on granitic alluvium: III. Hydrochemical evolution and contemporary solute fluxes and rates

USGS Publications Warehouse

White, A.F.; Schulz, M.S.; Vivit, D.V.; Blum, A.E.; Stonestrom, David A.; Harden, J.W.

2005-01-01

Although long-term changes in solid-state compositions of soil chronosequences have been extensively investigated, this study presents the first detailed description of the concurrent hydrochemical evolution and contemporary weathering rates in such sequences. The most direct linkage between weathering and hydrology over 3 million years of soil development in the Merced chronosequence in Central California relates decreasing permeability and increasing hydrologic heterogeneity to the development of secondary argillic horizons and silica duripans. In a highly permeable, younger soil (40 kyr old), pore water solutes reflect seasonal to decadal-scale variations in rainfall and evapotranspiration (ET). This climate signal is strongly damped in less permeable older soils (250 to 600 kyr old) where solutes increasingly reflect weathering inputs modified by heterogeneous flow. Elemental balances in the soils are described in terms of solid state, exchange and pore water reservoirs and input/output fluxes from precipitation, ET, biomass, solute discharge and weathering. Solute mineral nutrients are strongly dependent on biomass variations as evidenced by an apparent negative K weathering flux reflecting aggradation by grassland plants. The ratios of solute Na to other base cations progressively increase with soil age. Discharge fluxes of Na and Si, when integrated over geologic time, are comparable to solid-state mass losses in the soils, implying similar past weathering conditions. Similarities in solute and sorbed Ca/Mg ratios reflect short-term equilibrium with the exchange reservoir. Long-term consistency in solute ratios, when contrasted against progressive decreases in solid-state Ca/Mg, requires an additional Ca source, probably from dry deposition. Amorphous silica precipitates from thermodynamically-saturated pore waters during periods of high evapotranspiration and result in the formation of duripans in the oldest soils. The degree of feldspar and secondary gibbsite and kaolinite saturation varies both spatially and temporally due to the seasonality of plant-respired CO2 and a decrease in organically complexed Al. In deeper pore waters, K-feldspar is in equilibrium and plagioclase is about an order of magnitude undersaturated. Hydrologic heterogeneity produces a range of weathering gradients that are constrained by solute distributions and matrix and macropore flow regimes. Plagioclase weathering rates, based on precipitation-corrected Na gradients, vary between 3 and 7 ?? 10-16 mol m-2 s-1. These rates are similar to previously determined solid-state rates but are several orders of magnitude slower than for experimental plagioclase dissolution indicating strong inhibitions to natural weathering, partly due to near-equilibrium weathering reactions. Copyright ?? 2005 Elsevier Ltd.

Effect of Boron Doping on Cellular Discontinuous Precipitation for Age-Hardenable Cu–Ti Alloys

PubMed Central

Semboshi, Satoshi; Ikeda, Jun; Iwase, Akihiro; Takasugi, Takayuki; Suzuki, Shigeru

2015-01-01

The effects of boron doping on the microstructural evolution and mechanical and electrical properties of age-hardenable Cu–4Ti (at.%) alloys are investigated. In the quenched Cu–4Ti–0.03B (at.%) alloy, elemental B (boron) is preferentially segregated at the grain boundaries of the supersaturated solid-solution phase. The aging behavior of the B-doped alloy is mostly similar to that of conventional age-hardenable Cu–Ti alloys. In the early stage of aging at 450 °C, metastable β′-Cu4Ti with fine needle-shaped precipitates continuously form in the matrix phase. Cellular discontinuous precipitates composed of the stable β-Cu4Ti and solid-solution laminates are then formed and grown at the grain boundaries. However, the volume fraction of the discontinuous precipitates is lower in the Cu–4Ti–0.03B alloy than the Cu–4Ti alloy, particularly in the over-aging period of 72–120 h. The suppression of the formation of discontinuous precipitates eventually results in improvement of the hardness and tensile strength. It should be noted that minor B doping of Cu–Ti alloys also effectively enhances the elongation to fracture, which should be attributed to segregation of B at the grain boundaries.

Estimation of equilibrium surface precipitation constants for trivalent metal sorption onto hydrous ferric oxide and calcite

NASA Astrophysics Data System (ADS)

Ragavan, Anpalaki J.; Adams, Dean V.

2009-06-01

Equilibrium constants for modeling surface precipitation of trivalent metal cations ( M) onto hydrous ferric oxide and calcite were estimated from linear correlations of standard state Gibbs free energies of formation, ( ΔGf,MvX(ss)0) of the surface precipitates. The surface precipitation reactions were derived from Farley et. al. [K.J. Farley, D.A. Dzombak, F.M.M. Morel, J. Colloid Interface Sci. 106 (1985) 226] surface precipitation model, which are based on surface complexation model coupled with solid solution representation for surface precipitation on the solid surface. The ΔGf,MvX(ss)0 values were correlated through the following linear free energy relations ΔGf,M(OH)3(ss)0-791.70r=0.1587ΔGn,M0-1273.07 and ΔGf,M2(CO3)3(ss)0-197.241r=0.278ΔGn,M0-1431.27 where 'ss' stands for the end-member solid component of surface precipitate, ΔGf,MvX(ss)0 is in kJ/mol, r is the Shannon-Prewitt radius of M in a given coordination state (nm), and ΔGn,M0 is the non-solvation contribution to the Gibbs free energy of formation of the aqueous M ion. Results indicate that the above surface precipitation correlations are useful tools where experimental data are not available.

Solids precipitation in crude oils, gas-to-liquids and their blends

NASA Astrophysics Data System (ADS)

Ramanathan, Karthik

Gas-to-liquids (GTL) liquids are obtained from syngas by the Fischer-Tropsch synthesis. The blending of GTL liquids produced from natural gas/coal reserves and crude oils is a possibility in the near future for multiple reasons. Solids precipitation is a major problem in pipelines and refineries leading to significant additional operating costs. The effect of the addition of a paraffinic GTL liquid to crude oils on solids precipitation was investigated in this study. A Fourier transform infrared (FT-IR) spectroscopic technique was used to obtain solid-liquid equilibria (SLE) data for the various samples. The SLE of multiple systems of model oils composed of n-alkanes was investigated preliminarily. Blends of a model oil simulating a GTL liquid composition and a crude oil showed that the wax precipitation temperature (WPT) decreased upon blending. Three crude oils from different geographic regions (Alaskan North Slope, Colorado and Venezuela) and a laboratory-produced GTL liquid were used in the preparation of blends with five different concentrations of the GTL liquid. The wax precipitation temperatures of the blends were found to decrease with the increasing addition of the GTL liquid for all the oils. This effect was attributed to the solvent effect of the low molecular weight-paraffinic GTL liquid on the crude oils. The weight percent solid precipitated that was estimated as a function of temperature did not show a uniform trend for the set of crude oils. The asphaltene onset studies done on the blends with near-infrared spectroscopy indicated that the addition of GTL liquid could have a stabilizing effect on the asphaltenes in some oils. Analytical techniques such as distillation, solvent separation, HPLC, GC, and GPC were used to obtain detailed composition data on the samples. Two sets of compositional data with 49 and 86 pseudo-components were used to describe the three crude oils used in the blending work. The wax precipitation was calculated using a thermodynamic model based on a modified regular solution theory. A study was done to test the sensitivity of the thermodynamic model to varying levels of crude oil characterization input data for a fourth crude oil sample. The differentiation of the solute fraction (C25+) into the normal alkane, non-n-alkane and the aromatic fractions was found to be important for improving the predictive accuracy of the model. The n-alkane and non-n-alkane distribution used in the modeling of wax precipitation for the three crude oils blended with the GTL liquid gave the WPT's that agreed to within 5% of the experimental values. The precipitated solid amounts were overestimated using this method.

Enhancing the ag precipitation by surface mechanical attrition treatment on Cu-Ag alloys

NASA Astrophysics Data System (ADS)

Liu, Jiabin; Zhang, Lehao; Liu, Jingjing; Huang, Liuyi; Gu, Hao; Fang, Youtong; Meng, Liang; Zhang, Jian

2016-09-01

The influence of surface mechanical attrition treatment (SMAT) on Ag precipitation in Cu-Ag alloys was investigated. Cu-6 wt% Ag was melt, cold rolled and solution treated to be Cu-Ag solid solution, which was either aged at 250 and 350 °C for 24 h directly or SMAT-ed before aging. Ag precipitates were hard be found in the directly aged Cu-Ag sample while they were observed clearly in the SMAT-ed counterpart at 250 °C. The Ag precipitates formed in the surface layer by SMAT are much coarser than those in the un-SMAT-ed sample. It is obvious that the precipitating behavior of Ag was promoted significantly by SMAT approach. A large number of defects were generated by SMAT and they were acting as fast atomic diffusion channels that facilitated the atomic diffusion of Ag.

A Simple Experiment in the Separation of a Solid-Phase Mixture and Infrared Spectroscopy for Introductory Chemistry

ERIC Educational Resources Information Center

Szalay, Paul S.

2008-01-01

This experiment was developed as a means of incorporating instrumental analyses into an introductory chemistry laboratory. A two-component solid mixture of caffeine and ibuprofen is separated through a series of solution extractions and precipitation and their relative amounts measured. These compounds were chosen because the combination of…

Recycling paper-pulp waste liquors

NASA Technical Reports Server (NTRS)

Sarbolouki, M. N.

1981-01-01

Papermills in U.S. annually produce 3 million tons of sulfite waste liquor solids; other fractions of waste liquor are monomeric sugars and lignosulfonates in solution. Recovery of lignosulfonates involves precipitation and cross-linking of sulfonates to form useful solid ion-exchange resin. Contamination of sugars recovered from liquor is avoided by first converting them to ethanol, then removing ethanol by distillation.

SOLIDS PRECIPITATION EVENT IN MCU CAUSAL ANALYSIS AND RECOMMENDATIONS FROM SOLIDS RECOVERY TEAM

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

Garrison, A.; Aponte, C.

A process upset occurred in the Modular Caustic-Side Solvent Extraction Unit (MCU) facility on April 6th, 2014. During recovery efforts, a significant amount of solids were found in the Salt Solution Feed Tank (SSFT), Salt Solution Receipt Tanks (SSRTs), two extraction contactors, and scrub contactors. The solids were identified by Savannah River National Laboratory (SRNL) as primarily sodium oxalate and sodium alumina silicate (NAS) with the presence of some aluminum hydroxide. NAS solids have been present in the SSFT since simulant runs during cold chemical startup of MCU in 2007, and have not hindered operations since that time. During themore » process upset in April 2014, the oxalate solids partially blocked the aqueous outlet of the extraction contactors, causing salt solution to exit through the contactor organic outlet to the scrub contactors with the organic phase. This salt solution overwhelmed the scrub contactors and passed with the organic phase to the strip section of MCU. The partially reversed flow of salt solution resulted in a Strip Effluent (SE) stream that was high in Isopar™ L, pH and sodium. The primary cause of the excessive solids accumulation in the SSRTs and SSFT at MCU is attributed to an increase in the frequency of oxalic acid cleaning of the 512-S primary filter. Agitation in the SSRTs at MCU in response to cold weather likely provided the primary mechanism to transfer the solids to the contactors. Sources of the sodium oxalate solids are attributed to the oxalic acid cleaning solution used to clean the primary filter at the Actinide Removal Process (ARP) filtration at 512-S, as well as precipitation from the salt batch feed, which is at or near oxalate saturation. The Solids Recovery Team was formed to determine the cause of the solids formation and develop recommendations to prevent or mitigate this event in the future. A total of 53 recommendations were generated. These recommendations were organized into 4 focus areas: • Improve understanding of oxalate equilibrium and kinetics in salt solutions • Reduction/elimination of oxalic acid cleaning in 512-S • Flowsheet optimization • Improving diagnostic capability The recommendations implemented prior to resumption of MCU operations provide a risk mitigation or detection function through additional sampling and observation. The longer term recommendations provide a framework to increase the basic process knowledge of both oxalate chemistry and filtration behavior and then facilitate decisions that improve the salt flowsheet as a system.« less

Thermodynamic stability of CoOOH and its coprecipitation with manganese

USGS Publications Warehouse

Hem, J.D.; Roberson, C.E.; Lind, Carol J.

1985-01-01

A precipitate of cobalt oxyhydroxides formed by bubbling oxygen through a dilute solution of Co(NO3)2 held at pH 9.0 and 25??C was aged for 23 months in contact with the original solution, with access to atmospheric oxygen. Co3O4 and CoOOH were identified in the precipitate by X-ray diffraction. Chemical equilibria involving these solids were evaluated by measurements of solution pH and Co2+ activities and by redox potential measurements and gave a ??GcoOOH0 of -92.3 ?? 0.5 kcal/mole. This value and other thermodynamic data show relative feasibility of hypothetical reaction steps and changes in reaction paths during automated coprecipitation titrations and subsequent aging of a precipitate that finally contained ??MnOOH, MnO2 (birnessite) and CoOOH. ?? 1985.

Recovery of valuable elements from spent Li-batteries.

PubMed

Paulino, Jéssica Frontino; Busnardo, Natália Giovanini; Afonso, Julio Carlos

2008-02-11

This work examines two recycling processes for spent Li/MnO(2) and Li-ion batteries. The anode, cathode and electrolyte (LiPF(6)) were submitted to one of the following procedures: (a) calcination at 500 degrees C (5h) followed by solvent extraction to recover lithium salts (fluoride, phosphate) in good yield (90 wt%). The residual solid was treated with H(2)SO(4) containing H(2)O(2) and on evaporation gave high purity grade cobalt or manganese sulfate; (b) fusion with KHSO(4) (500 degrees C, 5h). The resulting aqueous solution was added dropwise to a solution of NaOH, giving cobalt or manganese as impure precipitate. Addition of KF precipitated high purity grade LiF in moderate yield (50 wt%). The final aqueous solution on treatment with calcium sulfate precipitated the corresponding phosphate and fluoride salts.

The influence of surface friction on the AA2024 microstructure

NASA Astrophysics Data System (ADS)

Eliseev, A. A.; Kolubaev, E. A.; Fortuna, S. V.

2017-12-01

This work is devoted to the study of the effect of sliding at velocities close to those achieved during friction stir welding or friction drilling on the microstructural evolution of 2024 aluminum alloy. The distribution of both solid solution grains and intermetallic precipitates is analyzed. No layers of recrystallized grains depleted by precipitates, which is a common finding in FSW or friction drilling, are found below the worn surface independently of the sliding velocity. A small precipitate content and size changes alone are observed.

Recovery of gold from computer circuit board scrap using aqua regia.

PubMed

Sheng, Peter P; Etsell, Thomas H

2007-08-01

Computer circuit board scrap was first treated with one part concentrated nitric acid and two parts water at 70 degrees C for 1 h. This step dissolved the base metals, thereby liberating the chips from the boards. After solid-liquid separation, the chips, intermixed with some metallic flakes and tin oxide precipitate, were mechanically crushed to liberate the base and precious metals contained within the protective plastic or ceramic chip cases. The base metals in this crushed product were dissolved by leaching again with the same type of nitric acid-water solution. The remaining solid constituents, crushed chips and resin, plus solid particles of gold, were leached with aqua regia at various times and temperatures. Gold was precipitated from the leachate with ferrous sulphate.

DISSOLUTION OF URANIUM FUELS BY MONOOR DIFLUOROPHOSPHORIC ACID

DOEpatents

Johnson, R.; Horn, F.L.; Strickland, G.

1963-05-01

A method of dissolving and separating uranium from a uranium matrix fuel element by dissolving the uraniumcontaining matrix in monofluorophosphoric acid and/or difluorophosphoric acid at temperatures ranging from 150 to 275 un. Concent 85% C, thereafter neutralizing the solution to precipitate uranium solids, and converting the solids to uranium hexafluoride by treatment with a halogen trifluoride is presented. (AEC)

Temperature dependence of nucleation rate in a binary solid solution

NASA Astrophysics Data System (ADS)

Wang, H. Y.; Philippe, T.; Duguay, S.; Blavette, D.

2012-12-01

The influence of regression (partial dissolution) effects on the temperature dependence of nucleation rate in a binary solid solution has been studied theoretically. The results of the analysis are compared with the predictions of the simplest Volmer-Weber theory. Regression effects are shown to have a strong influence on the shape of the curve of nucleation rate versus temperature. The temperature TM at which the maximum rate of nucleation occurs is found to be lowered, particularly for low interfacial energy (coherent precipitation) and high-mobility species (e.g. interstitial atoms).

Immobilization of 99-Technetium (VII) by Fe(II)-Goethite and Limited Reoxidation

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

Um, Wooyong; Chang, Hyun-Shik; Icenhower, Jonathan P.

2011-05-04

Synthesized goethite was successfully used with addition of Fe(II) to sequester Tc present in both deionized water and simulated off-gas scrubber waste solutions. Pertechnetate concentration in solution decreased immediately when the pH was raised above 7 by addition of sodium hydroxide. Removal of Tc(VII) from solution occurred most likely as a result of heterogeneous surface-catalyzed reduction to Tc(IV) and subsequent co-precipitation onto the goethite. The final Tc-bearing solid was identified as goethite-dominated Fe(III)-(oxy)hydroxide based on XRD analysis, confirming the widespread observation of its characteristic acicular habit by TEM/SEM images. Analysis of the solid precipitate by XAFS showed that the dominantmore » oxidation state of Tc was Tc(IV) and was in octahedral coordination with Tc-O, Fe-O, and Tc-Fe bond distances that are consistent with direct substitution of Tc for Fe in the goethite structure. In some experiments the final Tc-goethite product was subsequently armored with additional layers of freshly precipitated goethite. Successful incorporation of Tc(IV) within the goethite mineral lattice and subsequent goethite armoring can limit re-oxidation of Tc(IV) and its subsequent release from Tc-goethite waste forms, even when the final product is placed in oxidizing environments that typify shallow waste burial facilities.« less

On the Precipitation in an Ag-Containing Mg-Gd-Zr Alloy

NASA Astrophysics Data System (ADS)

Zhang, Yu; Zhu, Yuman; Rong, Wei; Wu, Yujuan; Peng, Liming; Nie, Jian-Feng; Birbilis, Nick

2018-02-01

The evolution of precipitates in a high-strength Mg-2.4Gd-0.4Ag-0.1Zr (at. pct) alloy was investigated using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The precipitation of Mg-2.4Gd-0.4Ag-0.1Zr includes β- and γ-type precipitates, the latter involving a hitherto unreported precipitation sequence that is the focus of the present study. The β-type precipitation sequence is described as follows: supersaturated solid solution (S.S.S.S.) → ordered solute clusters → zigzag GP zones → β' → βF' → β 1 → β. Compared with the precipitation sequence of the Mg-Gd system, the proposed β-type precipitation sequence includes ordered solute clusters, zigzag GP zones, and βF' , but excludes β″. The strain field around the coarsened β' phase is supposed to stimulate the formation of the β^'F phase. Furthermore, the βF' phase provides preferential nucleation site for the β 1 phase. The γ-type precipitation sequence is proposed as follows: S.S.S.S. → basal GP zones → γ''' → γ″ → γ. The crystal structures, morphologies, and orientations of the basal GP zone, γ''', γ″, γ phases were comprehensively examined and established herein. The results are described in the context of other, but similar, alloy systems. A holistic description of the precipitate evolution in Ag-containing Mg-Gd alloys is discussed and rationalized.

Solubility Limits of Dibutyl Phosphoric Acid in Uranium Solutions at SRS

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

Thompson, M.C.; Pierce, R.A.; Ray, R.J.

1998-06-01

The Savannah River Site has enriched uranium (EU) solution which has been stored for almost 10 years since being purified in the second uranium cycle of the H area solvent extraction process. The concentrations in solution are {tilde 6} g/L U and about 0.1 M nitric acid. Residual tributylphosphate in the solutions has slowly hydrolyzed to form dibutyl phosphoric acid (HDBP) at concentrations averaging 50 mg/L. Uranium is known to form compounds with DBP which have limited solubility. The potential to form uranium-DBP solids raises a nuclear criticality safety issue. SRTC tests have shown that U-DBP solids will precipitate atmore » concentrations potentially attainable during storage of enriched uranium solutions. Evaporation of the existing EUS solution without additional acidification could result in the precipitation of U-DBP solids if DBP concentration in the resulting solution exceeds 110 ppm at ambient temperature. The same potential exists for evaporation of unwashed 1CU solutions. The most important variables of interest for present plant operations are HNO{sub 3} and DBP concentrations. Temperature is also an important variable controlling precipitation. The data obtained in these tests can be used to set operating and safety limits for the plant. It is recommended that the data for 0 degrees C with 0.5 M HNO{sub 3} be used for setting the limits. The limit would be 80 mg/L which is 3 standard deviations below the average of 86 observed in the tests. The data shows that super-saturation can occur when the DBP concentration is as much as 50 percent above the solubility limit. However, super-saturation cannot be relied on for maintaining nuclear criticality safety. The analytical method for determining DBP concentration in U solutions was improved so that analyses for a solution are accurate to within 10 percent. However, the overall uncertainty of results for periodic samples of the existing EUS solutions was only reduced slightly. Thus, sampling appears to be the largest portion of the uncertainty for EUS sample results, although the number of samples analyzed here is low which could contribution to higher uncertainty. The analytical method can be transferred to the plant analytical labs for more routine analysis of samples.« less

Influence of formulation and processing variables on properties of itraconazole nanoparticles made by advanced evaporative precipitation into aqueous solution.

PubMed

Bosselmann, Stephanie; Nagao, Masao; Chow, Keat T; Williams, Robert O

2012-09-01

Nanoparticles, of the poorly water-soluble drug, itraconazole (ITZ), were produced by the Advanced Evaporative Precipitation into Aqueous Solution process (Advanced EPAS). This process combines emulsion templating and EPAS processing to provide improved control over the size distribution of precipitated particles. Specifically, oil-in-water emulsions containing the drug and suitable stabilizers are sprayed into a heated aqueous solution to induce precipitation of the drug in form of nanoparticles. The influence of processing parameters (temperature and volume of the heated aqueous solution; type of nozzle) and formulation aspects (stabilizer concentrations; total solid concentrations) on the size of suspended ITZ particles, as determined by laser diffraction, was investigated. Furthermore, freeze-dried ITZ nanoparticles were evaluated regarding their morphology, crystallinity, redispersibility, and dissolution behavior. Results indicate that a robust precipitation process was developed such that size distribution of dispersed nanoparticles was shown to be largely independent across the different processing and formulation parameters. Freeze-drying of colloidal dispersions resulted in micron-sized agglomerates composed of spherical, sub-300-nm particles characterized by reduced crystallinity and high ITZ potencies of up to 94% (w/w). The use of sucrose prevented particle agglomeration and resulted in powders that were readily reconstituted and reached high and sustained supersaturation levels upon dissolution in aqueous media.

METHOD OF SEPARATING FROTHS FROM LIQUIDS

DOEpatents

Monet, G.P.

1958-01-21

A method for separating solids and precipitates from liquids is described. The method is particularly adapted for and valuable in processing highly radioactive solutions. It consists in essence, in employing the principles of froth flotation to effect the separation of approximately 99% of the solids present. An apparatus, consisting of a system of pipes, valves and vessels, for carrying out the process of this patent is also described therein.

Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite I: X-ray absorption extended fine structure spectroscopy analysis

USGS Publications Warehouse

Waychunas, G.A.; Fuller, C.C.; Davis, J.A.

2002-01-01

"Two-line" ferrihydrite samples precipitated and then exposed to a range of aqueous Zn solutions (10-5 to 10-3 M), and also coprecipitated in similar Zn solutions (pH 6.5), have been examined by Zn and Fe K-edge X-ray absorption spectroscopy. Typical Zn complexes on the surface have Zn-O distances of 1.97(0.2) A?? and coordination numbers of about 4.0(0.5), consistent with tetrahedral oxygen coordination. This contrasts with Zn-O distances of 2.11(.02) A?? and coordination numbers of 6 to 7 in the aqueous Zn solutions used in sample preparation. X-ray absorption extended fine structure spectroscopy (EXAFS) fits to the second shell of cation neighbors indicate as many as 4 Zn-Fe neighbors at 3.44(.04) A?? in coprecipitated samples, and about two Zn-Fe neighbors at the same distance in adsorption samples. In both sets of samples, the fitted coordination number of second shell cations decreases as sorption density increases, indicating changes in the number and type of available complexing sites or the onset of competitive precipitation processes. Comparison of our results with the possible geometries for surface complexes and precipitates suggests that the Zn sorption complexes are inner sphere and at lowest adsorption densities are bidentate, sharing apical oxygens with adjacent edge-sharing Fe(O,OH)6 octahedra. Coprecipitation samples have complexes with similar geometry, but these are polydentate, sharing apices with more than two adjacent edge-sharing Fe(O,OH)6 polyhedra. The results are inconsistent with Zn entering the ferrihydrite structure (i.e., solid solution formation) or formation of other Zn-Fe precipitates. The fitted Zn-Fe coordination numbers drop with increasing Zn density with a minimum of about 0.8(.2) at Zn/(Zn + Fe) of 0.08 or more. This change appears to be attributable to the onset of precipitation of zinc hydroxide polymers with mainly tetrahedral Zn coordination. At the highest loadings studied, the nature of the complexes changes further, and a second type of precipitate forms. This has a structure based on a brucite layer topology, with mainly octahedral Zn coordination. Amorphous zinc hydroxide samples prepared for comparison had a closely similar local structure. Analysis of the Fe K-edge EXAFS is consistent with surface complexation reactions and surface precipitation at high Zn loadings with little or no Fe-Zn solid solution formation. The formation of Zn-containing precipitates at solution conditions two or more orders of magnitude below their solubility limit is compared with other sorption and spectroscopic studies that describe similar behavior. Copyright ?? 2002 Elsevier Science Ltd.

Reactive solute transport in streams: A surface complexation approach for trace metal sorption

USGS Publications Warehouse

Runkel, Robert L.; Kimball, Briant A.; McKnight, Diane M.; Bencala, Kenneth E.

1999-01-01

A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

Inhibition of precipitation and aggregation of metacinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

USGS Publications Warehouse

Ravichandran, M.; Aiken, G.R.; Ryan, J.N.; Reddy, M.M.

1999-01-01

Precipitation and aggregation of metacinnabar (black HgS) was inhibited in the presence of low concentrations (???3 mg C/L) of humic fractions of dissolved organic matter (DOM) isolated from the Florida Everglades. At low Hg concentrations (??? x 10-8 M), DOM prevented the precipitation of metacinnabar. At moderate Hg concentrations (5 x 10-5 M), DOM inhibited the aggregation of colloidal metacinnabar (Hg passed through a 0.1 ??m filter but was removed by centrifugation). At Hg concentrations greater than 5 x 10-4 M, mercury formed solid metacinnabar particles that were removed from solution by a 0.1 ??m filter. Organic matter rich in aromatic moleties was preferentially removed with the solid. Hydrophobic organic acids (humic and fulvic acids) inhibited aggregation better than hydrophilic organic acids. The presence of chloride, acetate, salicylate, EDTA, and cysteine did not inhibit the precipitation or aggregation of metacinnabar. Calcium enhanced metacinnabar aggregation even in the presence of DOM, but the magnitude of the effect was dependent on the concentrations of DOM, Hg, and Ca. Inhibition of metacinnabar precipitation appears to be a result of strong DOM-Hg binding. Prevention of aggregation of colloidal particles appears to be caused by adsorption of DOM and electrostatic repulsion.Precipitation and aggregation of metacinnabar (black HgS) was inhibited in the presence of low concentrations (???3 mg C/L) of humic fractions of dissolved organic matter (DOM) isolated from the Florida Everglades. At low Hg concentrations (???5??10-8 M), DOM prevented the precipitation of metacinnabar. At moderate Hg concentrations (5??10-5 M), DOM inhibited the aggregation of colloidal metacinnabar (Hg passed through a 0.1 ??m filter but was removed by centrifugation). At Hg concentrations greater than 5??10-4 M, mercury formed solid metacinnabar particles that were removed from solution by a 0.1 ??m filter. Organic matter rich in aromatic moieties was preferentially removed with the solid. Hydrophobic organic acids (humic and fulvic acids) inhibited aggregation better than hydrophilic organic acids. The presence of chloride, acetate, salicylate, EDTA, and cysteine did not inhibit the precipitation or aggregation of metacinnabar. Calcium enhanced metacinnabar aggregation even in the presence of DOM, but the magnitude of the effect was dependent on the concentrations of DOM, Hg, and Ca. Inhibition of metacinnabar precipitation appears to be a result of strong DOM-Hg binding. Prevention of aggregation of colloidal particles appears to be caused by adsorption of DOM and electrostatic repulsion.

Simulations of reactive transport and precipitation with smoothed particle hydrodynamics

NASA Astrophysics Data System (ADS)

Tartakovsky, Alexandre M.; Meakin, Paul; Scheibe, Timothy D.; Eichler West, Rogene M.

2007-03-01

A numerical model based on smoothed particle hydrodynamics (SPH) was developed for reactive transport and mineral precipitation in fractured and porous materials. Because of its Lagrangian particle nature, SPH has several advantages for modeling Navier-Stokes flow and reactive transport including: (1) in a Lagrangian framework there is no non-linear term in the momentum conservation equation, so that accurate solutions can be obtained for momentum dominated flows and; (2) complicated physical and chemical processes such as surface growth due to precipitation/dissolution and chemical reactions are easy to implement. In addition, SPH simulations explicitly conserve mass and linear momentum. The SPH solution of the diffusion equation with fixed and moving reactive solid-fluid boundaries was compared with analytical solutions, Lattice Boltzmann [Q. Kang, D. Zhang, P. Lichtner, I. Tsimpanogiannis, Lattice Boltzmann model for crystal growth from supersaturated solution, Geophysical Research Letters, 31 (2004) L21604] simulations and diffusion limited aggregation (DLA) [P. Meakin, Fractals, scaling and far from equilibrium. Cambridge University Press, Cambridge, UK, 1998] model simulations. To illustrate the capabilities of the model, coupled three-dimensional flow, reactive transport and precipitation in a fracture aperture with a complex geometry were simulated.

Heat and corrosion resistant cast CN-12 type stainless steel with improved high temperature strength and ductility

DOEpatents

Mazias, Philip J [Oak Ridge, TN; McGreevy, Tim [Morton, IL; Pollard, Michael James [East Peoria, IL; Siebenaler, Chad W [Peoria, IL; Swindeman, Robert W [Oak Ridge, TN

2007-08-14

A cast stainless steel alloy and articles formed therefrom containing about 0.5 wt. % to about 10 wt. % manganese, 0.02 wt. % to 0.50 wt. % N, and less than 0.15 wt. % sulfur provides high temperature strength both in the matrix and at the grain boundaries without reducing ductility due to cracking along boundaries with continuous or nearly-continuous carbides. Alloys of the present invention also have increased nitrogen solubility thereby enhancing strength at all temperatures because nitride precipitates or nitrogen porosity during casting are not observed. The solubility of nitrogen is dramatically enhanced by the presence of manganese, which also retains or improves the solubility of carbon thereby providing additional solid solution strengthening due to the presence of manganese and nitrogen, and combined carbon. Such solution strengthening enhances the high temperature precipitation-strengthening benefits of fine dispersions of NbC. Such solid solution effects also enhance the stability of the austenite matrix from resistance to excess sigma phase or chrome carbide formation at higher service temperatures. The presence of sulfides is substantially eliminated.

Lattice mismatch modeling of aluminum alloys

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

Shin, Dongwon; Roy, Shibayan; Watkins, Thomas R.

We present a theoretical framework to accurately predict the lattice mismatch between the fcc matrix and precipitates in the multi-component aluminum alloys as a function of temperature and composition. We use a computational thermodynamic approach to model the lattice parameters of the multi-component fcc solid solution and θ'-Al2Cu precipitate phase. Better agreement between the predicted lattice parameters of fcc aluminum in five commercial alloys (206, 319, 356, A356, and A356 + 0.5Cu) and experimental data from the synchrotron X-ray diffraction (SXD) has been obtained when simulating supersaturated rather than equilibrium solid solutions. We use the thermal expansion coefficient of thermodynamicallymore » stable θ-Al2Cu to describe temperature-dependent lattice parameters of meta-stable θ' and to show good agreement with the SXD data. Both coherent and semi-coherent interface mismatches between the fcc aluminum matrix and θ' in Al-Cu alloys are presented as a function of temperature. Our calculation results show that the concentration of solute atoms, particularly Cu, in the matrix greatly affects the lattice mismatch« less

Method of making supercritical fluid molecular spray films, powder and fibers

DOEpatents

Smith, Richard D.

1988-01-01

Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a heated nozzle having a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. In another embodiment, the temperature of the solution and nozzle is elevated above the melting point of the solute, which is preferably a polymer, and the solution is maintained at a pressure such that, during expansion, the solute precipitates out of solution within the nozzle in a liquid state. Alternatively, a secondary solvent mutually soluble with the solute and primary solvent and having a higher critical temperature than that of primary solvent is used in a low concentration (<20%) to maintain the solute in a transient liquid state. The solute is discharged in the form of long, thin fibers. The fibers are collected at sufficient distance from the orifice to allow them to solidify in the low pressure/temperature region.

Dynamics of Magnesite Formation at Low-Temperature and High pCO2 in Aqueous Solution

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

Qafoku, Odeta; Dixon, David A.; Rosso, Kevin M.

2015-09-17

Like many metal carbonate minerals, despite conditions of supersaturation, precipitation of magnesite from aqueous solution is kinetically hindered at low temperatures, for reasons that remain poorly understood. The present study examines precipitation products from reaction of Mg(OH)2 in aqueous solutions saturated with supercritical CO2 at high pressures (90 atm and 110 atm) and low temperatures (35 °C and 50 °C). Traditional bulk characterization (X-ray diffraction) of the initial solid formed indicated the presence of hydrated magnesium carbonates (hydromagnesite and nesquehonite), thermodynamically metastable phases that were found to slowly react during ageing to the more stable anhydrous form, magnesite, at temperaturesmore » as low as 35 °C (135-140 days) and at a faster rate at 50 °C (56 days). Undetected by bulk measurements, detailed examination of the precipitates by scanning electron microscopy (SEM) showed that magnesite is present as a minor component at relatively early reaction times (7 days) at 50 °C. In addition to magnesite dominating the solid phases over time, we find that mangesite nucleation and growth occurs more quickly with increasing partial pressure of CO2, and in electrolyte solutions with high bicarbonate content. Furthermore, formation of magnesite was found to be enhanced in sulfate-rich solutions, compared to chloride-rich solutions. We speculate that much of this behavior is possibly due to sulfate serving as sink of protons generated during carbonation reactions. These results support the importance of integrating magnesite as an equilibrium phase in reactive transport calculations of the effects of carbon dioxide sequestration on subsurface formations at long time scales.« less

Process for immobilizing radioactive boric acid liquid wastes

DOEpatents

Greenhalgh, Wilbur O.

1986-01-01

A method of immobilizing boric acid liquid wastes containing radionuclides by neutralizing the solution and evaporating the resulting precipitate to near dryness. The dry residue is then fused into a reduced volume, insoluble, inert, solid form containing substantially all the radionuclides.

40 CFR 421.122 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

... Ammonia (as N) 6,712.000 2,951.000 Total suspended solids 2,065.000 981.800 pH (1) (1) 1 Within the range... from precipitation and filtration of film stripping solutions Copper 1.843 .970 Zinc 1.416 .592 Ammonia... silver precipitated Copper 109.400 57.570 Zinc 84.050 35.120 Ammonia (as N) 7,674.000 3,374.000 Total...

40 CFR 421.122 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

... Ammonia (as N) 6,712.000 2,951.000 Total suspended solids 2,065.000 981.800 pH (1) (1) 1 Within the range... from precipitation and filtration of film stripping solutions Copper 1.843 .970 Zinc 1.416 .592 Ammonia... silver precipitated Copper 109.400 57.570 Zinc 84.050 35.120 Ammonia (as N) 7,674.000 3,374.000 Total...

40 CFR 421.122 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... Ammonia (as N) 6,712.000 2,951.000 Total suspended solids 2,065.000 981.800 pH (1) (1) 1 Within the range... from precipitation and filtration of film stripping solutions Copper 1.843 .970 Zinc 1.416 .592 Ammonia... silver precipitated Copper 109.400 57.570 Zinc 84.050 35.120 Ammonia (as N) 7,674.000 3,374.000 Total...

Effects of Preheat on Weldments of NICOP Steel.

DTIC Science & Technology

1983-09-01

copper in this low alloy steel . Taken into solid solution in the austenite phase , the copper can precipitate as fine... low alloy steel was intro- duced which contains 1.0-1.3% copper with a maximum of 0.07% carbon. This steel is designated as AST4 A710 grade A for... ferrite has formed, some copper may precipitate as a fine epsilon copper phase in the ferrite as the solubility of

Fluorescence Approaches to Growing Macromolecule Crystals

NASA Technical Reports Server (NTRS)

Pusey, Marc; Forsythe, Elizabeth; Achari, Aniruddha

2006-01-01

Trace fluorescent labeling, typically < 1%, can be a powerful aid in macromolecule crystallization. Precipitation concentrates a solute, and crystals are the most densely packed solid form. The more densely packed the fluorescing material, the more brightly the emission from it, and thus fluorescence intensity of a solid phase is a good indication of whether one has crystals or not. The more brightly fluorescing crystalline phase is easily distinguishable, even when embedded in an amorphous precipitate. This approach conveys several distinct advantages: one can see what the protein is doing in response to the imposed conditions, and distinguishing between amorphous and microcrystalline precipitated phases are considerably simpler. The higher fluorescence intensity of the crystalline phase led us to test if we could derive crystallization conditions from screen outcomes which had no obvious crystalline material, but simply "bright spots" in the precipitated phase. Preliminary results show that the presence of these bright spots, not observable under white light, is indeed a good indicator of potential crystallization conditions.

Chemistry of manganese precipitation in Pinal Creek, Arizona, USA: A laboratory study

USGS Publications Warehouse

Hem, J.D.; Lind, Carol J.

1994-01-01

Groundwater underlying the valley of Pinal Creek downstream from Globe, Arizona, has been contaminated by low-pH metal-enriched wastewater from copper mining and ore processing at Miami, Arizona. At present, the acidity and most of the dissolved metal content, except for Mn, of the wastewater is removed by reactions with carbonate and other solids in the alluvial aquifer before the neutralized contaminated water enters the creek channel and becomes surface flow. Where flow in the creek is perennial, Mn-bearing precipitates are formed in the stream bed and in some places in the subsurface. As an aid to understanding the processes involved and explaining the mineralogy of the precipitates, closely controlled laboratory redox titration experiments were performed on samples of surface flow and groundwater taken near the head of perennial flow in the creek. The high content of dissolved Ca, Mg, Mn and COP2 species in the neutralized contaminated groundwater caused precipitation of some of the Mn as kutnahorite, (Mn, Mg)Ca(CO3)2, when the experimental system was held between pH 8.5 and 9.0 while CO2-free air was bubbled into the solution. Hausmannite and manganite also were precipitated, in somewhat lower amounts. When the concentrations of dissolved CO2 species in the groundwater sample were decreased before the experiment was started, the Mn precipitated was predominantly in the oxides hausmannite and manganite. In some of the experimental titrations clinoenstatite, (MgSiO3), was precipitated. After titrations were stopped the solutions and precipitates were allowed to stand, with limited access to the atmosphere, for several months. During this aging period the degree of oxidation of the precipitated Mn increased and in one precipitate from an experimental solution the Ca + Mn4+ oxides todorokite and takanelite were identified. These oxides also have been identified in streambed precipitates. Some of these precipitates also gave X-ray diffraction reflections for kutnahorite. Thermodynamic feasibilities of eight potential chemical reactions forming solid phases of interest were evaluated by calculating their respective reaction affinities attained during titration and aging. The results are in general agreement with the indications for the presence of these species given by X-ray and electron diffraction. The presence of carbonates in precipitated encrustations formed from groundwater below the land surface and their occurrence in manganese oxide crusts that precipitate from the creek water, also are predicted by these results. ?? 1994.

Catalysis and chemical mechanisms of calcite dissolution in seawater

PubMed Central

Adkins, Jess F.; Rollins, Nick E.; Naviaux, John; Erez, Jonathan; Berelson, William M.

2017-01-01

Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric CO2 on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve 13C-labeled calcites in natural seawater. We show that the time-evolving enrichment of 𝜹13C in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the 13C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution–precipitation shifts significantly toward a dissolution-dominated mechanism below about Ω= 0.7. Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of CO2 is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid–solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at Ω= 0.7, which we interpret as the onset of homogeneous etch pit nucleation. PMID:28720698

Process for immobilizing radioactive boric acid liquid wastes

DOEpatents

Greenhalgh, W.O.

1984-05-10

Disclosed is a method of immobilizing boric acid liquid wastes containing radionuclides by neutralizing the solution and evaporating the resulting precipitate to near dryness. The dry residue is then fused into a reduced volume, insoluble, inert, solid form containing substantially all the radionuclides.

Purification of alkali metal nitrates

DOEpatents

Fiorucci, Louis C.; Gregory, Kevin M.

1985-05-14

A process is disclosed for removing heavy metal contaminants from impure alkali metal nitrates containing them. The process comprises mixing the impure nitrates with sufficient water to form a concentrated aqueous solution of the impure nitrates, adjusting the pH of the resulting solution to within the range of between about 2 and about 7, adding sufficient reducing agent to react with heavy metal contaminants within said solution, adjusting the pH of the solution containing reducing agent to effect precipitation of heavy metal impurities and separating the solid impurities from the resulting purified aqueous solution of alkali metal nitrates. The resulting purified solution of alkali metal nitrates may be heated to evaporate water therefrom to produce purified molten alkali metal nitrate suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of alkali metal nitrates.

Kinetic precipitation of solution-phase polyoxomolybdate followed by transmission electron microscopy: a window to solution-phase nanostructure.

PubMed

Zhu, Yan; Cammers-Goodwin, Arthur; Zhao, Bin; Dozier, Alan; Dickey, Elizabeth C

2004-05-17

This study aimed to elucidate the structural nature of the polydisperse, nanoscopic components in the solution and the solid states of partially reduced polyoxomolybdate derived from the [Mo132] keplerate, [(Mo)Mo5]12-[Mo2 acetate]30. Designer tripodal hexamine-tris-crown ethers and nanoscopic molybdate coprecipitated from aqueous solution. These microcrystalline solids distributed particle radii between 2-30 nm as assayed by transmission electron microscopy (TEM). The solid materials and their particle size distributions were snap shots of the solution phase. The mother liquor of the preparation of the [Mo132] keplerate after three days revealed large species (r=20-30 nm) in the coprecipitate, whereas [Mo132] keplerate redissolved in water revealed small species (3-7 nm) in the coprecipitate. Nanoparticles of coprecipitate were more stable than solids derived solely from partially reduced molybdate. The TEM features of all material analyzed lacked facets on the nanometer length scale; however, the structures diffracted electrons and appeared to be defect-free as evidenced by Moiré patterns in the TEM images. Moiré patterns and size-invariant optical densities of the features in the micrographs suggested that the molybdate nanoparticles were vesicular.

LEACHING OF TITANIUM FROM MONOSODIUM TITANATE AND MODIFIED MST

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

Taylor-Pashow, K.; Fondeur, F.; Fink, S.

2012-08-01

Analysis of a fouled coalescer and pre-filters from Actinide Removal Process/Modular Caustic Side Solvent Extraction Unit (ARP/MCU) operations showed evidence of Ti containing solids. Based on these results a series of tests were planned to examine the extent of Ti leaching from monosodium titanate (MST) and modified monosodium titanate (mMST) in various solutions. The solutions tested included a series of salt solutions with varying free hydroxide concentrations, two sodium hydroxide concentrations, 9 wt % and 15 wt %, nitric and oxalic acid solutions. Overall, the amount of Ti leached from the MST and mMST was much greater in the acidmore » solutions compared to the sodium hydroxide or salt solutions, which is consistent with the expected trend. The leaching data also showed that increasing hydroxide concentration, whether pure NaOH solution used for filter cleaning in ARP or the waste salt solution, increased the amount of Ti leached from both the MST and mMST. For the respective nominal contact times with the MST solids - for filter cleaning or the normal filter operation, the dissolved Ti concentrations are comparable suggesting either cause may contribute to the increased Ti fouling on the MCU coalescers. Tests showed that Ti containing solids could be precipitated from solution after the addition of scrub acid and a decrease in temperature similar to expected in MCU operations. FTIR analysis of these solids showed some similarity to the solids observed on the fouled coalescer and pre-filters. Although only a cursory study, this information suggests that the practice of increasing free hydroxide in feed solutions to MCU as a mitigation to aluminosilicate formation may be offset by the impact of formation of Ti solids in the overall process. Additional consideration of this finding from MCU and SWPF operation is warranted.« less

Structure, optical and phonon properties of bulk and nanocrystalline Al2-xScx(WO4)3 solid solutions doped with Cr3+

NASA Astrophysics Data System (ADS)

Mączka, M.; Hermanowicz, K.; Pietraszko, A.; Yordanova, A.; Koseva, I.

2014-01-01

Pure and Cr3+ doped nanosized Al2-xScx(WO4)3 solid solutions were prepared by co-precipitation method as well as Al2-xScx(WO4)3 single crystals were grown by high-temperature flux method. The obtained samples were characterized by X-ray, Raman, IR, absorption and luminescence methods. Single crystal X-ray diffraction showed that AlSc(WO4)3 is orthorhombic at room temperature with space group Pnca and trivalent cations are statistically distributed. Raman and IR studies showed that Al2-xScx(WO4)3 solid solutions show "two mode" behavior. They also showed that vibrational properties of nanosized samples have been weakly modified in comparison with the bulk materials. The luminescence and absorption spectra revealed that chromium ions occupy two sites of weak and strong crystal field strength.

A phase field model for segregation and precipitation induced by irradiation in alloys

NASA Astrophysics Data System (ADS)

Badillo, A.; Bellon, P.; Averback, R. S.

2015-04-01

A phase field model is introduced to model the evolution of multicomponent alloys under irradiation, including radiation-induced segregation and precipitation. The thermodynamic and kinetic components of this model are derived using a mean-field model. The mobility coefficient and the contribution of chemical heterogeneity to free energy are rescaled by the cell size used in the phase field model, yielding microstructural evolutions that are independent of the cell size. A new treatment is proposed for point defect clusters, using a mixed discrete-continuous approach to capture the stochastic character of defect cluster production in displacement cascades, while retaining the efficient modeling of the fate of these clusters using diffusion equations. The model is tested on unary and binary alloy systems using two-dimensional simulations. In a unary system, the evolution of point defects under irradiation is studied in the presence of defect clusters, either pre-existing ones or those created by irradiation, and compared with rate theory calculations. Binary alloys with zero and positive heats of mixing are then studied to investigate the effect of point defect clustering on radiation-induced segregation and precipitation in undersaturated solid solutions. Lastly, irradiation conditions and alloy parameters leading to irradiation-induced homogeneous precipitation are investigated. The results are discussed in the context of experimental results reported for Ni-Si and Al-Zn undersaturated solid solutions subjected to irradiation.

Solution Treatment Effect on Tensile, Impact and Fracture Behaviour of Trace Zr Added Al-12Si-1Mg-1Cu Piston Alloy

NASA Astrophysics Data System (ADS)

Kaiser, Md. Salim

2018-04-01

The effects of T6 solution treatment on tensile, impact and fracture properties of cast Al-12Si-1Mg-1Cu piston alloys with trace of zirconium were investigated. Cast alloys were given precipitation strengthening treatment having a sequence of homogenizing, solutionizing, quenching and ageing. Both cast and solutionized samples are isochronally aged for 90 min at different temperatures up to 300 °C. Tensile and impact properties of the differently processed alloys have been studied to understand the precipitation strengthening of the alloys. Fractograpy of the alloys were observed to understand the mode of fracture. It is observed that the improvement in tensile properties in the aged alloys through heat treatment is mainly attributed to the formation of the Al2Cu and Mg2Si precipitates within the Al matrix. Solution treatment improves the tensile strength for the reason that during solution treatment some alloying elements are re-dissolved to produce a solute-rich solid solution. Impact energy decreases with ageing temperature due to formation of GP zones, β' and β precipitates. The fractography shows large and small dimple structure and broken or cracked primary Si, particles. Microstructure study of alloys revealed that the solution treatment improved distribution of silicon grains. The addition of Zr produces an improvement in the tensile properties as a result of its grain refining action and grain coarsening resistance in the matrix at a higher temperature.

Influence of an americium solid phase on americium concentrations in solutions

NASA Astrophysics Data System (ADS)

Rai, Dhanpat; Strickert, R. G.; Moore, D. A.; Serne, R. J.

1981-11-01

Americium-241 concentrations in solutions contacting contaminated sediments for up to 2 yr were measured as a function of pH. Steady-state concentrations were reached within a few days. The solubility-limited Am concentration was found to decrease approximately 10-fold with one unit increase in pH. The log equilibrium constant for the solubility of Am (soil) solid [Am (soil) + H + ⇌ Am (aq complex)+] was found to be -4.12. The predictions based upon thermodynamic data suggest that Am (aq complex)+ is likely to be Am(OH) 2+. Although the chemical formula of Am (soil) was not determined, it does not appear to be Am(OH) 3(a). Published data on sorption coefficients of Am by different rocks, soils, and minerals were critically evaluated. Final Am solution concentrations calculated from the sorption coefficients of a variety of earth materials with several solutions agreed well with the concentrations predicted from the solubility of Am (soil) solid, indicating that the sorption coefficient data are controlled by Am precipitation.

A microstructure-based yield stress and work-hardening model for textured 6xxx aluminium alloys

NASA Astrophysics Data System (ADS)

Khadyko, M.; Myhr, O. R.; Dumoulin, S.; Hopperstad, O. S.

2016-04-01

The plastic properties of an aluminium alloy are defined by its microstructure. The most important factors are the presence of alloying elements in the form of solid solution and precipitates of various sizes, and the crystallographic texture. A nanoscale model that predicts the work-hardening curves of 6xxx aluminium alloys was proposed by Myhr et al. The model predicts the solid solution concentration and the particle size distributions of different types of metastable precipitates from the chemical composition and thermal history of the alloy. The yield stress and the work hardening of the alloy are then determined from dislocation mechanics. The model was largely used for non-textured materials in previous studies. In this work, a crystal plasticity-based approach is proposed for the work hardening part of the nanoscale model, which allows including the influence of the crystallographic texture. The model is evaluated by comparison with experimental data from uniaxial tensile tests on two textured 6xxx alloys in five temper conditions.

On the superposition of strengthening mechanisms in dispersion strengthened alloys and metal-matrix nanocomposites: Considerations of stress and energy

NASA Astrophysics Data System (ADS)

Ferguson, J. B.; Schultz, Benjamin F.; Venugopalan, Dev; Lopez, Hugo F.; Rohatgi, Pradeep K.; Cho, Kyu; Kim, Chang-Soo

2014-03-01

Yield strength improvement in dispersion strengthened alloys and nano particle-reinforced composites by well-known strengthening mechanisms such as solid solution, grain refinement, coherent and incoherent dispersed particles, and increased dislocation density resulting from work-hardening can all be described individually. However, there is no agreed upon description of how these mechanisms combine to determine the yield strength. In this work, we propose an analytical yield strength prediction model combining arithmetic and quadratic addition approaches based on the consideration of two types of yielding mechanisms; stress-activated and energy-activated. Using data available in the literature for materials of differing grain sizes, we consider the cases of solid solutions and coherent precipitates to show that they follow stress-activated behavior. Then, we applied our model with some empirical parameters to precipitationhardenable materials of various grain sizes in both coherent and incoherent precipitate conditions, which demonstrated that grain boundary and Orowan-strengthening can be treated as energy-activated mechanisms.

Multiscale microstructures and improved thermoelectric performance of Mg2(Si0.4Sn0.6)Sbx solid solutions

NASA Astrophysics Data System (ADS)

Zhang, Xin; Liu, Hongliang; Li, Songhao; Zhang, Feipeng; Lu, Qingmei; Li, Jingfeng

2014-03-01

A series of Sb-doped Mg2(Si0.4Sn0.6)Sbx (0 ≤ x ≤ 0.025) solid solutions were prepared by an induction melting, Melt Spinning (MS) and Spark Plasma Sintering (SPS) method, namely the non-equilibrium technique MS-SPS, using bulks of Magnesium, Silicon, Tin, and Antimony as raw materials. The non-equilibrium technique generates the unique multiscale microstructures of samples containing micronscale grains and nanoscale precipitates, the multiscale microstructures remarkably make the lattice thermal conductivities decreased, particularly for samples with the nanoscale precipitates having the size of 10-20 nm. Meanwhile, Sb-doping greatly increased the electrical performance of samples. Consequently, the Sb-doping combined with the multiscale microstructures strategy remarkably improves the overall thermoelectric (TE) performance of Sb doped samples, and a high dimensionless figure of merit (ZT) value of up to 1.25 at 723 K is obtained with Mg2(Si0.4Sn0.6)Sb0.02 sample in a relatively wide temperature range.

Effects of Solid Solution Strengthening Elements Mo, Re, Ru, and W on Transition Temperatures in Nickel-Based Superalloys with High γ'-Volume Fraction: Comparison of Experiment and CALPHAD Calculations

NASA Astrophysics Data System (ADS)

Ritter, Nils C.; Sowa, Roman; Schauer, Jan C.; Gruber, Daniel; Goehler, Thomas; Rettig, Ralf; Povoden-Karadeniz, Erwin; Koerner, Carolin; Singer, Robert F.

2018-06-01

We prepared 41 different superalloy compositions by an arc melting, casting, and heat treatment process. Alloy solid solution strengthening elements were added in graded amounts, and we measured the solidus, liquidus, and γ'-solvus temperatures of the samples by DSC. The γ'-phase fraction increased as the W, Mo, and Re contents were increased, and W showed the most pronounced effect. Ru decreased the γ'-phase fraction. Melting temperatures (i.e., solidus and liquidus) were increased by addition of Re, W, and Ru (the effect increased in that order). Addition of Mo decreased the melting temperature. W was effective as a strengthening element because it acted as a solid solution strengthener and increased the fraction of fine γ'-precipitates, thus improving precipitation strengthening. Experimentally determined values were compared with calculated values based on the CALPHAD software tools Thermo-Calc (databases: TTNI8 and TCNI6) and MatCalc (database ME-NI). The ME-NI database, which was specially adapted to the present investigation, showed good agreement. TTNI8 also showed good results. The TCNI6 database is suitable for computational design of complex nickel-based superalloys. However, a large deviation remained between the experiment results and calculations based on this database. It also erroneously predicted γ'-phase separations and failed to describe the Ru-effect on transition temperatures.

Manganese-calcium intermixing facilitates heteroepitaxial growth at the (1014) calcite-water interface

DOE PAGES

Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.; ...

2017-09-05

For this research, in situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10more » $$\\bar{1}$$4) surface of calcite (CaCO 3) single crystals following reaction with Mn2 +-bearing aqueous solutions. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces. In situ time-sequenced measurements demonstrated that the growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2 +-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO 3) and calcite display a 10% lattice mismatch, based on the area of their (10$$\\bar{1}$$4) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO 3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals in calcite-equilibrated aqueous solutions with up to 250 μM MnCl 2. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO 3 solid solution. The epitaxial solid solution had a spatially complex composition, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO 3 for the thickest coatings. The effective lattice mismatch was therefore much smaller than the nominal mismatch thus explaining the measured growth rates. Lastly, these findings highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.« less

Development of advanced high strength tantalum base alloys. Part 1: Screening investigation

NASA Technical Reports Server (NTRS)

Buckman, R. W., Jr.

1971-01-01

Five experimental tantalum alloy compositions containing 13-18% W+Re+Hf solid solution solute additions with dispersed phase strengthening achieved by carbon or nitrogen additions were prepared as 1.4 inch diameter ingot processed to 3/8 inch diameter rod and evaluated. Elevated temperature tensile and creep strength increased monotonically with increasing solute content. Room temperature elongation decreased for 20% to less than 2% as the solute content was increased above 16%. Phase identification indicated that the precipitating phase in the carbide containing alloys was Ta2C.

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

Mehta, Vrajesh; Maillot, Fabien; Wang, Zheming

Uranyl phosphate solids are often found with uranium ores, and their low solubility makes them promising target phases for in situ remediation of uranium-contaminated subsurface environments. The products and solubility of uranium(VI) precipitated with phosphate can be affected by the pH, dissolved inorganic carbon (DIC) concentration, and co-solute composition (e.g. Na+/Ca2+) of the groundwater. Batch experiments were performed to study the effect of these parameters on the products and extent of uranium precipitation induced by phosphate addition. In the absence of co-solute cations, chernikovite [H3O(UO2)(PO4)•3H2O] precipitated despite uranyl orthophosphate [(UO2)3(PO4)2•4H2O] being thermodynamically more favorable under certain conditions. As determined usingmore » X-ray diffraction, electron microscopy, and laser induced fluorescence spectroscopy, the presence of Na+ or Ca2+ as a co-solute led to the precipitation of sodium autunite ([Na2(UO2)2(PO4)2] and autunite [Ca(UO2)2(PO4)2]), which are structurally similar to chernikovite. In the presence of sodium, the dissolved U(VI) concentrations were generally in agreement with equilibrium predictions of sodium autunite solubility. However, in the calcium-containing systems, the observed concentrations were below the predicted solubility of autunite, suggesting the possibility of uranium adsorption to or incorporation in a calcium phosphate precipitate in addition to the precipitation of autunite.« less

Excitonic Solids.

DTIC Science & Technology

1983-11-03

we believe, structural second order phase transitions at the same temperatu "es that the anomalously large diamagnetism disappears and microwave...precipitation from aqueous solution, and by acid doping. The differently doped starting materials were analyzed for C1 and other impurities before being...solution can be given as IV. ACID -DOPING TECHNIQUE -a- [CdCl. ] Samples of pure CdS were stirred and heated with vari- am- = =K[C-]’a0, ous HCI and

Strengthening of metallic alloys with nanometer-size oxide dispersions

DOEpatents

Flinn, John E.; Kelly, Thomas F.

1999-01-01

Austenitic stainless steels and nickel-base alloys containing, by wt. %, 0.1 to 3.0% V, 0.01 to 0.08% C, 0.01 to 0.5% N, 0.05% max. each of Al and Ti, and 0.005 to 0.10% O, are strengthened and ductility retained by atomization of a metal melt under cover of an inert gas with added oxygen to form approximately 8 nanometer-size hollow oxides within the alloy grains and, when the alloy is aged, strengthened by precipitation of carbides and nitrides nucleated by the hollow oxides. Added strengthening is achieved by nitrogen solid solution strengthening and by the effect of solid oxides precipitated along and pinning grain boundaries to provide temperature-stabilization and refinement of the alloy grains.

Kinetics of struvite to newberyite transformation in the precipitation system MgCl2-NH4H2PO4NaOH-H2O.

PubMed

Babić-Ivancić, Vesna; Kontrec, Jasminka; Brecević, Ljerka; Kralj, Damir

2006-10-01

The influence of the initial reactant concentrations on the composition of the solid phases formed in the precipitation system MgCl(2)-NH(4)H(2)PO(4)-NaOH-H(2)O was investigated. The precipitation diagram constructed shows the approximate concentration regions within which struvite, newberyite, and their mixtures exist at 25 degrees C and an aging time of 60 min. It was found that immediately after mixing the reactant solutions, struvite (MgNH(4)PO(4).6H(2)O) precipitated in nearly the whole concentration area, while newberyite (MgHPO(4).3H(2)O) appeared mostly within the region of the excess of magnesium concentration. It was also found that after aging time of 60 min the precipitation domain of struvite alone is much broader than that of newberyite or the domain of their coexistence, and shows that struvite is more abundant in the systems in which the initial concentration of ammonium phosphate is higher than that of magnesium. The kinetics of struvite to newberyite transformation (conversion) was systematically studied under the conditions of different initial reactant concentrations and different initial pH in the systems in which a mixture of both phases precipitated spontaneously. The struvite to newberyite conversion period was found to be strongly related to the ratio of initial supersaturations, S(N)/S(S), rather than to the any particular physical quantity that can describe and predict the behavior of the precipitation system. Experimental data suggest a solution-mediated process as a most possible transformation mechanism. Along with a continuous monitoring of the changes in the liquid phase, the content of struvite in the solid phase was estimated by means of a Fourier transform infrared (FT-IR) method, developed for this particular precipitation system.

Method for removal and stabilization of mercury in mercury-containing gas streams

DOEpatents

Broderick, Thomas E.

2005-09-13

The present invention is directed to a process and apparatus for removing and stabilizing mercury from mercury-containing gas streams. A gas stream containing vapor phase elemental and/or speciated mercury is contacted with reagent, such as an oxygen-containing oxidant, in a liquid environment to form a mercury-containing precipitate. The mercury-containing precipitate is kept or placed in solution and reacts with one or more additional reagents to form a solid, stable mercury-containing compound.

Mechanical, Corrosion, and Fatigue Properties of 15-5 PH, Inconel 718, and Rene 41 Weldments

DTIC Science & Technology

1975-05-01

TUCUMvARI (PGH 2) It was originally developed for high - temperature use by Armco Steel Corporation. 2 High strength is obtained by the precipitation...Rene 41 was developed by General Electric Company as a high - temperature turbine alloy. It is a nickel-base alloy, high in chromium, cobalt, and... molybdenum . Its high strength comes from the precipitation of a gamma-prime phase consisting of Ni3AI and Ni5Ti, and from the solid solution effects of

3D Modeling of Transport Phenomena and the Injection of the Solution Droplets in the Solution Precursor Plasma Spraying

NASA Astrophysics Data System (ADS)

Shan, Yanguang; Coyle, Thomas W.; Mostaghimi, Javad

2007-12-01

Solution precursor plasma spraying has been used to produce finely structured ceramic coatings with nano- and sub-micrometric features. This process involves the injection of a solution spray of ceramic salts into a DC plasma jet under atmospheric condition. During the process, the solvent vaporizes as the droplet travel downstream. Solid particles are finally formed due to the precipitation of the solute, and the particle are heated up and accelerated to the substrate to generate the coating. This article describes a 3D model to simulate the transport phenomena and the trajectory and heating of the solution spray in the process. The jet-spray two-way interactions are considered. A simplified model is employed to simulate the evolution process and the formation of the solid particle from the solution droplet in the plasma jet. The temperature and velocity fields of the jet are obtained and validated. The particle size, velocity, temperature, and position distribution on the substrate are predicted.

Microstructural and microchemical studies of phase stability in V-O solid solution

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

Ghosh, Chanchal, E-mail: chanchal@igcar.gov.in

2017-02-15

Over the last couple of decades vanadium and V-based alloys have received significant attention as a potential structural material for fusion power applications because of their favourable mechanical properties under irradiation and at elevated temperatures. They are also considered as the advanced options of storage materials for hydrogen and its isotopes. However, the higher affinity of V for O, C and N poses critical challenges in its engineering applications since they lead to degradation of mechanical properties. They can further interact with the matrix to produce metallic oxy-carbo-nitride precipitates. To a certain limit, these precipitates are beneficial and can bemore » exploited to enhance the mechanical behaviour of the alloy through suitable microstructural design. However, this requires a prior knowledge of the interaction between the alloy and the impurity solutes. In the present work vanadium specific experiments have been designed and carried out to bring out the V-interstitial solute interaction by charging oxygen in the near surface region of vanadium. Microstructural and microchemical behaviour of the V-O solid solution has been studied through HRTEM (high resolution transmission electron microscopy) and HAADF (high angle annular dark field) coupled with EELS. Quantitative electron microscopy has been carried out to study structural modification of the alloy in atomic level caused by O charging. - Highlights: •Controlled experiments were carried out in pulsed laser ablation set-up to promote V-O interaction. • As a consequence of O dissolution, V transformed into a bct structure which is otherwise a bcc structure. •In V-O solid solution, dissolved O in the V matrix introduces significant amount of lattice strain. • Present work can be extended for introducing interstitial O in other pure transition metals and their alloys.« less

Equilibrium studies of oxalate and aluminum containing solutions

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

Hay, M. S.; King, W. D.; Peters, T. B.

2015-11-01

The Savannah River National Laboratory (SRNL) was tasked to develop data on the solubility and conditions leading to precipitation of sodium oxalate, sodium nitrate, Bayerite (a polymorph of gibbsite, Al(OH) 3), and sodium aluminosilicate solids recently found in the Modular Caustic Side Solvent Extraction Unit (MCU). The data generated will be used to improve the OLI Systems thermodynamic database for these compounds allowing better prediction of solids formation by the modeling software in the future.

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

Bradley, D. J.

The activity coefficient of carbon in nickel, nickel-titanium, nickel-titanium-chromium, nickel-titanium-molybdenum and nickel-titanium-molybdenum-chromium alloys has been measured at 900, 1100 and 1215/sup 0/C. The results indicate that carbon obeys Henry's Law over the range studied (0 to 2 at. percent). The literature for the nickel-carbon and iron-carbon systems are reviewed and corrected. For the activity of carbon in iron as a function of composition, a new relationship based on re-evaluation of the thermodynamics of the CO/CO/sub 2/ equilibrium is proposed. Calculations using this relationship reproduce the data to within 2.5 percent, but the accuracy of the calibrating standards used by manymore » investigators to analyze for carbon is at best 5 percent. This explains the lack of agreement between the many precise sets of data. The values of the activity coefficient of carbon in the various solid solutions are used to calculate a set of parameters for the Kohler-Kaufman equation. The calculations indicate that binary interaction energies are not sufficient to describe the thermodynamics of carbon in some of the nickel-based solid solutions. The results of previous workers for carbon in nickel-iron alloys are completely described by inclusion of ternary terms in the Kohler-Kaufman equation. Most of the carbon solid solution at high temperatures in nickel and nickel-titantium alloys precipitates from solution on quenching in water. The precipitate is composed of very small particles (greater than 2.5 nm) of elemental carbon. The results of some preliminary thermomigration experiments are discussed and recommendations for further work are presented.« less

Quantitative experimental determination of the solid solution hardening potential of rhenium, tungsten and molybdenum in single-crystal nickel-based superalloys

DOE PAGES

Fleischmann, Ernst; Miller, Michael K.; Affeldt, Ernst; ...

2015-01-31

Here, the solid-solution hardening potential of the refractory elements rhenium, tungsten and molybdenum in the matrix of single-crystal nickel-based superalloys was experimentally quantified. Single-phase alloys with the composition of the nickel solid-solution matrix of superalloys were cast as single crystals, and tested in creep at 980 °C and 30–75 MPa. The use of single-phase single-crystalline material ensures very clean data because no grain boundary or particle strengthening effects interfere with the solid-solution hardening. This makes it possible to quantify the amount of rhenium, tungsten and molybdenum necessary to reduce the creep rate by a factor of 10. Rhenium is moremore » than two times more effective for matrix strengthening than either tungsten or molybdenum. The existence of rhenium clusters as a possible reason for the strong strengthening effect is excluded as a result of atom probe tomography measurements. If the partitioning coefficient of rhenium, tungsten and molybdenum between the γ matrix and the γ' precipitates is taken into account, the effectiveness of the alloying elements in two-phase superalloys can be calculated and the rhenium effect can be explained.« less

Laboratory Experiments to Study Spherical, Iron Oxide Concretion Growth Without Solid Nuclei: Implications for Understanding Meridiani "Blueberries"

NASA Astrophysics Data System (ADS)

Ormö, J.; Souza-Egipsy, V.; Chan, M. A.; Park, A. J.; Stich, M.; Komatsu, G.

2006-03-01

Spherical hematite concretions can form without a nucleus. Self-organized zones of super-saturated solution cause spherical precipitates of amorphous iron-hydroxide. Diffusion of Fe ions towards the outer perimeter of the amorphous sphere forms a rind, which then grows inwards.

Characterization of Sb-doped Bi(2)UO(6) solid solutions by X-ray diffraction and X-ray absorption spectroscopy.

PubMed

Misra, N L; Yadav, A K; Dhara, Sangita; Mishra, S K; Phatak, Rohan; Poswal, A K; Jha, S N; Sinha, A K; Bhattacharyya, D

2013-01-01

The preparation and characterization of Sb-doped Bi(2)UO(6) solid solutions, in a limited composition range, is reported for the first time. The solid solutions were prepared by solid-state reactions of Bi(2)O(3), Sb(2)O(3) and U(3)O(8) in the required stoichiometry. The reaction products were characterized by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) measurements at the Bi and U L(3) edges. The XRD patterns indicate the precipitation of additional phases in the samples when Sb doping exceeds 4 at%. The chemical shifts of the Bi absorption edges in the samples, determined from the XANES spectra, show a systematic variation only up to 4 at% of Sb doping and support the results of XRD measurements. These observations are further supported by the local structure parameters obtained by analysis of the EXAFS spectra. The local structure of U is found to remain unchanged upon Sb doping indicating that Sb(+3) ions replace Bi(+3) during the doping of Bi(2)UO(6) by Sb.

Nano-sized precipitate stability and its controlling factors in a NiAl-strengthened ferritic alloy

PubMed Central

Sun, Zhiqian; Song, Gian; Ilavsky, Jan; Ghosh, Gautam; Liaw, Peter K.

2015-01-01

Coherent B2-ordered NiAl-type precipitates have been used to reinforce solid-solution body-centered-cubic iron for high-temperature application in fossil-energy power plants. In this study, we investigate the stability of nano-sized precipitates in a NiAl-strengthened ferritic alloy at 700–950 °C using ultra-small angle X-ray scattering and electron microscopies. Here we show that the coarsening kinetics of NiAl-type precipitates is in excellent agreement with the ripening model in multicomponent alloys. We further demonstrate that the interfacial energy between the matrix and NiAl-type precipitates is strongly dependent on differences in the matrix/precipitate compositions. Our results profile the ripening process in multicomponent alloys by illustrating controlling factors of interfacial energy, diffusivities, and element partitioning. The study provides guidelines to design and develop high-temperature alloys with stable microstructures for long-term service. PMID:26537060

Mechanisms of scale formation and carbon dioxide partial pressure influence. Part I. Elaboration of an experimental method and a scaling model.

PubMed

Gal, Jean-Yves; Fovet, Yannick; Gache, Nathalie

2002-02-01

Scale formation in industrial or domestic installations is still an important economic problem. The existence of a metastable domain for calcium carbonate supersaturated solutions and its breakdown are observed under conditions rarely well defined. In most cases it is the pH rise caused by the carbon dioxide loss that involves calcium carbonate precipitation. Before studying this problem, we suggest in this first part, a new model for the evolution of the calcocarbonic system that takes into account the hydrated forms of CaCO3: CaCO3 amorphous, CaCO3 x 6H2O (ikaite) and CaCO3 x H2O (monohydrate). According to this model, the precipitation of any one of these hydrated forms could be responsible for the breakdown of the metastable state. After this first step, the solids evolve into dehydrated forms. At first, the metastable domain spread of the calcium carbonate supersaturated solutions was studied by the elaboration of computer programs in which the formation of CaCO3(0)(aq) ion pairs was taken into account. These ion pairs are supposed to evolve through dehydration to form the various calcium carbonate solid form precursors. This thermodynamic study was then compared to the experimental methods of the critical pH. Here the pH rise was caused by adding sodium hydroxide under different conditions for sodium hydroxide addition speed, agitation mode and ageing of solutions. For the highest speed of sodium hydroxide addition, the CaCO3 ionic product reached the value of the amorphous calcium carbonate solubility product, and the reaction of the amorphous calcium carbonate precipitation was of the homogenous type. Decreasing the reagent's addition speed caused an extension of the titration time. Then, the breakdown of the metastable state was obtained with the CaCO3 x H2O heterogeneous precipitation. This clearly illustrates the probable ageing of the precursors of the solid states that are considered in this model.

Dibutyl Phosphoric Acid Solubility in High-Acid, Uranium-Bearing Solutions at SRS

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

Pierce, R.A.

1998-10-02

The Savannah River Site has enriched uranium (EU) solution which has been stored for almost 10 years since being purified in the second uranium cycle of the H area solvent extraction process. The concentrations in solution are approximately 6 g/L U and about 0.1 M nitric acid. Residual tributylphosphate in the solutions has slowly hydrolyzed to form dibutyl phosphoric acid (HDBP) at concentrations averaging 50 mg/L. Uranium is known to form compounds with the dibutylphosphate ion (DBP) which have limited solubility. The potential to form uranium-DBP solids raises a nuclear criticality safety issue. Prior SRTC tests (WSRC-TR-98-00188) showed that U-DBPmore » solids precipitate at concentrations potentially attainable during the storage of enriched uranium solutions. Furthermore, evaporation of the existing EUS solution without additional acidification could result in the precipitation of U-DBP solids if the DBP concentration in the resulting solution exceeds 110 mg/L at ambient temperature. The same potential exists for evaporation of unwashed 1CU solutions. As a follow-up to the earlier studies, SRTC studied the solubility limits for solutions containing acid concentrations above 0.5M HNO3. The data obtained in these tests reveals a shift to higher levels of DBP solubility above 0.5M HNO3 for both 6 g/L and 12 g/L uranium solutions. Analysis of U-DBP solids from the tests identified a mixture of different molecular structures for the solids created. The analysis distinguished UO2(DBP)2 as the dominant compound present at low acid concentrations. As the acid concentration increases, the crystalline UO2(DBP)2 shows molecular substitutions and an increase in amorphous content. Further analysis by methods not available at SRS will be needed to better identify the specific compounds present. This data indicates that acidification prior to evaporation can be used to increase the margin of safety for the storage of the EUS solutions. Subsequent experimentation evaluated options for absorbing HDBP from solution using either activated carbon or anion exchange resin. The activated carbon outperformed the anion exchange resin. Activated carbon absorbs DBP rapidly and has demonstrated the capability of absorbing 15 mg of DBP per gram of activated carbon. Analytical results also show that activated carbon absorbs uranium up to 17 mg per gram of carbon. It is speculated that the uranium absorbed is part of a soluble U-DBP complex that has been absorbed. Additional testing must still be performed to 1) establish absorption limits for uranium for anion exchange resin, 2) evaluate desorption characteristics of uranium and DBP, and 3) study the possibility of re-using the absorbent.« less

Effect of softening precipitate composition and surface characteristics on natural organic matter adsorption.

PubMed

Russell, Caroline G; Lawler, Desmond F; Speitel, Gerald E; Katz, Lynn E

2009-10-15

Natural organic matter (NOM) removal during water softening is thought to occur through adsorption onto or coprecipitation with calcium and magnesium solids. However, details of precipitate composition and surface chemistry and subsequent interactions with NOM are relatively unknown. In this study, zeta potentiometry analyses of precipitates formed from inorganic solutions under varying conditions (e.g., Ca-only, Mg-only, Ca + Mg, increasing lime or NaOH dose) indicated that both CaCO3 and Mg(OH)2 were positively charged at higher lime (Ca(OH)2) and NaOH doses (associated with pH values above 11.5), potentially yielding a greater affinity for adsorbing negatively charged organic molecules. Environmental scanning electron microscopy (ESEM) images of CaCO3 solids illustrated the rhombohedral shape characteristic of calcite. In the presence of increasing concentrations of magnesium, the CaCO3 rhombs shifted to more elongated crystals. The CaCO3 solids also exhibited increasingly positive surface charge from Mg incorporation into the crystal lattice, potentially creating more favorable conditions for adsorption of organic matter. NOM adsorption experiments using humic substances extracted from Lake Austin and Missouri River water elucidated the role of surface charge and surface area on adsorption.

Microstructure and Hardness of Mg - 9Li - 6Al Alloy After Different Variants of Solid Solution Treatment

NASA Astrophysics Data System (ADS)

Zheng, Haipeng; Fei, Pengfei; Wu, Ruizhi; Hou, Legan; Zhang, Milin

2018-03-01

The microstructure and the hardness of cast magnesium alloy Mg - 9% Li - 6% Al are studied after a treatment for solid solution at 300, 350, and 450°C for 0.5 - 5 h. The phase composition of the alloy is represented by α-Mg, β-Li, thin-plate and faceted particles of an AlLi phase, and particles of a MgLi2Al θ-phase. The θ-phase dissolves in the matrix in the initial stage of the solution treatment, which causes growth in the hardness of the alloy. At a temperature above 350°C the AlLi phase dissolves giving way to short rod-like precipitates of a θ-phase, which remain steady in the process of solution treatment. The hardness of the alloy deceases in this stage for this reason.

Using the Binary Phase-Field Crystal Model to Describe Non-Classical Nucleation Pathways in Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Smith, Nathan; Provatas, Nikolas

Recent experimental work has shown that gold nanoparticles can precipitate from an aqueous solution through a non-classical, multi-step nucleation process. This multi-step process begins with spinodal decomposition into solute-rich and solute-poor liquid domains followed by nucleation from within the solute-rich domains. We present a binary phase-field crystal theory that shows the same phenomology and examine various cross-over regimes in the growth and coarsening of liquid and solid domains. We'd like to the thank Canada Research Chairs (CRC) program for funding this work.

System and method for conditioning a hardwood pulp liquid hydrolysate

DOEpatents

Waite, Darrell M; Arnold, Richard; St. Pierre, James; Pendse, Hemant P; Ceckler, William H

2013-12-17

A system and method for hardwood pulp liquid hydrolysate conditioning includes a first evaporator receives a hardwood mix extract and outputting a quantity of vapor and extract. A hydrolysis unit receives the extract, hyrolyzes and outputs to a lignin separation device, which separates and recovers a quantity of lignin. A neutralization device receives extract from the lignin separation device and a neutralizing agent, producing a mixture of solid precipitate and a fifth extract. The solid precipitate is removed from the fifth extract. A second evaporator removes a quantity of acid from the fifth extract in a vapor form. This vapor may be recycled to improve total acid recovery or discarded. A desalination device receives the diluted extract, separates out some of the acid and salt and outputs a desalinated solution.

Strengthening of metallic alloys with nanometer-size oxide dispersions

DOEpatents

Flinn, J.E.; Kelly, T.F.

1999-06-01

Austenitic stainless steels and nickel-base alloys containing, by wt. %, 0.1 to 3.0% V, 0.01 to 0.08% C, 0.01 to 0.5% N, 0.05% max. each of Al and Ti, and 0.005 to 0.10% O, are strengthened and ductility retained by atomization of a metal melt under cover of an inert gas with added oxygen to form approximately 8 nanometer-size hollow oxides within the alloy grains and, when the alloy is aged, strengthened by precipitation of carbides and nitrides nucleated by the hollow oxides. Added strengthening is achieved by nitrogen solid solution strengthening and by the effect of solid oxides precipitated along and pinning grain boundaries to provide temperature-stabilization and refinement of the alloy grains. 20 figs.

Sirolimus formulation with improved pharmacokinetic properties produced by a continuous flow method.

PubMed

Solymosi, Tamás; Angi, Réka; Basa-Dénes, Orsolya; Ránky, Soma; Ötvös, Zsolt; Glavinas, Hristos; Filipcsei, Genovéva; Heltovics, Gábor

2015-08-01

The oral bioavailability of Sirolimus is limited by poor dissolution of the compound in the gastrointestinal tract resulting in a low bioavailability and large inter-individual differences in blood levels. Several different formulation approaches were applied to overcome these disadvantageous pharmacokinetic properties including the marketed oral solution and a tablet form containing wet milled nanocrystals. These approaches deliver improved pharmacokinetics, yet, they share the characteristics of complex production method and composition. We have developed a nanostructured Sirolimus formulation prepared by the controlled continuous flow precipitation of the compound from its solution in the presence of stabilizers. We have shown that contrary to the batch production the process could be easily intensified and scaled up; apparently the uniformity of the precipitation is heavily dependent on the production parameters, most likely the mixing of the solvent and antisolvent. We compared the physicochemical and pharmacokinetic properties of the nanostructured formula with the marketed nanoformula. We found that our method produces particles in the size range of less than 100nm. The solid form redispersed instantaneously in water and in biorelevant media. Both the solid form and the redispersed colloid solution showed excellent stability even in accelerated test conditions. The oral administration of the nanostructured formula resulted in faster absorption, higher exposure and higher trough concentrations when compared to the marked form. These advantageous properties could allow the development of solid oral Sirolimus formulae with lower strength and gel based topical delivery systems. Copyright © 2015 Elsevier B.V. All rights reserved.

Thermodynamic Investigation of the Effect of Interface Curvature on the Solid-Liquid Equilibrium and Eutectic Point of Binary Mixtures.

PubMed

Liu, Fanghui; Zargarzadeh, Leila; Chung, Hyun-Joong; Elliott, Janet A W

2017-10-12

Thermodynamic phase behavior is affected by curved interfaces in micro- and nanoscale systems. For example, capillary freezing point depression is associated with the pressure difference between the solid and liquid phases caused by interface curvature. In this study, the thermal, mechanical, and chemical equilibrium conditions are derived for binary solid-liquid equilibrium with a curved solid-liquid interface due to confinement in a capillary. This derivation shows the equivalence of the most general forms of the Gibbs-Thomson and Ostwald-Freundlich equations. As an example, the effect of curvature on solid-liquid equilibrium is explained quantitatively for the water/glycerol system. Considering the effect of a curved solid-liquid interface, a complete solid-liquid phase diagram is developed over a range of concentrations for the water/glycerol system (including the freezing of pure water or precipitation of pure glycerol depending on the concentration of the solution). This phase diagram is compared with the traditional phase diagram in which the assumption of a flat solid-liquid interface is made. We show the extent to which nanoscale interface curvature can affect the composition-dependent freezing and precipitating processes, as well as the change in the eutectic point temperature and concentration with interface curvature. Understanding the effect of curvature on solid-liquid equilibrium in nanoscale capillaries has applications in the food industry, soil science, cryobiology, nanoporous materials, and various nanoscience fields.

Atom probe tomographic studies of precipitation in Al-0.1Zr-0.1Ti (at.%) alloys.

PubMed

Knipling, Keith E; Dunand, David C; Seidman, David N

2007-12-01

Atom probe tomography was utilized to measure directly the chemical compositions of Al(3)(Zr(1)-(x)Ti(x)) precipitates with a metastable L1(2) structure formed in Al-0.1Zr-0.1Ti (at.%) alloys upon aging at 375 degrees C or 425 degrees C. The alloys exhibit an inhomogeneous distribution of Al(3)(Zr(1)-(x)Ti(x)) precipitates, as a result of a nonuniform dendritic distribution of solute atoms after casting. At these aging temperatures, the Zr:Ti atomic ratio in the precipitates is about 10 and 5, respectively, indicating that Ti remains mainly in solid solution rather than partitioning to the Al(3)(Zr(1)-(x)Ti(x)) precipitates. This is interpreted as being due to the very small diffusivity of Ti in alpha-Al, consistent with prior studies on Al-Sc-Ti and Al-Sc-Zr alloys, where the slower diffusing Zr and Ti atoms make up a small fraction of the Al(3)(Zr(1)-(x)Ti(x)) precipitates. Unlike those alloys, however, the present Al-Zr-Ti alloys exhibit no interfacial segregation of Ti at the matrix/precipitate heterophase interface, a result that may be affected by a significant disparity in the evaporation fields of the alpha-Al matrix and Al(3)(Zr(1)-(x)Ti(x)) precipitates and/or a lack of local thermodynamic equilibrium at the interface.

Serial Sectioning Methods for Generating 3D Characterization Data of Grain- and Precipitate-Scale Microstructures (Preprint)

DTIC Science & Technology

2010-04-01

Nielsen SF, Gundlach C, Margulies L, Huang X, Juul Jensen D (2004) Watch- ing the Growth of Bulk Grains During Recrystallization of Deformed Metals. Science...solid-solution dendrites, while the voids in the reconstruction correspond to the Pb-Sn eutectic phase (B) 3D reconstruction of an Al-Cu alloy after...a 3 week coarsening experiment. The solid corresponds to Al dendrites, while the voids in the reconstruction correspond to the Al-Cu eutectic phase

Thermal effects of carbonated hydroxyapatite modified by glycine and albumin

NASA Astrophysics Data System (ADS)

Gerk, S. A.; Golovanova, O. A.; Kuimova, M. V.

2017-01-01

In this work calcium phosphate powders were obtained by precipitation method from simulated solutions of synovial fluid containing glycine and albumin. X-ray diffraction and IR spectroscopy determined that all samples are single-phase and are presented by carbonate containing hydroxyapatite (CHA). The thermograms of solid phases of CHA were obtained and analyzed; five stages of transformation in the temperature range of 25-1000°C were marked. It is shown that in this temperature range dehydration, decarboxylation and thermal degradation of amino acid and protein connected to the surface of solid phase occur. The tendency of temperature lowering of the decomposition of powders synthesized from a medium containing organic substances was determined. Results demonstrate a direct dependence between the concentration of the amino acid in a model solution and its content in the solid phase.

Rapid solidification of high-conductivity copper alloys. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Bloom, Theodore Atlas

1989-01-01

The main objective was to develop improved copper alloys of high strength and high thermal and electric conductivity. Chill block melt spinning was used to produce binary alloys of Cu-Cr and Cu-Zr, and ternary alloys of Cu-Cr-Ag. By quenching from the liquid state, up to 5 atomic percent of Cr and Zr were retained in metastable extended solid solution during the rapid solidification process. Eutectic solidification was avoided and the full strengthening benefits of the large volume fraction of precipitates were realized by subsequent aging treatment. The very low solid solubility of Cr and Zr in Cu result in a high conductivity Cu matrix strengthened by second phase precipitates. Tensile properties on as-cast and aged ribbons were measured at room and elevated temperatures. Precipitate coarsening of Cr in Cu was studied by changes in electrical resistance during aging. X-ray diffraction was used to measure the lattice parameter and the degree of supersaturation of the matrix. The microstructures were characterized by optical and electron microscopy.

Microstructure evolution in the fusion zone of laser-welded Mg–Gd–Y–Zr alloy during solution and aging treatment

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

Wang, Lyuyuan

The microstructure evolution in the fusion zone of laser-welded Mg-Gd-Y-Zr alloy during solution and aging treatment is investigated. The morphology of the Mg{sub 24}(Gd,Y){sub 5} in the divorced eutectic at the grain boundary transforms from a continuous network to disconnected and fragmentized islands and then to spheroidal particles before complete dissolution during the solution treatment at 430 °C. During the subsequent aging treatment at 225 °C, the precipitation sequence in the fusion zone follows the order of supersaturated solid solution (SSSS) → βʺ(D0{sub 19}) → βʹ(cbco) → β{sub 1}(fcc) → β(fcc). High-density precipitates are present at the original grain boundariesmore » of the fusion zone from the welded structure but there are less precipitates in the interior of the original grains. The grain growth during the solution treatment at 430 °C comprises the slowly increasing stage, rapidly increasing stage, and stable stage. The network-distributed Mg{sub 24}(Gd,Y){sub 5} impedes migration of the grain boundaries, restricts grain growth in the first slowly increasing stage, and segregation of zirconium near the grain boundaries also affects migration of the grain boundaries. - Highlights: •Different quantities of precipitates are present at different location of grain. •The network-distributed Mg{sub 24}(Gd,Y){sub 5} restricts grain growth. •Segregation of Zr affects migration of grain boundaries.« less

Solubility of jarosite solid solutions precipitated from acid mine waters, Iron Mountain, California

USGS Publications Warehouse

Alpers, Charles N.; Nordstrom, D. Kirk; Ball, J.W.

1989-01-01

Because of the common occurrence of 15 to 25 mole percent hydronium substitution on the alkali site in jarosites, it is necessary to consider the hydronium content of jarosites in any attempt at rigorous evaluation of jarosite solubility or of the saturation state of natural waters with respect to jarosite. A Gibbs free energy of 3293.5±2.1 kJ mol-1 is recommended for a jarosite solid solution of composition K.77Na.03(H3O).20Fe3(SO4)2(OH)6. Solubility determinations for a wider range of natural and synthetic jarosite solid solutions will be necessary to quantify the binary and ternary mixing parameters in the (K-Na-H3O) system. In the absence of such studies, molar volume data for endmember minerals indicate that the K-H3O substitution in jarosite is probably closer to ideal mixing than either the Na-K or Na-H3O substitution.

Major- and minor-metal composition of three distinct solid material fractions associated with Juan de Fuca hydrothermal fluids (northeast Pacific), and calculation of dilution fluid samples

USGS Publications Warehouse

Hinkley, T.K.; Seeley, J.L.; Tatsumoto, M.

1988-01-01

Three distinct types of solid material are associated with each sample of the hydrothermal fluid that was collected from the vents of the Southern Juan de Fuca Ridge. The solid materials appear to be representative of deposits on ocean floors near mid-ocean ridges, and interpretation of the chemistry of the hydrothermal solutions requires understanding of them. Sr isotopic evidence indicates that at least two and probably all three of these solid materials were removed from the solution with which they are associated, by precipitation or adsorption. This occurred after the "pure" hydrothermal fluid was diluted and thoroughly mixed with ambient seawater. The three types of solid materials, are, respectively, a coarse Zn- and Fe-rich material with small amounts of Na and Ca; a finer material also rich in Zn and Fe, but with alkali and alkaline-earth metals; and a scum composed of Ba or Zn, with either considerable Fe or Si, and Sr. Mineral identification is uncertain because of uncertain anion composition. Only in the cases of Ba and Zn were metal masses greater in solid materials than in the associated fluids. For all other metals measured, masses in fluids dwarf those in solids. The fluids themselves contain greater concentrations of all metals measured, except Mg, than seawater. We discuss in detail the relative merits of two methods of determining the mixing proportions of "pure" hydrothermal solution and seawater in the fluids, one based on Sr isotopes, and another previously used method based on Mg concentrations. Comparison of solute concentrations in the several samples shows that degree of dilution of "pure" hydrothermal solutions by seawater, and amounts of original solutes that were removed from it as solid materials, are not related. There is no clear evidence that appreciable amounts of solid materials were not conserved (lost) either during or prior to sample collection. ?? 1988.

Formation and Release of Cobalt(II) Sorption and Precipitation Products in Aging Kaolinite-Water Slurries.

PubMed

Thompson; Parks; Brown

2000-02-15

The uptake and release behavior of cobalt(II) was studied over thousands of hours in CO(2)-free aqueous suspensions of kaolinite under three pairs of total cobalt concentration (Co(T)) and near-neutral pH (7.5-7.8) conditions. Dissolved cobalt, aluminum, and silicon concentrations were monitored by ICPMS, and cobalt-containing products were identified by EXAFS spectroscopy. In each uptake experiment, cobalt sorbed to kaolinite as a mixture of surface-adsorbed monomers or polymers and hydrotalcite-like precipitates of the approximate composition Co(x)Al(OH)(2x+2)(A(n-))(1/n), where 2

Wash Solution Bath Life Extension for the Space Shuttle Rocket Motor Aqueous Cleaning System

NASA Technical Reports Server (NTRS)

Saunders, Chad; Evans, Kurt; Sagers, Neil

1999-01-01

A spray-in-air aqueous cleaning system, which replaced 1,1,1 trichloroethane (TCA) vapor degreasing, is used for critical cleaning of Space Shuttle Redesigned Solid Rocket Motor (RSRM) metal parts. Small-scale testing demonstrated that the alkaline-based wash solution possesses adequate soil loading and cleaning properties. However, full-scale testing exhibited unexpected depletion of some primary components of the wash solution. Specifically, there was a significant decrease in the concentration of sodium metasilicate which forced change-out of the wash solution after eight days. Extension of wash solution bath life was necessary to ease the burden of frequent change-out on manufacturing. A laboratory study supports a depletion mechanism that is initiated by the hydrolysis of sodium tripolyphosphate (STPP) lowering the pH of the solution. The decrease in pH causes polymerization and subsequent precipitation of sodium metasilicate (SM). Further investigation showed that maintaining the pH was the key to preventing the precipitation of the sodium metasilicate. Implementation to the full scale operation demonstrated that periodic additions of potassium hydroxide (KOH) extended the useful bath life to more than four months.

Role of Molecular Interactions for Synergistic Precipitation Inhibition of Poorly Soluble Drug in Supersaturated Drug-Polymer-Polymer Ternary Solution.

PubMed

Prasad, Dev; Chauhan, Harsh; Atef, Eman

2016-03-07

We are reporting a synergistic effect of combined Eudragit E100 and PVP K90 in precipitation inhibition of indomethacin (IND) in solutions at low polymer concentration, a phenomenon that has significant implications on the usefulness of developing novel ternary solid dispersion of poorly soluble drugs. The IND supersaturation was created by cosolvent technique, and the precipitation studies were performed in the absence and the presence of individual and combined PVP K90 and Eudragit E100. The studies were also done with PEG 8000 as a noninteracting control polymer. A continuous UV recording of the IND absorption was used to observe changes in the drug concentration over time. The polymorphic form and morphology of precipitated IND were characterized by Raman spectroscopy and scanning electron microscopy. The change in the chemical shift in solution (1)H NMR was used as novel approach to probe IND-polymer interactions. Molecular modeling was used for calculating binding energy between IND-polymer as another indication of IND-polymer interaction. Spontaneous IND precipitation was observed in the absence of polymers. Eudragit E100 showed significant inhibitory effect on nuclei formation due to stronger interaction as reflected in higher binding energy and greater change in chemical shift by NMR. PVP K90 led to significant crystal growth inhibition due to adsorption on growing IND crystals as confirmed by modified crystal habit of precipitate in the presence of PVP K90. Combination of polymers resulted in a synergistic precipitation inhibition and extended supersaturation. The NMR confirmed interaction between IND-Eudragit E100 and IND-PVP K90 in solution. The combination of polymers showed similar peak shift albeit using lower polymer concentration indicating stronger interactions. The results established the significant synergistic precipitation inhibition effect upon combining Eudragit E100 and PVP K90 due to drug-polymer interaction.

Morphology and phase identification of synthesized precipitated calcium carbonate from acetylene gas industry waste

NASA Astrophysics Data System (ADS)

Sabri, Siti Noorzidah Mohd; Othman, Rohaya; Othman, Anuar

2017-12-01

Precipitated calcium carbonate (PCC) is also known as synthetic calcium carbonate. In this paper, PCC was synthesized from carbide lime, which is the by-product from acetylene gas industry. The method used to produce PCC from carbide lime waste was ionic sucrose precipitation technique. The experiments were performed by varying the stirring rate. In this technique, carbide lime was first dissolved in ionic sucrose solution and then chilled at 10 °C for 24 hours before carbon dioxide gasses was introduced into the solution. The carbonation and precipitation process was took place and PCC was formed. The PCC was further filtered to obtain the solid PCC. The sample was then further characterised by using FESEM and XRD to determine the morphology and to identify the phase that exists in the synthesized compound respectively. The XRD and FESEM results clearly shown that the PCC obtained has mixed phases of calcite and vaterite, with mixtures of spherical and irregular shape morphologies formed. The irregular shapes corresponded to vaterite formation, meanwhile spherical shapes corresponded to calcite formation.

Effect of pre-strain on precipitation and exfoliation corrosion resistance in an Al-Zn-Mg alloy

NASA Astrophysics Data System (ADS)

Lu, Xianghan; Du, Zhiwei; Han, Xiaolei; Li, Ting; Wang, Guojun; Lu, Liying; Bai, Xiaoxia; Zhou, Tietao

2017-12-01

To investigate the effect of pre-strain on behaviors in a specially developed Al-4.5Zn-1.2Mg alloy, transmission electron microscopy (TEM) bright field (BF) imaging combined with select area electron diffraction (SAED), Vickers-hardness tests and electrical conductivity tests was conducted for insight into precipitation in aluminum (Al) matrix during two step ageing, and standard exfoliation corrosion (EXCO) test combined with high-angle angular dark field scanning transmission electron microscopy (HAADF-STEM) and scanning electron microscopy (SEM) was carried out for corrosion behavior. Results showed that pre-strain accelerated precipitation during two step ageing as the sequence of: (i) supersaturated solid solution (SSS), GPI zones precipitations, GPI dissolution; (ii) SSS, fcc precipitates, η’ phases or η phases. And the precipitation hardening of the fcc precipitates was not effective as GPI zones. Pre-strain also accelerated EXCO developing, which was mainly attributed to the coverage ratio of η phases on high-angle grain boundaries (HAGBs) increasing as pre-strain increase.

Controlled precipitation for enhanced dissolution rate of flurbiprofen: development of rapidly disintegrating tablets.

PubMed

Essa, Ebtessam A; Elmarakby, Amira O; Donia, Ahmed M A; El Maghraby, Gamal M

2017-09-01

The aim of this work was to investigate the potential of controlled precipitation of flurbiprofen on solid surface, in the presence or absence of hydrophilic polymers, as a tool for enhanced dissolution rate of the drug. The work was extended to develop rapidly disintegrated tablets. This strategy provides simple technique for dissolution enhancement of slowly dissolving drugs with high scaling up potential. Aerosil was dispersed in ethanolic solution of flurbiprofen in the presence and absence of hydrophilic polymers. Acidified water was added as antisolvent to produce controlled precipitation. The resultant particles were centrifuged and dried at ambient temperature before monitoring the dissolution pattern. The particles were also subjected to FTIR spectroscopic, X-ray diffraction and thermal analyses. The FTIR spectroscopy excluded any interaction between flurbiprofen and excipients. The thermal analysis reflected possible change in the crystalline structure and or crystal size of the drug after controlled precipitation in the presence of hydrophilic polymers. This was further confirmed by X-ray diffraction. The modulation in the crystalline structure and size was associated with a significant enhancement in the dissolution rate of flurbiprofen. Optimum formulations were successfully formulated as rapidly disintegrating tablet with subsequent fast dissolution. Precipitation on a large solid surface area is a promising strategy for enhanced dissolution rate with the presence of hydrophilic polymers during precipitation process improving the efficiency.

Structure and composition of Fe-OM co-precipitates that form in soil-derived solutions

NASA Astrophysics Data System (ADS)

Fritzsche, Andreas; Schröder, Christian; Wieczorek, Arkadiusz K.; Händel, Matthias; Ritschel, Thomas; Totsche, Kai U.

2015-11-01

Iron oxides represent a substantial fraction of secondary minerals and particularly affect the reactive properties of natural systems in which they formed, e.g. in soils and sediments. Yet, it is still obscure how transient conditions in the solution will affect the properties of in situ precipitated Fe oxides. Transient compositions, i.e. compositions that change with time, arise due to predominant non-equilibrium states in natural systems, e.g. between liquid and solid phases in soils. In this study, we characterize Fe-OM co-precipitates that formed in pH-neutral exfiltrates from anoxic topsoils under transient conditions. We applied soil column outflow experiments, in which Fe2+ was discharged with the effluent from anoxic soil and subsequently oxidized in the effluent due to contact with air. Our study features three novel aspects being unconsidered so far: (i) the transient composition of soil-derived solutions, (ii) that pedogenic Fe oxides instead of Fe salts serve as major source for Fe2+ in soil solution and (iii) the presence of exclusively soil-derived organic and inorganic compounds during precipitation. The experiments were carried out with two topsoil materials that differed in composition, texture and land use. Derived from Mössbauer spectroscopy, broad distributions in quadrupole splittings (0-2 mm s-1) and magnetic hyperfine fields (35-53 T) indicated the presence of low-crystalline ferrihydrite and even lower crystalline Fe phases in all Fe-OM co-precipitates. There was no unequivocal evidence for other Fe oxides, i.e. lepidocrocite and (nano)goethite. The Fe-OM co-precipitates contained inorganic (P, sulfate, silicate, Al, As) and organic compounds (proteins, polysaccharides), which were concurrently discharged from the soils. Their content in the Fe-OM co-precipitates was controlled by their respective concentration in the soil-derived solution. On a molar basis, OC and Fe were the main components in the Fe-OM co-precipitates (OC/Fe ratio = 0.5-2). The elemental composition of the Fe-OM co-precipitates was in accordance with the sequential precipitation of Fe(III)phosphates/arsenates prior to the formation of ferrihydrite. This explains decreasing Si contents in the Fe-OM co-precipitates with increasing availability of P. With respect to constant mean quadrupole splittings and slightly decreasing mean magnetic hyperfine fields, increasing contents of OC, P and Al in the Fe-OM co-precipitates did not further increase the structural disorder of the Fe polyhedra, while the crystallite interactions slightly decreased. Scanning electron microscopy and dynamic light scattering revealed the coincidental presence of variably sized aggregates and a considerable amount of Fe-OM co-precipitates, which remained dispersed in solution for months. Thus, variably composed Fe-OM co-precipitates with highly diverse aggregate sizes and comparably constant poor crystallinity can be expected after the oxidation of Fe2+ in transient, soil-derived solutions.

Influence of airflow rate and substrate nature on heterogeneous struvite precipitation.

PubMed

Saidou, H; Ben Moussa, S; Ben Amor, M

2009-01-01

In wastewater treatment plants a hard scale consisting of struvite crystals can be formed, in pipes and recirculation pumps, during anaerobic digestion of wastewater. This study was conducted to evaluate the effect of airflow rate and substrate nature on nucleation type, induction period and supersaturation coefficient during struvite precipitation. A crystallization reactor similar to that designed for calcium carbonate precipitation was used. The pH of synthetic wastewater solution was increased by air bubbling. Experimental results indicated that the airflow increased heterogeneous precipitation of struvite. The susceptibility to scale formation was more important on polyamide and polyvinyl chloride than on stainless steel. In all cases, X-ray diffraction and infrared spectroscopy showed that the precipitated solid phase was solely struvite. No difference in crystal morphology was observed. However, at similar experimental conditions, the particle size of struvite was higher for stainless-steel material than that for plastic materials.

Calcium and lanthanum solid base catalysts for transesterification

DOEpatents

Ng, K. Y. Simon; Yan, Shuli; Salley, Steven O.

2015-07-28

In one aspect, a heterogeneous catalyst comprises calcium hydroxide and lanthanum hydroxide, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g. In another aspect, a heterogeneous catalyst comprises a calcium compound and a lanthanum compound, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g, and a total basicity of about 13.6 mmol/g. In further another aspect, a heterogeneous catalyst comprises calcium oxide and lanthanum oxide, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g. In still another aspect, a process for preparing a catalyst comprises introducing a base precipitant, a neutral precipitant, and an acid precipitant to a solution comprising a first metal ion and a second metal ion to form a precipitate. The process further comprises calcining the precipitate to provide the catalyst.

System and method for conditioning a hardwood pulp liquid hydrolysate

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

Waite, Darrell; Arnold, Richard; St. Pierre, James

2015-06-30

A system and method for hardwood pulp liquid hydrolysate conditioning includes a first evaporator receives a hardwood mix extract and outputting a quantity of vapor and extract. A hydrolysis unit receives the extract, hydrolyzes and outputs to a lignin separation device, which separates and recovers a quantity of lignin. A neutralization device receives extract from the lignin separation device and a neutralizing agent, producing a mixture of solid precipitate and a fifth extract. The solid precipitate is removed from the fifth extract. A second evaporator removes a quantity of acid from the fifth extract in a vapor form. This vapormore » may be recycled to improve total acid recovery or discarded. A desalination device receives the diluted extract, separates out some of the acid and salt and outputs a desalinated solution.« less

Enhancement of High Temperature Strength of 2219 Alloys Through Small Additions of Nb and Zr and a Novel Heat Treatment

NASA Astrophysics Data System (ADS)

Mondol, S.; Makineni, S. K.; Kumar, S.; Chattopadhyay, K.

2018-07-01

This paper presents a detailed investigation on the effect of small amount of Nb and Zr additions to 2219 Al alloy coupled with a novel three-stage heat treatment process. The main aim of the work is to increase the high temperature strength of 2219 alloy by introducing thermally stable L12 type ordered precipitates in the matrix as well as by reducing the coarsening of metastable strengthening θ″ and θ' precipitates. To achieve this, small amounts of Nb and Zr are added to 2219 alloy melt and retained in solid solution by suction casting in a water-cooled copper mould having a cooling rate of 102 to 103 K/s. The suction cast alloy is directly aged at 673 K (400 °C) to form L12 type ordered coherent Al3Zr precipitates. Subsequently, the alloy is solution treated at 808 K (535 °C) for 30 minutes to get supersaturation of Cu in the matrix without significantly affecting the Al3Zr precipitates. Finally, the alloy is aged at 473 K (200 °C), which results in the precipitation of θ″ and θ'. Microstructural characterization reveals that θ″ and θ' are heterogeneously precipitated on pre-existing uniformly distributed Al3Zr precipitates, which leads to a higher number density of these precipitates. This results in a significant increase in strength at room temperature as well as at 473 K (200 °C) as compared to the 2219 alloy. Furthermore, the alloy remains thermally stable after prolonged exposure at 473 K (200 °C), which is attributed to the elastic strain energy minimization by the conjoint Al3Zr/ θ' or Al3Zr/ θ″ precipitates, and the high Zr and Nb solute-vacancy binding energy, retarding the growth and coarsening of θ″ and θ' precipitates.

Enhancement of High Temperature Strength of 2219 Alloys Through Small Additions of Nb and Zr and a Novel Heat Treatment

NASA Astrophysics Data System (ADS)

Mondol, S.; Makineni, S. K.; Kumar, S.; Chattopadhyay, K.

2018-05-01

This paper presents a detailed investigation on the effect of small amount of Nb and Zr additions to 2219 Al alloy coupled with a novel three-stage heat treatment process. The main aim of the work is to increase the high temperature strength of 2219 alloy by introducing thermally stable L12 type ordered precipitates in the matrix as well as by reducing the coarsening of metastable strengthening θ″ and θ' precipitates. To achieve this, small amounts of Nb and Zr are added to 2219 alloy melt and retained in solid solution by suction casting in a water-cooled copper mould having a cooling rate of 102 to 103 K/s. The suction cast alloy is directly aged at 673 K (400 °C) to form L12 type ordered coherent Al3Zr precipitates. Subsequently, the alloy is solution treated at 808 K (535 °C) for 30 minutes to get supersaturation of Cu in the matrix without significantly affecting the Al3Zr precipitates. Finally, the alloy is aged at 473 K (200 °C), which results in the precipitation of θ″ and θ'. Microstructural characterization reveals that θ″ and θ' are heterogeneously precipitated on pre-existing uniformly distributed Al3Zr precipitates, which leads to a higher number density of these precipitates. This results in a significant increase in strength at room temperature as well as at 473 K (200 °C) as compared to the 2219 alloy. Furthermore, the alloy remains thermally stable after prolonged exposure at 473 K (200 °C), which is attributed to the elastic strain energy minimization by the conjoint Al3Zr/θ' or Al3Zr/θ″ precipitates, and the high Zr and Nb solute-vacancy binding energy, retarding the growth and coarsening of θ″ and θ' precipitates.

Process for removing metals from water

DOEpatents

Napier, J.M.; Hancher, C.M.; Hackett, G.D.

1987-06-29

A process for removing metals from water including the steps of prefiltering solids from the water, adjusting the pH to between about 2 and 3, reducing the amount of dissolved oxygen in the water, increasing the pH to between about 6 and 8, adding water-soluble sulfide to precipitate insoluble sulfide- and hydroxide-forming metals, adding a containing floc, and postfiltering the resultant solution. The postfiltered solution may optionally be eluted through an ion exchange resin to remove residual metal ions. 2 tabs.

Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions

DOEpatents

Anderson, Iver E.; Lograsso, Barbara K.; Ellis, Timothy W.

1994-01-01

A metallic melt is atomized using a high pressure atomizing gas wherein the temperature of the melt and the composition of the atomizing gas are selected such that the gas and melt react in the atomization spray zone to form a refractory or intermetallic compound in the as-atomized powder particles. A metallic melt is also atomized using a high pressure atomizing gas mixture gas wherein the temperature of the melt and the ratio of a reactive gas to a carrier gas are selected to form powder particles comprising a supersaturated solid solution of the atomic species of the reactive gas in the particles. The powder particles are then heat treated to precipitate dispersoids in-situ therein to form a dispersion strengthened material.

[Multiply upconversion emission in oxyfluoride ceramics].

PubMed

Xiao, Si-guo; Yang, Xiao-liang; Liu, Zhen-wei

2003-02-01

Oxyfluoride ceramics with the host composition of SiO2 and PbF2 have been prepared. X-ray diffraction analysis of the ceramics revealed that fluoride type beta-PbF2 solid solution regions are precipitated in the glass matrix. Rare earth ions in the beta-PbF2 solid solution show highly efficient upconversion performance due to the very small multi-phonon relaxation rates. Eight upconversion emission bands whose central wavelength are 846, 803, 665, 549, 523, 487, 456 and 411 nm have been observed when the sample was excited with 930 nm diode light. Four possible energy transfer processes between Er3+ and Yb3+ cause the electronic population of high energy level of Er3+ and realize the abound upconversion luminescence bands.

Determination of 15N/14N and 13C/12C in Solid and Aqueous Cyanides

USGS Publications Warehouse

Johnson, C.A.

1996-01-01

The stable isotopic compositions of nitrogen and carbon in cyanide compounds can be determined by combusting aliquots in sealed tubes to form N2 gas and CO2 gas and analyzing the gases by mass spectrometry. Free cyanide (CN-aq + HCNaq) in simple solutions can also be analyzed by first precipitating the cyanide as copper(II) ferrocyanide and then combusting the precipitate. Reproducibility is ??0.5??? or better for both ??15N and ??13C. If empirical corrections are made on the basis of carbon yields, the reproducibility of ??13C can be improved to ??0.2???. The analytical methods described herein are sufficiently accurate and precise to apply stable isotope techniques to problems of cyanide degradation in natural waters and industrial process solutions.

Aluminate effect on desilication product phase transformation

NASA Astrophysics Data System (ADS)

Peng, Hong; Vaughan, James

2018-06-01

It remains a grand challenge in the treatment of bauxite residue to physically separate zeolite (also known as the DeSilication Product, DSP) from other unleached mineral phases owing to their fine sizes, typically less than 2 μm in diameter. In this study, the effect of aluminate concentration on DSP phase transformation was investigated from synthetic NaOH-NaAl(OH)4-Na2SiO3-H2O solution at 90 °C. The results show how at relatively low aluminate concentrations of 0.125 and 0.25 M NaAl(OH)4(aq), larger zeolite crystals of up to 60 μm in diameter are formed during homogenous precipitation from aqueous solution. The precipitation process involves the conversion of zeolite LTA to sodalite via the formation of an intermediate phase, octahedral LTN. Initial amorphous solids precipitate as aggregates in which cubic zeolite LTA nucleation occurs. As the reaction proceeds, truncated octahedral LTN appears with the cubic zeolite LTA and finally sodalite crystallizes on the LTA-LTN aggregates resulting in coarsened particles.

Recovery of soluble chloride salts from the wastewater generated during the washing process of municipal solid wastes incineration fly ash.

PubMed

Tang, Hailong; Erzat, Aris; Liu, Yangsheng

2014-01-01

Water washing is widely used as the pretreatment method to treat municipal solid waste incineration fly ash, which facilitates the further solidification/stabilization treatment or resource recovery of the fly ash. The wastewater generated during the washing process is a kind of hydrosaline solution, usually containing high concentrations of alkali chlorides and sulphates, which cause serious pollution to environment. However, these salts can be recycled as resources instead of discharge. This paper explored an effective and practical recovery method to separate sodium chloride, potassium chloride, and calcium chloride salts individually from the hydrosaline water. In laboratory experiments, a simulating hydrosaline solution was prepared according to composition of the waste washing water. First, in the three-step evaporation-crystallization process, pure sodium chloride and solid mixture of sodium and potassium chlorides were obtained separately, and the remaining solution contained potassium and calcium chlorides (solution A). And then, the solid mixture was fully dissolved into water (solution B obtained). Finally, ethanol was added into solutions A and B to change the solubility of sodium, potassium, and calcium chlorides within the mixed solvent of water and ethanol. During the ethanol-adding precipitation process, each salt was separated individually, and the purity of the raw production in laboratory experiments reached about 90%. The ethanol can be recycled by distillation and reused as the solvent. Therefore, this technology may bring both environmental and economic benefits.

Immunoaffinity centrifugal precipitation chromatography.

PubMed

Qi, Lin; Ito, Yoichiro

2007-06-01

Purification of proteins based on immunoaffinity has been performed using a solid support coated with antibody against the target proteins. The method requires immobilizing the antibody onto the solid support using protein A or G, and has a risk of adsorptive loss of target proteins onto the solid support. Centrifugal precipitation chromatography has been successfully used to purify enzymes, such as ketosteroid isomerase and hyaluronidase without the use of solid support. The purpose of this study is to demonstrate that immunoaffinity centrifugal precipitation chromatography is capable of isolating an antigen by exploiting antigen-antibody binding. The separation was initiated by filling both channels with 40% saturated ammonium sulfate (AS) of pH 4-4.5 followed by loading 20 microl of human plasma (National Institutes of Health blood bank) mixed with 2 mg of rabbit anti-HSA (human serum protein) antibody (Sigma). Then, the sample channel was eluted with water at 0.03 ml/min and AS channel with 40% AS solution of pH 4-4.5 at 1 ml/min until all non-binding components were eluted. Then, the releasing reagent (50% AS solution containing 0.5 M glycine and 10% ammonium hydroxide at pH 10) was introduced through the AS channel to release the target protein (HSA). The retained antibody was recovered by eluting the sample channel with water at 1 ml/min. A hollow fiber membrane device at the outlet (MicroKros, Spectrum, New Brunswick, NJ, USA) was provided on-line dialysis of the eluent before fractions were collected, so that the fractions could be analyzed by SDS-PAGE (sodium dodecyl sulfate - polyacrylamide gel electrophoresis) without further dialysis. The current method does not require immobilizing the antibody onto a matrix, which is used by the conventional immunoaffinity chromatography. This method ensures full recovery of the antigen and antibody, and it may be applied to purification of other proteins.

Processing and analysis techniques involving in-vessel material generation

DOEpatents

Schabron, John F [Laramie, WY; Rovani, Jr., Joseph F.

2011-01-25

In at least one embodiment, the inventive technology relates to in-vessel generation of a material from a solution of interest as part of a processing and/or analysis operation. Preferred embodiments of the in-vessel material generation (e.g., in-vessel solid material generation) include precipitation; in certain embodiments, analysis and/or processing of the solution of interest may include dissolution of the material, perhaps as part of a successive dissolution protocol using solvents of increasing ability to dissolve. Applications include, but are by no means limited to estimation of a coking onset and solution (e.g., oil) fractionating.

Processing and analysis techniques involving in-vessel material generation

DOEpatents

Schabron, John F [Laramie, WY; Rovani, Jr., Joseph F.

2012-09-25

In at least one embodiment, the inventive technology relates to in-vessel generation of a material from a solution of interest as part of a processing and/or analysis operation. Preferred embodiments of the in-vessel material generation (e.g., in-vessel solid material generation) include precipitation; in certain embodiments, analysis and/or processing of the solution of interest may include dissolution of the material, perhaps as part of a successive dissolution protocol using solvents of increasing ability to dissolve. Applications include, but are by no means limited to estimation of a coking onset and solution (e.g., oil) fractionating.

A Novel Cu-10Zn-1.5Ni-0.34Si Alloy with Excellent Mechanical Property Through Precipitation Hardening

NASA Astrophysics Data System (ADS)

Chen, Wei; Wang, Mingpu; Li, Zhou; Dong, Qiyi; Jia, Yanlin; Xiao, Zhu; Zhang, Rui; Yu, Hongchun

2016-11-01

A novel Cu-10Zn-1.5Ni-0.34Si alloy was designed to replace the expensive tin-phosphor bronze in this paper. The alloy had better comprehensive mechanical properties than traditional C5191 alloy. The aged Cu-10Zn-1.5Ni-0.34Si alloy had a hardness of 220 HV, electrical conductivity of 28.5% IACS, tensile strength of 650 MPa, yield strength of 575 MPa and elongation of 13%. Ni2Si precipitates formed during aging, and the crystal orientation relationship between matrix and precipitates was: (001)α//(001)δ, and [110]α//[100]δ. Ductile fracture surface with deep cavities was found in the alloy. Solid solution strengthening, deformation strengthening and precipitation strengthening were found to be core strengthening mechanisms in the alloy.

Nano-sized precipitate stability and its controlling factors in a NiAl-strengthened ferritic alloy

DOE PAGES

Sun, Zhiqian; Song, Gian; Ilavsky, Jan; ...

2015-11-05

Coherent B2-ordered NiAl-type precipitates have been used to reinforce solid-solution bodycentered- cubic iron for high-temperature application in fossil-energy power plants. In this study, the stability of nano-sized precipitates in a NiAl-strengthened ferritic alloy was investigated at 700 - 950°C using ultra-small angle X-ray scattering and electron microscopies. Here we show that the coarsening kinetics of NiAl-type precipitates is in excellent agreement with the ripening model in multicomponent alloys. We further demonstrate that the interfacial energy between the matrix and NiAl-type precipitates is strongly dependent to differences in the matrix/precipitate compositions. The results profile the ripening process in multicomponent alloys bymore » illustrating controlling factors (i.e., interfacial energy, diffusivities, and element partitioning). As a result, the study provides guidelines to design and develop high-temperature alloys with stable microstructures for long-term service.« less

Solid-state reduction of iron in olivine-planetary and meteoritic evolution.

PubMed

Boland, J N; Duba, A

1981-11-12

Iron-nickel metallic particles have been reported in meteorites 1 and lunar 2-5 and terrestrial 6,7 rocks. The origin of these metallic particles is not unique as they may be formed by (1) condensation from a primordial solar nebula 8 ; (2) crystallization from a melt; and (3) subsolidus reduction reactions under low oxygen or sulphur fugacity. We report here an electron microscopy study of the solid-state microstructural development in olivine single crystals (Fo 92 ) in which half of the iron has been reduced to the metallic state by a gas-solid interaction in the temperature range 950-1,500 °C. The reaction, Fo 92 →Fo 96 +metallic Fe(Ni in solid solution)+pyroxene, begins with a homogeneous transformation involving fine-scale metallic precipitates resembling Guinier-Preston zones 9 . The microstructure develops by the growth of the first-formed precipitates during an Ostwald ripening process 9 in which the precipitates located in the dislocation sub-boundaries develop in preference to precipitates in the subgrains. On the other hand, pyroxene is first observed to nucleate heterogeneously at pre-existing dislocations and its coarsening rate is more than an order-of-magnitude faster than that of the metallic phase. Besides the textural similarity of the observed microstructures with that reported for some of the lunar materials 2 , these results have important implications for the physical models of accretion of terrestrial planets, planetesimals and meteorites 10 , especially with respect to the distribution of siderophile elements. The rate of reaction observed here places constraints on models for the formation of the Earth's core by segregation of a metallic phase with or without reduction.

Barium isotope fractionation during witherite (BaCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; van Zuilen, Kirsten; Purgstaller, Bettina; Baldermann, Andre; Nägler, Thomas F.; Dietzel, Martin

2016-10-01

This study examines the behavior of Ba isotope fractionation between witherite and fluid during mineral dissolution, precipitation and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 10-2 M NaCl solution where the pH was adjusted by continuous bubbling of a water saturated gas phase of CO2 or atmospheric air. During witherite dissolution no Ba isotope fractionation was observed between solid and fluid. In contrast, during witherite precipitation, caused by a pH increase, a preferential uptake of the lighter 134Ba isotopomer in the solid phase was observed. In this case, the isotope fractionation factor αwitherite-fluid is calculated to be 0.99993 ± 0.00004 (or Δ137/134Bawitherite-fluid ≈ -0.07 ± 0.04‰, 2 sd). The most interesting feature of this study, however, is that after the attainment of chemical equilibrium, the Ba isotope composition of the aqueous phase is progressively becoming lighter, indicating a continuous exchange of Ba2+ ions between witherite and fluid. Mass balance calculations indicate that the detachment of Ba from the solid is not only restricted to the outer surface layer of the solid, but affects several (∼7 unit cells) subsurface layers of the crystal. This observation comes in excellent agreement with the concept of a dynamic system at chemical equilibrium in a mineral-fluid system, denoting that the time required for the achievement of isotopic equilibrium in the witherite-fluid system is longer compared to that observed for chemical equilibrium. Overall, these results indicate that the isotopic composition of Ba bearing carbonates in natural environments may be altered due to changes in fluid composition without a net dissolution/precipitation to be observed.

Influence of crystal structure on the Co{sup II} diffusion behavior in the Zn{sub 1-x}Co{sub x}O system

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

Peiteado, M.; Makovec, D.; Villegas, M.

2008-09-15

The solid state interaction of the Zn{sub 1-x}Co{sub x}O nominal system is investigated by means of diffusion couples and analysis of co-precipitated samples. The formation of a homogeneous Co:ZnO solid solution is found to be determined by the crystal structure from which Co{sup II} ions diffuse into the wurtzite lattice. No diffusion is observed whenever the CoO rock-salt structure is formed from the Co{sup II} precursor. On the contrary, the diffusion from the Co{sub 3}O{sub 4} spinel phase is feasible but has a limited temperature range defined by the reduction at a high temperature of Co{sup III}-Co{sup II}, since thismore » process again leads to the formation of the rock-salt structure. However, when using a highly reactive and homogeneous co-precipitated starting powder, neither the spinel phase nor the rock-salt structure is formed, and a Co{sup II}:ZnO solid solution is obtained, which remains stable up to high temperatures. - Graphical abstract: Maximum diffusion distance for the ZnO-CoO{sub x} couple as a function of temperature. Dashed gray lines represent the temperature values at which the transformations between CoO and Co{sub 3}O{sub 4} compounds take place.« less

Surface chemistry of ferrihydrite: Part 2. Kinetics of arsenate adsorption and coprecipitation

USGS Publications Warehouse

Fuller, C.C.; Dadis, J.A.; Waychunas, G.A.

1993-01-01

The kinetics of As(V) adsorption by ferrihydrite was investigated in coprecipitation and postsynthesis adsorption experiments conducted in the pH range 7.5-9.0. In coprecipitation experiments, As(V) was present in solution during the hydrolysis and precipitation of iron. In adsorption experiments, a period of rapid (<5 min) As(V) uptake from solution was followed by continued uptake for at least eight days, as As(V) diffused to adsorption sites on ferrihydrite surfaces within aggregates of colloidal particles. The time dependence of As(V) adsorption is well described by a general model for diffusion into a sphere if a subset of surface sites located near the exterior of aggregates is assumed to attain adsorptive equilibrium rapidly. The kinetics of As(V) desorption after an increase in pH were also consistent with diffusion as a rate-limiting process. Aging of pure ferrihydrite prior to As(V) adsorption caused a decrease in adsorption sites on the precipitate owing to crystallite growth. In coprecipitation experiments, the initial As(V) uptake was significantly greater than in post-synthesis adsorption experiments, and the rate of uptake was not diffusion limited because As(V) was coordinated by surface sites before crystallite growth and coagulation processes could proceed. After the initial adsorption, As(V) was slowly released from coprecipitates for at least one month, as crystallite growth caused desorption of As(V). Adsorption densities as high as 0.7 mole As(V) per mole of Fe were measured in coprecipitates, in comparison to 0.25 mole As(V) per mole of Fe in post-synthesis adsorption experiments. Despite the high Concentration of As(V) in the precipitates, EXAFS spectroscopy (Waychunas et al., 1993) showed that neither ferric arsenate nor any other As-bearing surface precipitate or solid solution was formed. The high adsorption densities are possible because the ferrihydrite particles are extremely small, approaching the size of small dioctahedral chains at the highest As(V) adsorption density. The results suggest that the solid solution model proposed by Fox (1989, 1992) for control of arsenate and phosphate concentrations in natural waters may be invalid. ?? 1993.

Synthesis and characterization of cadmium-calcium hydroxyapatite solid solutions

NASA Astrophysics Data System (ADS)

Zhao, Xin; Zhu, Yi-nian; Dai, Liu-qin

2014-06-01

A series of cadmium-calcium hydroxyapatite solid solutions was prepared by an aqueous precipitation method. By various means, the characterizations confirmed the formation of continuous solid solutions over all ranges of Cd/(Cd+Ca) atomic ratio. In the results, both lattice parameters a and c display slight deviations from Vegard's rule when the Cd/(Cd+Ca) atomic ratio is greater than 0.6. The particles change from smaller acicular to larger hexagonal columnar crystals as the Cd/(Cd+Ca) atomic ratio increases from 0-0.60 to 0.60-1.00. The area of the phosphate peak for symmetric P-O stretching decreases with the increase in Cd/(Cd+Ca) atomic ratio, and the peak disappears when the Cd/(Cd+Ca) atomic ratio is greater than 0.6; the two phosphate peaks of P-O stretching gradually merge together for the Cd/(Cd+Ca) atomic ratio near 0.60. These variations can be explained by a slight tendency of larger Cd ions to occupy M(2) sites and smaller Ca ions to prefer M(1) sites in the structure.

Ultrasonic recovery of copper and iron through the simultaneous utilization of Printed Circuit Boards (PCB) spent acid etching solution and PCB waste sludge.

PubMed

Huang, Zhiyuan; Xie, Fengchun; Ma, Yang

2011-01-15

A method was developed to recover the copper and iron from Printed Circuit Boards (PCB) manufacturing generated spent acid etching solution and waste sludge with ultrasonic energy at laboratory scale. It demonstrated that copper-containing PCB spent etching solution could be utilized as a leaching solution to leach copper from copper contained PCB waste sludge. It also indicated that lime could be used as an alkaline precipitating agent in this method to precipitate iron from the mixture of acidic PCB spent etching solution and waste sludge. This method provided an effective technique for the recovery of copper and iron through simultaneous use of PCB spent acid solution and waste sludge. The leaching rates of copper and iron enhanced with ultrasound energy were reached at 93.76% and 2.07% respectively and effectively separated copper from iron. Followed by applying lime to precipitate copper from the mixture of leachate and rinsing water produced by the copper and iron separation, about 99.99% and 1.29% of soluble copper and calcium were settled as the solids respectively. Furthermore the settled copper could be made as commercial rate copper. The process performance parameters studied were pH, ultrasonic power, and temperature. This method provided a simple and reliable technique to recover copper and iron from waste streams generated by PCB manufacturing, and would significantly reduce the cost of chemicals used in the recovery. Copyright © 2010 Elsevier B.V. All rights reserved.

[Study on solid dispersion of precipitated calcium carbonate-based oleanolic acid].

PubMed

Yan, Hong-mei; Zhang, Zhen-hai; Jia, Xiao-bin; Jiang, Yan-rong; Sun, E

2015-05-01

Oleanolic acid-precipitated calcium carbonate solid dispersion was prepared by using solvent evaporation method. The microscopic structure and physicochemical properties of solid dispersion were analyzed using differential scanning calorimetry and scanning electron microscopy (SEM). And its in vitro release also was investigated. The properties of the precipitated calcium carbonate was studied which was as a carrier of oleanolic acid solid dispersion. Differential scanning calorimetry analysis suggested that oleanolic acid may be present in solid dispersion as amorphous substance. The in vitro release determination results of oleanolic acid-precipitated calcium carbonate (1: 5) solid dispersion showed accumulated dissolution rate of.oleanolic acid was up to 90% at 45 min. Accelerating experiment showed that content and in vitro dissolution of oleanolic acid solid dispersion did not change after storing over 6 months. The results indicated that in vitro dissolution of oleanolic acid was improved greatly by the solid dispersion with precipitated calcium carbonate as a carrier. The solid dispersion is a stabilizing system which has actual applied value.

Internal Shear Forging Processes for Missile Primary Structures.

DTIC Science & Technology

1981-07-20

received condition. The as-received micro- structure displayed elongated recrystallized grains interspersed with particles of precipitate phases. SEM...re- crystallization regime for this alloy, and rolled specimens were reheated to 3160 C between passes, some recrystallization and grain size changes...experiment revealed that the actual solution treatment temperature was probably higher than 5000C. This resulted in melting of the eutectic and solid

ENVIRONMENTALMANAGEMENT SCIENCE PROGRAM PROJECT NUMBER 87016 CO-PRECIPITATION OF TRACEMETALS INGROUNDWATER AND VADOSE ZONE CALCITE: IN SITU CONTAINMENT AND STABILIZATION OF STRONTIUM-90 ANDOTHER DIVALENT METALS AND RADIONUCLIDES AT ARIDWESTERN DOE SITES

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

Ferris, F. Grant; Fujita, Yoshiko; Smith, Robert W.

2004-06-15

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) weapons complex. In situ containment and stabilization of these contaminants in vadose zones or groundwater is a cost-effective treatment strategy. Our facilitated approach relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal coprecipitation) by increasing groundwater pH and alkalinity (Fujita et al., 2000; Warren et al., 2001). Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface ureamore » hydrolyzing microorganisms. Because the precipitation processes are irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from groundwater. The rate at which trace metals are incorporated into calcite is a function of calcite precipitation kinetics, adsorption interactions between the calcite surface and the trace metal in solution (Zachara et al., 1991), solid solution properties of the trace metal in calcite (Tesoriero and Pankow, 1996), and also the surfaces upon which the calcite is precipitating. A fundamental understanding of the coupling of calcite precipitation and trace metal partitioning, and how this occurs in aquifers and vadose environments is lacking. This report summarizes work undertaken during the second year of this project.« less

The Influence of Vanadium on Ferrite and Bainite Formation in a Medium Carbon Steel

NASA Astrophysics Data System (ADS)

Sourmail, T.; Garcia-Mateo, C.; Caballero, F. G.; Cazottes, S.; Epicier, T.; Danoix, F.; Milbourn, D.

2017-09-01

The influence of vanadium additions on transformation kinetics has been investigated in a medium carbon forging steel. Using dilatometry to track transformation during continuous cooling or isothermal transformation, the impact of vanadium on both ferrite-pearlite and bainite has been quantified. Transmission electron microscopy and atom probe tomography have been used to establish whether vanadium was present in solid solution, or as clusters and precipitates. The results show that vanadium in solid solution has a pronounced retarding influence on ferrite-pearlite formation and that, unlike in the case of niobium, this effect can be exploited even during relatively slow cooling. The influence on bainite transformation was found to depend on temperature; an explanation in terms of the effect of vanadium on heterogeneous nucleation is tentatively proposed.

A study of phosphate absorption by magnesium iron hydroxycarbonate.

PubMed

Du, Yi; Rees, Nicholas; O'Hare, Dermot

2009-10-21

A study of the mechanism of phosphate adsorption by magnesium iron hydroxycarbonate, [Mg(2.25)Fe(0.75)(OH)(6)](CO(3))(0.37).0.65H(2)O over a range of pH has been carried out. The efficiency of the phosphate removal from aqueous solution has been investigated between pH 3-9 and the resulting solid phases have been studied by elemental analysis, XRD, FT-IR, Raman, HRTEM, EDX and solid-state MAS (31)P NMR. The analytical and spectroscopic data suggest that phosphate removal from solution occurs not by anion intercalation of the relevant phosphorous oxyanion (H(2)PO(4)(-) or HPO(4)(2-)) into the LDH but by the precipitation of either an insoluble iron hydrogen phosphate hydrate and/or a magnesium phosphate hydrate.

Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions

DOEpatents

Anderson, I.E.; Lograsso, B.K.; Ellis, T.W.

1994-11-29

A metallic melt is atomized using a high pressure atomizing gas wherein the temperature of the melt and the composition of the atomizing gas are selected such that the gas and melt react in the atomization spray zone to form a refractory or intermetallic compound in the as-atomized powder particles. A metallic melt is also atomized using a high pressure atomizing gas mixture gas wherein the temperature of the melt and the ratio of a reactive gas to a carrier gas are selected to form powder particles comprising a supersaturated solid solution of the atomic species of the reactive gas in the particles. The powder particles are then heat treated to precipitate dispersoids in-situ therein to form a dispersion strengthened material. 9 figures.

Glass-liquid phase separation in highly supersaturated aqueous solutions of telaprevir.

PubMed

Mosquera-Giraldo, Laura I; Taylor, Lynne S

2015-02-02

Amorphous solid dispersions are of great current interest because they can improve the delivery of poorly water-soluble compounds. It has been recently noted that the highly supersaturated solutions generated by dissolution of some ASDs can undergo a phase transition to a colloidal, disordered, drug-rich phase when the concentration exceeds the "amorphous solubility" of the drug. The purpose of this study was to investigate the phase behavior of supersaturated solutions of telaprevir, which is formulated as an amorphous solid dispersion in the commercial product. Different analytical techniques including proton nuclear magnetic resonance spectroscopy (NMR), ultraviolet spectroscopy (UV), fluorescence spectroscopy and flux measurements were used to evaluate the properties of aqueous supersaturated solutions of telaprevir. It was found that highly supersaturated solutions of telaprevir underwent glass-liquid phase separation (GLPS) when the concentration exceeded 90 μg/mL, forming a water-saturated colloidal, amorphous drug-rich phase with a glass transition temperature of 52 °C. From flux measurements, it was observed that the "free" drug concentration reached a maximum at the concentration where GLPS occurred, and did not increase further as the concentration was increased. This phase behavior, which results in a precipitate and a metastable equilibrium between a supersaturated solution and a drug-rich phase, is obviously important in the context of evaluating amorphous solid dispersion formulations and their crystallization routes.

Method of extracting coal from a coal refuse pile

DOEpatents

Yavorsky, Paul M.

1991-01-01

A method of extracting coal from a coal refuse pile comprises soaking the coal refuse pile with an aqueous alkali solution and distributing an oxygen-containing gas throughout the coal refuse pile for a time period sufficient to effect oxidation of coal contained in the coal refuse pile. The method further comprises leaching the coal refuse pile with an aqueous alkali solution to solubilize and extract the oxidized coal as alkali salts of humic acids and collecting the resulting solution containing the alkali salts of humic acids. Calcium hydroxide may be added to the solution of alkali salts of humic acid to form precipitated humates useable as a low-ash, low-sulfur solid fuel.

Method for production of hydrocarbons from hydrates

DOEpatents

McGuire, Patrick L.

1984-01-01

A method of recovering natural gas entrapped in frozen subsurface gas hydrate formations in arctic regions. A hot supersaturated solution of CaCl.sub.2 or CaBr.sub.2, or a mixture thereof, is pumped under pressure down a wellbore and into a subsurface hydrate formation so as to hydrostatically fracture the formation. The CaCl.sub.2 /CaBr.sub.2 solution dissolves the solid hydrates and thereby releases the gas entrapped therein. Additionally, the solution contains a polymeric viscosifier, which operates to maintain in suspension finely divided crystalline CaCl.sub.2 /CaBr.sub.2 that precipitates from the supersaturated solution as it is cooled during injection into the formation.

Quantitative examination of carbide and sulphide precipitates in chemically complex steels processed by direct strip casting

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

Dorin, Thomas, E-mail: thomas.dorin@deakin.edu.au; Wood, Kathleen; Taylor, Adam

2016-02-15

A high strength low alloy steel composition has been melted and processed by two different routes: simulated direct strip casting and slow cooled ingot casting. The microstructures were examined with scanning and transmission electron microscopy, atom probe tomography and small angle neutron scattering (SANS). The formation of cementite (Fe{sub 3}C), manganese sulphides (MnS) and niobium carbo-nitrides (Nb(C,N)) was investigated in both casting conditions. The sulphides were found to be significantly refined by the higher cooling rate, and developed an average diameter of only 100 nm for the fast cooled sample, and a diameter too large to be measured with SANSmore » in the slow cooled condition (> 1.1 μm). Slow cooling resulted in the development of classical Nb(C,N) precipitation, with an average diameter of 7.2 nm. However, after rapid cooling both the SANS and atom probe tomography data indicated that the Nb was retained in the matrix as a random solid solution. There was also some evidence that O, N and S are also retained in solid solution in levels not found during conventional processing. - Highlights: • The influence of cooling rate on microstructure is investigated in a HSLA steel. • SANS, TEM and APT are used to characterise the sulphides and Nb(C,N) precipitates. • The slow cooling rate result in the formation of Nb(C,N) precipitates. • The fast cooling rate results in a microstructure supersaturated in Nb, C and N. • The sulphides are 100 nm in the fast cooled sample and > 1 μm in the slow cooled one.« less

Microstructural Characteristics of Plasma Nitrided Layer on Hot-Rolled 304 Stainless Steel with a Small Amount of α-Ferrite

NASA Astrophysics Data System (ADS)

Xu, Xiaolei; Yu, Zhiwei; Cui, Liying; Niu, Xinjun; Cai, Tao

2016-02-01

The hot-rolled 304 stainless steel with γ-austenite and approximately 5 pct α-ferrite elongated along the rolling direction was plasma-nitrided at a low temperature of 693 K (420 °C). X-ray diffraction results revealed that the nitrided layer was mainly composed of the supersaturated solid solution of nitrogen in austenite ( γ N). Transmission electron microscopy (TEM) observations showed that the microstructure of the γ N phase exhibited "fracture factor contrast" reflective of the occurrence of fine pre-precipitations in γ N by the continuous precipitation. The occurrence of a diffuse scattering effect on the electron diffraction spots of γ N indicated that the pre-precipitation took place in γ N in the form of strongly bonded Cr-N clusters or pairs due to a strong attractive interaction of nitrogen with chromium. Scanning electron microscopy and TEM observations indicated that the discontinuous precipitation initiated from the γ/ α interfaces and grew from the austenite boundaries into austenite grains to form a lamellar structure consisting of CrN and ferrite. The orientation relationship between CrN and ferrite corresponded to a Baker-Nutting relationship: (100)CrN//(100) α ; [011]CrN//[001] α . A zigzag boundary line following the banded structure of alternating γ-austenite and elongated α-ferrite was presented between the nitrided layer and the substrate to form a continuous varying layer thickness, which resulted from the difference in diffusivities of nitrogen in α-ferrite and γ-austenite, along the γ/ α interfaces and through the lattice. Microstructural features similar to the γ N were also revealed in the ferrite of the nitrided layer by TEM. It was not excluded that a supersaturated solid solution of nitrogen in ferrite ( α N) formed in the nitrided layer.

Tin recovery from tin slag using electrolysis method

NASA Astrophysics Data System (ADS)

Jumari, Arif; Purwanto, Agus; Nur, Adrian; Budiman, Annata Wahyu; Lerian, Metty; Paramita, Fransisca A.

2018-02-01

The process in industry, including in mining industry, would surely give negative effect such as waste polluting to the environment. Some of waste could be potentially reutilized to be a commodity with the higher economic value. Tin slag is one of them. The aim of this research was to recover the tin contained in tin slag. Before coming to the electrolysis, tin slag must be treated by dissolution. The grinded tin slag was dissolved into HCl solution to form a slurry. During dissolution, the slurry was agitated and heated, and finally filtered. The filtrate obtained was then electrolyzed. During the process of electrolysis, solid material precipitated on the used cathode. The precipitated solid was then separated and dried. The solid was then analyzed using XRD, XRF and SEM. The XRD analysis showed that the longest time of dissolution and electrolysis the highest the purity obtained in the product. The SEM analysis showed that the longest time of electrolysis the smallest tin particle obtained. Optimum time achieved in this research was 2 hours for the recovering time and 3 hours for the electrolysis time, with 9% tin recovered.

Inorganic Precipitation of Aragonite from Artificial Seawater at Low Oxygen Content and in the Presence of Methane.

NASA Astrophysics Data System (ADS)

Mitchell, J. L.; Gabitov, R. I.

2016-02-01

Calcium carbonate minerals are important for our understanding of past marine conditions as well as tools for constructing paleoclimate. However, very little work has been done to determine the influence of oxygen depletion on the geochemistry of calcium carbonate minerals. At lower depths, conditions become increasingly anoxic. Methane oxidation, sulfate reduction, and respiration and fermentation of organic compounds are among the associated microbial metabolisms that may cause precipitation of carbonate or dolomite [1]. As a result the oxidation state of a number of elements change, which should affect their incorporation into carbonate phase. To determine how oxygen depletion affects elemental incorporation and partitioning, aragonite was inorganically grown in the laboratory using artificial seawater. In order to induce precipitation, a small amount of 0.1 M Na2CO3was added into solution. Pumping at a slow rate and stirring was done in order to avoid immediate CaCO3 precipitation. N2 was bubbled through solution in order to minimize oxygen content in experiments at atmospheric pressure. Two experiments were conducted at 5 bars of 0.1%CH4-N2mixture. Further oxygen trapping was done by the addition of Fe powder to some experiments. The aragonite was precipitated over a period of five to seven days, during which fluid subsamples were taken daily to measure pH. A drop in pH indicated that precipitation had started. Precipitated aragonite samples as well as final fluid solutions were collected and analyzed with ICP-MS, and isotope ratio mass spectrometer. In addition, solids were measured with electron microprobe. Our preliminary data showed aragonite grown with the presence of Fe powder is depleted in S/Ca and is enriched in Mn/Ca relative to aragonite precipitated without Fe powder. No significant effect of CH4 on aragonite d13C was observed. 1. Boetius A. et al. (2000) Nature, 407, 623-626.

Kinetic Fractionation of Stable Isotopes in Carbonates on Mars: Terrestrial Analogs

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Gibson, Everett K., Jr.; Golden, D. C.; Ming, Douglas W.; McKay, Gordon A.

2003-01-01

An ancient Martian hydrosphere consisting of an alkali-rich ocean would likely produce solid carbonate minerals through the processes of evaporation and/or freezing. We postulate that both (or either) of these kinetically-driven processes would produce carbonate minerals whose stable isotopic compositions are highly fractionated (enriched) with respect to the source carbon. Various scenarios have been proposed for carbonate formation on Mars, including high temperature formation, hydrothermal alteration, precipitation from evaporating brines, and cryogenic formation. 13C and 18O -fractionated carbonates have previously been shown to form kinetically under some of these conditions, ie.: 1) alteration by hydrothermal processes, 2) low temperature precipitation (sedimentary) from evaporating bicarbonate (brine) solutions, and 3) precipitation during the process of cryogenic freezing of bicarbonate-rich fluids. Here we examine several terrestrial field settings within the context of kinetically controlled carbonate precipitation where stable isotope enrichments have been observed.

Processing and characterization of Al-Al3Nb prepared by mechanical alloying and equal channel angular pressing

NASA Astrophysics Data System (ADS)

Chandran, P.; Zafari, A.; Lui, E. W.; Xia, K.

2017-05-01

Mechanically alloyed Al with immiscible elements such as Nb can lead to a uniform distribution of nanoscaled precipitates which are highly stable compared to conventional alloying and with excellent interface, resulting in significant increase in strength without problems associated with nano ceramic particles in metal matrix composites. Although immiscible, Nb can be alloyed with Al through mechanical milling, forming trialuminide (Al3Nb), either directly or upon subsequent precipitation, which possesses high strength, stiffness and stability at elevated temperatures. In the present study, Al-5 at.% Nb supersaturated solid solution was achieved after prolonged ball milling and nano Al3Nb precipitates were formed during subsequent ageing at 530°C. The Al-Al3Nb powder was consolidated by equal channel angular pressing (ECAP) at 400°C, resulting in a fully dense material with a uniform distribution of nanoscaled Al3Nb precipitates in the Al matrix.

Cr(VI) removal by FeS-coated alumina, silica, and natural sand

NASA Astrophysics Data System (ADS)

Park, M.; Lee, S.; Jeong, H. Y.

2014-12-01

Removal of Cr(VI) was investigated using mackinawite (FeS)-coated mineral sorbents under anoxic conditions. The sorbents included alumina (Al), silica (WS), and natural sand (NS). By analysis of both solution and solid phases, all FeS-coated sorbents were found to reduce Cr(VI) into Cr(III). The sorption extent and mechanism of Cr(VI) strongly depended on the pH conditions. Only at pH 4.5, significant amounts of the dissolved Cr remained in the solution. Titration of dissolved Cr(III) and Fe(III) by NaOH solutions indicated that no bulk-phase precipitation occurred at pH 4.5. Also, the removal of Cr(VI) at pH 4.5 was the greatest by FeS-coated NS. Consistent with these, Cr-K edge EXAFS revealed that Cr was removed by FeS-coated NS via surface precipitation, and that it was immobilized by FeS-coated WS and Al by forming surface clusters. Regardless of FeS-coated sorbents, at pH 7.0 and pH 9.5, the initially added Cr(VI) was quantitatively removed from the solution phase. By EXAFS analysis, the Cr sorption by FeS-coated Al was mainly due to the bulk-phase precipitation of Cr(OH)3(s) or [Cr, Fe](OH)3(s). In case of FeS-coated WS and NS, the short Cr-Cr distance (~2.6 Å) at pH 7.0 and pH 9.5 was not simply accounted for by the bulk precipitation as either hydroxide (rCr-Cr ~ 3.0 Å), and it would rather result from the surface precipitation. Such a difference in the coordination structure among FeS-coated sorbents was likely due to in the lower surface area of the former available for the surface precipitation.

Interdiffusion in Ternary Magnesium Solid Solutions of Aluminum and Zinc

DOE PAGES

Kammerer, Catherine; Kulkarni, Nagraj S; Warmack, Robert J Bruce; ...

2016-01-11

Al and Zn are two of the most common alloying elements in commercial Mg alloys, which can improve the physical properties through solid solution strengthening and precipitation hardening. Diffusion plays a key role in the kinetics of these and other microstructural design relevant to Mg-alloy development. However, there is a lack of multicomponent diffusion data available for Mg alloys. Through solid-to-solid diffusion couples, diffusional interactions of Al and Zn in ternary Mg solid-solution at 400° and 450 °C were examined by an extension of the Boltzmann-Matano analysis based on Onsager s formalism. Concentration profiles of Mg-Al-Zn ternary alloys were determinedmore » by electron probe microanalysis, and analyzed to determine the ternary interdiffusion coefficients as a function of composition. Zn was determined to interdiffuse the fastest, followed by Mg and Al. Appreciable diffusional interactions among Mg, Al, and Zn were observed by variations in sign and magnitude of cross interdiffusion coefficients. In particular, Zn was found to significantly influence the interdiffusion of Mg and Al significantly: the and ternary cross interdiffusion coefficients were both negative, and large in magnitude, in comparison to and , respectively. Al and Mg were observed influence the interdiffusion of Mg and Al, respectively, with positive and interdiffusion coefficients, but their influence on the Zn interdiffusion was negligible.« less

Targeted Control of Permeability Using Carbonate Dissolution/Precipitation Reactions

NASA Astrophysics Data System (ADS)

Clarens, A. F.; Tao, Z.; Plattenberger, D.

2016-12-01

Targeted mineral precipitation reactions are a promising approach for controlling fluid flow in the deep subsurface. Here we studied the potential to use calcium and magnesium bearing silicates as cation donors that would react with aqueous phase CO2 under reservoir conditions to form solid carbonate precipitates. Preliminary experiments in high pressure and temperature columns suggest that these reactions can effectively lower the permeability of a porous media. Wollastonite (CaSiO3) was used as the model silicate, injected as solid particles into the pore space of a packed column, which was then subsequently flooded with CO2(aq). The reactions occur spontaneously, leveraging the favorable kinetics that occur at the high temperature and pressure conditions characteristic of the deep subsurface, to form solid phase calcium carbonate (CaCO3) and amorphous silica (SiO2) within the pore space. Both x-ray tomography imaging of reacted columns and electron microscopy imaging of thin sections were used to characterize where dissolution/precipitation occurred within the porous media. The spatial distribution of the products was closely tied to the flow rate and the duration of the experiment. The SiO2 product precipitated in close spatial proximity to the CaSiO3 reactant. The CaCO3 product, which is sensitive to the low pH and high pCO2 brine, precipitated out of solution further down the column as Ca2+ ions moved with the brine. The permeability of the columns decreased by several orders of magnitude after injecting the CaSiO3 particles. Following carbonation, the permeability decreased even further as precipitates filled flow paths within the pore network. A pore network model was developed to help understand the interplay between precipitation kinetics and flow in altering the permeability of the porous media. The effect of particle concentration and size, pore size, reaction time, and pCO2, are explored on pore/fracture aperture and reaction extent. To provide better control of these dynamics and ultimately devise a mechanism to deliver carbonation seed particles into leakage pathways, we are exploring the potential to functionalize the silicate particles using temperature sensitive polymer coatings.

Co-crystallization of cholesterol and calcium phosphate as related to atherosclerosis

NASA Astrophysics Data System (ADS)

Hirsch, Danielle; Azoury, Reuven; Sarig, Sara

1990-09-01

Calcification of atherosclerotic plaques occurs very frequently and aggravates the disease. In biological systems, epitaxial relationships between crystal structures may be important in nucleating the deposit of a solid phase. The biologically preferred calcium phosphate species, apatite, and cholesterol crystal have structurally compatible crystallographic faces which allow epitaxial growth of one crystal upon another. The present study describes a new approach to explore, in vitro, the crystallization processes of calcium phosphate (CaP) with cholesterol (CS) and cholestanol (CN) which are related to atherosclerosis. Aqueous solutions containing calcium and phosphate ions or CaP crystals as hydroxyapatite were added into saturated ethanolic solutions of CS or CS and 10% CN. After precipitation, crystals were collected and analyzed by nuclear magnetic resonance (NMR), infra-red (IR), X-ray, scanning electron microscope (SEM-LINK), differential scanning calorimeter (DSC) and atomic absorption. The principal result is the well-formed crystals precipitation when an aqueous solution and CaP seed crystals were added to saturated solutions of CS and 10% CN. Cholesterol-cholestanol dihydrate (CC2W) crystals precipitated in the presence of CaP seeds were compared to the CC2W crystals obtained without the mineral compound. The results of this comparison indicate a special link between crystals of CaP and CC2W, and support the epitaxial relationship between the two kinds of crystals. The potential of CC2W crystals to be precipitated by CaP seed crystals prove likewise the possible significant role of the cholestanol metabolite in the process of cholesterol crystallization and calcification in the arteries.

Non-Metallic Ti Oxides and MnS/FeS2 Complex Precipitation in Ti-Killed Steel

NASA Astrophysics Data System (ADS)

Chen, Jieyun; Zhao, Dan; Li, Huigai; Zheng, Shaobo

Titanium deoxidized experiments can be carried in vacuum induction furnace by adding Ti-Fe alloy in molten steel to simulate strip casting. Sub-rapid solidification samples were obtained in the method of suing copper mold. The morphology, the chemical composition and the structures of nanometer precipitations were carried out to investigate by transmission electron microscope (TEM) with Energy Dispersive X ray Spectrum (EDX) and by collecting diffraction patterns with carbon extraction specimens. It has been found that titanium oxides were TiO monoclinic, Ti4O7 anorthic and TiO2 orthogonal structure in one nanometer inclusion, as the composite oxide was precipitated MnS/FeS2 cubic structure during sub-rapid solidification. Thermodynamic calculation analysis showed that it was possible to precipitate different kinds of nonstoichiometric TiOx. The solid solution between MnS/FeS2 will precipitate on the surface of titanium oxides because of good coherency relationship.

Solubility limits of dibutyl phosphoric acid in uranium-nitric acid solutions

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

Pierce, R.A.

2000-01-04

The Savannah River Site has enriched uranium (EU) solution that has been stored since being purified in its solvent extraction processes. The concentrations in solution are approximately 6 g/L U and 0.1 M nitric acid. Residual tributylphosphate in solution has slowly hydrolyzed to form dibutyl phosphoric acid (HDBP) at concentrations averaging 30--50 mg/L. Dibutyl phosphoric acid, in turn, is in equilibrium with (HDBP){sub 2} and DBP{sup {minus}}. Uranium can form compounds with the dibutylphosphate ion (DBP{sup {minus}}) which have limited solubility, thereby creating a nuclear criticality safety issue. Literature reports and earlier SRTC tests have shown that it is feasiblemore » to precipitate U-DBP solid during the storage and processing of EU solutions. As a result, a series of solubility experiments were run at nitric acid concentrations from 0--4.0 M HNO{sub 3}, uranium at 0--90 g/L, and temperatures from 0--30 C. The data shows temperature and nitric acid concentration dependence consistent with what would be expected. With respect to uranium concentration, U-DBP solubility passes through a minimum between 6 and 12 g/L U at the acid concentrations and temperatures studied. However, the minimum shows a slight shift toward lower uranium concentrations at lower nitric acid concentrations. The shifts in solubility are strongly dependent upon the overall ionic strength of the solution. The data also reveal a shift to higher DBP solubility above 0.5 M HNO{sub 3} for both 6 g/L and 12 g/L uranium solutions. Analysis of U-DBP solids from the tests identified distinct differences between precipitates from less than 0.5 M solutions and those from greater than 4 M acid. Analyses identified UO{sub 2}(DBP){sub 2} as the dominant compound present at low acid concentrations in accordance with literature reports. As the acid concentration increases, the crystalline UO{sub 2}(DBP){sub 2} shows molecular substitutions and an increase in amorphous content.« less

Building Units Design and Scale Chemistry

NASA Astrophysics Data System (ADS)

Férey, Gérard

2000-06-01

The concept of a building unit (BU) is used in two ways: the first is an a posteriori tool for description of structures which can be used to imagine new topologies originating from the description; the second one, restricted to the routes leading to the solid from the solution, starts from the reality of these building units in the solution to design new solids obtained by the tuned precipitation of these BUs with proper counterions. The room temperature and the hydrothermal routes are examined. The existence of BUs with different sizes with close topologies, revealed by numerous examples, leads us to define the notion of "scale chemistry" which concerns the edification of solids with various BUs, either organic, hybrid, or inorganic, and the consequences it has for the corresponding frameworks and the voids they generate. Not only the framework is important, and applications of the existence of large cavities are discussed. The paper ends with a discussion of the new trends which arise from this topological concept.

Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites

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

Qi, Long; Alamillo, Ricardo; Elliott, William A.

Liquid-phase processing of molecules using heterogeneous catalysts – an important strategy for obtaining renewable chemicals sustainably from biomass – involves reactions that occur at solid-liquid interfaces. In glucose isomerization catalyzed by basic faujasite zeolites, the catalytic activity depends strongly on the solvent composition: initially, it declines precipitously when water is mixed with a small amount of the organic co-solvent γ-valerolactone (GVL), then recovers as the GVL content increases. Using solid-state 13C NMR spectroscopy, we observed glucose isomers located inside the zeolite pores directly, and followed their transformations into fructose and mannose in real time. At low GVL concentrations, glucose ismore » depleted in the zeolite pores relative to the liquid phase, while higher GVL concentrations in solution drive glucose inside the pores, resulting in up to a 32 enhancement in the local glucose concentration. Although their populations exchange rapidly, molecules present at the reactive interface experience a significantly different environment from the bulk solution.« less

Solubility of nano-zinc oxide in environmentally and biologically important matrices

PubMed Central

Reed, Robert B.; Ladner, David A.; Higgins, Christopher P.; Westerhoff, Paul; Ranville, James F.

2011-01-01

Increasing manufacture and use of engineered nanoparticles (NPs) is leading to a greater probability for release of ENPs into the environment and exposure to organisms. In particular, zinc oxide (ZnO) is toxic, although it is unclear whether this toxicity is due to the zinc oxide nanoparticles (ZnO), dissolution to Zn2+, or some combination thereof. The goal of this study was to determine the relative solubilites of both commercially available and in-house synthesized ZnO in matrices used for environmental fate and transport or biological toxicity studies. Dissolution of ZnO was observed in nanopure water (7.18– 7.40 mg/L dissolved Zn, as measured by filtration) and Roswell Park Memorial Institute medium (RPMI-1640) (~5 mg/L), but much more dissolution was observed in Dulbecco’s Modified Eagle’s Medium (DMEM), where the dissolved Zn concentration exceeded 34 mg/L. Moderately hard water exhibited low zinc solubility, likely due to precipitation of a zinc carbonate solid phase. Precipitation of a zinc-containing solid phase in RPMI also appeared to limit zinc solubility. Equilibrium conditions with respect to ZnO solubility were not apparent in these matrices, even after more than 1,000 h of dissolution. These results suggest that solution chemistry exerts a strong influence on ZnO dissolution and can result in limits on zinc solubility due to precipitation of less soluble solid phases. PMID:21994124

Synthesis of Er-doped Lu2O3 nanoparticles and transparent ceramics

NASA Astrophysics Data System (ADS)

Serivalsatit, K.; Wasanapiarnpong, T.; Kucera, C.; Ballato, J.

2013-05-01

Transparent rare earth-doped Lu2O3 ceramics have received much attention for use in solid-state scintillator and laser applications. The fabrication of these ceramics, however, requires ultrafine and uniform powders as precursors. Presented here is the synthesis of Er-doped Lu2O3 nanopowders by a solution precipitation method using Er-doped lutetium sulfate solution and hexamethylenetetramine as a precipitant and the fabrication of Er-doped Lu2O3 transparent ceramics from these nanopowders. The precipitated precursors were calcined at 1100 °C for 4 h in order to convert the precursors into Lu2O3 nanoparticles with an average particle size of 60 nm. Thermal decomposition and phase evolution of the precursors were studied by simultaneous thermal analysis (STA), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). Er-doped Lu2O3 transparent ceramics were fabricated from these nanopowders using vacuum sintering followed by hot isostatic pressing at 1700 °C for 8 h. The transparent ceramics exhibit an optical transmittance of 78% at a wavelength of 1.55 μm.

Quercetin loaded biopolymeric colloidal particles prepared by simultaneous precipitation of quercetin with hydrophobic protein in aqueous medium.

PubMed

Patel, Ashok R; Heussen, Patricia C M; Hazekamp, Johan; Drost, Ellen; Velikov, Krassimir P

2012-07-15

Quercetin loaded biopolymeric colloidal particles were prepared by precipitating quercetin (water insoluble polyphenol) and zein (hydrophobic protein), simultaneously, by adding their hydro-alcoholic solution to aqueous solution in presence of sodium caseinate as an electrosteric stabiliser. The presence of protein resulted in altering the shape of quercetin precipitates from needle-like to spherical shape at higher zein proportions, as confirmed by transmission electron microscopy. The average particle size of zein:quercetin composite particles was below 200 nm (130-161 nm) with negative surface charge (-30 to -41 mV), as confirmed by dynamic light scattering and electrophoretic mobility data. Solid state characterisation (X-ray diffraction) and spectroscopic measurements (UV-Vis and IR spectroscopy) confirmed characteristic changes in quercetin due to the entrapment in the biopolymeric matrix of colloidal particles. Results from anti-oxidant study demonstrated the advantage of entrapping quercetin in the colloidal particles in terms of the chemical stability in the alkaline pH and against photodegradation under UV-light irradiation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Precipitation of calcium carbonate in aqueous solutions in presence of ethylene glycol and dodecane.

NASA Astrophysics Data System (ADS)

Natsi, Panagiota D.; Rokidi, Stamatia; Koutsoukos, Petros G.

2015-04-01

The formation of calcium carbonate (CaCO3) in aqueous supersaturated solutions has been intensively studied over the past decades, because of its significance for a number of processes of industrial and environmental interest. In the oil and gas production industry the deposition of calcium carbonate affects adversely the productivity of the wells. Calcium carbonate scale deposits formation causes serious problems in water desalination, CO2 sequestration in subsoil wells, in geothermal systems and in heat exchangers because of the low thermal coefficient of the salt. Amelioration of the operational conditions is possible only when the mechanisms underlying nucleation and crystal growth of calcium carbonate in the aqueous fluids is clarified. Given the fact that in oil production processes water miscible and immiscible hydrocarbons are present the changes of the dielectric constant of the fluid phase has serious impact in the kinetics of calcium carbonate precipitation, which remains largely unknown. The problem becomes even more complicated if polymorphism exhibited by calcium carbonate is also taken into consideration. In the present work, the stability of aqueous solutions supersaturated with respect to all calcium carbonate polymorphs and the subsequent kinetics of calcium carbonate precipitation were measured. The measurements included aqueous solutions and solutions in the presence of water miscible (ethylene glycol, MEG) and water immiscible organics (n-dodecane). All measurements were done at conditions of sustained supersaturation using the glass/ Ag/AgCl combination electrode as a probe of the precipitation and pH as the master variable for the addition of titrant solutions with appropriate concentration needed to maintenance the solution supersaturation. Initially, the metastable zone width was determined from measurements of the effect of the solution supersaturation on the induction time preceding the onset of precipitation at free-drift conditions. The rates of crystal growth were measured as a function of the solution supersaturation using the highly accurate and reproducible methodology of constant supersaturation. The dependence of the rates of crystal growth on supersaturation suggested surface diffusion controlled mechanism. At constant supersaturation it was possible to extend the time period for the growth of the initially forming polymorph, in a way that sufficient amount is precipitated for characterization with X-ray diffraction (XRD). Moreover, scanning electron microscopy (SEM) was used for the characterization of the morphology of the precipitated solid. In all cases and depending on the solution supersaturation vaterite formed first from solutions of high supersaturation while at low supersaturations calcite formed exclusively. The presence of dodecane reduced the stability of the supersaturated solutions with the crystals forming at the oil-water interface. The presence of ethylene glycol (concentrations between 10-80%) also affected the stability and the kinetics of calcium carbonate precipitation. The morphology of the formed crystals showed habit modifications: Spherical formations consisting of aggregated nanocrystals and calcite crystals with profound pits on the faces were the characteristic feature in the presence of dodecane. ACKNOWLEDGMENT This research was partially funded by the European Union (European Social Fund-ESF) and Greek National Funds through the Operational program Education and Lifelong Learning under the action Aristeia II( Code No 4420).

Modeling the Transport Phenomena in the Solution Precursor Plasma Spraying

NASA Astrophysics Data System (ADS)

Shan, Yanguang

2008-10-01

Solution precursor plasma spraying has been used to produce finely structured ceramic coatings with nano- and sub-micrometric features. This process involves the injection of a solution spray of ceramic salts into a DC plasma jet under atmospheric condition. During the process, the solvent vaporizes as the droplet travel downstream. Solid particles are finally formed due to the precipitation of the solute, and the particle are heated up and accelerated to the substrate to generate the coating. This work describes a 3D model to simulate the transport phenomena and the trajectory and heating of the solution spray in the process. The jet-spray two-way interactions are considered. A simplified model is employed to simulate the evolution process and the formation of the solid particle from the solution droplet in the plasma jet. O'Rourke's droplet collision model is used to take into account of the influence of droplet collision. The influence of droplet breakup is also considered by implementing TAB droplet breakup models into the plasma jet model. The temperature and velocity fields of the jet are obtained and validated. The particle size, velocity, temperature and position distribution on the substrate are predicted.

Synthesis of Al₂Ca Dispersoids by Powder Metallurgy Using a Mg-Al Alloy and CaO Particles.

PubMed

Fujita, Junji; Umeda, Junko; Kondoh, Katsuyoshi

2017-06-28

The elemental mixture of Mg-6 wt %Al-1 wt %Zn-0.3 wt %Mn (AZ61B) alloy powder and CaO particles was consolidated by an equal-channel angular bulk mechanical alloying (ECABMA) process to form a composite precursor. Subsequently, the precursor was subjected to a heat treatment to synthesize fine Al₂Ca particles via a solid-state reaction between the Mg-Al matrix and CaO additives. Scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS) and electron probe micro-analysis on the precursor indicated that 4.7-at % Al atoms formed a supersaturated solid solution in the α-Mg matrix. Transmission electron microscopy-EDS and X-ray diffraction analyses on the AZ61B composite precursor with 10-vol % CaO particles obtained by heat treatment confirmed that CaO additives were thermally decomposed in the Mg-Al alloy, and the solid-soluted Ca atoms diffused along the α-Mg grain boundaries. Al atoms also diffused to the grain boundaries because of attraction to the Ca atoms resulting from a strong reactivity between Al and Ca. As a result, needle-like (Mg,Al)₂Ca intermetallics were formed as intermediate precipitates in the initial reaction stage during the heat treatment. Finally, the precipitates were transformed into spherical Al₂Ca particles by the substitution of Al atoms for Mg atoms in (Mg,Al)₂Ca after a long heat treatment.

Improving Dissolution Rate of Carbamazepine-Glutaric Acid Cocrystal Through Solubilization by Excess Coformer.

PubMed

Yamashita, Hiroyuki; Sun, Changquan Calvin

2017-12-29

The use of soluble cocrystals is a promising strategy for delivering poorly soluble drugs. However, precipitation of poorly soluble crystal form during dissolution hinders the successful tablet development of cocrystals. This work was aimed to understand the mechanisms for improving dissolution performance of a soluble cocrystals by using excess coformer. A highly soluble carbamazepine (CBZ) cocrystal with- glutaric acid (GLA) was studied. Impact of excess GLA on solubility and intrinsic dissolution rate (IDR) was assessed. Viscosity of GLA solutions was also measured. Solid form of powders and pellets was examined using powder X-ray diffractometry. IDRs of cocrystal and GLA mixtures in different ratios were measured to identify a suitable formulation for maintaining high dissolution rate of CBZ-GLA in an aqueous environment. IDR of CBZ-GLA in a pH 1.2 HCl solution was improved when GLA was present in the solution. Precipitation of CBZ·2H 2 O was eliminated when GLA concentration was ≥100 mg/mL. The improved IDR was accompanied by higher solubility of CBZ in GLA solution and increased solution viscosity. The trend in IDR profile matched well with the solubility profile normalized by solution viscosity. Mixture of cocrystal and GLA led to improved IDR in simulated intestinal fluid. The excess GLA increased the aqueous solubility of CBZ·2H 2 O and, thereby, reduced the propensity to precipitation of CBZ·2H 2 O during dissolution by lowering the degree of supersaturation. This strategy allowed development of a CBZ-GLA formulation with a significantly enhanced dissolution rate than CBZ-GLA.

Effect of Heat Treatments on Microstructures and Tensile Properties of Cu-3 wt%Ag-0.5 wt%Zr Alloy

NASA Astrophysics Data System (ADS)

Chen, Gang; Wang, ChuanJie; Zhang, Ying; Yi, Cen; Zhang, Peng

2018-03-01

The microstructures and tensile properties of Cu-3 wt%Ag-0.5 wt%Zr alloy sheets under different aging treatments are investigated in this research. As one kind of precipitate, Ag nanoparticles with coherent orientation relationship with matrix precipitate. However, after the peak-age point, most of Ag nanoparticles grow into short rod shape with the interface translating to semi-coherent, which leads to the lower strength of over-aging sample. The yield strength is estimated by considering solid solute, grain boundary and precipitation strengthening mechanisms. The result shows that the Ag precipitates provide the main strengthening role. Then a constitutive equation representing the evolution of dislocation density with plastic strain is built by considering work-hardening behavior coming from shearable and non-shearable precipitates which is mainly the particles containing Zr. The flow stress contributed by shearable particle hardening is higher than that of non-shearable one. Due to the coarsening of grain boundary precipitates and low rate of damage accumulation of these non-shearable particles, the micro-cracks nucleate easily at grain boundary which leads to intergranular fracture.

Application of solution calorimetry in pharmaceutical and biopharmaceutical research.

PubMed

Royall, P G; Gaisford, S

2005-06-01

In solution calorimetry the heat of solution (Delta(sol)H) is recorded as a solute (usually a solid) dissolves in an excess of solvent. Such measurements are valuable during all the phases of pharmaceutical formulation and the number of applications of the technique is growing. For instance, solution calorimetry is extremely useful during preformulation for the detection and quantification of polymorphs, degrees of crystallinity and percent amorphous content; knowledge of all of these parameters is essential in order to exert control over the manufacture and subsequent performance of a solid pharmaceutical. Careful experimental design and data interpretation also allows the measurement of the enthalpy of transfer (Delta(trans)H) of a solute between two phases. Because solution calorimetry does not require optically transparent solutions, and can be used to study cloudy or turbid solutions or suspensions directly, measurement of Delta(trans)H affords the opportunity to study the partitioning of drugs into, and across, biological membranes. It also allows the in-situ study of cellular systems. Furthermore, novel experimental methodologies have led to the increasing use of solution calorimetry to study a wider range of phenomena, such as the precipitation of drugs from supersaturated solutions or the formation of liposomes from phospholipid films. It is the purpose of this review to discuss some of these applications, in the context of pharmaceutical formulation and preformulation, and highlight some of the potential future areas where solution calorimetry might find applications.

Reducing acid leaching of manganiferous ore: effect of the iron removal operation on solid waste disposal.

PubMed

De Michelis, Ida; Ferella, Francesco; Beolchini, Francesca; Vegliò, Francesco

2009-01-01

The process of reducing acid leaching of manganiferous ore is aimed at the extraction of manganese from low grade manganese ores. This work is focused on the iron removal operation. The following items have been considered in order to investigate the effect of the main operating conditions on solid waste disposal and on the process costs: (i) type and quantity of the base agent used for iron precipitation, (ii) effective need of leaching waste separation prior to the iron removal operation, (iii) presence of a second leaching stage with the roasted ore, which might also act as a preliminary iron removal step, and (iv) effect of tailings washing on the solid waste classification. Different base compounds have been tested, including CaO, CaCO3, NaOH, and Na2CO3. The latter gave the best results concerning both the precipitation process kinetics and the reagent consumption. The filtration of the liquor leach prior to iron removal was not necessary, implying significant savings in capital costs. A reduction of chemical consumption and an increase of manganese concentration in the solution were obtained by introducing secondary leaching tests with the previously roasted ore; this additional step was introduced without a significant decrease of global manganese extraction yield. Finally, toxicity characteristic leaching procedure (TCLP) tests carried out on the leaching solid waste showed: (i) a reduction of arsenic mobility in the presence of iron precipitates, and (ii) the need for a washing step in order to produce a waste that is classifiable as not dangerous, taking into consideration the existing Environmental National Laws.

ENVIRONMENTAL MANAGEMENT SCIENCE PROGRAM PROJECT NUMBER 87016 CO-PRECIPITATION OF TRACE METALS IN GROUNDWATER AND VADOSE ZONE CALCITE: IN SITU CONTAINMENT AND STABILIZATION OF STRONTIUM-90 AND OTHER DIVALENT METALS AND RADIONUCLIDES AT ARID WESTERN DOE SITES

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

Ferris, F. Grant; Fujita, Yoshiko; Smith, Robert W.

2004-06-15

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) weapons complex. In situ containment and stabilization of these contaminants in vadose zones or groundwater is a cost-effective treatment strategy. Our facilitated approach relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal coprecipitation) by increasing groundwater pH and alkalinity (Fujita et al., 2000; Warren et al., 2001). Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface ureamore » hydrolyzing microorganisms. Because the precipitation processes are irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from groundwater. The rate at which trace metals are incorporated into calcite is a function of calcite precipitation kinetics, adsorption interactions between the calcite surface and the trace metal in solution (Zachara et al., 1991), solid solution properties of the trace metal in calcite (Tesoriero and Pankow, 1996), and also the surfaces upon which the calcite is precipitating. A fundamental understanding of the coupling of calcite precipitation and trace metal partitioning, and how this occurs in aquifers and vadose environments is lacking. This report summarizes work undertaken during the second year of this project.« less

Solid state and aqueous behavior of uranyl peroxide cage clusters

NASA Astrophysics Data System (ADS)

Pellegrini, Kristi Lynn

Uranyl peroxide cage clusters include a large family of more than 50 published clusters of a variety of sizes, which can incorporate various ligands including pyrophosphate and oxalate. Previous studies have reported that uranyl clusters can be used as a method to separate uranium from a solid matrix, with potential applications in reprocessing of irradiated nuclear fuel. Because of the potential applications of these novel structures in an advanced nuclear fuel cycle and their likely presence in areas of contamination, it is important to understand their behavior in both solid state and aqueous systems, including complex environments where other ions are present. In this thesis, I examine the aqueous behavior of U24Pp 12, as well as aqueous cluster systems with added mono-, di-, and trivalent cations. The resulting solutions were analyzed using dynamic light scattering and ultra-small angle X-ray scattering to evaluate the species in solution. Precipitates of these systems were analyzed using powder X-ray diffraction, X-ray fluorescence spectrometry, and Raman spectroscopy. The results of these analyses demonstrate the importance of cation size, charge, and concentration of added cations on the aqueous behavior of uranium macroions. Specifically, aggregates of various sizes and shapes form rapidly upon addition of cations, and in some cases these aggregates appear to precipitate into an X-ray amorphous material that still contains U24Pp12 clusters. In addition, I probe aggregation of U24Pp12 and U60, another uranyl peroxide cage cluster, in mixed solvent water-alcohol systems. The aggregation of uranyl clusters in water-alcohol systems is a result of hydrogen bonding with polar organic molecules and the reduction of the dielectric constant of the system. Studies of aggregation of uranyl clusters also allow for comparison between the newer uranyl polyoxometalate family and century-old transition metal polyoxometalates. To complement the solution studies of uranyl cage clusters, solid state analyses of U24Pp12 are presented, including single crystal X-ray diffraction and preliminary single crystal neutron diffraction. Solid state analyses are used to probe the complicated bonding environments between U24Pp12 and crystallized counterions, giving further insight into the importance of cluster protonation and counterions in uranyl cluster systems. The combination of solid state and solution techniques provides information about the complicated nature of uranyl peroxide nanoclusters, and insight towards future applications of clusters in the advanced nuclear fuel cycle and the environment.

Precipitation and Solubility of Calcium Hydrogenurate Hexahydrate

PubMed Central

Babić-Ivančić, V.; Füredi-Milhofer, H.; Brničević, N.; Marković, M.

1992-01-01

Solid phases formed in the quaternary system: uric acid—calcium hydroxide —hydrochloric acid—water aged for 2 months at 310 K were studied to determine conditions for calcium hydrogenurate hexahydrate, Ca(C5H3N4O)2 · 6H2O precipitation. The precipitates were identified by chemical and thermogravimetric analyses, x-ray powder diffraction, infrared spectroscopy, light microscopy, and scanning electron microscopy. In the precipitation diagram the concentration region in which calcium hydrogenurate hexahydrate precipitated as a single solid phase was established. The solubility of calcium hydrogenurate hexahydrate was investigated in the pH range from 6.2 to 10.1 at different temperatures. The total soluble and ionic concentration of calcium (atomic absorption spectroscopy and Ca-selective electrode), total urate concentration (spectrophotometry), and pH were determined in equilibrated solutions. The data are presented in the form of tables and chemical potential diagrams. By using these data the thermodynamic solubility products of calcium hydrogenurate hexahydrate, Ks = a(Ca2+) · a2(C5H3N4O3−), were determined: pKs=10.12±0.07at288K,pKs=9.81±0.09at298K,pKs=9.28±0.04at310K,andpKs=9.01±0.03at318K.The formation of calcium hydrogenurate hexahydrate crystals in urinary tract of patients with pathologically high concentrations of calcium and urates (hypercalciuria and hyperuricosiuria) is possible. PMID:28053438

The influence of precipitation kinetics on trace element partitioning between solid and liquid solutions: A coupled fluid dynamics/thermodynamics framework to predict distribution coefficients

NASA Astrophysics Data System (ADS)

Kavner, A.

2017-12-01

In a multicomponent multiphase geochemical system undergoing a chemical reaction such as precipitation and/or dissolution, the partitioning of species between phases is determined by a combination of thermodynamic properties and transport processes. The interpretation of the observed distribution of trace elements requires models integrating coupled chemistry and mechanical transport. Here, a framework is presented that predicts the kinetic effects on the distribution of species between two reacting phases. Based on a perturbation theory combining Navier-Stokes fluid flow and chemical reactivity, the framework predicts rate-dependent partition coefficients in a variety of different systems. We present the theoretical framework, with applications to two systems: 1. species- and isotope-dependent Soret diffusion of species in a multicomponent silicate melt subjected to a temperature gradient, and 2. Elemental partitioning and isotope fractionation during precipitation of a multicomponent solid from a multicomponent liquid phase. Predictions will be compared with results from experimental studies. The approach has applications for understanding chemical exchange in at boundary layers such as the Earth's surface magmatic systems and at the core/mantle boundary.

Investigations on Mg-borate kinetics and mechanisms during evaporation, dilution and crystallization by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Peng, Jiaoyu; Chen, Jing; Dong, Yaping; Li, Wu

2018-06-01

Raman spectra of boron-concentrated, diluted, and corresponding mother solutions of brine were recorded at 298.15 K. The main polyborate anions present and their interactions in brine during evaporation and dilution were proposed according to the Raman spectra. The polyborate anions B(OH)3, B3O3(OH)4-, B5O6(OH)4-, and B6O7(OH)62- were found to be the main forms in boron-concentrated brine with B3O3(OH)4- ion being the principal form. Diluting brines with water accelerated depolymerization of B5O6(OH)4- and B6O7(OH)62- anions into B(OH)3 and B3O3(OH)4- ions and generated OH- ions, causing the pH of the solutions to increase from 4.2 to almost 8.0. Mg-borates precipitated from all diluted solutions could be classified as either hexaborates or triborates. A mechanism of solid phase transformation was also proposed and discussed based on Raman spectra analysis and solid species and solution pH data.

Tensile strength and creep behaviour of austenitic stainless steel type 18Cr - 12Ni with niobium additions at 700°C

NASA Astrophysics Data System (ADS)

Sordi, V. L.; Bueno, L. O.

2010-07-01

The effect of niobium additions up to 2.36 wt% on the creep behavior of a series of seven extra low carbon 18Cr-12Ni austenitic stainless steels at 700°C has been investigated. Grain size and hardness measurements, hot tensile tests and constant stress creep tests from 90 to 180 MPa were carried out for each alloy, in the solution treated condition at 1050, 1200 and 1300°C followed by quench in water. The mechanical behavior at high temperature was related to the amount of NbC precipitation occurring during the tests. Solid solution and intermetallic compound effects were also considered. Creep data analysis was done to determine the parameters of the creep power-law equation dot epsilon = A.σn and the Monkman-Grant relation dot epsilon.tmR = K. Niobium-carbide precipitation in these steels reduces the secondary stage dependence of strain rate with applied stress, resulting in n-values which indicate the possibility of operation of various creep mechanisms. The creep strength during the secondary stage is primarily controlled by the amount of NbC available for precipitation. However, the rupture times increase progressively with niobium content, as the amount of undissolved carbide particles in grain boundaries and the Laves phase precipitation increase.

Radioactive springs geochemical data related to uranium exploration

USGS Publications Warehouse

Cadigan, R.A.; Felmlee, J.K.

1977-01-01

Radioactive mineral springs and wells at 33 localities in the States of Colorado, Utah, Arizona and New Mexico in the United States were sampled and studied to obtain geochemical data which might be used for U exploration. The major source of radioactivity at mineral spring sites is 226Ra. Minor amounts of 228Ra, 238U and 232Th are also present. Ra is presumed to have been selectively removed from possibly quite deep uranium-mineralized rock by hydrothermal solutions and is either precipitated at the surface or added to fresh surface water. In this way, the source rocks influence the geochemistry of the spring waters and precipitates. Characteristics of the spring waters at or near the surface are also affected by variations in total dissolved solids, alkalinity, temperature and co-precipitation. Spring precipitates, both hard and soft, consist of four major types: (1) calcite travertine; (2) iron- and arsenic-rich precipitates; (3) manganese- and barium-rich precipitates; and (4) barite, in some instances accompanied by S, Ra and U, if present in the spring water, are co-precipitated with the barite, Mn-Ba and Fe-As precipitates. Using parameters based on U and Ra concentrations in waters and precipitates springsite areas are tentatively rated for favourability as potential uraniferous areas. ?? 1977.

Neutralization of Plutonium and Enriched Uranium Solutions Containing Gadolinium as a Neutron Poison

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

BRONIKOWSKI, MG.

2004-04-01

Materials currently being dissolved in the HB-Line Facility will result in an accumulated solution containing an estimated uranium:plutonium (U:Pu) ratio of 4.3:1 and an 235U enrichment estimated at 30 per cent The U:Pu ratio and the enrichment are outside the evaluated concentration range for disposition to high level waste (HLW) using gadolinium (Gd) as a neutron poison. To confirm that the solution generated during the current HB-Line dissolving campaign can be poisoned with Gd, neutralized and discarded to the Savannah River Site (SRS) high level waste (HLW) system without undue nuclear safety concerns the caustic precipitation of surrogate solutions wasmore » examined. Experiments were performed with a U/Pu/Gd solution representative of the HB-Line estimated concentration ratio and also a U/Gd solution. Depleted U was used in the experiments as the enrichment of the U will not affect the chemical behavior during neutralization, but will affect the amount of Gd added to the solution. Settling behavior of the neutralized solutions was found to be comparable to previous studies. The neutralized solutions mixed easily and had expected densities of typical neutralized waste. The neutralized solids were found to be homogeneous and less than 20 microns in size. Partially neutralized solids were more amorphous than the fully neutralized solids. Based on the results of these experiments, Gd was found to be a viable poison for neutralizing a U/Pu/Gd solution with a U:Pu mass ratio of 4.3:1 thus extending the U:Pu mass ratio from the previously investigated 0-3:1 to 4.3:1. However, further work is needed to allow higher U concentrations or U:Pu ratios greater than investigated in this work.« less

Multiscale modeling of dislocation-precipitate interactions in Fe: From molecular dynamics to discrete dislocations.

PubMed

Lehtinen, Arttu; Granberg, Fredric; Laurson, Lasse; Nordlund, Kai; Alava, Mikko J

2016-01-01

The stress-driven motion of dislocations in crystalline solids, and thus the ensuing plastic deformation process, is greatly influenced by the presence or absence of various pointlike defects such as precipitates or solute atoms. These defects act as obstacles for dislocation motion and hence affect the mechanical properties of the material. Here we combine molecular dynamics studies with three-dimensional discrete dislocation dynamics simulations in order to model the interaction between different kinds of precipitates and a 1/2〈111〉{110} edge dislocation in BCC iron. We have implemented immobile spherical precipitates into the ParaDis discrete dislocation dynamics code, with the dislocations interacting with the precipitates via a Gaussian potential, generating a normal force acting on the dislocation segments. The parameters used in the discrete dislocation dynamics simulations for the precipitate potential, the dislocation mobility, shear modulus, and dislocation core energy are obtained from molecular dynamics simulations. We compare the critical stresses needed to unpin the dislocation from the precipitate in molecular dynamics and discrete dislocation dynamics simulations in order to fit the two methods together and discuss the variety of the relevant pinning and depinning mechanisms.

Transient Liquid-Phase Diffusion Bonding of Aluminum Metal Matrix Composite Using a Mixed Cu-Ni Powder Interlayer

NASA Astrophysics Data System (ADS)

Maity, Joydeep; Pal, Tapan Kumar

2012-07-01

In the present study, the transient liquid-phase diffusion bonding of an aluminum metal matrix composite (6061-15 wt.% SiCp) has been investigated for the first time using a mixed Cu-Ni powder interlayer at 560 °C, 0.2 MPa, for different holding times up to 6 h. The microstructure of the isothermally solidified zone contains equilibrium precipitate CuAl2, metastable precipitate Al9Ni2 in the matrix of α-solid solution along with the reinforcement particles (SiC). On the other hand, the microstructure of the central bond zone consists of equilibrium phases such as NiAl3, Al7Cu4Ni and α-solid solution along with SiC particles (without any segregation) and the presence of microporosities. During shear test, the crack originates from microporosities and propagates along the interphase interfaces resulting in poor bond strength for lower holding times. As the bonding time increases, with continual diffusion, the structural heterogeneity is diminished, and the microporosities are eliminated at the central bond zone. Accordingly, after 6-h holding, the microstructure of the central bond zone mainly consists of NiAl3 without any visible microporosity. This provides a joint efficiency of 84% with failure primarily occurring through decohesion at the SiC particle/matrix interface.

The Influence of Processing on Strengthening Mechanisms in Pb-Free Solder Joints

NASA Astrophysics Data System (ADS)

Mutuku, Francis; Arfaei, Babak; Cotts, Eric J.

2017-04-01

The number, and the spacing, of Ag3Sn precipitates in Sn-Ag-Cu/Cu solder joints were related to separate processing parameters. The mechanical properties of an individual solder joint were directly related to the resulting distribution of different dispersoids in the joint. As the number of Ag3Sn precipitates increased, so did solder joint strength and shear fatigue lifetime. The room-temperature shear fatigue lifetime was inversely correlated with the separation between Ag3Sn precipitates. Bi and Sb solid solution strengthening was found to result in significantly larger values of shear strength and shear fatigue lifetime for one Pb-free solder. Room-temperature shear fatigue lifetime tests were identified as a relatively straightforward, yet sensitive means to gain insight into the reliability of Sn-Ag-Cu (SAC) solder joints.

SEPARATION OF TRANSURANIC ELEMENTS FROM RARE EARTH COMPOUNDS

DOEpatents

Kohman, T.P.

1961-11-21

A process of separating neptunium and plutonium values from rare earths and alkaline earth fission products present on a solid mixed actinide carrier (Th or U(IV) oxalate or fluoride) --fission product carrier (LaF/sub 3/, CeF/sub 3/, SrF/sub 2/, CaF/sub 2/, YF/sub 3/, La oxalate, cerous oxalate, Sr oxalate, Ca oxalate or Y oxalate) by extraction of the actinides at elevated temperature with a solution of ammonium fluoride and/or ammonium oxalate is described. Separation of the fission-product-containing carriers from the actinide solution formed and precipitation of the neptunium and plutonium from the solution with mineral acid are also accomplished. (AEC)

Supercritical fluid precipitation of ketoprofen in novel structured lipid carriers for enhanced mucosal delivery--a comparison with solid lipid particles.

PubMed

Gonçalves, V S S; Matias, A A; Rodríguez-Rojo, S; Nogueira, I D; Duarte, C M M

2015-11-10

Structured lipid carriers based on mixture of solid lipids with liquid lipids are the second generation of solid lipid particles, offering the advantage of improved drug loading capacity and higher storage stability. In this study, structured lipid carriers were successfully prepared for the first time by precipitation from gas saturated solutions. Glyceryl monooleate (GMO), a liquid glycerolipid, was selected in this work to be incorporated into three solid glycerolipids with hydrophilic-lipophilic balance (HLB) ranging from 1 to 13, namely Gelucire 43/01™, Geleol™ and Gelucire 50/13™. In general, microparticles with a irregular porous morphology and a wide particle size distribution were obtained. The HLB of the individual glycerolipids might be a relevant parameter to take into account during the processing of solid:liquid lipid blends. As expected, the addition of a liquid lipid into a solid lipid matrix led to increased stability of the lipid carriers, with no significant modifications in their melting enthalpy after 6 months of storage. Additionally, Gelucire 43/01™:GMO particles were produced with different mass ratios and loaded with ketoprofen. The drug loading capacity of the structured lipid carriers increased as the GMO content in the particles increased, achieving a maximum encapsulation efficiency of 97% for the 3:1 mass ratio. Moreover, structured lipid carriers presented an immediate release of ketoprofen from its matrix with higher permeation through a mucous-membrane model, while solid lipid particles present a controlled release of the drug with less permeation capacity. Copyright © 2015. Published by Elsevier B.V.

Precipitation in cold-rolled Al–Sc–Zr and Al–Mn–Sc–Zr alloys prepared by powder metallurgy

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

Vlach, M., E-mail: martin.vlach@mff.cuni.cz; Stulikova, I.; Smola, B.

2013-12-15

The effects of cold-rolling on thermal, mechanical and electrical properties, microstructure and recrystallization behaviour of the AlScZr and AlMnScZr alloys prepared by powder metallurgy were studied. The powder was produced by atomising in argon with 1% oxygen and then consolidated by hot extrusion at 350 °C. The electrical resistometry and microhardness together with differential scanning calorimetry measurements were compared with microstructure development observed by transmission and scanning electron microscopy, X-ray diffraction and electron backscatter diffraction. Fine (sub)grain structure developed and fine coherent Al{sub 3}Sc and/or Al{sub 3}(Sc,Zr) particles precipitated during extrusion at 350 °C in the alloys studied. Additional precipitationmore » of the Al{sub 3}Sc and/or Al{sub 3}(Sc,Zr) particles and/or their coarsening was slightly facilitated by the previous cold rolling. The presence of Sc,Zr-containing particles has a significant antirecrystallization effect that prevents recrystallization at temperatures minimally up to 420 °C. The precipitation of the Al{sub 6}Mn- and/or Al{sub 6}(Mn,Fe) particles of a size ∼ 1.0 μm at subgrain boundaries has also an essential antirecrystallization effect and totally suppresses recrystallization during 32 h long annealing at 550 °C. The texture development of the alloys seems to be affected by high solid solution strengthening by Mn. The precipitation of the Mn-containing alloy is highly enhanced by a cold rolling. The apparent activation energy of the Al{sub 3}Sc particles formation and/or coarsening and that of the Al{sub 6}Mn and/or Al{sub 6}(Mn,Fe) particle precipitation in the powder and in the compacted alloys were determined. The cold deformation has no effect on the apparent activation energy values of the Al{sub 3}Sc-phase and the Al{sub 6}Mn-phase precipitation. - Highlights: • The Mn, Sc and Zr additions to Al totally suppresses recrystallization at 550 °C. • The Sc,Zr-containing particle precipitation is slightly facilitated by cold rolling. • The Mn-containing particle precipitation is highly enhanced by cold rolling. • Cold rolling has no effect on activation energy of the Al{sub 3}Sc and Al{sub 6}Mn precipitation. • The texture development is affected by high solid solution strengthening by Mn.« less

Controlling the size and morphology of precipitated calcite particles by the selection of solvent composition

NASA Astrophysics Data System (ADS)

Konopacka-Łyskawa, Donata; Kościelska, Barbara; Karczewski, Jakub

2017-11-01

Precipitated calcium carbonate is used as an additive in the manufacture of many products. Particles with specific characteristics can be obtained by the selection of precipitation conditions, including temperature and the composition of solvent. In this work, calcium carbonate particles were obtained in the reaction of calcium hydroxide with carbon dioxide at 65 °C. Initial Ca(OH)2 suspensions were prepared in pure water and aqueous solutions of ethylene glycol or glycerol of the concentration range up to 20% (vol.). The course of reaction was monitored by conductivity measurements. Precipitated solids were analyzed by FTIR, XRD, SEM and the particles size distribution was determined by a laser diffraction method. The adsorption of ethylene glycol or glycerol on the surface of scalenohedral and rhombohedral calcite was testes by a normal-phase high-performance liquid chromatography. The addition of organic solvents changed the viscosity of reaction mixtures, the rate of carbon dioxide absorption and the solubility of inorganic components and therefore influence calcium carbonate precipitation conditions. All synthesized calcium carbonate products were in a calcite form. Scalenohedral calcite crystals were produced when water was a liquid phase, whereas addition of organic solvents resulted in the formation of rhombo-scalenohedral particles. The increase in organic compounds concentration resulted in the decrease of mean particles size from 2.4 μm to 1.7 μm in ethylene glycol solutions and to 1.4 μm in glycerol solutions. On the basis of adsorption tests, it was confirm that calcite surface interact stronger with glycerol than ethylene glycol. The interaction between scalenohedral calcite and used organic additives was higher in comparison to the pure rhombohedral form applied as a stationary phase.

Analysis of 2H-Evaporator Acid Cleaning Samples

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

Hay, M.; Diprete, D.; Edwards, T.

The 2H-Evaporator acid cleaning solution samples were analyzed by SRNL to determine a composition for the scale present in the evaporator before recent acid cleaning. Composite samples were formed from the solution samples from the two acid cleaning cycles. The solution composition was converted to a weight percent scale solids basis under an assumed chemical composition. The scale composition produced from the acid cleaning solution samples indicates a concentration of 6.85 wt% uranium. An upper bound, onesided 95% confidence interval on the weight percent uranium value may be given as 6.9 wt% + 1.645 × 0.596 wt% = 7.9 wt%.more » The comparison of the composition from the current acid cleaning solutions with the composition of recent scale samples along with the thermodynamic modeling results provides reasonable assurance that the sample results provide a good representation of the overall scale composition in the evaporator prior to acid cleaning. The small amount of scale solids dissolved in the 1.5 M nitric acid during the evaporator cleaning process likely produced only a small amount of precipitation based on modeling results and the visual appearance of the samples.« less

Temporal and spatial variability of chemical and isotopic composition of soil solutions from cambisols - field study and experiments.

PubMed

Schön, Walter; Mittermayr, Florian; Leis, Albrecht; Mischak, Irene; Dietzel, Martin

2016-12-01

The chemical and isotopic composition of soil solutions is highly relevant for environmental and forensic tasks. We investigated interstitial solutions from soil horizons of three cambisols in Styria (Austria). The soils consisted mainly of quartz, feldspar and clay minerals with a vertical variability. Two soil solution fractions from meso-, macro- and micropores (m) and micropores only (μ) were extracted at two subsequent hydraulic pressure steps corresponding to matrix potentials of up to pF 5.43 and from 5.43 to 5.73, respectively. While solute concentrations indicated diverse distribution in soil solution fractions m and μ, heavy stable hydrogen and oxygen isotopes of H 2 O (-92.5‰<δ 2 H<-34.4‰; -11.9‰<δ 18 O<-4.0‰, VSMOW) are clearly enriched in the μ versus m fractions. Principal component analysis on the hydrochemical data set indicates that the intensity of the overall silicate weathering is higher in autumn versus spring, whereas the anthropogenic impact on weathering behaves inversely. The anthropogenic impact is related to seasonal variability of nitrification of N-fertilizers. In consequence of evaluated signals for overall silicate weathering about three-fourths of the soil solutions sampled in autumn indicated elevated total dissolved solid concentration vs. those in spring accompanied with washing out solutes from the soil cover following precipitation events in autumn before sampling. Isotopic shift of soil solutions from the local meteoric water line in spring obviously followed an evaporation trend because of less precipitation and high evaporation before sampling. Experimentally simulated evaporation of soil samples confirmed the observed isotopic evaporation trend. Wetting experiments indicated the infiltration of water within minutes into the micropores of the soils. Exchange of water molecules between micro-, meso- and macropores is an almost instantaneous process and soil solutions in micropores are not as isolated from the soil water system as it was formerly suggested, e.g. for plant uptake. Highly dynamic and complex mechanisms in the gas-water-solid system of soils have to be considered for the application of elemental and isotope proxies related to environmental, forensic and agricultural tasks. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of Ag and Pb Addition on Microstructural and Mechanical Properties of SAC 105 Solders

NASA Astrophysics Data System (ADS)

Molnar, Aliz; Janovszky, Dora; Kardos, Ibolya; Molnar, Istvan; Gacsi, Zoltan

2015-10-01

Melting and crystallization processes of lead-free and lead-contaminated alloys in near-equilibrium state were investigated. In addition, the effect of silver content up to 4 wt.% on the microstructure of Sn-Ag-Cu alloys was studied. The volume fraction of β-Sn decreased by half owing to 4 wt.% Ag content. Furthermore, contamination by lead strongly influences the properties of the solidified microstructure. The Pb grains appear as a result of two processes when the Pb content is equal to 0.5 wt.% or higher: Pb phase solidifies in the quaternary eutectic at 176°C, and Pb grains precipitate from the primary β-Sn solid solution grain during a solid state reaction. The freezing range enlarges to 51°C due to 2 wt.% Pb content owing to quaternary eutectic. Above 1 wt.% Pb content, the mechanical properties also improve due to grains of quaternary eutectic Pb and precipitated Pb grains with a size <1 μm.

Organic matter and containment of uranium and fissiogenic isotopes at the Oklo natural reactors

USGS Publications Warehouse

Nagy, B.; Gauthier-Lafaye, F.; Holliger, P.; Davis, D.W.; Mossman, D.J.; Leventhal, J.S.; Rigali, M.J.; Parnell, J.

1991-01-01

SOME of the Precambrian natural fission reactors at Oklo in Gabon contain abundant organic matter1,2, part of which was liquefied at the time of criticality and subsequently converted to a graphitic solid3,4. The liquid organic matter helps to reduce U(VI) to U(IV) from aqueous solutions, resulting in the precipitation of uraninite5. It is known that in the prevailing reactor environments, precipitated uraninite grains incorporated fission products. We report here observations which show that these uraninite crystals were held immobile within the resolidified, graphitic bitumen. Unlike water-soluble (humic) organic matter, the graphitic bituminous organics at Oklo thus enhanced radionu-clide containment. Uraninite encased in solid graphitic matter in the organic-rich reactor zones lost virtually no fissiogenic lan-thanide isotopes. The first major episode of uranium and lead migration was caused by the intrusion of a swarm of adjacent dolerite dykes about 1,100 Myr after the reactors went critical. Our results from Oklo imply that the use of organic, hydrophobic solids such as graphitic bitumen as a means of immobilizing radionuclides in pretreated nuclear waste warrants further investigation. ?? 1991 Nature Publishing Group.

Testing and development of transfer functions for weighing precipitation gauges in WMO-SPICE

NASA Astrophysics Data System (ADS)

Kochendorfer, John; Nitu, Rodica; Wolff, Mareile; Mekis, Eva; Rasmussen, Roy; Baker, Bruce; Earle, Michael E.; Reverdin, Audrey; Wong, Kai; Smith, Craig D.; Yang, Daqing; Roulet, Yves-Alain; Meyers, Tilden; Buisan, Samuel; Isaksen, Ketil; Brækkan, Ragnar; Landolt, Scott; Jachcik, Al

2018-02-01

Weighing precipitation gauges are used widely for the measurement of all forms of precipitation, and are typically more accurate than tipping-bucket precipitation gauges. This is especially true for the measurement of solid precipitation; however, weighing precipitation gauge measurements must still be adjusted for undercatch in snowy, windy conditions. In WMO-SPICE (World Meteorological Organization Solid Precipitation InterComparison Experiment), different types of weighing precipitation gauges and shields were compared, and adjustments were determined for the undercatch of solid precipitation caused by wind. For the various combinations of gauges and shields, adjustments using both new and previously existing transfer functions were evaluated. For most of the gauge and shield combinations, previously derived transfer functions were found to perform as well as those more recently derived. This indicates that wind shield type (or lack thereof) is more important in determining the magnitude of wind-induced undercatch than the type of weighing precipitation gauge. It also demonstrates the potential for widespread use of the previously developed transfer functions. Another overarching result was that, in general, the more effective shields, which were associated with smaller unadjusted errors, also produced more accurate measurements after adjustment. This indicates that although transfer functions can effectively reduce measurement biases, effective wind shielding is still required for the most accurate measurement of solid precipitation.

Rationale for Haze Formation after Carboxymethyl Cellulose (CMC) Addition to Red Wine.

PubMed

Sommer, Stephan; Dickescheid, Christian; Harbertson, James F; Fischer, Ulrich; Cohen, Seth D

2016-09-14

The aim of this study was to identify the source of haze formation in red wine after the addition of carboxymethyl cellulose (CMC) and to characterize the dynamics of precipitation. Ninety commercial wines representing eight grape varieties were collected, tested with two commercial CMC products, and analyzed for susceptibility to haze formation. Seventy-four of these wines showed a precipitation within 14 days independent of the CMC product used. The precipitates of four representative samples were further analyzed for elemental composition (CHNS analysis) and solubility under different conditions to determine the nature of the solids. All of the precipitates were composed of approximately 50% proteins and 50% CMC and polyphenols. It was determined that the interactions between CMC and bovine serum albumin are pH dependent in wine-like model solution. Furthermore, it was found that the color loss associated with CMC additions required the presence of proteins and cannot be observed with CMC and anthocyanins alone.

Superstrength of nanograined steel with nanoscale intermetallic precipitates transformed from shock-compressed martensitic steel

PubMed Central

Yu, Hailiang; Yan, Ming; Lu, Cheng; Tieu, Anh Kiet; Li, Huijun; Zhu, Qiang; Godbole, Ajit; Li, Jintao; Su, Lihong; Kong, Charlie

2016-01-01

An increasing number of industrial applications need superstrength steels. It is known that refined grains and nanoscale precipitates can increase strength. The hardest martensitic steel reported to date is C0.8 steel, whose nanohardness can reach 11.9 GPa through incremental interstitial solid solution strengthening. Here we report a nanograined (NG) steel dispersed with nanoscale precipitates which has an extraordinarily high hardness of 19.1 GPa. The NG steel (shock-compressed Armox 500T steel) was obtained under these conditions: high strain rate of 1.2 μs−1, high temperature rise rate of 600 Kμs−1 and high pressure of 17 GPa. The mean grain size achieved was 39 nm and reinforcing precipitates were indexed in the NG steel. The strength of the NG steel is expected to be ~3950 MPa. The discovery of the NG steel offers a general pathway for designing new advanced steel materials with exceptional hardness and excellent strength. PMID:27892460

Effect of Prestrain on Precipitation Behaviors of Ti-2.5Cu Alloy

NASA Astrophysics Data System (ADS)

Lincai, Zhang; Xiaoming, Ding; Wei, Ye; Man, Zhang; Zhenya, Song

2018-04-01

As a special hardenable α titanium alloy, Ti-2.5 Cu alloy was a candidate material for high temperature components requiring high strength and plasticity. The effect of prestrain on the precipitation behaviors was investigated in the present study. Tensile tests show that elongation up to 22 % can be obtained after solid solution (SS) treatment. Thereafter, prestrain in tension with 5 %, 10 %, 15 % and 20 % was carried out for the SS samples and then duplex aging was applied. Transmitting electron microscopy (TEM) investigations show that larger Ti2Cu particles were observed in the prestrained condition than free aging one, as prestrain significantly speeds up the precipitation kinetics. The strength firstly increases and then decreases for the prestrained samples after duplex aging, where the competition between precipitation hardening and recovery softening should be responsible. With the consideration of SS, precipitation and recovery, a strength model for duplex aging combined with prestrain was established, which is in well agreement with experiments. Present study may provide a promising way to obtain the strength of deformed hcp materials in industry application.

Precipitate Redistribution during Creep of Alloy 617

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

S. Schlegel; S. Hopkins; E. Young

2009-12-01

Nickel-based superalloys are being considered for applications within advanced nuclear power generation systems due to their high temperature strength and corrosion resistance. Alloy 617, a candidate for use in heat exchangers, derives its strength from both solid solution strengthening and the precipitation of carbide particles. However, during creep, carbides that are supposed to retard grain boundary motion are found to dissolve and re-precipitate on boundaries in tension. To quantify the redistribution, we have used electron backscatter diffraction and energy dispersive spectroscopy to analyze the microstructure of 617 after creep testing at 900 and 1000°C. The data were analyzed with respectmore » to location of the carbides (e.g., intergranular vs. intragranular), grain boundary character, and precipitate type (i.e., Cr-rich or Mo-rich). We find that grain boundary character is the most important factor in carbide distribution; some evidence of preferential distribution to boundaries in tension is also observed at higher applied stresses. Finally, the results suggest that the observed redistribution is due to the migration of carbides to the boundaries and not the migration of boundaries to the precipitates.« less

Phase Behavior Modeling of Asphaltene Precipitation for Heavy Crudes: A Promising Tool Along with Experimental Data

NASA Astrophysics Data System (ADS)

Tavakkoli, M.; Kharrat, R.; Masihi, M.; Ghazanfari, M. H.; Fadaei, S.

2012-12-01

Thermodynamic modeling is known as a promising tool for phase behavior modeling of asphaltene precipitation under different conditions such as pressure depletion and CO2 injection. In this work, a thermodynamic approach is used for modeling the phase behavior of asphaltene precipitation. The precipitated asphaltene phase is represented by an improved solid model, while the oil and gas phases are modeled with an equation of state. The PR-EOS was used to perform flash calculations. Then, the onset point and the amount of precipitated asphaltene were predicted. A computer code based on an improved solid model has been developed and used for predicting asphaltene precipitation data for one of Iranian heavy crudes, under pressure depletion and CO2 injection conditions. A significant improvement has been observed in predicting the asphaltene precipitation data under gas injection conditions. Especially for the maximum value of asphaltene precipitation and for the trend of the curve after the peak point, good agreement was observed. For gas injection conditions, comparison of the thermodynamic micellization model and the improved solid model showed that the thermodynamic micellization model cannot predict the maximum of precipitation as well as the improved solid model. The non-isothermal improved solid model has been used for predicting asphaltene precipitation data under pressure depletion conditions. The pressure depletion tests were done at different levels of temperature and pressure, and the parameters of a non-isothermal model were tuned using three onset pressures at three different temperatures for the considered crude. The results showed that the model is highly sensitive to the amount of solid molar volume along with the interaction coefficient parameter between the asphaltene component and light hydrocarbon components. Using a non-isothermal improved solid model, the asphaltene phase envelope was developed. It has been revealed that at high temperatures, an increase in the temperature results in a lower amount of asphaltene precipitation and also it causes the convergence of lower and upper boundaries of the asphaltene phase envelope. This work illustrates successful application of a non-isothermal improved solid model for developing the asphaltene phase envelope of heavy crude which can be helpful for monitoring and controlling of asphaltene precipitation through the wellbore and surface facilities during heavy oil production.

Reducing acid leaching of manganiferous ore: Effect of the iron removal operation on solid waste disposal

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

De Michelis, Ida; Ferella, Francesco; Beolchini, Francesca

2009-01-15

The process of reducing acid leaching of manganiferous ore is aimed at the extraction of manganese from low grade manganese ores. This work is focused on the iron removal operation. The following items have been considered in order to investigate the effect of the main operating conditions on solid waste disposal and on the process costs: (i) type and quantity of the base agent used for iron precipitation, (ii) effective need of leaching waste separation prior to the iron removal operation, (iii) presence of a second leaching stage with the roasted ore, which might also act as a preliminary ironmore » removal step, and (iv) effect of tailings washing on the solid waste classification. Different base compounds have been tested, including CaO, CaCO{sub 3}, NaOH, and Na{sub 2}CO{sub 3}. The latter gave the best results concerning both the precipitation process kinetics and the reagent consumption. The filtration of the liquor leach prior to iron removal was not necessary, implying significant savings in capital costs. A reduction of chemical consumption and an increase of manganese concentration in the solution were obtained by introducing secondary leaching tests with the previously roasted ore; this additional step was introduced without a significant decrease of global manganese extraction yield. Finally, toxicity characteristic leaching procedure (TCLP) tests carried out on the leaching solid waste showed: (i) a reduction of arsenic mobility in the presence of iron precipitates, and (ii) the need for a washing step in order to produce a waste that is classifiable as not dangerous, taking into consideration the existing Environmental National Laws.« less

PROCESS OF TREATING OR FORMING AN INSOLUBLE PLUTONIUM PRECIPITATE IN THE PRESENCE OF AN ORGANIC ACTIVE AGENT

DOEpatents

Balthis, J.H.

1961-07-18

Carrier precipitation processes for the separation of plutonium from fission products are described. In a process in which an insoluble precipitate is formed in a solution containing plutonium and fission products under conditions whereby plutonium is carried by the precipitate, and the precipitate is then separated from the remaining solution, an organic surface active agent is added to the mixture of precipitate and solution prior to separation of the precipitate from the supernatant solution, thereby improving the degree of separation of the precipitate from the solution.

RETRACTED ARTICLE: Microstructure and strengthening mechanism of Ni3Al intermetallic compound

NASA Astrophysics Data System (ADS)

Oh, Chang-Sup; Han, Chang-Suk

2013-09-01

Structural studies have been performed on precipitation hardening found in Ni3Al-base ordered alloys using transmission electron microscopy. The γ' phase hardens appreciably by the fine precipitation of disordered γ. The strength of γ' increases over the temperature range of experiment by the precipitation of fine γ particles. The peak temperature where a maximum strength was obtained shifted to higher temperature. Superlattice dislocations dissociate into fourfold Shockley partial dislocations in a uniform supersaturated solid solution of the γ' phase. Dislocations are attracted into the disordered γ phase and dissociate further in the particles. At any stage of aging, dislocations cut through the particles and the Orowan bypassing process does not occur even in the overaged stage of this alloy system. When the applied stress is removed, the dislocations make cross slip into (010) plane, while those in γ precipitates remain on the (111) primary slip plane. The increase of high temperature strength in γ' containing γ precipitates is due to the restraint of cross slip of dislocations from (111) to (010) by the dispersion of disordered γ particles. The orientation dependence of strength is decreased by the fine precipitation of a disordered γ phase.

Method of producing superplastic alloys and superplastic alloys produced by the method

NASA Technical Reports Server (NTRS)

Troeger, Lillianne P. (Inventor); Starke, Jr., Edgar A. (Inventor); Crooks, Roy (Inventor)

2002-01-01

A method for producing new superplastic alloys by inducing in an alloy the formation of precipitates having a sufficient size and homogeneous distribution that a sufficiently refined grain structure to produce superplasticity is obtained after subsequent PSN processing. An age-hardenable alloy having at least one dispersoid phase is selected for processing. The alloy is solution heat-treated and cooled to form a supersaturated solid solution. The alloy is plastically deformed sufficiently to form a high-energy defect structure useful for the subsequent heterogeneous nucleation of precipitates. The alloy is then aged, preferably by a multi-stage low and high temperature process, and precipitates are formed at the defect sites. The alloy then is subjected to a PSN process comprising plastically deforming the alloy to provide sufficient strain energy in the alloy to ensure recrystallization, and statically recrystallizing the alloy. A grain structure exhibiting new, fine, equiaxed and uniform grains is produced in the alloy. An exemplary 6xxx alloy of the type capable of being produced by the present invention, and which is useful for aerospace, automotive and other applications, is disclosed and claimed. The process is also suitable for processing any age-hardenable aluminum or other alloy.

Trends in the precipitation and crystallization behavior of supersaturated aqueous solutions of poorly water-soluble drugs assessed using synchrotron radiation.

PubMed

Raina, Shweta A; Van Eerdenbrugh, Bernard; Alonzo, David E; Mo, Huaping; Zhang, Geoff G Z; Gao, Yi; Taylor, Lynne S

2015-06-01

Amorphous materials are high-energy solids that can potentially enhance the bioavailability of poorly soluble compounds. A major impediment to their widespread use as a formulation platform is the tendency of amorphous materials to crystallize. The aim of this study was to evaluate the relative crystallization tendency of six structural analogues belonging to the dihydropyridine class, in an aqueous environment in the absence and presence of polymers, using wide-angle X-ray scattering synchrotron radiation and polarized light microscopy. The crystallization behavior of precipitates generated from supersaturated solutions of the active pharmaceutical ingredients was found to be highly variable ranging from immediate to several hours in the absence of polymers. Polymers with intermediate hydrophilicity/hydrophobicity were found to substantially delay crystallization, whereas strongly hydrophilic or hydrophobic polymers were largely ineffective. Nuclear magnetic resonance spectroscopy experiments supported the supposition that polymers need to have affinity for both the drug-rich precipitate and the aqueous phase in order to be effective crystallization inhibitors. This study highlights the variability in the crystallization tendency of different compounds and provides insight into the mechanism of inhibition by polymeric additives. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Identification of Fragile Microscopic Structures during Mineral Transformations in Wet Supercritical CO2

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

Arey, Bruce W.; Kovarik, Libor; Qafoku, Odeta

2013-04-01

In this study we examine the nature of highly fragile reaction products that form in low water content super critical carbon dioxide (scCO2) using a combination of scanning electron microscopy/focus ion beam (SEM/FIB), confocal Raman spectroscopy, helium ion microscopy (HeIM), and transmission electron microscopy (TEM). HeIM images show these precipitates to be fragile rosettes that can readily decompose even under slight heating from an electron beam. Using the TEM revealed details on the interfacial structure between the newly formed surface precipitates and the underlying initial solid phases. The detailed microscopic analysis revealed that the growth of the precipitates either followedmore » a tip growth mechanism with precipitates forming directly on the forsterite surface if the initial solid was non-porous (natural forsterite) or growth from the surface of the precipitates where fluid was conducted through the porous (nanoforsterite) agglomerates to the growth center. The mechanism of formation of the hydrated/hydroxylated magnesium carbonate compound (HHMC) phases offers insight into the possible mechanisms of carbonate mineral formation from scCO2 solutions which has recently received a great deal of attention as the result of the potential for CO2 to act as an atmospheric greenhouse gas and impact overall global warming. The techniques used here to examine these fragile structures an also be used to examine a wide range of fragile material surfaces. SEM and FIB technologies have now been brought together in a single instrument, which represents a powerful combination for the studies in biological, geological and materials science.« less

Coprecipitation mechanisms and products in manganese oxidation in the presence of cadmium

USGS Publications Warehouse

Hem, J.D.; Lind, Carol J.

1991-01-01

Manganese oxidation products were precipitated in an aerated open-aqueous system where a continuous influx of mixed Mn2+ and Cd2+ solution was supplied and pH was maintained with an automated pH-stat adding dilute NaOH. X-ray diffraction and electron diffraction identified the solids produced as mixtures of Cd2Mn34+O8, Mn2+2Mn4+3O8, MnO2 (ramsdellite), and CdCO3. Mean oxidation numbers of the total precipitated Mn as great as 3.6 were reached during titrations. During subsequent aging in solution, oxidation numbers between 3.8 and 3.9 were reached in some precipitates in less than 40 days. Conditional oxidation rate constants calculated from a crystal-growth equation applied to titration data showed the overall precipitation rate, without considering manganese oxidation state in the precipitate, was increased by a factor of ~4 to ~7 when the mole ratio (Cd/Mn + Cd) of cadmium in the feed solution was 0.40 compared with rate constants for hausmannite (Mn2+Mn23+O4 precipitation under similar conditions but without accessory metals. Kinetic experiments were made to test effects of various Cd/Mn + Cd mole ratios and rates of addition of the feed solution, different temperatures from 5.0 to 35??C, and pH from 8.0 to 9.0. Oxidation rates were slower when the Cd mole ratio was less than 0.40. The rate increased by a factor of ~10 when pH was raised one-half unit. The effect of temperature on the rate constants was also substantial, but the meaning of this is uncertain because the rate of formation of Mn4+ oxide in the absence of Cd or other accessory metals was too slow to be measurable in titration experiments. The increased rate of Mn4+ oxide formation in the presence of Cd2+ can be ascribed to the formation of a labile adsorbed intermediate, CdMn2O4 Int, an analog of hausmannite, formed on precipitate surfaces at the beginning of the oxidation process. The increased lability of this structure, resulting from coordination-chemical behavior of Cd2+ during the titration, causes a rapid second-stage rearrangement and facilitates disproportionation of the Mn3+ ions. The Mn2+ ions thus released provide a positive feedback mechanism that couples the two steps of the conversion of Mn2+ to Mn4+ more closely than is possible when other metal ions besides manganese are not present. During aging of precipitates in contact with solutions, proportions of Cd2Mn3O8 and MnO2 increased at the expense of other precipitate components. ?? 1991.

Microstructure-Property Correlations in Fiber Laser Welded Nb-Ti Microalloyed C-Mn Steel

NASA Astrophysics Data System (ADS)

Sun, Qian; Nie, Xiao-Kang; Li, Yang; Di, Hong-Shuang

2018-02-01

Mechanical Performance of traditional gas-shielded arc welded joints of 700 MPa grade microalloyed C-Mn steel cannot meet service requirements. Laser welding, with its characteristic high energy density, is known to improve the welding performance of experimental steels. In the present study, Nb-Ti microalloyed steel with a thickness of 4.5 mm was welded using a 4 kW fiber laser. The microstructure, precipitation, and mechanical properties of the welded joints were studied. The hardness and tensile strength of the welded joints were higher than those of the base metal (BM). The microstructure of the fusion zone (FZ) and coarse grain heat affected zone (CGHAZ) was lath martensite (LM), while the microstructure of the fine grain HAZ and mixed grain HAZ consisted of ferrite and martensite/austenite islands. Although LM was observed in both the FZ and CGHAZ, the hardness and calculated tensile strength of the FZ were lower than those of the CGHAZ, due to a reduction in solid solution strengthening by element loss and the dissolution of high-hardness precipitates in FZ. Most precipitates such as [(Nb,Ti)C and (Nb,Ti)(C,N)] that were present in the BM were dissolved, which led to an increase in C and N in solid solution in the FZ. Thus, the elastic modulus of the FZ was higher than that of the BM. Similarly, the elastic modulus of the CGHAZ was higher than that of the BM due to the segregation of C and N atoms during the welding process. The toughness of the FZ was superior to that of the BM, and the toughness of the HAZ approached 91% of that of the BM. The change in toughness primarily depended on the microstructural refinement, the increase in the fraction of grains with high misorientation, the residual austenite in the FZ and CGHAZ, and the dissolution of coarse precipitates.

Multiscale structural characterizations of mixed U(iv)-An(iii) oxalates (An(iii) = Pu or Am) combining XAS and XRD measurements.

PubMed

Arab-Chapelet, B; Martin, P M; Costenoble, S; Delahaye, T; Scheinost, A C; Grandjean, S; Abraham, F

2016-04-28

Mixed actinide(III,IV) oxalates of the general formula M2.2UAn(C2O4)5·nH2O (An = Pu or Am and M = H3O(+) and N2H5(+)) have been quantitatively precipitated by oxalic precipitation in nitric acid medium (yield >99%). Thorough multiscale structural characterization using XRD and XAS measurements confirmed the existence of mixed actinide oxalate solid solutions. The XANES analysis confirmed that the oxidation states of the metallic cations, tetravalent for uranium and trivalent for plutonium and americium, are maintained during the precipitation step. EXAFS measurements show that the local environments around U(+IV), Pu(+III) and Am(+III) are comparable, and the actinides are surrounded by ten oxygen atoms from five bidentate oxalate anions. The mean metal-oxygen distances obtained by XAS measurements are in agreement with those calculated from XRD lattice parameters.

Kinetics of the cellular decomposition of supersaturated solid solutions

NASA Astrophysics Data System (ADS)

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

2014-09-01

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

The Importance of pH, Oxygen, and Bitumen on the Oxidation and Precipitation of Fe(III)-(oxy)hydroxides during Hydraulic Fracturing of Oil/Gas Shales

NASA Astrophysics Data System (ADS)

Jew, A. D.; Dustin, M. K.; Harrison, A. L.; Joe-Wong, C. M.; Thomas, D.; Maher, K.; Brown, G. E.; Bargar, J.

2016-12-01

Due to the rapid growth of hydraulic fracturing in the United States, understanding the cause for the rapid production drop off of new wells over the initial months of production is paramount. One possibility for the production decrease is pore occlusion caused by the oxidation of Fe(II)-bearing phases resulting in Fe(III) precipitates. To understand the release and fate of Fe in the shale systems, we reacted synthesized fracture fluid at 80oC with shale from four different geological localities (Marcellus Fm., Barnett Fm., Eagle Ford Fm., and Green River Fm.). A variety of wet chemical and synchrotron-based techniques (XRF mapping and x-ray absorption spectroscopy) were used to understand Fe release and solid phase Fe speciation. Solution pH was found to be the greatest factor for Fe release. Carbonate-poor Barnett and Marcellus shale showed rapid Fe release into solution followed by a plateau or significant drop in Fe concentrations indicating mineral precipitation. Conversely, in high carbonate shales, Eagle Ford and Green River, no Fe was detected in solution indicating fast Fe oxidation and precipitation. For all shale samples, bulk Fe EXAFS data show that a significant amount of Fe in the shales is bound directly to organic carbon. Throughout the course of the experiments inorganic Fe(II) phases (primarily pyrite) reacted while Fe(II) bound to C showed no indication of reaction. On the micron scale, XRF mapping coupled with μ-XANES spectroscopy showed that at pH < 4.0, Fe(III) bearing phases precipitated as diffuse surface precipitates of ferrihydrite, goethite, and magnetite away from Fe(II) point sources. In near circum-neutral pH systems, Fe(III)-bearing phases (goethite and hematite) form large particles 10's of μm's in diameter near Fe(II) point sources. Idealized systems containing synthesized fracturing fluid, dissolved ferrous chloride, and bitumen showed that bitumen released during reaction with fracturing fluids is capable of oxidizing Fe(II) to Fe(III) at pH's 2.0 and 7.0. This indicates that bitumen can play a large role in Fe oxidation and speciation in the subsurface. This work shows that shale mineralogy has a significant impact on the morphology and phases of Fe(III) precipitates in the subsurface which in turn can significantly impact subsurface solution flow.

Kinetics and Equilibrium of Age-Induced Precipitation in Cu-4 At. Pct Ti Binary Alloy

NASA Astrophysics Data System (ADS)

Semboshi, Satoshi; Amano, Shintaro; Fu, Jie; Iwase, Akihiro; Takasugi, Takayuki

2017-03-01

Transformation kinetics and phase equilibrium of metastable and stable precipitates in age-hardenable Cu-4 at. pct Ti binary alloy have been investigated by monitoring the microstructural evolution during isothermal aging at temperatures between 693 K (420 °C) and 973 K (700 °C). The microstructure of the supersaturated solid solution evolves in four stages: compositional modulation due to spinodal decomposition, continuous precipitation of the needle-shaped metastable β'-Cu4Ti with a tetragonal structure, discontinuous precipitation of cellular components containing stable β-Cu4Ti lamellae with an orthorhombic structure, and eventually precipitation saturation at equilibrium. In specimens aged below 923 K (650 °C), the stable β-Cu4Ti phase is produced only due to the cellular reaction, whereas it can be also directly obtained from the intergranular needle-shaped β'-Cu4Ti precipitates in specimens aged at 973 K (700 °C). The precipitation kinetics and phase equilibrium observed for the specimens aged between 693 K (420 °C) and 973 K (700 °C) were characterized in accordance with a time-temperature-transformation (TTT) diagram and a Cu-Ti partial phase diagram, which were utilized to determine the alloy microstructure, strength, and electrical conductivity.

Synthesis and characterization of the LDH hydrotalcite-pyroaurite solid-solution series

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

Rozov, K., E-mail: urs.berner@psi.c; Rock-Water Interaction Group, Institute of Geological Sciences, University of Bern, Baltzerstrasse 3, CH-3012; Berner, U.

2010-08-15

A layered double hydroxide (LDH) hydrotalcite-pyroaurite solid-solution series Mg{sub 3}(Al{sub x}Fe{sub 1-x})(CO{sub 3}){sub 0.5}(OH){sub 8} with 1 - x = 0.0, 0.1...1.0 was prepared by co-precipitation at 23 {+-} 2 {sup o}C and pH = 11.40 {+-} 0.03. The compositions of the solids and the reaction solutions were determined using ICP-OES (Mg, Al, Fe, and Na) and TGA techniques (CO{sub 3}{sup 2-}, OH{sup -}, and H{sub 2}O). Powder X-ray diffraction was employed for phase identification and determination of the unit cell parameters a{sub o} and c{sub o} from peak profile analysis. The parameter a{sub o} = b{sub o} was foundmore » to be a linear function of the composition. This dependency confirms Vegard's law and indicates the presence of a continuous solid-solution series in the hydrotalcite-pyroaurite system. TGA data show that the temperatures at which interlayer H{sub 2}O molecules and CO{sub 3}{sup 2-} anions are lost, and at which dehydroxylation of the layers occurs, all decrease with increasing mole fraction of iron within the hydroxide layers. Features of the Raman spectra also depend on the iron content. The absence of Raman bands for Fe-rich members (x{sub Fe} > 0.5) is attributed to possible fluorescence phenomena. Based on chemical analysis of both the solids and the reaction solutions after synthesis, preliminary Gibbs free energies of formation have been estimated. Values of {Delta}G{sup o}{sub f}(hydrotalcite) = - 3773.3 {+-} 51.4 kJ/mol and {Delta}G{sup o}{sub f}(pyroaurite) = - 3294.5 {+-} 95.8 kJ/mol were found at 296.15 K. The formal uncertainties of these formations constants are very high. Derivation of more precise values would require carefully designed solubility experiments and improved analytical techniques.« less

The Effect of Milling Time on the Microstructural Characteristics and Strengthening Mechanisms of NiMo-SiC Alloys Prepared via Powder Metallurgy.

PubMed

Yang, Chao; Muránsky, Ondrej; Zhu, Hanliang; Thorogood, Gordon J; Avdeev, Maxim; Huang, Hefei; Zhou, Xingtai

2017-04-06

A new generation of alloys, which rely on a combination of various strengthening mechanisms, has been developed for application in molten salt nuclear reactors. In the current study, a battery of dispersion and precipitation-strengthened (DPS) NiMo-based alloys containing varying amounts of SiC (0.5-2.5 wt %) were prepared from Ni-Mo-SiC powder mixture via a mechanical alloying (MA) route followed by spark plasma sintering (SPS) and rapid cooling. Neutron Powder Diffraction (NPD), Electron Back Scattering Diffraction (EBSD), and Transmission Electron Microscopy (TEM) were employed in the characterization of the microstructural properties of these in-house prepared NiMo-SiC DPS alloys. The study showed that uniformly-dispersed SiC particles provide dispersion strengthening, the precipitation of nano-scale Ni₃Si particles provides precipitation strengthening, and the solid-solution of Mo in the Ni matrix provides solid-solution strengthening. It was further shown that the milling time has significant effects on the microstructural characteristics of these alloys. Increased milling time seems to limit the grain growth of the NiMo matrix by producing well-dispersed Mo₂C particles during sintering. The amount of grain boundaries greatly increases the Hall-Petch strengthening, resulting in significantly higher strength in the case of 48-h-milled NiMo-SiC DPS alloys compared with the 8-h-milled alloys. However, it was also shown that the total elongation is considerably reduced in the 48-h-milled NiMo-SiC DPS alloy due to high porosity. The porosity is a result of cold welding of the powder mixture during the extended milling process.

The Effect of Milling Time on the Microstructural Characteristics and Strengthening Mechanisms of NiMo-SiC Alloys Prepared via Powder Metallurgy

PubMed Central

Yang, Chao; Muránsky, Ondrej; Zhu, Hanliang; Thorogood, Gordon J.; Avdeev, Maxim; Huang, Hefei; Zhou, Xingtai

2017-01-01

A new generation of alloys, which rely on a combination of various strengthening mechanisms, has been developed for application in molten salt nuclear reactors. In the current study, a battery of dispersion and precipitation-strengthened (DPS) NiMo-based alloys containing varying amounts of SiC (0.5–2.5 wt %) were prepared from Ni-Mo-SiC powder mixture via a mechanical alloying (MA) route followed by spark plasma sintering (SPS) and rapid cooling. Neutron Powder Diffraction (NPD), Electron Back Scattering Diffraction (EBSD), and Transmission Electron Microscopy (TEM) were employed in the characterization of the microstructural properties of these in-house prepared NiMo-SiC DPS alloys. The study showed that uniformly-dispersed SiC particles provide dispersion strengthening, the precipitation of nano-scale Ni3Si particles provides precipitation strengthening, and the solid-solution of Mo in the Ni matrix provides solid-solution strengthening. It was further shown that the milling time has significant effects on the microstructural characteristics of these alloys. Increased milling time seems to limit the grain growth of the NiMo matrix by producing well-dispersed Mo2C particles during sintering. The amount of grain boundaries greatly increases the Hall–Petch strengthening, resulting in significantly higher strength in the case of 48-h-milled NiMo-SiC DPS alloys compared with the 8-h-milled alloys. However, it was also shown that the total elongation is considerably reduced in the 48-h-milled NiMo-SiC DPS alloy due to high porosity. The porosity is a result of cold welding of the powder mixture during the extended milling process. PMID:28772747

Synthesis and formation mechanism of pinnoite by the phase transition process

NASA Astrophysics Data System (ADS)

Lin, Feng; Dong, Yaping; Peng, Jiaoyu; Wang, Liping; Li, Wu

2016-06-01

Pinnoite (MgB2O(OH)6) for the first time was synthesized using the solid-liquid-solid conversion method. The effects of reaction time, pH value and concentrations of magnesium and borate were investigated. Pinnoite was synthesized under the optimum condition of 8 mmol hungtsaoite and 1% boric acid solution at 80 °C. The products were determined using X-ray diffraction, Fourier-transform infrared spectroscopy, TG-DSC and a UV-vis spectrometer. The change processes of the surface morphology of pinnoite were investigated using scanning electron microscopy. In addition, the formation mechanism of pinnoite was discussed according to the changes in the content of precipitation and pH value.

Solution-mediated phase transformation of haloperidol mesylate in the presence of sodium lauryl sulfate.

PubMed

Greco, Kristyn; Bogner, Robin

2011-09-01

Forming a salt is a common way to increase the solubility of a poorly soluble compound. However, the solubility enhancement gained by salt formation may be lost due to solution-mediated phase transformation (SMPT) during dissolution. The SMPT of a salt can occur due to a supersaturated solution near the dissolving surface caused by pH or other solution conditions. In addition to changes in pH, surfactants are also known to affect SMPT. In this study, SMPT of a highly soluble salt, haloperidol mesylate, at pH 7 in the presence of a commonly used surfactant, sodium lauryl sulfate (SLS), was investigated. Dissolution experiments were performed using a flow-through dissolution apparatus with solutions containing various concentrations of SLS. Compacts of haloperidol mesylate were observed during dissolution in the flow-through apparatus using a stereomicroscope. Raman microscopy was used to characterize solids. The dissolution of haloperidol mesylate was significantly influenced by the addition of sodium lauryl sulfate. In conditions where SMPT was expected, the addition of SLS at low concentrations (0.1-0.2 mM) reduced the dissolution of haloperidol mesylate. In solutions containing concentrations of SLS above the critical micelle concentration (CMC) (10-15 mM), the dissolution of haloperidol mesylate increased compared to below the CMC. The solids recovered from solubility experiments of haloperidol mesylate indicated that haloperidol free base precipitated at all concentrations of SLS. Above 5 mM of SLS, Raman microscopy suggested a new form, perhaps the estolate salt. The addition of surfactant in solids that undergo solution-mediated phase transformation can add complexity to the dissolution profiles and conversion.

Sorption of chromium with struvite during phosphorus recovery.

PubMed

Rouff, Ashaki A

2012-11-20

Struvite (MgNH(4)PO(4)·6H(2)O; MAP) precipitation is a viable means of phosphorus (P) recovery from animal and human wastes. The behavior of metal contaminants such as chromium (Cr) during struvite precipitation, however, requires consideration. Here the influence of both Cr concentration and oxidation state on sorption is assessed. The Cr content of struvite precipitated in the presence of 1-100 μM Cr as Cr(III) (22.3-3030.1 mg/kg) was higher than that of solids from Cr(VI) (4.5-5.1 mg/kg) solutions. For 1-20 μM Cr(III) solids, scanning electron microscopy (SEM) revealed etch pit formation on struvite crystal surfaces, indicative of a surface interaction. The formation of an adsorbate was confirmed by X-ray absorption fine structure spectroscopy (XAFS). At initial concentrations ≥20 μM Cr(III), XAFS confirmed the formation of a Cr(OH)(3)·nH(2)O(am) precipitate. Fourier transform infrared (FT-IR) spectroscopy revealed that both Cr(III) and Cr(VI) sorption resulted in distortion of the PO(4)(3-) tetrahedra in the mineral structure. This, combined with SEM results revealed that even at low sorbed concentrations, the Cr impurity can affect the mineral surface and structure. Thus, the initial Cr concentration and oxidation state in wastes targeted for P recovery will dictate the final Cr content, the mechanism of sorption, and impact on the struvite structure.

Cracking Tendancies of Restrained Welds in High Strength Low Alloy Steels under Hyperbaric Conditions.

DTIC Science & Technology

1987-06-01

refinement of NICUAGE by addition of Chromium and Molybdenum with prescribed heat ’I. 24 [I.% treatments to even further lower the DBTT to -115 degrees F...sulpher a., reduces hi temp transformation products " provides solid solution strengthening copper - precipitation strengthening O chromium - optimize...contractors and oil companies include GTAW , GMAW, FCAW, and SMAW. My sense was -, that the most popular technique was the GTAW root pass * followed by the

Behaviour of the pH Adjustment, Ion Exchange and Concentrate Precipitation Stages in the Acid Leaching of Uranium Phosphate Ores; TRATAMIENTO DE DISOLUCIONES DE LIXIVIACION DE MINERALES DE URANIO EN PRESENCIA DE FOSFATOS. COMPORTAMIENTO EN LAS ETAPAS DE AJUSTE DE PH, CAMBIO DE ION Y PRECIPITACION DE CONCENTRADOS (in Spanish)

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

Aguilar, J.E.; Hueda, A.U.

Recovery of U from acid leach solutions of phosphate ore was studied. It was found that predictions can be made concerning solids removal and U recovery in the pH adjustment stage, resin U capacity, eluating agent suitability, ion exchange stage eluation velocity and eluate U concentration, and composition of the precipitate formed in the concentration stage. The results are valid in the concentration range 0.3 to 0. 8 g U/sub 3/O/sub 8//1. (J.R.D.)

Methods and apparatus for catalytic hydrothermal gasification of biomass

DOEpatents

Elliott, Douglas C.; Butner, Robert Scott; Neuenschwander, Gary G.; Zacher, Alan H.; Hart, Todd R.

2012-08-14

Continuous processing of wet biomass feedstock by catalytic hydrothermal gasification must address catalyst fouling and poisoning. One solution can involve heating the wet biomass with a heating unit to a temperature sufficient for organic constituents in the feedstock to decompose, for precipitates of inorganic wastes to form, for preheating the wet feedstock in preparation for subsequent separation of sulfur contaminants, or combinations thereof. Treatment further includes separating the precipitates out of the wet feedstock, removing sulfur contaminants, or both using a solids separation unit and a sulfur separation unit, respectively. Having removed much of the inorganic wastes and the sulfur that can cause poisoning and fouling, the wet biomass feedstock can be exposed to the heterogeneous catalyst for gasification.

Searching for Clues to the Processes and Conditions of Past Martian Environments: The Roles of Episodic Solutions, Analog Sites and Fe-O(-H) Phases

NASA Astrophysics Data System (ADS)

King, P. L.; De Deckker, P.

2012-12-01

On Mars, limited solutions (water/brine) were likely present episodically. Gradients in solution abundance may have caused salt precipitation and re-solution, brine reflux, pH gradients, and cycling of anions and cations; we provide an example of such processes in a playa lake. We propose that on Mars, the limited, episodic solutions, pH and abundant Fe-O(-H) phases are significant factors in salt precipitation and in promoting adsorption/desorption of anions and cations. FACTORS LEADING TO EPISODIC SOLUTIONS: Episodic movement of solutions may be driven by punctuated processes that 1) remove surface materials (e.g., impact and sedimentary mass wasting and deflation); 2) add surface materials (e.g., impact, volcanic and sedimentary processes); and 3) increase temperature and/or decrease atmospheric pressure (e.g., seasons, diurnal cycles, variation in obliquity). Removal and addition of surface materials results in topographic gradients that change pressure gradients of any potential groundwater, films, or buried ground ice. For example, episodic fluid flow and salt precipitation/re-solution may occur at topographic discontinuities like craters/basins, channel walls, mounds and dunes. Such areas provide the opportunity to sample multiple fluid sources (with different pH, Eh and total dissolved solids, TDS) and they may be the foci of subsurface solution flow and surface transport. EARTH ANALOG: Interplay of the three processes above is seen in Lake Tyrrell (playa), western Victoria, Australia (McCumber, P, 1991 http://vro.dpi.vic.gov.au). During wetter periods, springs from the regional groundwater (low pH, oxidized, mod-high TDS) mix with lake waters and saline 'reflux' brines (mod. pH, reduced, high TDS) at the lake edge at the base of higher ground. The Br/Cl of the reflux brines indicates mineral re-solution. Gypsum and Fe-O(-H) phases precipitate near the lake edge. During hot, dry climate episodes the lake precipitates gypsum and carbonate, efflorescent salts are common, and these salts may form eolian dunes with fine particles. We may expect similar processes and mineral and chemical gradients in craters/basins on Mars like Gale Crater, the site of the Mars Science Laboratory mission. ROLE OF Fe-O(-H) PHASES: Nanophase Fe-O(-H)-phases are abundant on Mars and their precipitation results in an Fe-poor solution and salts (like Lake Tyrrell). Fe-O(-H) phases precipitate most readily at near-neutral pH; however, the high Fe of Mars' surface allows for pH>1. Nanophase Fe-O(-H)-phases have surface species that promote adsorption; which may be important in dry conditions like Mars. If we take goethite (FeO(OH)), the surface species and aqueous ions in solution are Fe3+ (pH<~2); Fe(OH)2+ (pH~2-3.5); Fe(OH)2+ (pH~3.5-~8); and FeOH4- (pH>~8). Other Fe-O(-H) phases have slightly different pH limits. Thus, at pH<~8, Fe-O(-H) surfaces sequester anions in surface complexes or in Fe-bearing salts (e.g. Fe3+-phosphate and sulfates, especially at pH<4). PO43- species have high adsorption affinity, followed by SO42-, Cl-(O) and Br-(O) species. At pH>~8, adsorption and exchange of cations are likely. These chemical variations may provide us with clues of the past pH on Mars.

Thermodynamic assessment of microencapsulated sodium carbonate slurry for carbon capture

DOE PAGES

Stolaroff, Joshuah K.; Bourcier, William L.

2014-01-01

Micro-encapsulated Carbon Sorbents (MECS) are a new class of carbon capture materials consisting of a CO₂- absorbing liquid solvent contained within solid, CO₂-permeable, polymer shells. MECS enhance the rate of CO₂ absorption for solvents with slow kinetics and prevent solid precipitates from scaling and fouling equipment, two factors that have previously limited the use of sodium carbonate solution for carbon capture. Here, we examine the thermodynamics of sodium carbonate slurries for carbon capture. We model the vapour-liquid-solid equilibria of sodium carbonate and find several features that can contribute to an energy-efficient capture process: very high CO₂ pressures in stripping conditions,more » relatively low water vapour pressures in stripping conditions, and good swing capacity. The potential energy savings compared with an MEA system are discussed.« less

Mobility of Heavy Metals (Pb, Cd, Zn) in the Pampeano and Puelche Aquifers, Argentina: Partition and Retardation Coefficients.

PubMed

Jakomin, L M; Marbán, L; Grondona, S; Glok Galli, M; Martínez, D E

2015-09-01

The prediction about metals behaviour in soil requires knowledge on their solid-liquid partitioning. Usually it is expressed with an empirical distribution coefficient or Kd, which gives the ratio of the metal concentration in the solid phase to that in the solution. Kd values have been determined for Zn, Pb and Cd from samples representing the two most exploited aquifers in Argentina, Pampeano and Puelche, at three different locations in the province of Buenos Aires. The Pampeano aquifer presented higher Kd values than the Puelche aquifer. Comparing Kd values, different relationships could be observed: (a) Pampeano aquifer: Pb > Zn > Cd, and (b) Puelche aquifer: Pb > Cd > Zn. Kd for Cd seems to be linked to cationic exchange capacity, but solid phases precipitation can be more determining for Pb and Zn.

Hydrochemistry of the Lake Magadi basin, Kenya

USGS Publications Warehouse

Jones, B.F.; Eugster, H.P.; Rettig, S.L.

1977-01-01

New and more complete compositional data are presented for a large number of water samples from the Lake Magadi area, Kenya. These water samples range from dilute inflow (300 g/kg dissolved solids). Five distinct hydrologic stages can be recognized in the evolution of the water compositions: dilute streamflow, dilute ground water, saline ground water (or hot spring reservoir), saturated brines, and residual brines. Based on the assumption that chloride is conserved in the waters during evaporative concentration, these stages are related to each other by the concentration factors of about 1:28:870:7600:16,800. Dilute streamflow is represented by perennial streams entering the Rift Valley from the west. All but one (Ewaso Ngiro) of these streams disappear in the alluvium and do not reach the valley floor. Dilute ground water was collected from shallow pits and wells dug into lake sediments and alluvial channels. Saline ground water is roughly equivalent to the hot springs reservoir postulated by Eugster (1970) and is represented by the hottest of the major springs. Saturated brines represent surficial lake brines just at the point of saturation with respect to trona (Na2CO3.NaHCO3.2H2O), while residual brines are essentially interstitial to the evaporite deposit and have been subjected to a complex history of precipitation and re-solution. The new data confirm the basic hydrologic model presented by Eugster (1970) which has now been refined, particularly with respect to the early stages of evaporative concentration. Budget calculations show that only bromide is conserved as completely as chloride. Sodium follows chloride closely until trona precipitation, whereas silica and sulfate are largely lost during the very first concentration' step (dilute streamflow-dilute ground water). A large fraction of potassium and all calcium plus magnesium are removed during the first two concentration steps (dilute streamflow-dilute ground water-saline ground water). Carbonate and bicarbonate are the dominant anions, and mechanisms by which they are extracted from the solution include precipitation of alkali and alkaline-earth carbonates, and degassing, as well as precipitation and re-solution of efflorescent crusts. Much sulfate is apparently lost from solution by sorption as well as subsurface reduction. Seasonal runoff, principally from the valley floor north of Lake Magadi, is considered to be the principal recharge to the Magadi ground water system. Evaporative concentration is the overall process responsible for the chemical evolution of the brines. This includes not only simple evaporation, but also mineral precipitation as films and cements in the unsaturated zone, re-solution, and reprecipitation of efflorescent crusts, with consequent recycling of salts. In fact, a large fraction of the solutes are acquired through dissolution of efflorescent crusts. Data were obtained for borehole brines from as deep as 297 m. They show the existence of two distinct brine bodies below the present lake, one shallow, coexistent with bedded salts, and highly concentrated (260 g/kg average dissolved solids), and the other deeper in lacustrine sediments or fractured lavas, and only half as concentrated. ?? 1977.

A facile method to prepare "green" nano-phosphors with a large Stokes-shift and solid-state enhanced photophysical properties based on surface-modified gold nanoclusters.

PubMed

Cheng, C H; Huang, H Y; Talite, M J; Chou, W C; Yeh, J M; Yuan, C T

2017-12-15

Colloidal nano-materials, such as quantum dots (QDs) have been applied to light-conversion nano-phosphors due to their unique tunable emission. However, most of the QDs involve toxic elements and are synthesized in a hazardous solvent. In addition, conventional QD nano-phosphors with a small Stokes shift suffered from reabsorption losses and aggregation-induced quenching in the solid state. Here, we demonstrate a facile, matrix-free method to prepare eco-friendly nano-phosphors with a large Stokes shift based on aqueous thiolate-stabilized gold nanoclusters (GSH-AuNCs) with simple surface modifications. Our method is just to drop GSH-AuNCs solution on the aluminum foil and then surface-modified AuNCs (Al-GSH-AuNCs) can be spontaneously precipitated out of the aqueous solution. Compared with pristine GSH-AuNCs in solution, the Al-GSH-AuNCs exhibit enhanced solid-state PL quantum yields, lengthened PL lifetime, and spectral blue shift, which can be attributed to the aggregation-induced emission enhancement facilitated by surface modifications. Such surface-treatment induced aggregation of AuNCs can restrict the surface-ligand motion, leading to the enhancement of PL properties in the solid state. In addition, the Al-GSH-AuNCs nano-phosphors with a large Stokes shift can mitigate the aggregation-induced PL quenching and reabsorption losses, which would be potential candidates for "green" nano-phosphors. Copyright © 2017 Elsevier Inc. All rights reserved.

Chemical Equilibrium of Aluminate in Hanford Tank Waste Originating from Tanks 241-AN-105 and 241-AP-108

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

McCoskey, Jacob K.; Cooke, Gary A.; Herting, Daniel L.

The purposes of the study described in this document follow; Determine or estimate the thermodynamic equilibrium of gibbsite in contact with two real tank waste supernatant liquids through both dissolution of gibbsite (bottom-up approach) and precipitation of aluminum-bearing solids (top-down approach); determine or estimate the thermodynamic equilibrium of a mixture of gibbsite and real tank waste saltcake in contact with real tank waste supernatant liquid through both dissolution of gibbsite and precipitation of aluminum-bearing solids; and characterize the solids present after equilibrium and precipitation of aluminum-bearing solids.

Application of advanced oxidation processes for cleaning of industrial water generated in wet dedusting of shaft furnace gases.

PubMed

Czaplicka, Marianna; Kurowski, Ryszard; Jaworek, Katarzyna; Bratek, Łukasz

2013-01-01

The paper presents results of studies into advanced oxidation processes in 03 and 03/UV systems. An advanced oxidation process (AOP) was conducted to reduce the load of impurities in circulating waters from wet de-dusting of shaft furnace gases. Besides inorganic impurities, i.e. mainly arsenic compounds (16 g As L(-1) on average), lead, zinc, chlorides and sulphates, the waters also contain some organic material. The organic material is composed of a complex mixture that contains, amongst others, aliphatic compounds, phenol and its derivatives, pyridine bases, including pyridine, and its derivatives. The test results show degradation of organic and inorganic compounds during ozonation and photo-oxidation processes. Analysis of the solutions from the processes demonstrated that the complex organic material in the industrial water was oxidized in ozonation and in photo-oxidation, which resulted in formation of aldehydes and carboxylic acids. Kinetic degradation of selected pollutants is presented. Obtained results indicated that the O3/UV process is more effective in degradation of organic matter than ozonation. Depending on the process type, precipitation of the solid phase was observed. The efficiency of solid-phase formation was higher in photo-oxidation with ozone. It was found that the precipitated solid phase is composed mainly of arsenic, iron and oxygen.

Modeled Sources, Transport, and Accumulation of Dissolved Solids in Water Resources of the Southwestern United States.

PubMed

Anning, David W

2011-10-01

Information on important source areas for dissolved solids in streams of the southwestern United States, the relative share of deliveries of dissolved solids to streams from natural and human sources, and the potential for salt accumulation in soil or groundwater was developed using a SPAtially Referenced Regressions On Watershed attributes model. Predicted area-normalized reach-catchment delivery rates of dissolved solids to streams ranged from <10 (kg/year)/km(2) for catchments with little or no natural or human-related solute sources in them to 563,000 (kg/year)/km(2) for catchments that were almost entirely cultivated land. For the region as a whole, geologic units contributed 44% of the dissolved-solids deliveries to streams and the remaining 56% of the deliveries came from the release of solutes through irrigation of cultivated and pasture lands, which comprise only 2.5% of the land area. Dissolved-solids accumulation is manifested as precipitated salts in the soil or underlying sediments, and (or) dissolved salts in soil-pore or sediment-pore water, or groundwater, and therefore represents a potential for aquifer contamination. Accumulation rates were <10,000 (kg/year)/km(2) for many hydrologic accounting units (large river basins), but were more than 40,000 (kg/year)/km(2) for the Middle Gila, Lower Gila-Agua Fria, Lower Gila, Lower Bear, Great Salt Lake accounting units, and 247,000 (kg/year)/km(2) for the Salton Sea accounting unit.

Modeled Sources, Transport, and Accumulation of Dissolved Solids in Water Resources of the Southwestern United States1

PubMed Central

Anning, David W

2011-01-01

Abstract Information on important source areas for dissolved solids in streams of the southwestern United States, the relative share of deliveries of dissolved solids to streams from natural and human sources, and the potential for salt accumulation in soil or groundwater was developed using a SPAtially Referenced Regressions On Watershed attributes model. Predicted area-normalized reach-catchment delivery rates of dissolved solids to streams ranged from <10 (kg/year)/km2 for catchments with little or no natural or human-related solute sources in them to 563,000 (kg/year)/km2 for catchments that were almost entirely cultivated land. For the region as a whole, geologic units contributed 44% of the dissolved-solids deliveries to streams and the remaining 56% of the deliveries came from the release of solutes through irrigation of cultivated and pasture lands, which comprise only 2.5% of the land area. Dissolved-solids accumulation is manifested as precipitated salts in the soil or underlying sediments, and (or) dissolved salts in soil-pore or sediment-pore water, or groundwater, and therefore represents a potential for aquifer contamination. Accumulation rates were <10,000 (kg/year)/km2 for many hydrologic accounting units (large river basins), but were more than 40,000 (kg/year)/km2 for the Middle Gila, Lower Gila-Agua Fria, Lower Gila, Lower Bear, Great Salt Lake accounting units, and 247,000 (kg/year)/km2 for the Salton Sea accounting unit. PMID:22457583

Impact of fluid-rock chemical interactions on tracer transport in fractured rocks.

PubMed

Mukhopadhyay, Sumit; Liu, H-H; Spycher, N; Kennedy, B M

2013-11-01

In this paper, we investigate the impact of chemical interactions, in the form of mineral precipitation and dissolution reactions, on tracer transport in fractured rocks. When a tracer is introduced in fractured rocks, it moves through the fracture primarily by advection and it also enters the stagnant water of the surrounding rock matrix through diffusion. Inside the porous rock matrix, the tracer chemically interacts with the solid materials of the rock, where it can precipitate depending on the local equilibrium conditions. Alternatively, it can be dissolved from the solid phase of the rock matrix into the matrix pore water, diffuse into the flowing fluids of the fracture and is advected out of it. We show that such chemical interactions between the fluid and solid phases have significant impact on tracer transport in fractured rocks. We invoke the dual-porosity conceptualization to represent the fractured rocks and develop a semi-analytical solution to describe the transient transport of tracers in interacting fluid-rock systems. To test the accuracy and stability of the semi-analytical solution, we compare it with simulation results obtained with the TOUGHREACT simulator. We observe that, in a chemically interacting system, the tracer breakthrough curve exhibits a pseudo-steady state, where the tracer concentration remains more or less constant over a finite period of time. Such a pseudo-steady condition is not observed in a non-reactive fluid-rock system. We show that the duration of the pseudo-state depends on the physical and chemical parameters of the system, and can be exploited to extract information about the fractured rock system, such as the fracture spacing and fracture-matrix interface area. © 2013.

The use of dissolvable layered double hydroxide components in an in situ solid-phase extraction for chromatographic determination of tetracyclines in water and milk samples.

PubMed

Phiroonsoontorn, Nattaphorn; Sansuk, Sira; Santaladchaiyakit, Yanawath; Srijaranai, Supalax

2017-10-13

This research presents a simple and green in situ solid phase extraction (is-SPE) combined with high-performance liquid chromatography (HPLC) for the simultaneous analysis of tetracyclines (TCs) including tetracycline, oxytetracycline, and chlortetracycline. In is-SPE, TCs were efficiently extracted through the precipitation formation of dissolvable layered double hydroxides (LDHs) by mixing the LDH components such as magnesium and aluminum ions (both in metal chloride salts) thoroughly in an alkaline sample solution. After the centrifugation, the precipitate was completely dissolved with trifluoroacetic acid to release the enriched TCs, and then analyzed by HPLC. Under optimized conditions, this method gave good enrichment factors (EFs) of 41-93 with low limits of detection (LODs) of 0.7-6μg/L and limits of quantitation (LOQs) of 3-15μg/L. Also, the proposed method was successfully applied for the determination of TCs in water and milk samples with the recoveries ranging from 81.7-108.1% for water and 55.7-88.7% for milk. Copyright © 2017 Elsevier B.V. All rights reserved.

Epitaxial insertion of gold silicide nanodisks during the growth of silicon nanowires.

PubMed

Um, Han-Don; Jee, Sang-Won; Park, Kwang-Tae; Jung, Jin-Young; Guo, Zhongyi; Lee, Jung-Ho

2011-07-01

Nanodisk-shaped, single-crystal gold silicide heterojunctions were inserted into silicon nanowires during vapor-liquid-solid growth using Au as a catalyst within a specific range of chlorine-to-hydrogen atomic ratio. The mechanism of nanodisk formation has been investigated by changing the source gas ratio of SiCl4 to H2. We report that an over-supply of silicon into the Au-Si liquid alloy leads to highly supersaturated solution and enhances the precipitation of Au in the silicon nanowires due to the formation of unstable phases within the liquid alloy. It is shown that the gold precipitates embedded in the silicon nanowires consisted of a metastable gold silicide. Interestingly, faceting of gold silicide was observed at the Au/Si interfaces, and silicon nanowires were epitaxially grown on the top of the nanodisk by vapor-liquid-solid growth. High resolution transmission electron microscopy confirmed that gold silicide nanodisks are epitaxially connected to the silicon nanowires in the direction of growth direction. These gold silicide nanodisks would be useful as nanosized electrical junctions for future applications in nanowire interconnections.

DISSOLUTION OF LANTHANUM FLUORIDE PRECIPITATES

DOEpatents

Fries, B.A.

1959-11-10

A plutonium separatory ore concentration procedure involving the use of a fluoride type of carrier is presented. An improvement is given in the derivation step in the process for plutonium recovery by carrier precipitation of plutonium values from solution with a lanthanum fluoride carrier precipitate and subsequent derivation from the resulting plutonium bearing carrier precipitate of an aqueous acidic plutonium-containing solution. The carrier precipitate is contacted with a concentrated aqueous solution of potassium carbonate to effect dissolution therein of at least a part of the precipitate, including the plutonium values. Any remaining precipitate is separated from the resulting solution and dissolves in an aqueous solution containing at least 20% by weight of potassium carbonate. The reacting solutions are combined, and an alkali metal hydroxide added to a concentration of at least 2N to precipitate lanthanum hydroxide concomitantly carrying plutonium values.

Effect of Nb Addition to Ti-Bearing Super Martensitic Stainless Steel on Control of Austenite Grain Size and Strengthening

NASA Astrophysics Data System (ADS)

Ma, Xiaoping; Langelier, Brian; Gault, Baptiste; Subramanian, Sundaresa

2017-05-01

The role of Nb in normalized and tempered Ti-bearing 13Cr5Ni2Mo super martensitic stainless steel is investigated through in-depth characterization of the bimodal chemistry and size of Nb-rich precipitates/atomic clusters and Nb in solid solution. Transmission electron microscopy and atom probe tomography are used to analyze the samples and clarify precipitates/atom cluster interactions with dislocations and austenite grain boundaries. The effect of 0.1 wt pct Nb addition on the promotion of (Ti, Nb)N-Nb(C,N) composite precipitates, as well as the retention of Nb in solution after cooling to room temperature, are analyzed quantitatively. (Ti, Nb)N-Nb(C,N) composite precipitates with average diameters of approximately 24 ± 8 nm resulting from epitaxial growth of Nb(C,N) on pre-existing (Ti,Nb)N particles, with inter-particle spacing on the order of 205 ± 68 nm, are found to be associated with mean austenite grain size of 28 ± 10 µm in the sample normalized at 1323 K (1050 °C). The calculated Zener limiting austenite grain size of 38 ± 13 µm is in agreement with the experimentally observed austenite grain size distribution. 0.08 wt pct Nb is retained in the as-normalized condition, which is able to promote Nb(C, N) atomic clusters at dislocations during tempering at 873 K (600 °C) for 2 hours, and increases the yield strength by 160 MPa, which is predicted to be close to maximum increase in strengthening effect. Retention of solute Nb before tempering also leads to it preferentially combing with C and N to form Nb(C, N) atom clusters, which suppresses the occurrence of Cr- and Mo-rich carbides during tempering.

Indirect synthesis of Al{sub 2}O{sub 3}via radiation- or photochemical formation of its hydrated precursors

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

Barta, Jan, E-mail: jan.barta@fjfi.cvut.cz; Pospisil, Milan; Cuba, Vaclav

Graphical abstract: - Highlights: • Al{sub 2}O{sub 3} precursors were produced by UV/e-beam irradiation of aqueous solutions. • Depending on the aluminium salt (Cl{sup −} or NO{sub 3}{sup −}), either γ-AlOOH or Al(OH){sub 3} is formed. • The mechanism involved strongly depends on the presence of formate anion. • Prepared mesoporous solid phase has high specific surface area (<190 m{sup 2} g{sup −1}). • Calcination of the precursor leads to the formation of γ-/η-, θ- and α-Al{sub 2}O{sub 3}. - Abstract: γ-, θ- and α-modifications of aluminium oxide (alumina) were successfully prepared by calcination of precursor solid phase obtained bymore » irradiation of clear aqueous solutions by UV light or electron beam. For the precipitate to form, formate anion must be present in the solution in sufficient concentration. According to X-ray diffraction, the precipitate was found to consist of γ-AlOOH or a mixture of γ- and α-Al(OH){sub 3}, when aluminium chloride or aluminium nitrate was used, respectively. The addition of hydrogen peroxide as a ·OH radical source and sensitizer markedly improved the efficiency of the preparation. Some hints for the apparently very complex mechanism involved were listed and discussed. Calcination of the dried precipitate at 500–800 °C produced highly porous γ-alumina with high specific surface area (ca. 150 m{sup 2} g{sup −1}). Mixture of γ- and θ-transition aluminas was obtained at 1000 °C and pure, stable corundum α-Al{sub 2}O{sub 3} formed at 1200 °C. Samples were further investigated by means of scanning electron microscopy and specific surface area or porosity measurement. According to N{sub 2} adsorption isotherm, the precipitate contains mostly mesopores with average pore size 7 nm with specific surface area of ca. 100 m{sup 2} g{sup −1}. Possible applications of the material as sorbent or catalyst as well as a pure matrix for thermoluminescence dosimetry were briefly contemplated. Strong light-induced thermoluminescence was observed in both γ- and α-Al{sub 2}O{sub 3} samples at 300–400 °C, whereas in the absence of light, only an inexpressive glow peak at 179 °C was observed.« less

Water-Free Proton-Conducting Membranes for Fuel Cells

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram; Yen, Shiao-Pin

2007-01-01

Poly-4-vinylpyridinebisulfate (P4VPBS) is a polymeric salt that has shown promise as a water-free proton-conducting material (solid electrolyte) suitable for use in membrane/electrode assemblies in fuel cells. Heretofore, proton-conducting membranes in fuel cells have been made from perfluorinated ionomers that cannot conduct protons in the absence of water and, consequently, cannot function at temperatures >100 C. In addition, the stability of perfluorinated ionomers at temperatures >100 C is questionable. However, the performances of fuel cells of the power systems of which they are parts could be improved if operating temperatures could be raised above 140 C. What is needed to make this possible is a solid-electrolyte material, such as P4VPBS, that can be cast into membranes and that both retains proton conductivity and remains stable in the desired higher operating temperature range. A family of solid-electrolyte materials different from P4VPBS was described in Anhydrous Proton-Conducting Membranes for Fuel Cells (NPO-30493), NASA Tech Briefs, Vol. 29, No. 8 (August 2005), page 48. Those materials notably include polymeric quaternized amine salts. If molecules of such a polymeric salt could be endowed with flexible chain structures, it would be possible to overcome the deficiencies of simple organic amine salts that must melt before being able to conduct protons. However, no polymeric quaternized amine salts have yet shown to be useful in this respect. The present solid electrolyte is made by quaternizing the linear polymer poly- 4-vinylpyridine (P4VP) to obtain P4VPBS. It is important to start with P4VP having a molecular weight of 160,000 daltons because P4VPBS made from lower-molecular-weight P4VP yields brittle membranes. In an experimental synthesis, P4VP was dissolved in methanol and then reacted with an excess of sulfuric acid to precipitate P4VPBS. The precipitate was recovered, washed several times with methanol to remove traces of acid, and dried to a white granular solid. In another synthesis, nanoparticles of silica rich with surface hydroxyl groups were added to P4VP in methanol solution, which was then reacted with excess sulfuric acid to precipitate granules of a composite that most probably had the composition (P4VPBS)-SiO2-SiO(HSO4)2. The granular P4VPBS produced in the first-mentioned synthesis was dissolved in water to make a glue-like, turbid solution; the granular P4VPBS/silica composite produced in the second-mentioned synthesis was mixed with water to make a turbid, glue-like suspension. The proportions of polymer salt to water in such preparations can be varied; it was found that approximately equal parts of water and polymer salt yield a solution or suspension amenable to further processing.

Mechanical properties and microstructures of Al-Cu Thin films with various heat treatments

NASA Astrophysics Data System (ADS)

Joo, Young-Chang

1998-10-01

The relationship between microstructure and mechanical properties has been investigated in Al-Cu thin films. The Cu content in Al-Cu samples used in this study ranges from 0 to 2 wt.% and substrate curvature measurement was used to measure film stress. In thin films, the constraints on the film by the substrate influence the microstructure and mechanical properties. Al-Cu thin films cooled from high temperatures have a large density of dislocations due to the plastic deformation caused by the thermal mismatch between the film and substrate. The high density of dislocations in the thin film enables precipitates to form inside the grain even during a very rapid quenching. The presence of a large density of dislocations and precipitates will in turn cause precipitation hardening of the Al-Cu films. The precipitation hardening is dominant at lower temperatures, and solid solution hardening is observed at higher temperatures in the tensile regime. Pure Al films showed the same values of tensile and compressive yield stresses at a given temperature during stress-temperature cycling.

TANK 26F SUPERNATANT AND 2F EVAPORATOR EDUCTOR PUMP SAMPLE CHARACTERIZATION RESULTS

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

King, W.; Hay, M.; Coleman, C.

2011-08-23

In an effort to understand the reasons for system plugging problems in the SRS 2F evaporator, supernatant samples were retrieved from the evaporator feed tank (Tank 26F) and solids were collected from the evaporator eductor feed pump for characterization. The variable depth supernatant samples were retrieved from Tank 26F in early December of 2010 and samples were provided to SRNL and the F/H Area laboratories for analysis. Inspection and analysis of the samples at SRNL was initiated in early March of 2011. During the interim period, samples were frequently exposed to temperatures as low as 12 C with daily temperaturemore » fluctuations as high as 10 C. The temperature at the time of sample collection from the waste tank was 51 C. Upon opening the supernatant bottles at SRNL, many brown solids were observed in both of the Tank 26F supernatant samples. In contrast, no solids were observed in the supernatant samples sent to the F/H Area laboratories, where the analysis was completed within a few days after receipt. Based on these results, it is believed that the original Tank 26F supernatant samples did not contain solids, but solids formed during the interim period while samples were stored at ambient temperature in the SRNL shielded cells without direct climate control. Many insoluble solids (>11 wt. % for one sample) were observed in the Tank 26F supernatant samples after three months of storage at SRNL which would not dissolve in the supernatant solution in two days at 51 C. Characterization of these solids along with the eductor pump solids revealed the presence of sodium oxalate and clarkeite (uranyl oxyhydroxide) as major crystalline phases. Sodium nitrate was the dominant crystalline phase present in the unwashed Eductor Pump solids. Crystalline sodium nitrate may have formed during the drying of the solids after filtration or may have been formed in the Tank 26F supernatant during storage since the solution was found to be very concentrated (9-12 M Na{sup +}). Concentrated mineral acids and elevated temperature were required to dissolve all of these solids. The refractory nature of some of the solids is consistent with the presence of metal oxides such as aluminosilicates (observed as a minor phase by XRD). Characterization of the water wash solutions and the digested solids confirmed the presence of oxalate salts in both solid samples. Sulfate enrichment was also observed in the Tank 26F solids wash solution, indicating the presence of sulfate precipitates such as burkeite. OLI modeling of the Tank 26F filtered supernatant composition revealed that sodium oxalate has a very low solubility in this solution. The model predicts that the sodium oxalate solubility in the Tank 26F supernatant is only 0.0011 M at 50 C. The results indicate that the highly concentrated nature of the evaporator feed solution and the addition of oxalate anion to the waste stream each contribute to the formation of insoluble solids in the 2F evaporator system.« less

Unraveling the Structure of Mn-Promoted Co/TiO2 Fischer-Tropsch Catalysts by In Situ X-Ray Absorption Spectroscopy

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

Grandjean, Didier; Morales, Fernando; Mens, Ad

2007-02-02

Combination of in situ X-ray absorption spectroscopy (XAFS) at the Co and Mn K-edges with electron microscopy (STEM-EELS) has allowed to unravel the complex structure of a series of unpromoted and Mn promoted TiO2-supported cobalt Fischer-Tropsch catalysts prepared by homogeneous deposition precipitation (HDP), both in their calcined and reduced states. After calcination the catalysts are generally composed of large Co3O4 aggregates (13-20 nm) and a MnO2-type phase that is either dispersed on the TiO2 surface or, for the major part, covering the Co3O4 particles. Additionally Mn is also forming a spinel-type Co3-xMnxO4 solid solution at the surface of the Co3O4more » particles. In pure Co or when small amount of this spinel-type phase are formed during calcination, reduction in H2 at 350 deg. C produces Co0 particles of variable sizes (3.5-15 nm) otherwise Co reduction is limited to the Co2+ state. Manganese that exists entirely in a Mn2+ state in the reduced catalysts is forming (1) a highly dispersed Ti2MnO4-type phase at the TiO2 surface, (2) a less dispersed MnO phase close to the cobalt particles that coexists with (3) a rock salt-type Mn1-xCoxO solid solution. Similarly, large amount of spinel solid solution in the calcined state favors the formation of Mn1-xCoxO-type solid solution during reduction showing that one of the main roles of the Mn promoter is to limit Co reducibility.« less

Evaluation of Weapons’ Combustion Products in Armored Vehicles. Appendix A: Sampling and Analysis Methods. Appendix B: Analytical Data

DTIC Science & Technology

1989-01-01

25 wt % Solid Sorbent Collection solution in water 1. Glass tubing (6.0 mm OD, (Aldrich G400-y or equivalent) 4.0 mm ID) 2. 2,4- Dinitrophenylhydrazine ... dinitrophenylhydrazine in boiling 4M HCI. When the DNPH has dissolved completely, cool the Folution in an ice bath. Collect the yellow crystalline precipitate... dinitrophenylhydrazine . Add the aldehyde in excess to assure that no underivatized DNPH remains. Extract the derivative with dichloromethane. Remove the

Investigation into the use of cement kiln dust in high density sludge (HDS) treatment of acid mine water.

PubMed

Mackie, Allison L; Walsh, Margaret E

2015-11-15

The purpose of this study was to investigate the potential to replace lime with cement kiln dust (CKD) in high density sludge (HDS) treatment of acid mine drainage (AMD). The bench-scale study used two water samples: AMD sampled from a lead-zinc mine with high concentrations of iron (Fe), zinc (Zn), and arsenic (As) (Fe/Zn-AMD) and a synthetic AMD solution (Syn-AMD) spiked with ferric sulfate (Fe2(SO4)3). Arsenic was found to be significantly reduced with CKD-HDS treatment of Fe/Zn-AMD compared to lime-HDS treatment, to concentrations below the stringent mine effluent discharge regulation of 0.10 mg As/L (i.e., 0.04 ± 0.02 mg/L). Both CKD- and lime-HDS treatment of the two AMD samples resulted in settled water Fe concentrations above the stringent discharge guideline of 0.3 mg Fe/L. CKD addition in the HDS process also resulted in high settled water turbidity, above typical discharge guidelines of 15 mg TSS/L. CKD-HDS treatment was found to result in significantly improved settled solids (i.e., sludge) quality compared to that generated in the lime-HDS process. HDS treatment with CKD resulted in 25-88% lower sludge volume indices, 2 to 9 times higher % wet solids, and 10 to 20 times higher % dry solids compared to lime addition. XRD and XPS testing indicated that CKD-HDS sludge consisted of mainly CaCO3 and SiO2 with Fe(3+) precipitates attached at particle surfaces. XRD and XPS testing of the lime-HDS generated sludge showed that it consisted of non-crystalline Fe oxides typical of sludge formed from precipitates with a high water concentration. Increased sedimentation rates were also found for CKD (1.3 cm/s) compared to lime (0.3 cm/s). The increased solids loading with CKD addition compared to lime addition in the HDS process was suggested to both promote surface complexation of metal precipitates with insoluble CKD particles and increase compression effects during Type IV sedimentation. These mechanisms collectively contributed to the reduced water content of CKD-HDS sludge. The results of this study suggest that solids loading is a significant factor in increased sludge density found with the HDS process compared to conventional lime precipitation-sedimentation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions.

PubMed

Newsome, Laura; Morris, Katherine; Lloyd, Jonathan R

2015-01-01

Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV) by U(VI)- and Fe(III)-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI) as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI), via reduction to nano-crystalline U(IV) uraninite. Some evidence for the reduction of solid phase uranyl(VI) phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions.

Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions

PubMed Central

Newsome, Laura; Morris, Katherine; Lloyd, Jonathan. R.

2015-01-01

Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV) by U(VI)- and Fe(III)-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI) as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI), via reduction to nano-crystalline U(IV) uraninite. Some evidence for the reduction of solid phase uranyl(VI) phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions. PMID:26132209

Effect of heat treatment on morphology evolution of Ti2Ni phase in Ti-Ni-Al-Zr alloy

NASA Astrophysics Data System (ADS)

Sheng, Liyuan; Yang, Yang; Xi, Tingfei

2018-03-01

The Ti6Al2Zr alloy with 15 wt.% Ni addition was prepared and then heat treated in the research. The microstructure of the alloy and evolution of Ti2Ni precipitate were investigated. The microstructure observations demonstrate that the Ni addition could promote the formation of eutectoid and eutectic structures in Ti-Al-Zr alloy. In the eutectoid structure, the ultrafine Ti2Ni fiber precipitates in the α-Ti matrix, but in the eutectic structure, the fine α-Ti phases precipitate in the Ti2Ni matrix. The heat treatment could change the morphology of Ti2Ni precipitates by thinning, fragmenting, merging and spherizing. In the alloy heat treated at and below 1073K, the coarsening of α-Ti precipitates in eutectic structure and Ti2Ni precipitates in eutectoid structure is the mainly characteristic. In the alloy heat treated above 1073K, the phase transformation of α to β phase is the main characteristic, which changes the morphology and amount of Ti2Ni phase by the solid solution of Ni. The phase transformation temperature of Ti-Ni-Al-Zr alloy is between 1073-1123K, which is increased compared with that of the Ti-Ni binary phase diagram.

Efficacy and toxicity of formalin solutions containing paraformaldehyde for fish and egg treatments

USGS Publications Warehouse

Howe, G.E.; Marking, L.L.; Bills, T.D.; Schreier, Theresa M.

1995-01-01

Formalin used for fish and egg treatments at hatcheries often develops a white precipitate called paraformaldehyde when stored at low temperatures. This presents a problem for hatchery managers because most of the literature and treatment procedures claim that formalin containing paraformaldehyde is more toxic than pure formalin and is not safe for fish or egg treatments. Acute toxicity tests with rainbow trout (Oncorhynchus mykiss) and channel catfish (Ictalurus punctatus) showed that the toxicity of formalin solutions containing a moderate amount of fine paraformaldehyde was similar to that of pure formalin. In efficacy tests on fish eggs, the bottom fraction of a formalin solution containing paraformaldehyde and a sample from the clear top fraction were equally effective in controlling fungal infection on rainbow trout eggs and caused no treatment-related mortality. Chemical assays found on average a 3% difference in formaldehyde concentration between top and bottom fractions of a formalin solution containing paraformaldehyde. We recommend normal use of formalin solutions containing light to moderate amounts of fine paraformaldehyde. Allowing solutions to warm to room temperature may resolubilize moderate amounts of paraformaldehyde if the exposure to cold was not prolonged. If precipitation is heavier, clear top fractions can be decanted and used as normal because paraformaldehyde settles to the bottom of containers. Formalin solutions that have been exposed to freezing temperatures for long periods (more than 6 weeks) and have developed large amounts of paraformaldehyde solids should not be used and resolubilization by warming is not possible. Formation of paraformaldehyde in formalin solutions can be easily avoided by storing formalin at room temperature.

Manganese-calcium intermixing facilitates heteroepitaxial growth at the 10 1 ¯ 4 calcite-water interface

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

Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.

2017-10-01

In situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10-14) surface of calcite (CaCO3) single crystals following reaction with Mn2+-bearing aqueous solutions with a range of initial concentrations. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces and in situ time-sequenced measurements demonstrated that their growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2+-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO3) and calcite display amore » 10% lattice mismatch, based on the area of their (10-14) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals with calcite-equilibrated aqueous solutions with concentrations of up to 250 µM MnCl2 and analyzed to determine the composition of the surface precipitates. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO3 solid solution with a spatially complex composition atop the calcite surface, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO3 for the thickest coatings. These findings explain the measured growth rates (the effective lattice mismatch was much smaller than nominal mismatch) and highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.« less

Dynamically controlled crystallization method and apparatus and crystals obtained thereby

NASA Technical Reports Server (NTRS)

Arnowitz, Leonard (Inventor); Steinberg, Emanuel (Inventor)

2003-01-01

A method and apparatus for dynamically controlling the crystallization of molecules including a crystallization chamber (14) or chambers for holding molecules in a precipitant solution, one or more precipitant solution reservoirs (16, 18), communication passages (17, 19) respectively coupling the crystallization chamber(s) with each of the precipitant solution reservoirs, and transfer mechanisms (20, 21, 22, 24, 26, 28) configured to respectively transfer precipitant solution between each of the precipitant solution reservoirs and the crystallization chamber(s). The transfer mechanisms are interlocked to maintain a constant volume of precipitant solution in the crystallization chamber(s). Precipitant solutions of different concentrations are transferred into and out of the crystallization chamber(s) to adjust the concentration of precipitant in the crystallization chamber(s) to achieve precise control of the crystallization process. The method and apparatus can be used effectively to grow crystals under reduced gravity conditions such as microgravity conditions of space, and under conditions of reduced or enhanced effective gravity as induced by a powerful magnetic field.

Three-dimensional digital microfluidic manipulation of droplets in oil medium

PubMed Central

Hong, Jiwoo; Kim, Young Kwon; Won, Dong-Joon; Kim, Joonwon; Lee, Sang Joon

2015-01-01

We here develop a three-dimensional DMF (3D DMF) platform with patterned electrodes submerged in an oil medium to provide fundamental solutions to the technical limitations of 2D DMF platforms and water–air systems. 3D droplet manipulation on patterned electrodes is demonstrated by programmably controlling electrical signals. We also demonstrate the formation of precipitates on the 3D DMF platform through the reaction of different chemical samples. A droplet containing precipitates, hanging on the top electrode, can be manipulated without adhesion of precipitates to the solid surface. This method could be a good alternative strategy to alleviate the existing problems of 2D DMF systems such as cross-contamination and solute adsorption. In addition, we ascertain the feasibility of temperature-controlled chemical reaction on the 3D DMF platform by introducing a simple heating process. To demonstrate applicability of the 3D DMF system to 3D biological process, we examine the 3D manipulation of droplets containing mouse fibroblasts in the 3D DMF platform. Finally, we show detachment of droplets wrapped by a flexible thin film by adopting the electro-elasto-capillarity (EEC). The employment of the EEC may offer a strong potential in the development of 3D DMF platforms for drug encapsulation and actuation of microelectromechanical devices. PMID:26033440

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

Moeschner, Goeril; Lothenbach, Barbara; Figi, Renato

Citric acid can be used to retard the hydration of cement. Experiments were carried out to investigate the influence of citric acid on the composition of solid and liquid phases during cement hydration. Analyses of the solid phases showed that dissolution of alite and aluminate slowed down while analyses of the pore solution showed that citric acid was removed almost completely from the pore solution within the first hours of hydration. The complexation of the ions by citrate was weak, which could also be confirmed by thermodynamic calculations. Only 2% of the dissolved Ca and 0.001% of the dissolved Kmore » formed complexes with citrate during the first hours. Thus, citric acid retards cement hydration not by complex formation, but by slowing down the dissolution of the clinker grains. Thermodynamic calculations did not indicate precipitation of a crystalline citrate species. Thus, it is suggested that citrate sorbed onto the clinker surface and formed a protective layer around the clinker grains retarding their dissolution.« less

Geochemical modeling of leaching of Ca, Mg, Al, and Pb from cementitious waste forms

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

Martens, E., E-mail: evelien.martens@csiro.a; Jacques, D.; Van Gerven, T.

2010-08-15

Results from extraction tests on cement-waste samples were simulated with a thermodynamic equilibrium model using a consistent database, to which lead data were added. Subsequent diffusion tests were modeled by means of a 3D diffusive transport model combined with the geochemical model derived from the extraction tests. Modeling results of the leached major element concentrations for both uncarbonated and (partially) carbonated samples agreed well with the extraction test using the set of pure minerals and solid solutions present in the database. The observed decrease in Ca leaching with increasing carbonation level was qualitatively predicted. Simulations also revealed that Pb leachingmore » is not controlled by dissolution/precipitation only. The addition of the calcite-cerrusite solid solution and adsorption reactions on amorphous Fe- and Al-oxides improved the predictions and are considered to control the Pb leaching during the extractions tests. The dynamic diffusive leaching tests were appropriately modeled for Na, K, Ca and Pb.« less

Synthesis and binding studies of Alzheimer ligands on solid support.

PubMed

Rzepecki, Petra; Geib, Nina; Peifer, Manuel; Biesemeier, Frank; Schrader, Thomas

2007-05-11

Aminopyrazole derivatives constitute the first class of nonpeptidic rationally designed beta-sheet ligands. Here we describe a double solid-phase protocol for both synthesis and affinity testing. The presented solid-phase synthesis of four types of hybrid compounds relies on the Fmoc strategy and circumvents subsequent HPLC purification by precipitating the final product from organic solution in pure form. Hexa- and octapeptide pendants with internal di- and tetrapeptide bridges are now amenable in high yields to combinatorial synthesis of compound libraries for high-throughput screening purposes. Solid-phase peptide synthesis (SPPS) on an acid-resistant PAM allows us, after PMB deprotection, to subject the free aminopyrazole binding sites in an immobilized state to on-bead assays with fluorescence-labeled peptides. From the fluorescence emission intensity decrease, individual binding constants can be calculated via reference curves by simple application of the law of mass action. Gratifyingly, host/guest complexation can be monitored quantitatively even for those ligands, which are almost insoluble in water.

Nature of diffraction fringes originating in the core of core-shell nanoparticle Cu/SiO2 and formation mechanism of the structures

NASA Astrophysics Data System (ADS)

Radnaev, A. R.; Kalashnikov, S. V.; Nomoev, A. V.

2016-05-01

This article is devoted to the analysis of the reasons for the occurrence of diffraction fringes in the cores of the core-shell nanoparticles Cu/SiO2. Moiré and diffraction fringes are observed while studying the nanoparticle cores under a transmission electron microscope. The formation of diffraction fringes is closely connected to the mechanism of nanoparticle formation under study and appears to be its consequence, letting us develop a hypothesis of metastable phase formation in nanoparticle cores. In our opinion, the emergence of diffraction fringes in cores of copper is connected to clasterisation in solid solution oversaturated with silicon α-Cu with the diffused interphase state. Only copper and oxygen (oxygen is presented as oxides in such types of copper as M0 - up to 0.01%; and M1 - up to 0.03%), Copper and silicon with oxygen in a stoichiometric proportion that is only sufficient for silicon dioxide formation (SiO2), Copper and silicon with oxygen in an amount that is sufficient not only for silicon dioxide formation, but also for the dissolution of silicon in the α-Cu solid solution, The amount of silicon in the alloy is not sufficient for the total fixation of oxygen contained in copper, Copper, oxygen and silicon whose contamination is greater than 8 wt.%. In the first case, the top-cut of oxygen in α-Cu solid solution is 0.03% at the temperature of 1066 °C. At slow cooling, secondary recrystallisation leads to the formation of equilibrium Cu2O on the line of the ultimate solubility (Figure 1a - line of maximum solubility of oxygen in copper). In the case of fast cooling fixation of oversaturated, single-phase, non-equilibrium α-Cu, solid solution (heat-treated) takes place, which contains saluted oxygen in an interstice crystal lattice of copper.Room temperature for nonferrous alloys (metals) is sufficient for the diffusive mobility of atoms, but insufficient for the formation of an equilibrium phase and stable phase of Cu2O. This is why diffusion of oxygen atoms in certain areas (clusters) with their increased diffusion of oxygen atoms in certain areas (clusters) with their increased number has been suggested [4]. At the same time, there is a boundary between the stable phase of α-Cu and 'pre-precipitations' containing oxygen, but not having the full value oxide: red copper ore, Cu2O (Figure 1b - solvus of suggested metastable phase). In this case, diffraction fringes can be treated as 'pre-precipitations' in the form of Guinier-Preston zones with diffuse interfaces and a stable α-Cu phase.In the second case, all oxygen and silicon after condensation and crystallisation are fixed in the form of amorphous SiO2 on the core surface of copper. As far as there are no atoms of saluted oxygen or silicon in copper, there are no conditions for the formation of non-equilibrium structures. Consequently, the diffraction pattern of nanoparticle cores is not observed (Figure 2a).In the third case, in the presence of quite a large amount of silicon in the stoichiometric drop, the process of copper oxide formation is not possible, because all the oxygen is used for the production of silicon dioxide since the sensitivity of oxygen to silicon is higher than to copper. This can be explained by the difference in Gibbs energy for the oxidising reaction of components. At the temperature of 25 °C it is 29.0 J/(g mol) - for copper, and 80.8 J/(g mol) for silicon. Silicon dioxide occurring due to the oxygen content in copper will be displaced on the surface of the drop in the form of ash, forming the SiO2 shell [24]. The reason lies in the lower specific density of silicon (approximately 2.2 g/cm3) compared to copper (8.92 g/cm3). This is why, in our case, it is appropriate to study the system where there is no influence of oxygen on the crystallisation of the Cu-Si system [5]. In the cores of such nanoparticles, prominent diffraction fringes can be observed in the α-Cu core (Figure 3b).Analysis of the Cu-Si phase diagram (Figure 3) shows that the maximum solubility of silicon α-Cu at the temperature 552 °C comprises 4.65 wt.% Si. This part of the Cu-Si phase diagram containing up to 8 wt.% silicon represents a classical example of the well-studied phase diagram of Al-Cu components, with the formation of Guinier-Preston zones in the quenched aluminium alloy [25].Single-phase solid solution of silicon α-Cu is fixed at fast cooling in our case. During its formation, cooling and natural ageing of the nanoparticle core, and redistribution of silicon into certain areas, takes place, forming metastable clusters in the matrix with high silicon content. They seem to be 'pre-precipitations' of the γ-phase of copper, though they really are not. In our opinion, diffraction fringes observed in these particles appear to be metastable phases according to Guinier-Preston zone type, i.e. α-Cu area with excessive silicon content.For nonferrous alloys, room temperature is sufficient for diffusive mobility of atoms of the saluted component [19]. Clusters are formed both at the time of cooling and in the long-term process (i.e. natural ageing). Provided that it is not a new phase, but rather the area of the initial matrix α-Cu solid solution enriched with dissolved silicon, such areas may be treated as Guinier-Preston zones. In contrast to intermediate phases with qualitatively new structures, characterised by their own lattices, Guinier-Preston zones have the same lattice as the matrix solution, but are deformed because of the difference in the atomic diameters of the solute and solvent. There is no clear boundary between the zone and solid solution by which it is surrounded. Compared to concentration fluctuations that appear continuously and are diffused by thermal motion, Guinier-Preston zones are stable for a long time (at low temperatures, for an intermediate amount of time). Experiments have shown that, with the increase of ageing duration, zone sizes are also increased. Furthermore, larger zones grow due to dissolution of the smaller ones, i.e. the same way as in coagulation of crystal grains in the solid state (i.e. collective crystallisation) [19]. The number of the zones at the given ageing temperature does not depend on the alloy composition.In some alloys, Guinier-Preston zones appear immediately after heat treatment or even during the cooling after heat treatment. At the same time, intermediate phases and stable phases appear after the incubation interval. All these facts show that Guinier-Preston zones are different to intermediate and stable phases. This is why Guinier-Preston zones are often called 'pre-precipitations' to differentiate them from real precipitations of intermediate and stable phases with a qualitatively new structure [19].Unlike such a structured approach that treats Guinier-Preston zones as 'pre-precipitations' from a thermodynamic point of view, they can be treated as independent stable phases, intermediate between the matrix solution and the stable phase. Consequently, these zones can be treated as the second phase that is in metastable equilibrium with the matrix solution.Moreover, a Guinier-Preston zone in the dual Cu-Si system with limited solubility of silicon in solid state can have its own line limit of solubility km (Figure 3). Metastable phases with a high content of silicon in the α-Cu matrix crystalline lattice appear below this line.Provided that the Guinier-Preston zone is treated as a phase, at the moment of its origin, the change of the free energy of the alloy is as follows: ΔU = -ΔUtot + ΔUsurf + ΔUel (Utot - total energy of the system, Usurf - surface energy of the crystal, Uel - elastic energy component). Because of the coherence property of the zone and the matrix, the ΔUsurf component can be neglected as its value is very small. Then, at relatively high oversaturation, the energy barrier for the origin of the Guinier-Preston zone should be relatively small, which explains the occurrence of clusters immediately after heat treatment or even at the moment of cooling and following natural ageing.The fact that Guinier-Preston zones can easily appear throughout the whole volume of the matrix solid solution and give the structure of equable decay with high density is of high practical value for us (Figure 2b).Thus, diffraction fringes in copper cores of core-shell nanoparticles should be treated as the second metastable phase, which is in equilibrium with the matrix solid solution. Similar to the exfoliation curve km in the solid solution α-Cu, the solvus curve for γ-Cu with intermediate 'pre-precipitations' can be built. The structure of the boundary with the matrix differentiates Guinier-Preston zones from other intermediate phases. These zones are fully coherent extractions, which is why their boundary with the matrix is poorly defined.As the rate accuracy of basal spacing with the method of electronic diffraction does not exceed 1 Å, according to the data it is not possible to evaluate accurately the change dα-Cu in diffraction fringes of the nanoparticle core; phase nonuniformity of structures has been suggested [26]. This is why it is necessary to treat such structures as solid solutions of α-Cu matrix, with the presence of metastable phases with the deformed crystal lattice.In the fourth case, formation of core-shell nanoparticle Cu/SiO2 happens much like in the third case, but due to the fact the amount of silicon is insufficient for the total fixation of oxygen and copper, a transition zone containing Cu2O is formed. Moiré in such particles are observed at the possible placing of double diffraction from two or more crystals of solid solution α-Cu (Figure 4a) [3]. The nanoparticle according to SAED analysis is very much like a 'sandwich': core α-Cu (Figure 4b, basal spacing d(111) ≈ 2.0 Å, corresponding to the tabular data for Cu), transition zone - copper oxide Cu2O (Figure 5a, basal spacing d(111) ≈ 2.4 Å) and shell - amorphous silicon dioxide, according to the EDAX data, the content of oxygen in this area is greater than 12% [11]. High copper oxide (CuO) was discovered only on the surface of the nanoparticle shell SiO2 (Figure 5b, basal spacing d(111) ≈ 2.5 Å).In the fifth case, when the silicon content is from 8.3-8.5 wt.% to 13 wt.%, copper with silicon in solid state at room temperature forms a continuous series of solid solutions of copper α, γ, ɛ and η. Silicon containing more than 13 wt.% copper undergoes eutectic decomposition only at (η″ + Si) [5]; structurally, such a solution contains eutectics in eutectics. In the obtained powder of nanoparticles, there are no modifications of solid solutions of copper, except for α-Cu.

Carbon dioxide adsorbents containing magnesium oxide suitable for use at high temperatures

DOEpatents

Mayorga, Steven Gerard; Weigel, Scott Jeffrey; Gaffney, Thomas Richard; Brzozowski, Jeffrey Richard

2001-01-01

Adsorption of carbon dioxide from gas streams at temperatures in the range of 300 to 500.degree. C. is carried out with a solid adsorbent containing magnesium oxide, preferably promoted with an alkali metal carbonate or bicarbonate so that the atomic ratio of alkali metal to magnesium is in the range of 0.006 to 2.60. Preferred adsorbents are made from the precipitate formed on addition of alkali metal and carbonate ions to an aqueous solution of a magnesium salt. Atomic ratios of alkali metal to magnesium can be adjusted by washing the precipitate with water. Low surface area adsorbents can be made by dehydration and CO.sub.2 removal of magnesium hydroxycarbonate, with or without alkali metal promotion. The process is especially valuable in pressure swing adsorption operations.

Hierarchical La0.7Ce0.3FeO3/halloysite nanocomposite for photocatalytic degradation of antibiotics

NASA Astrophysics Data System (ADS)

Li, Xiazhang; Zhu, Wei; Yan, Xiangyu; Lu, Xiaowang; Yao, Chao; Ni, Chaoying

2016-08-01

The hierarchical La0.7Ce0.3FeO3/halloysite nanotubes (HNTs) composites have been successfully prepared via sol-gel method. XRD and TEM characterizations indicated that the sheet-like La0.7Ce0.3FeO3 coupled with the co-precipitated CeO2 were evenly deposited onto the surface of halloysite. The photocatalytic degradation of chlortetracycline under visible light irradiation using La0.7Ce0.3FeO3/HNTs as catalyst was evaluated by high-performance liquid chromatography, which exhibited remarkable photocatalytic activity with the removal rate up to 99 % in 90 min, due to the formation of "solid solution/co-precipitation" heterostructure as well as the excellent adsorptive capability of halloysite for antibiotics.

Development and Validation of HPLC Method for Determination of Crocetin, a constituent of Saffron, in Human Serum Samples.

PubMed

Mohammadpour, Amir Hooshang; Ramezani, Mohammad; Tavakoli Anaraki, Nasim; Malaekeh-Nikouei, Bizhan; Amel Farzad, Sara; Hosseinzadeh, Hossein

2013-01-01

The present study reports the development and validation of a sensitive and rapid extraction method beside high performance liquid chromatographic method for the determination of crocetin in human serum. The HPLC method was carried out by using a C18 reversed-phase column and a mobile phase composed of methanol/water/acetic acid (85:14.5:0.5 v/v/v) at the flow rate of 0.8 ml/min. The UV detector was set at 423 nm and 13-cis retinoic acid was used as the internal standard. Serum samples were pretreated with solid-phase extraction using Bond Elut C18 (200mg) cartridges or with direct precipitation using acetonitrile. The calibration curves were linear over the range of 0.05-1.25 µg/ml for direct precipitation method and 0.5-5 µg/ml for solid-phase extraction. The mean recoveries of crocetin over a concentration range of 0.05-5 µg/ml serum for direct precipitation method and 0.5-5 µg/ml for solid-phase extraction were above 70 % and 60 %, respectively. The intraday coefficients of variation were 0.37- 2.6% for direct precipitation method and 0.64 - 5.43% for solid-phase extraction. The inter day coefficients of variation were 1.69 - 6.03% for direct precipitation method and 5.13-12.74% for solid-phase extraction, respectively. The lower limit of quantification for crocetin was 0.05 µg/ml for direct precipitation method and 0.5 µg/ml for solid-phase extraction. The validated direct precipitation method for HPLC satisfied all of the criteria that were necessary for a bioanalytical method and could reliably quantitate crocetin in human serum for future clinical pharmacokinetic study.

Development and Validation of HPLC Method for Determination of Crocetin, a constituent of Saffron, in Human Serum Samples

PubMed Central

Mohammadpour, Amir Hooshang; Ramezani, Mohammad; Tavakoli Anaraki, Nasim; Malaekeh-Nikouei, Bizhan; Amel Farzad, Sara; Hosseinzadeh, Hossein

2013-01-01

Objective(s): The present study reports the development and validation of a sensitive and rapid extraction method beside high performance liquid chromatographic method for the determination of crocetin in human serum. Materials and Methods: The HPLC method was carried out by using a C18 reversed-phase column and a mobile phase composed of methanol/water/acetic acid (85:14.5:0.5 v/v/v) at the flow rate of 0.8 ml/min. The UV detector was set at 423 nm and 13-cis retinoic acid was used as the internal standard. Serum samples were pretreated with solid-phase extraction using Bond Elut C18 (200mg) cartridges or with direct precipitation using acetonitrile. Results: The calibration curves were linear over the range of 0.05-1.25 µg/ml for direct precipitation method and 0.5-5 µg/ml for solid-phase extraction. The mean recoveries of crocetin over a concentration range of 0.05-5 µg/ml serum for direct precipitation method and 0.5-5 µg/ml for solid-phase extraction were above 70 % and 60 %, respectively. The intraday coefficients of variation were 0.37- 2.6% for direct precipitation method and 0.64 - 5.43% for solid-phase extraction. The inter day coefficients of variation were 1.69 – 6.03% for direct precipitation method and 5.13-12.74% for solid-phase extraction, respectively. The lower limit of quantification for crocetin was 0.05 µg/ml for direct precipitation method and 0.5 µg/ml for solid-phase extraction. Conclusion: The validated direct precipitation method for HPLC satisfied all of the criteria that were necessary for a bioanalytical method and could reliably quantitate crocetin in human serum for future clinical pharmacokinetic study. PMID:23638292

The evolution of γ-Mg17Al12 intermetallic compound during accumulative back extrusion and subsequent ageing treatment

NASA Astrophysics Data System (ADS)

Maghsoudi, M. H.; Zarei-Hanzaki, A.; Abedi, H. R.; Shamsolhodaei, A.

2015-11-01

Accumulative back extrusion (ABE) processing, as a novel severe plastic deformation (SPD) method, has been recently justified to be capable of modifying the microstructural characteristics of alloys. In line to its ongoing researches, the present work has been planned to study the evolution of γ-Mg17Al12 intermetallic phase during ABE and subsequent ageing treatment in a high Al-bearing Mg-Al-Zn alloy. The behaviour of γ intermetallic has been systematically examined as following points of view: (i) strain-temperature-dependent morphology changes, (ii) strain-induced dissolution, and (iii) re-ageing behaviour as a function of time and temperature. Aiming to analyse the morphology of eutectic γ compound with respect to the strain and temperature, 2D projections of effective diameter, shape factor and globularity have been made in strain/temperature graphs. The processing conditions (strain and temperature) corresponding to the desired and undesired morphologies are introduced and microstructurally explained through underlying plasticity mechanisms, i.e., 'necking-thinning-particle separation' and 'brittle fragmentation.' The former mechanism is suggested to be in relation with partial strain-induced dissolution of eutectic γ phase, leading to generation of a supersaturated solid solution. This has resulted to the observation of 'off-stoichiometry' phenomena in Mg17Al12 phase and has been justified through dislocation-assisted deformation mechanism at elevated temperature. Surprisingly, a unique re-ageing behaviour has been found for the obtained solid solutions, where a modified kinetics and morphology of γ phase precipitation were characterized. The altered precipitation behaviour is attributed to the specific defect structure achieved by SPD acting as fast diffusion channel for Al solutes.

Silicon Isotopes doping experiments to measure quartz dissolution and precipitation rates at equilibrium and test the principle of detailed balance

NASA Astrophysics Data System (ADS)

Zhu, C.; Rimstidt, J. D.; Liu, Z.; Yuan, H.

2016-12-01

The principle of detailed balance (PDB) has been a cornerstone for irreversible thermodynamics and chemical kinetics for a long time, and its wide application in geochemistry has mostly been implicit and without experimental testing of its applicability. Nevertheless, many extrapolations based on PDB without experimental validation have far reaching impacts on society's mega environmental enterprises. Here we report an isotope doping method that independently measures simultaneous dissolution and precipitation rates and can test this principle. The technique reacts a solution enriched in a rare isotope of an element with a solid having natural isotopic abundances (Beck et al., 1992; Gaillardet, 2008; Gruber et al., 2013). Dissolution and precipitation rates are found from the changing isotopic ratios. Our quartz experiment doped with 29Si showed that the equilibrium dissolution rate remains unchanged at all degrees of undersaturation. We recommend this approach to test the validity of using the detailed balance relationship in rate equations for other substances.

Detailed Investigation of Core-Shell Precipitates in a Cu-Containing High Entropy Alloy

NASA Astrophysics Data System (ADS)

Alam, T.; Gwalani, B.; Viswanathan, G.; Fraser, H.; Banerjee, R.

2018-05-01

Due to the competing influences of configurational entropy and enthalpy of mixing, in recent years, secondary (including intermetallic) phases have been reported in many high entropy alloy (HEA) systems. These secondary phases offer great potential in terms of strengthening the HEA beyond the solid solution strengthening effects, and as such are of great interest in regards to alloy design for engineering applications. The present research investigates novel nano-scale core-shell precipitates forming within the disordered bcc matrix phase of an Al2CrCuFeNi2 HEA, utilizing complementary high-resolution microscopy techniques of atom probe tomography (APT) and transmission electron microscopy (TEM). The size, morphology, and local chemistry of these core-shell precipitates was measured by APT, and the composition was further corroborated by high-resolution scanning transmission electron microscopy-energy dispersive spectroscopy in an aberration-corrected TEM. Furthermore, high-resolution TEM imaging of the core-shell structure indicates that the Cu-rich core exhibits a bcc crystal structure.

In situ removal of arsenic from groundwater by using permeable reactive barriers of organic matter/limestone/zero-valent iron mixtures.

PubMed

Gibert, O; de Pablo, J; Cortina, J-L; Ayora, C

2010-08-01

In this study, two mixtures of municipal compost, limestone and, optionally, zero-valent iron were assessed in two column experiments on acid mine treatment. The effluent solution was systematically analysed throughout the experiment and precipitates from both columns were withdrawn for scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffractometry analysis and, from the column containing zero-valent iron, solid digestion and sequential extraction analysis. The results showed that waters were cleaned of arsenic, metals and acidity, but chemical and morphological analysis suggested that metal removal was not due predominantly to biogenic sulphide generation but to pH increase, i.e. metal (oxy)hydroxide and carbonate precipitation. Retained arsenic and metal removal were clearly associated to co-precipitation with and/or sorption on iron and aluminum (oxy)hydroxides. An improvement on the arsenic removal efficiency was achieved when the filling mixture contained zero-valent iron. Values of arsenic concentrations were then always below 10 microg/L.

CONCENTRATION OF Pu USING AN IODATE PRECIPITATE

DOEpatents

Fries, B.A.

1960-02-23

A method is given for separating plutonium from lanthanum in a lanthanum fluoride carrier precipitation process for the recovery of plutonium values from an aqueous solution. The carrier precipitation process includes the steps of forming a lanthanum fluoride precipi- . tate, thereby carrying plutonium out of solution, metathesizing the fluoride precipitate to a hydroxide precipitate, and then dissolving the hydroxide precipitate in nitric acid. In accordance with the invention, the nitric acid solution, which contains plutonium and lanthanum, is made 0.05 to 0.15 molar in potassium iodate. thereby precipitating plutonium as plutonous iodate and the plutonous iodate is separated from the lanthanum- containing supernatant solution.

Solids precipitation and polymerization of asphaltenes in coal-derived liquids

DOEpatents

Kydd, Paul H.

1984-01-01

The precipitation and removal of particulate solids from coal-derived liquids by adding a process-derived anti-solvent liquid fraction and continuing the precipitation process at a temperature above the melting point of the mixed liquids for sufficient time to allow the asphaltenes to polymerize and solids to settle at atmospheric pressure conditions. The resulting clarified light hydrocarbon overflow liquid contains less than about 0.02 W % ash and is suitable as turbine fuel or as boiler fuel for burning without particulate emission control equipment. An underflow liquid fraction containing less than about 0.1 W % solids along with low sulfur and nitrogen concentrations is suitable as a boiler fuel with emission control equipment.

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

Viklund, H.I.; Kennedy, R.H.

Uranium precipitates obtained from Congo leach liquors by an ion exchange process contained more than 0.1% chloride. Attempts were made to reduce the chloride content of typical precipitates by calcination of dried precipitate, releaching of dried precipitate with water, and washing of wet precipitate with water. Washing of wet precipitate with an aqueous solution of 0.25% Na/sub 2/SO/ sub 4/, to prevent peptization, provided a simple solution to the problem. Precipitation tests on Congo ion exchange eluates showed a marked advantage in subsequent thickening and filtration operations for precipitation from hot solution. (auth)

Identification of functional groups of Opuntia ficus-indica involved in coagulation process after its active part extraction.

PubMed

Bouaouine, Omar; Bourven, Isabelle; Khalil, Fouad; Baudu, Michel

2018-04-01

Opuntia ficus-indica that belongs to the Cactaceae family and is a member of Opuntia kind has received increasing research interest for wastewater treatment by flocculation. The objectives of this study were (i) to provide more information regarding the active constituents of Opuntia spp. and (ii) to improve the extracting and using conditions of the flocculant molecules for water treatment. A classic approach by jar test experiments was used with raw and extracted material by solubilization and precipitation. The surface properties of solid material were characterized by FTIR, SEM, zeta potential measurement, and surface titration. The splitting based on the solubility of the material with pH and the titration of functional groups completed the method. The optimal pH value for a coagulation-flocculation process using cactus solid material (CSM) was 10.0 and a processing rate of 35 mg L -1 . The alkaline pH of flocculation suggests an adsorption mechanism with bridging effect between particles by water-soluble extracted molecules. To validate this mechanism, an extraction water was carried out at pH = 10 (optimum of flocculation) and the solution was acidified (pH = 7) to allow precipitation of so considered active flocculant molecules. The strong flocculant property of this extract was verified, and titration of this solution showed at least one specific pKa of 9.0 ± 0.6. This pKa corresponds to phenol groups, which could be assigned to lignin and tannin.

Production of aligned microfibers and nanofibers and derived functional monoliths

DOEpatents

Hu, Michael Z [Knoxville, TN; DePaoli, David W [Knoxville, TN; Kuritz, Tanya [Kingston, TN; Omatete, Ogbemi [New Port Richey, FL

2007-08-14

The present invention comprises a method for producing microfibers and nanofibers and further fabricating derived solid monolithic materials having aligned uniform micro- or nanofibrils. A method for producing fibers ranging in diameter from micrometer-sized to nanometer-sized comprises the steps of producing an electric field and preparing a solid precipitative reaction media wherein the media comprises at least one chemical reactive precursor and a solvent having low electrical conductivity and wherein a solid precipitation reaction process for nucleation and growth of a solid phase occurs within the media. Then, subjecting the media to the electric field to induce in-situ growth of microfibers or nanofibers during the reaction process within the media causing precipitative growth of solid phase particles wherein the reaction conditions and reaction kinetics control the size, morphology and composition of the fibers. The fibers can then be wet pressed while under electric field into a solid monolith slab, dried and consolidated.

Precipitation characteristics of uranyl ions at different pHs depending on the presence of carbonate ions and hydrogen peroxide.

PubMed

Kim, Kwang-Wook; Kim, Yeon-Hwa; Lee, Se-yoon; Lee, Jae-Won; Joe, Kih-Soo; Lee, Eil-Hee; Kim, Jong-Seung; Song, Kyuseok; Song, Kee-Chan

2009-04-01

This work studied the dissolution of uranium dioxide and precipitation characteristics of uranyl ions in alkaline and acidic solutions depending on the presence of carbonate ions and H2O2 in the solutions at different pHs controlled by adding HNO3 or NaOH in the solution. The chemical structures of the precipitates generated in different conditions were evaluated and compared by using XRD, SEM, TG-DT, and IR analyses together. The sizes and forms of the precipitates in the solutions were evaluated, as well. The uranyl ions were precipitated in the various forms, depending on the solution pH and the presences of hydrogen peroxide and carbonate ions in the solution. In a 0.5 M Na2CO3 solution with H2O2, where the uranyl ions formed mixed uranyl peroxy-carbonato complexes, the uranyl ions were precipitated as a uranium peroxide of UO4(H20)4 at pH 3-4, and precipitated as a clarkeite of Na2U2Ox(OH)y(H2O)z above pH 13. In the same carbonate solution without H2O2, where the uranyl ions formed uranyl tris-carbonato complex, the uranyl ions were observed to be precipitated as a different form of clarkeite above pH 13. The precipitate of uranyl ions in a nitrate solution without carbonate ions and H2O2 at a high pH were studied together to compare the precipitate forms in the carbonate solutions.

High temperature coarsening of Cr2Nb precipitates in Cu-8 Cr-4 Nb alloy

NASA Technical Reports Server (NTRS)

Anderson, Kenneth Reed

1996-01-01

A new high-temperature-strength, high-conductivity Cu-Cr-Nb alloy with a CrNb ratio of 2:1 was developed to achieve improved performance and durability. The Cu-8 Cr4 Nb alloy studied has demonstrated remarkable thermal and microstructural stability after long exposures at temperatures up to 0.98 T(sub m). This stability was mainly attributed to the slow coarsening kinetics of the Cr2Nb precipitates present in the alloy. At all temperatures, the microstructure consists of a bimodal and sometimes trimodal distribution of strengthening Cr2Nb precipitates, depending on precipitation condition, i.e. from liquid or solid solution, and cooling rates. These precipitates remain in the same size range, i.e. large precipitates of approximately I pm, and small precipitates less dm 300 nm, and effectively pin the grain boundaries thus retaining a fine grain size of 2.7 micro-m after 100 h at 1323 K. (A relatively small number of Cr-rich and Nb-rich particles were also present.) This grain boundary pinning and sluggish coarsening of Cr2Nb particles explain the retention of good mechanical properties after prolonged holding at very high temperatures, e.g., 75% of the original hardness after aging for 100 h at 1273 K. Application of LSW-based coarsening models indicated that the coarsening kinetics of the large precipitates are most likely governed by grain boundary diffsion and, to a lesser extent, volume diffusion mechanisms.

Hot tensile behaviour in silicon-killed boron microalloyed steels

NASA Astrophysics Data System (ADS)

Chown, Lesley H.; Cornish, Lesley A.

2017-10-01

Low carbon steel for drawing and cold heading applications should have low strength, high ductility and low strain ageing rates. To achieve this, nitrogen must be removed from solid solution, which can be done by low additions of boron. A wire producer had been experiencing occasional problems with severe cracking on silicon-killed, boron steel billets during continuous casting, but the solution was not obvious. Samples from four billets, each from different casts, were removed for analysis and testing. The tested steel compositions were within the specification limits, with boron to nitrogen ratios of 0.40-1.19. Hot ductility testing was performed on a Gleeble 1500 using parameters approximating the capabilities of this particular billet caster. The steel specimens were subjected to in situ melting, then cooled at a rate of 2 C.s-1 to temperatures in the range 750-1250°C, where they were then pulled to failure at a strain rate of 8x10-4 s-1. In this work, it was found that both the boron to nitrogen ratio and the manganese to sulphur ratio influenced the hot ductility and hence the crack susceptibility. Excellent hot ductility was found for B:N ratios above 1.0, which confirmed that the B:N ratio should be above a stoichiometric value of 0.8 to remove all nitrogen from solid solution. TEM analysis showed that coarse BN precipitates nucleated on other precipitates, such as (Fe,Mn)S, which have relatively low melting points, and are detrimental to hot ductility. Low Mn:S ratios of 10 - 12 were shown to promote precipitation of FeS, so a Mn:S > 14 was recommended. A narrower billet surface temperature range for straightening was recommended to prevent transverse surface cracking. Additionally, analysis of industrial casting data showed that the scrap percentage due to transverse cracking increased significantly for Mn:S < 14. An exponential decay relationship between the manganese to sulphur ratio and the average scrap percentage due to transverse cracking was derived as a simple tool to predict, and hence mitigate, scrap levels in the casting plant.

Synthesis and application of hydroxyapatite and fluoroapatite to scorodite encapsulation

NASA Astrophysics Data System (ADS)

Katsarou, Lydia

Recent research has investigated the precipitation of crystalline scorodite (FeAsO4˙2H2O) as a method to stabilise arsenic for disposal due to its good stability performance according to EPA's TCLP test. It has been determined, however, that scorodite releases arsenic in significant concentrations under alkaline pH or under anoxic conditions. With the objective of enhancing the stability of scorodite, its encapsulation with minerals inert to pH and redox potential variations is considered in this work. Such encapsulation materials are hydroxyapatite (HAP-Ca5(PO4)3OH) and fluoroapatite (FAP-Ca5(PO4)3F), the two most stable of the calcium phosphates. The work described in this thesis includes: 1) the preparation of hydroxyapatite and fluoroapatite powders and their characterisation, 2) the synthesis of crystalline scorodite under atmospheric conditions and its characterisation, 3) the encapsulation of scorodite with hydroxyapatite and fluoroapatite, and 4) the long term stability testing of the encapsulated solids. Hydroxyapatite and fluoroapatite were prepared first by homogeneous precipitation from a metastable solution, to which "Ca" and "PO4" source reagents of different concentrations were added at variable rates. The crystallinity of the produced materials was found to increase with temperature. Crystalline scorodite was produced by seeded crystallisation in ambient pressure. For the encapsulation of the scorodite particles various methods of direct precipitation by controlled supersaturation were attempted, by adjusting the pH and adding/mixing feed solutions of individual calcium and phosphate source reagents. Heterogeneous deposition of HAP on scorodite proved rather difficult. Optimum results were obtained via prior conditioning of the scorodite substrate in a calcium solution and employment of low agitation regime and high (37 °C rather than 22°C) temperature. The stability tests were done in oxic and anoxic environments and their results demonstrated that the encapsulated solids had enhanced stability, since the release of arsenic was lower than it was for naked scorodite. The presence of gypsum was found to help reduce the release of arsenic further as well as phosphorus under oxic, but not anoxic conditions due to possible interaction with the sulphite ions used as reducing agent.

Development of phosphate rock integrated with iron amendment for simultaneous immobilization of Zn and Cr(VI) in an electroplating contaminated soil.

PubMed

Zhao, Ling; Ding, Zhenliang; Sima, Jingke; Xu, Xiaoyun; Cao, Xinde

2017-09-01

This study aims to develop an amendment for simultaneous immobilization of Zn and Cr(VI) in an abandoned electroplating contaminated soil. Nature phosphate rock was first activated with oxalic acid (O-PR) and then combined with FeSO 4 or zero-valent iron (ZVI) for immobilization of Zn and Cr(VI) from aqueous solutions. Finally, the optimized approach showing the highest immobilization ability in solution was applied in an electroplating contaminated soil. The O-PR combined with FeSO 4 was more effective in simultaneously removing Zn and Cr(VI) than the O-PR integrated with ZVI within the tested solution pH range of 5.5-8.5. Both O-PR with FeSO 4 and with ZVI removed over 95% of Zn from the solution; however, only 42-46% of Cr(VI) was immobilized by O-PR with ZVI, while O-PR with FeSO 4 almost precipitated all Cr(VI). Moreover, there were 75-95% Zn and 95-100% Cr(VI) remaining in the exhausted O-PR with FeSO 4 solid after toxicity characteristic leaching test (TCLP) while the exhausted O-PR with ZVI solid only retained 44-83% Zn and 32-72% Cr(VI). Zinc was immobilized mainly via formation of insoluble Fe-Zn phosphate co-precipitates, while iron-induced reduction of Cr(VI) into stable Cr(OH) 3 or Cr x Fe (1-x) (OH) 3 was responsible for Cr(VI) immobilization. Application of the O-PR integrated with FeSO 4 in the electroplating contaminated soil rapidly reduced the TCLP extractable Zn and Cr(VI) to below the standard limits, with decrease by 50% and 94%, respectively. This study revealed that combination of oxalic acid activated phosphate rock with FeSO 4 could be an effective amendment for remediation of Zn and Cr(VI) contaminated soil. Copyright © 2017 Elsevier Ltd. All rights reserved.

METHOD FOR RECOVERING PLUTONIUM VALUES FROM SOLUTION USING A BISMUTH HYDROXIDE CARRIER PRECIPITATE

DOEpatents

Faris, B.F.

1961-04-25

Carrier precipitation processes for separating plutonium values from aqueous solutions are described. In accordance with the invention a bismuth hydroxide precipitate is formed in the plutonium-containing solution, thereby carrying plutonium values from the solution.

Modeled Sources, Transport, and Accumulation of Dissolved Solids in Water Resources of the Southwestern United States

USGS Publications Warehouse

Anning, D.W.

2011-01-01

Information on important source areas for dissolved solids in streams of the southwestern United States, the relative share of deliveries of dissolved solids to streams from natural and human sources, and the potential for salt accumulation in soil or groundwater was developed using a SPAtially Referenced Regressions On Watershed attributes model. Predicted area-normalized reach-catchment delivery rates of dissolved solids to streams ranged from <10(kg/year)/km2 for catchments with little or no natural or human-related solute sources in them to 563,000(kg/year)/km2 for catchments that were almost entirely cultivated land. For the region as a whole, geologic units contributed 44% of the dissolved-solids deliveries to streams and the remaining 56% of the deliveries came from the release of solutes through irrigation of cultivated and pasture lands, which comprise only 2.5% of the land area. Dissolved-solids accumulation is manifested as precipitated salts in the soil or underlying sediments, and (or) dissolved salts in soil-pore or sediment-pore water, or groundwater, and therefore represents a potential for aquifer contamination. Accumulation rates were <10,000(kg/year)/km2 for many hydrologic accounting units (large river basins), but were more than 40,000(kg/year)/km2 for the Middle Gila, Lower Gila-Agua Fria, Lower Gila, Lower Bear, Great Salt Lake accounting units, and 247,000(kg/year)/km2 for the Salton Sea accounting unit. ?? 2011 American Water Resources Association. This article is a U.S. Government work and is in the public domain in the USA.

Individual Reactions of Permanganate and Various Reductants - Student Report to the DOE ERULF Program for Work Conducted May to July 2000

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

Gauger, Amber M.; Hallen, Richard T.

2012-09-15

Tank waste on the Hanford Site contains radioactive elements that need to be removed from solution prior to disposal. One effective way to do this is to precipitate the radioactive elements with manganese solids, produced by permanganate oxidation. When added to tank waste, the permanganate reacts quickly producing manganese (IV) dioxide precipitate. Because of the speed of the reaction it is difficult to tell what exactly is happening. Individual reactions using non-radioactive reductants found in the tanks were done to determine reaction kinetics, what permanganate was reduced to, and what oxidation products were formed. In this project sodium formate, sodiummore » nitrite, glycolic acid, glycine, and sodium oxalate were studied using various concentrations of reductant in alkaline sodium hydroxide solutions. It was determined that formate reacted the quickest, followed by glycine and glycolic acid. Oxalate and nitrite did not appear to react with the permanganate solutions. The products of the oxidation reaction were examined. Formate was oxidized to carbonate and water. Glycolic acid was oxidized slower producing oxalate and water. Glycine reactions formed some ammonia in solution, oxalate, and water. The research reported by Amber Gauger in this report was part of a DOE ERULF student intern program at Pacific Northwest National Laboratory under the direction of Richard Hallen in the summer of 2000.« less

Nanostructural hierarchy increases the strength of aluminium alloys.

PubMed

Liddicoat, Peter V; Liao, Xiao-Zhou; Zhao, Yonghao; Zhu, Yuntian; Murashkin, Maxim Y; Lavernia, Enrique J; Valiev, Ruslan Z; Ringer, Simon P

2010-09-07

Increasing the strength of metallic alloys while maintaining formability is an interesting challenge for enabling new generations of lightweight structures and technologies. In this paper, we engineer aluminium alloys to contain a hierarchy of nanostructures and possess mechanical properties that expand known performance boundaries-an aerospace-grade 7075 alloy exhibits a yield strength and uniform elongation approaching 1 GPa and 5%, respectively. The nanostructural architecture was observed using novel high-resolution microscopy techniques and comprises a solid solution, free of precipitation, featuring (i) a high density of dislocations, (ii) subnanometre intragranular solute clusters, (iii) two geometries of nanometre-scale intergranular solute structures and (iv) grain sizes tens of nanometres in diameter. Our results demonstrate that this novel architecture offers a design pathway towards a new generation of super-strong materials with new regimes of property-performance space.

PROCESS FOR SEPARATING PLUTONIUM BY REPEATED PRECIPITATION WITH AMPHOTERIC HYDROXIDE CARRIERS

DOEpatents

Faris, B.F.

1960-04-01

A multiple carrier precipitation method is described for separating and recovering plutonium from an aqueous solution. The hydroxide of an amphoteric metal is precipitated in an aqueous plutonium-containing solution. This precipitate, which carries plutonium, is then separated from the supernatant liquid and dissolved in an aqueous hydroxide solution, forming a second plutonium- containing solution. lons of an amphoteric metal which forms an insoluble hydroxide under the conditions existing in this second solution are added to the second solution. The precipitate which forms and which carries plutonium is separated from the supernatant liquid. Amphoteric metals which may be employed are aluminum, bibmuth, copper, cobalt, iron, lanthanum, nickel, and zirconium.

Performance of a biogas upgrading process based on alkali absorption with regeneration using air pollution control residues.

PubMed

Baciocchi, Renato; Carnevale, Ennio; Costa, Giulia; Gavasci, Renato; Lombardi, Lidia; Olivieri, Tommaso; Zanchi, Laura; Zingaretti, Daniela

2013-12-01

This work analyzes the performance of an innovative biogas upgrading method, Alkali absorption with Regeneration (AwR) that employs industrial residues and allows to permanently store the separated CO2. This process consists in a first stage in which CO2 is removed from the biogas by means of chemical absorption with KOH or NaOH solutions followed by a second stage in which the spent absorption solution is contacted with waste incineration Air Pollution Control (APC) residues. The latter reaction leads to the regeneration of the alkali reagent in the solution and to the precipitation of calcium carbonate and hence allows to reuse the regenerated solution in the absorption process and to permanently store the separated CO2 in solid form. In addition, the final solid product is characterized by an improved environmental behavior compared to the untreated residues. In this paper the results obtained by AwR tests carried out in purposely designed demonstrative units installed in a landfill site are presented and discussed with the aim of verifying the feasibility of this process at pilot-scale and of identifying the conditions that allow to achieve all of the goals targeted by the proposed treatment. Specifically, the CO2 removal efficiency achieved in the absorption stage, the yield of alkali regeneration and CO2 uptake resulting for the regeneration stage, as well as the leaching behavior of the solid product are analyzed as a function of the type and concentration of the alkali reagent employed for the absorption reaction. Copyright © 2013 Elsevier Ltd. All rights reserved.

Method of precipitating uranium from an aqueous solution and/or sediment

DOEpatents

Tokunaga, Tetsu K; Kim, Yongman; Wan, Jiamin

2013-08-20

A method for precipitating uranium from an aqueous solution and/or sediment comprising uranium and/or vanadium is presented. The method includes precipitating uranium as a uranyl vanadate through mixing an aqueous solution and/or sediment comprising uranium and/or vanadium and a solution comprising a monovalent or divalent cation to form the corresponding cation uranyl vanadate precipitate. The method also provides a pathway for extraction of uranium and vanadium from an aqueous solution and/or sediment.

Effect of calcium oxide on the efficiency of ferrous ion oxidation and total iron precipitation during ferrous ion oxidation in simulated acid mine drainage treatment with inoculation of Acidithiobacillus ferrooxidans.

PubMed

Liu, Fenwu; Zhou, Jun; Jin, Tongjun; Zhang, Shasha; Liu, Lanlan

2016-01-01

Calcium oxide was added into ferrous ion oxidation system in the presence of Acidithiobacillus ferrooxidans at concentrations of 0-4.00 g/L. The pH, ferrous ion oxidation efficiency, total iron precipitation efficiency, and phase of the solid minerals harvested from different treatments were investigated during the ferrous ion oxidation process. In control check (CK) system, pH of the solution decreased from 2.81 to 2.25 when ferrous ions achieved complete oxidation after 72 h of Acidithiobacillus ferrooxidans incubation without the addition of calcium oxide, and total iron precipitation efficiency reached 20.2%. Efficiency of ferrous ion oxidation and total iron precipitation was significantly improved when the amount of calcium oxide added was ≤1.33 g/L, and the minerals harvested from systems were mainly a mixture of jarosite and schwertmannite. For example, the ferrous ion oxidation efficiency reached 100% at 60 h and total iron precipitation efficiency was increased to 32.1% at 72 h when 1.33 g/L of calcium oxide was added. However, ferrous ion oxidation and total iron precipitation for jarosite and schwertmannite formation were inhibited if the amount of calcium oxide added was above 2.67 g/L, and large amounts of calcium sulfate dihydrate were generated in systems.

Experimental study of the replacement of calcite by calcium sulphates

NASA Astrophysics Data System (ADS)

Ruiz-Agudo, E.; Putnis, C. V.; Hövelmann, J.; Álvarez-Lloret, P.; Ibáñez-Velasco, A.; Putnis, A.

2015-05-01

Among the most relevant mineral replacement reactions are those involving sulphates and carbonates, which have important geological and technological implications. Here it is shown experimentally that during the interaction of calcite (CaCO3) cleavage surfaces with sulphate-bearing acidic solutions, calcite is ultimately replaced by gypsum (CaSO4 2H2O) and anhydrite (CaSO4), depending on the reaction temperature. Observations suggest that this occurs most likely via an interface-coupled dissolution-precipitation reaction, in which the substrate is replaced pseudomorphically by the product. At 120 and 200 °C gypsum and/or bassanite (CaSO4·0.5H2O) form as precursor phases for the thermodynamically stable anhydrite. Salinity promotes the formation of less hydrated precursor phases during the replacement of calcite by anhydrite. The reaction stops before equilibrium with respect to calcite is reached and during the course of the reaction most of the bulk solutions are undersaturated with respect to the precipitating phase(s). A mechanism consisting of the dissolution of small amounts of solid in a thin layer of fluid at the mineral-fluid interface and the subsequent precipitation of the product phase from this layer is in agreement with these observations. PHREEQC simulations performed in the framework of this mechanism highlight the relevance of transport and surface reaction kinetics on the volume change associated with the CaCO3-CaSO4 replacement. Under our experimental conditions, this reaction occurs with a positive volume change, which ultimately results in passivation of the unreacted substrate before calcite attains equilibrium with respect to the bulk solution.

Climatic Drivers for Multi-Decadal Shifts in Solute Transport and Methane Production Zones within a Large Peat Basin

NASA Technical Reports Server (NTRS)

Glaser, Paul H.; Siegel, Donald I.; Chanton, Jeffrey P.; Reeve, Andrew S.; Rosenberry, Donald O.; Corbett, J. Elizabeth; Dasgupta, Soumitri; Levy, Zeno

2016-01-01

Northern peatlands are an important source for greenhouse gases but their capacity to produce methane remains uncertain under changing climatic conditions. We therefore analyzed a 43-year time series of pore-water chemistry to determine if long-term shifts in precipitation altered the vertical transport of solutes within a large peat basin in northern Minnesota. These data suggest that rates of methane production can be finely tuned to multi-decadal shifts in precipitation that drive the vertical penetration of labile carbon substrates within the Glacial Lake Agassiz Peatlands. Tritium and cation profiles demonstrate that only the upper meter of these peat deposits was flushed by downwardly moving recharge from 1965 through 1983 during a Transitional Dry-to-Moist Period. However, a shift to a moister climate after 1984 drove surface waters much deeper, largely flushing the pore waters of all bogs and fens to depths of 2 m. Labile carbon compounds were transported downward from the rhizosphere to the basal peat at this time producing a substantial enrichment of methane in Delta C-14 with respect to the solid-phase peat from 1991 to 2008. These data indicate that labile carbon substrates can fuel deep production zones of methanogenesis that more than doubled in thickness across this large peat basin after 1984. Moreover, the entire peat profile apparently has the capacity to produce methane from labile carbon substrates depending on climate-driven modes of solute transport. Future changes in precipitation may therefore play a central role in determining the source strength of peatlands in the global methane cycle.

Climatic drivers for multidecadal shifts in solute transport and methane production zones within a large peat basin

USGS Publications Warehouse

Glaser, Paul H.; Siegel, Donald I.; Chanton, Jeffrey P.; Reeve, Andrew S.; Rosenberry, Donald O.; Corbett, J. Elizabeth; Dasgupta, Soumitri; Levy, Zeno

2016-01-01

Northern peatlands are an important source for greenhouse gases, but their capacity to produce methane remains uncertain under changing climatic conditions. We therefore analyzed a 43 year time series of the pore-water chemistry to determine if long-term shifts in precipitation altered the vertical transport of solutes within a large peat basin in northern Minnesota. These data suggest that rates of methane production can be finely tuned to multidecadal shifts in precipitation that drive the vertical penetration of labile carbon substrates within the Glacial Lake Agassiz Peatlands. Tritium and cation profiles demonstrate that only the upper meter of these peat deposits was flushed by downwardly moving recharge from 1965 to 1983 during a Transitional Dry-to-Moist Period. However, a shift to a moister climate after 1984 drove surface waters much deeper, largely flushing the pore waters of all bogs and fens to depths of 2 m. Labile carbon compounds were transported downward from the rhizosphere to the basal peat at this time producing a substantial enrichment of methane in Δ14C with respect to the solid-phase peat from 1991 to 2008. These data indicate that labile carbon substrates can fuel deep production zones of methanogenesis that more than doubled in thickness across this large peat basin after 1984. Moreover, the entire peat profile apparently has the capacity to produce methane from labile carbon substrates depending on climate-driven modes of solute transport. Future changes in precipitation may therefore play a central role in determining the source strength of peatlands in the global methane cycle.

SEPARATION OF AMERICIUM FROM PROMETHIUM

DOEpatents

Pressly, R.E.

1959-07-01

Promethium-147 is separated from americium in acidic aqueous solution by adding fluosilicic acid to the solution, heating the solution to form a promethium precipitate and separating the precipitate from solution. The precipitate is then re-dissolved by ihe addition of boric acid and nitric acid, and re-precipitated by the addition of fluosilicic acid. This procedure is repeated six or more times to obtain a relatively americium-free promeihium precipitate. Americium may be separately recovered from the supernatant liquids. This process is applicable to the recovery of promethium from fission-product solutions which have been allowed to decay for a period of two to four years.

Germanium recovery from gasification fly ash: evaluation of end-products obtained by precipitation methods.

PubMed

Arroyo, Fátima; Font, Oriol; Fernández-Pereira, Constantino; Querol, Xavier; Juan, Roberto; Ruiz, Carmen; Coca, Pilar

2009-08-15

In this study the purity of the germanium end-products obtained by two different precipitation methods carried out on germanium-bearing solutions was evaluated as a last step of a hydrometallurgy process for the recovery of this valuable element from the Puertollano Integrated Gasification Combined Cycle (IGCC) fly ash. Since H(2)S is produced as a by-product in the gas cleaning system of the Puertollano IGCC plant, precipitation of germanium as GeS(2) was tested by sulfiding the Ge-bearing solutions. The technological and hazardous issues that surround H(2)S handling conducted to investigate a novel precipitation procedure: precipitation as an organic complex by adding 1,2-dihydroxy benzene pyrocatechol (CAT) and cetyltrimethylammonium bromide (CTAB) to the Ge-bearing solutions. Relatively high purity Ge end-products (90 and 93% hexagonal-GeO(2) purity, respectively) were obtained by precipitating Ge from enriched solutions, as GeS(2) sulfiding the solutions with H(2)S, or as organic complex with CAT/CTAB mixtures and subsequent roasting of the precipitates. Both methods showed high efficiency (>99%) to precipitate selectively Ge using a single precipitation stage from germanium-bearing solutions.

Recovery of high purity phosphorus from municipal wastewater secondary effluent by a high-speed adsorbent.

PubMed

Midorikawa, I; Aoki, H; Omori, A; Shimizu, T; Kawaguchi, Y; Kassai, K; Murakami, T

2008-01-01

High purity phosphorus was recovered from municipal wastewater secondary effluent as phosphate, using a newly developed phosphorus adsorption and recovery system. A high-speed adsorbent having a unique porous structure was used in this system. The secondary effluent, showing total phosphorus (TP) of 0.1-2.1 mg P/L, was passed through an adsorbent packed column at high space velocity (SV) of 15 h(-1). The TP of the treated water was as low as 0.02-0.04 mg P/L, indicating that 97% of phosphorus in the secondary effluent was removed. The removed phosphorus was desorbed from the adsorbent by passing a sodium hydroxide aqueous solution through the column. Calcium hydroxide was added to this solution to precipitate the phosphorus as calcium phosphate. This precipitate was neutralized with hydrochloric acid aqueous solution, washed with water, and then solid-liquid separation was performed for the phosphorus recovery. The main constituent of the recovered phosphorus was apatite-type calcium phosphate, with 16% phosphorus content, which matched that of high-grade phosphorus ore. The hazardous elements content of the recovered phosphorus was exceedingly low. Therefore the recovered phosphorus can be applied to an alternative for phosphorus ore, or to a phosphate fertilizer. IWA Publishing 2008.

Process parameters and morphology in puerarin, phospholipids and their complex microparticles generation by supercritical antisolvent precipitation.

PubMed

Li, Ying; Yang, Da-Jian; Chen, Shi-Lin; Chen, Si-Bao; Chan, Albert Sun-Chi

2008-07-09

The aim of the study was to develop and evaluate a new method for the production of puerarin phospholipids complex (PPC) microparticles. The advanced particle formation method, solution enhanced dispersion by supercritical fluids (SEDS), was used for the preparation of puerarin (Pur), phospholipids (PC) and their complex particles for the first time. Evaluation of the processing variables on PPC particle characteristics was also conducted. The processing variables included temperature, pressure, solution concentration, the flow rate of supercritical carbon dioxide (SC-CO2) and the relative flow rate of drug solution to CO2. The morphology, particle size and size distribution of the particles were determined. Meanwhile Pur and phospholipids were separately prepared by gas antisolvent precipitation (GAS) method and solid characterization of particles by the two supercritical methods was also compared. Pur formed by GAS was more orderly, purer crystal, whereas amorphous Pur particles between 0.5 and 1microm were formed by SEDS. The complex was successfully obtained by SEDS exhibiting amorphous, partially agglomerated spheres comprised of particles sized only about 1microm. SEDS method may be useful for the processing of other pharmaceutical preparations besides phospholipids complex particles. Furthermore adopting a GAS process to recrystallize pharmaceuticals will provide a highly versatile methodology to generate new polymorphs of drugs in addition to conventional techniques.

Insensitive High-Performance Replacements for RDX in Explosive and Propellant Formulations

DTIC Science & Technology

2007-03-16

1) was prepared in good yield and purity from 3,4,5- triamino-1,2,4-triazole (guanazine) and picric acid (eq. 1, see experimental). C2H6N6...g (5 mmol) of 3,4,5-triamino-1,2,4-triazole (prepared as described in the literature [6]) was added 1.15 g of picric acid (1 wt.% in H2O from...hydrobromic acid in MeOH. A white solid precipitated, was filtered off and washed with a saturated solution of sodium carbonate in cold water. It was

Influence of grain boundaries on the distribution of components in binary alloys

NASA Astrophysics Data System (ADS)

L'vov, P. E.; Svetukhin, V. V.

2017-12-01

Based on the free-energy density functional method (the Cahn-Hilliard equation), a phenomenological model that describes the influence of grain boundaries on the distribution of components in binary alloys has been developed. The model is built on the assumption of the difference between the interaction parameters of solid solution components in the bulk and at the grain boundary. The difference scheme based on the spectral method is proposed to solve the Cahn-Hilliard equation with interaction parameters depending on coordinates. Depending on the ratio between the interaction parameters in the bulk and at the grain boundary, temperature, and alloy composition, the model can give rise to different types of distribution of a dissolved component, namely, either depletion or enrichment of the grain-boundary area, preferential grainboundary precipitation, competitive precipitation in the bulk and at the grain boundary, etc.

Phosphate recovery through struvite-family crystals precipitated in the presence of citric acid: mineralogical phase and morphology evaluation.

PubMed

Perwitasari, D S; Edahwati, L; Sutiyono, S; Muryanto, S; Jamari, J; Bayuseno, A P

2017-11-01

Precipitation strategy of struvite-family crystals is presented in this paper to recover phosphate and potassium from a synthetic wastewater in the presence of citric acid at elevated temperature. The crystal-forming solutions were prepared from crystals of MgCl 2 and NH 4 H 2 PO 4 with a molar ratio of 1:1:1 for Mg +2 , [Formula: see text], and [Formula: see text], and the citric acid (C 6 H 8 O 7 ) was prepared (1.00 and 20.00 ppm) from citric acid crystals. The Rietveld analysis of X-ray powder diffraction pattern confirmed a mixed product of struvite, struvite-(K), and newberyite crystallized at 30°C in the absence of citric acid. In the presence of citric acid at 30° and 40°C, an abundance of struvite and struvite-(K) were observed. A minute impurity of sylvite and potassium peroxide was unexpectedly found in certain precipitates. The crystal solids have irregular flake-shaped morphology, as shown by scanning electron microscopy micrograph. All parameters (citric acid, temperature, pH, Mg/P, and N/P) were deliberately arranged to control struvite-family crystals precipitation.

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

Ma, Xi; Blue Sky Technology Corporation, Beijing 100083; Ma, Hongwen, E-mail: mahw@cugb.edu.cn

Highlights: • We use the anti-drop precipitation method for synthesis of magnesium hydroxide. • Boron mud which is solid waste from a borax factory is used as the magnesium source. • The magnesium hydroxide nanoflowers are prepared in a short time. • The as-prepared magnesium hydroxide can be used as an effective flame retardant. - Abstract: Using boron mud as the starting material, the flower-like magnesium hydroxide (MH) has been successfully prepared via anti-drop precipitation method. The effect of NH{sub 3}·H{sub 2}O concentration, aging time, and surfactant on the morphology of MH was investigated. The optimum precipitation conditions are droppingmore » MgSO{sub 4} solution in 5% NH{sub 3}·H{sub 2}O solution, with 3% polyethylene glycol as surfactant, aging for 30 min. XRD, SEM, FI-IR, and TG/DTA have been employed to characterize the as-prepared samples. XRD reveals that MH with high purity has the brucite structure. SEM images show that the flower-like MH exists in the form of mono-disperse well uniform spherical aggregation with diameter of 3–5 μm. TG/DTA shows a total percentage of weight loss 33.6% with a well-defined endothermic peak near 381.3 °C corresponding to the decomposition of MH. Furthermore, it reports that the extremely fast primary nucleation is of significance for crystal growth of MH.« less

Factors affecting alkali jarosite precipitation

NASA Astrophysics Data System (ADS)

Dutrizac, J. E.

1983-12-01

Several factors affecting the precipitation of the alkali jarosites (sodium jarosite, potassium jarosite, rubidium jarosite, and ammonium jarosite) have been studied systematically using sodium jarosite as the model. The pH of the reacting solution exercises a major influence on the amount of jarosite formed, but has little effect on the composition of the washed product. Higher temperatures significantly increase the yield and slightly raise the alkali content of the jarosites. The yield and alkali content both increase greatly with the alkali concentration to about twice the stoichiometric requirement but, thereafter, remain nearly constant. At 97 °C, the amount of product increases with longer retention times to about 15 hours, but more prolonged reaction times are without significant effect on the amount or composition of the jarosite. Factors such as the presence of seed or ionic strength have little effect on the yield or jarosite composition. The amount of precipitate augments directly as the iron concentration of the solution increases, but the product composition is nearly independent of this variable. A significant degree of agitation is necessary to suspend the product and to prevent the jarosite from coating the apparatus with correspondingly small yields. Once the product is adequately suspended, however, further agitation is without significant effect. The partitioning of alkali ions during jarosite precipitation was ascertained for K:Na, Na:NH4, K:NH4, and K:Rb. Potassium jarosite is the most stable of the alkali jarosites and the stability falls systematically for lighter or heavier congeners; ammonium jarosite is slightly more stable than the sodium analogue. Complete solid solubility among the various alkali jarosite-type compounds was established.

Conceptual models governing leaching behavior and their long-term predictive capability

USGS Publications Warehouse

Claassen, Hans C.

1981-01-01

Six models that may be used to describe the interaction of radioactive waste solids with aqueous solutions are as follows:Simple linear mass transfer;Simple parabolic mass transfer;Parabolic mass transfer with the formation of a diffusion-limiting surface layer at an arbitrary time;Initial parabolic mass transfer followed by linear mass transfer at an arbitrary time;Parabolic (or linear) mass transfer and concomitant surface sorption; andParabolic (or linear) mass transfer and concomitant chemical precipitation.Some of these models lead to either illogical or unrealistic predictions when published data are extrapolated to long times. These predictions result because most data result from short-term experimentation. Probably for longer times, processes will occur that have not been observed in the shorter experiments. This hypothesis has been verified by mass-transfer data from laboratory experiments using natural volcanic glass to predict the composition of groundwater. That such rate-limiting mechanisms do occur is reassuring, although now it is not possible to deduce a single mass-transfer limiting mechanism that could control the solution concentration of all components of all waste forms being investigated. Probably the most reasonable mechanisms are surface sorption and chemical precipitation of the species of interest. Another is limiting of mass transfer by chemical precipitation on the waste form surface of a substance not containing the species of interest, that is, presence of a diffusion-limiting layer. The presence of sorption and chemical precipitation as factors limiting mass transfer has been verified in natural groundwater systems, whereas the diffusion-limiting mechanism has not been verified yet.

Concrete-Water-Interaction and Ikaite (CaCO3.6H2O) Precipitation in a Man-Made River Bed

NASA Astrophysics Data System (ADS)

Boch, R.; Dietzel, M.; Reichl, P.; Leis, A.; Pölt, P.; Baldermann, A.

2014-12-01

Centimetre-thick, beige-colored and soft crusts were observed shortly after construction of a man-made river bed, i.e. a small natural river was bypassed flowing through a new bed lined with concrete and blocks. Hydrochemical investigations during wintertime - when water temperatures dropped down close to freezing - showed surprisingly high pH values up to 13.0 and elevated Ca2+ concentrations up to 200 mg/l. Both, the artifical and natural (downstream) section of the river bed were affected by the anomalous hydrochemistry and formation of prominent secondary precipitates. In order to better understand the particular and rapid water-rock-interaction, a hydrochemical monitoring program was launched and several of the delicate precipitates were recovered in refrigerator boxes in their original solution. The samples were analyzed in the laboratory within a few hours after sampling and stored at 1 °C. XRD and FT-IR patterns clearly revealed the predominant occurrence of "ikaite" in the crusts next to minor amounts of other carbonates (calcite, aragonite, vaterite) and detrital minerals. Ikaite - calcium carbonate hexahydrate - is a worldwide rarely documented carbonate mineral. This mineral is metastable and needs particular and narrow conditions in order to precipitate from solutions, i.e. a very limited water-temperature range between 0 and 4 °C (with ambient-pressure and low-salinity), highly alkaline pH conditions, high supersaturation values, and in many cases carbonate precipitation inhibitors (e.g. phosphates). Outside these conditions it disintegrates into calcite and water within minutes to hours. The few places of ikaite formation include Ikka Fjord in Greenland, Arctic- and Antarctic sea-ice and some sites of water mixing at Mono Lake, California. Combining detailed field monitoring results, solid-phase analyses and regional meteorological data (rainfall, water discharge, temperature) with hydrogeochemical modeling allows constraining the mechanisms of ikaite formation, as well as the temporal and spatial evolution of the waters and precipitates in the river bed.

Equilibrium aluminium hydroxo-oxalate phases during initial clay formation; H +-Al 3+-oxalic acid-Na + system

NASA Astrophysics Data System (ADS)

Bilinski, Halka; Horvath, Laszlo; Ingri, Nils; Sjöberg, Staffan

1986-09-01

The conditions necessary for initial clay formation have been studied in different model systems comprising different organic acids besides Si and Al. In the present paper the solid phases and the precipitation boundary characterizing the subsystem H +-Al 3+-oxalic acid (H 2L) are discussed. pH and tyndallometric measurements were performed in an ionic medium of 0.6 M Na(Cl) at 25 °C. The two phases Al 3(OH) 7(C 2O 4) · 3H 2O (phase I) and NaAl(OH) 2(C 2O 4) · 3H 2O (phase II) determine the precipitation boundary. The following formation constants for the two phases were deduced: lgβ1 = lg([ Al3+] -3[ H2C2O4] -1[ H+] 9 = -21.87 ± 0.08 and lgβ11 = lg([ Al3+] -1[ H2C2O4] -1[ H+] 4 = -5.61 ± 0.06. Phase I exists in the range [ Al] tot≥ 10 -4.4moldm-3,[ H2C2O4] tot ≥ 10 -4.9moldm-3 and at pH < 6.8, thus being a possible precipitate in oxalic-rich natural waters. The more soluble sodium phase is unlikely to exist in natural waters. The two phases are metastable relative to crystalline gibbsite and may be considered as the first precipitation step in the transition from aqueous Al oxalates down to stable Al hydroxide. Model calculations illustrating these competing hydrolysis-complexation reactions are discussed in terms of predominance and speciation diagrams. The solid phases have been characterized by X-ray analysis of powders, TGA and IR spectra, and tentative structures are proposed. Phase I seems to be an octahedral layer structure, in which 3/5 of the octahedral sites between two close packed oxygen sheets are occupied by Al 3+ and the oxalate ion acts as a bridge ligand between two aluminium atoms. Phase II forms a more open sheet structure and has ion exchange properties. Powder data for a phase crystallized from the studied solution after a year are also presented. This phase, Na 4Al 2(OH) 2(C 2O 4) 4 · 10H 2O, supports the results from the equilibrium analysis of recent solution data by SJöBERG and ÖHMAN (1985), who have found the dinuclear complex Al 2(OH) 2(C 2O 4) 44- to exist in a solution in which the ligand is in excess.

Dilution physics modeling: Dissolution/precipitation chemistry

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

Onishi, Y.; Reid, H.C.; Trent, D.S.

This report documents progress made to date on integrating dilution/precipitation chemistry and new physical models into the TEMPEST thermal-hydraulics computer code. Implementation of dissolution/precipitation chemistry models is necessary for predicting nonhomogeneous, time-dependent, physical/chemical behavior of tank wastes with and without a variety of possible engineered remediation and mitigation activities. Such behavior includes chemical reactions, gas retention, solids resuspension, solids dissolution and generation, solids settling/rising, and convective motion of physical and chemical species. Thus this model development is important from the standpoint of predicting the consequences of various engineered activities, such as mitigation by dilution, retrieval, or pretreatment, that can affectmore » safe operations. The integration of a dissolution/precipitation chemistry module allows the various phase species concentrations to enter into the physical calculations that affect the TEMPEST hydrodynamic flow calculations. The yield strength model of non-Newtonian sludge correlates yield to a power function of solids concentration. Likewise, shear stress is concentration-dependent, and the dissolution/precipitation chemistry calculations develop the species concentration evolution that produces fluid flow resistance changes. Dilution of waste with pure water, molar concentrations of sodium hydroxide, and other chemical streams can be analyzed for the reactive species changes and hydrodynamic flow characteristics.« less

PROCESS OF SEPARATING PLUTONIUM FROM URANIUM

DOEpatents

Brown, H.S.; Hill, O.F.

1958-09-01

A process is presented for recovering plutonium values from aqueous solutions. It comprises forming a uranous hydroxide precipitate in such a plutonium bearing solution, at a pH of at least 5. The plutonium values are precipitated with and carried by the uranium hydroxide. The carrier precipitate is then redissolved in acid solution and the pH is adjusted to about 2.5, causing precipitation of the uranous hydroxide but leaving the still soluble plutonium values in solution.

pH-Induced precipitation behavior of weakly basic compounds: determination of extent and duration of supersaturation using potentiometric titration and correlation to solid state properties.

PubMed

Hsieh, Yi-Ling; Ilevbare, Grace A; Van Eerdenbrugh, Bernard; Box, Karl J; Sanchez-Felix, Manuel Vincente; Taylor, Lynne S

2012-10-01

To examine the precipitation and supersaturation behavior of ten weak bases in terms of the relationship between pH-concentration-time profiles and the solid state properties of the precipitated material. Initially the compound was dissolved at low pH, followed by titration with base to induce precipitation. Upon precipitation, small aliquots of acid or base were added to induce slight subsaturation and supersaturation respectively and the resultant pH gradient was determined. The concentration of the unionized species was calculated as a function of time and pH using mass and charge balance equations. Two patterns of behavior were observed in terms of the extent and duration of supersaturation arising following an increase in pH and this behavior could be rationalized based on the crystallization tendency of the compound. For compounds that did not readily crystallize, an amorphous precipitate was formed and a prolonged duration of supersaturation was observed. For compounds that precipitated to crystalline forms, the observed supersaturation was short-lived. This study showed that supersaturation behavior has significant correlation with the solid-state properties of the precipitate and that pH-metric titration methods can be utilized to evaluate the supersaturation behavior.

BASIC PEROXIDE PRECIPITATION METHOD OF SEPARATING PLUTONIUM FROM CONTAMINANTS

DOEpatents

Seaborg, G.T.; Perlman, I.

1959-02-10

A process is described for the separation from each other of uranyl values, tetravalent plutonium values and fission products contained in an aqueous acidic solution. First the pH of the solution is adjusted to between 2.5 and 8 and hydrogen peroxide is then added to the solution causing precipitation of uranium peroxide which carries any plutonium values present, while the fission products remain in solution. Separation of the uranium and plutonium values is then effected by dissolving the peroxide precipitate in an acidic solution and incorporating a second carrier precipitate, selective for plutonium. The plutonium values are thus carried from the solution while the uranium remains flissolved. The second carrier precipitate may be selected from among the group consisting of rare earth fluorides, and oxalates, zirconium phosphate, and bismuth lihosphate.

Microstructure and Shear Strength in Brazing Joint of Mo-Cu Composite with 304 Stainless Steel by Ni-Cr-P Filler Metal

NASA Astrophysics Data System (ADS)

Wang, Juan; Wang, Jiteng; Li, Yajiang; Zheng, Deshuang

2015-07-01

The brazing of Mo-Cu composite and 304 stainless steel was carried out in vacuum with Ni-Cr-P filler metal at 980 °C for 20 min. Microstructure in Mo-Cu/304 stainless steel joint was investigated by field-emission scanning electron microscope (FE-SEM) with energy dispersive spectrometer (EDS) and shear strength was measured by shearing test. The results indicate that shear strength of the Mo-Cu/304 stainless steel joint is about 155 MPa. There forms eutectic structure of γ-Ni solid solution with Ni3P in the braze seam. Ni-Cu(Mo) and Ni-Fe solid solution are at the interface beside Mo-Cu composite and 304 stainless steel, respectively. Shear fracture exhibits mixed ductile-brittle fracture feature with trans-granular fracture, ductile dimples and tearing edges. Fracture originates from the interface between brazing seam and Mo-Cu composite and it propagates to the braze seam due to the formation of brittle Ni5P2 and Cr3P precipitation.

Elastic moduli and thermal expansion coefficients of medium-entropy subsystems of the CrMnFeCoNi high-entropy alloy

DOE PAGES

Laplanche, Guillaume; Gadaud, P.; Barsch, C.; ...

2018-02-23

Elastic moduli of a set of equiatomic alloys (CrFeCoNi, CrCoNi, CrFeNi, FeCoNi, MnCoNi, MnFeNi, and CoNi), which are medium-entropy subsystems of the CrMnFeCoNi high-entropy alloy were determined as a function of temperature over the range 293 K–1000 K. Thermal expansion coefficients were determined for these alloys over the temperature range 100 K–673 K. All alloys were single-phase and had the face-centered cubic (FCC) crystal structure, except CrFeNi which is a two-phase alloy containing a small amount of body-centered cubic (BCC) precipitates in a FCC matrix. The temperature dependences of thermal expansion coefficients and elastic moduli obtained here are useful formore » quantifying fundamental aspects such as solid solution strengthening, and for structural analysis/design. Furthermore, using the above results, the yield strengths reported in literature for these alloys were normalized by their shear moduli to reveal the influence of shear modulus on solid solution strengthening.« less

Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example

DOE PAGES

Jin, Geng Bang; Lin, Jian; Estes, Shanna L.; ...

2017-11-17

Here, the influence of countercations (A n+) in directing the composition of monomeric metal–ligand (ML) complexes that precipitate from solution are often overlooked despite the wide usage of A n+ in materials synthesis. Herein, we describe a correlation between the composition of ML complexes and A + hydration enthalpies found for two related series of thorium (Th)–nitrate molecular compounds obtained by evaporating acidic aqueous Th–nitrate solutions in the presence of A + counterions. Analyses of their chemical composition and solid-state structures demonstrate that A + not only affects the overall solid-state packing of the Th–nitrato complexes but also influences themore » composition of the Th–nitrato monomeric anions themselves. Trends in composition and structure are found to correlate with A + hydration enthalpies, such that the A + with smaller hydration enthalpies associate with less hydrated and more anionic Th–nitrato complexes. This perspective, broader than the general assumption of size and charge as the dominant influence of A n+, opens a new avenue for the design and synthesis of targeted metal–ligand complexes.« less

Microstructure of Vacuum-Brazed Joints of Super-Ni/NiCr Laminated Composite Using Nickel-Based Amorphous Filler Metal

NASA Astrophysics Data System (ADS)

Ma, Qunshuang; Li, Yajiang; Wu, Na; Wang, Juan

2013-06-01

Vacuum brazing of super-Ni/NiCr laminated composite and Cr18-Ni8 stainless steel was carried out using Ni-Cr-Si-B amorphous filler metal at 1060, 1080, and 1100 °C, respectively. Microstructure and phase constitution were investigated by means of optical and scanning electron microscopy, energy-dispersive spectroscopy, x-ray diffraction, and micro-hardness tester. When brazed at 1060-1080 °C, the brazed region can be divided into two distinct zones: isothermally solidified zone (ISZ) consisting of γ-Ni solid solution and athermally solidified zone (ASZ) consisting of Cr-rich borides. Micro-hardness of the Cr-rich borides formed in the ASZ was as high as 809 HV50 g. ASZ decreased with increase of the brazing temperature. Isothermal solidification occurred sufficiently at 1100 °C and an excellent joint composed of γ-Ni solid solution formed. The segregation of boron from ISZ to residual liquid phase is the reason of Cr-rich borides formed in ASZ. The formation of secondary precipitates in diffusion-affected zone is mainly controlled by diffusion of B.

Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example

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

Jin, Geng Bang; Lin, Jian; Estes, Shanna L.

Here, the influence of countercations (A n+) in directing the composition of monomeric metal–ligand (ML) complexes that precipitate from solution are often overlooked despite the wide usage of A n+ in materials synthesis. Herein, we describe a correlation between the composition of ML complexes and A + hydration enthalpies found for two related series of thorium (Th)–nitrate molecular compounds obtained by evaporating acidic aqueous Th–nitrate solutions in the presence of A + counterions. Analyses of their chemical composition and solid-state structures demonstrate that A + not only affects the overall solid-state packing of the Th–nitrato complexes but also influences themore » composition of the Th–nitrato monomeric anions themselves. Trends in composition and structure are found to correlate with A + hydration enthalpies, such that the A + with smaller hydration enthalpies associate with less hydrated and more anionic Th–nitrato complexes. This perspective, broader than the general assumption of size and charge as the dominant influence of A n+, opens a new avenue for the design and synthesis of targeted metal–ligand complexes.« less

Mineralogy controls on reactive transport of Marcellus Shale waters.

PubMed

Cai, Zhang; Wen, Hang; Komarneni, Sridhar; Li, Li

2018-07-15

Produced or flowback waters from Marcellus Shale gas extraction (MSWs) typically are highly saline and contain chemicals including trace metals, which pose significant concerns on water quality. The natural attenuation of MSW chemicals in groundwater is poorly understood due to the complex interactions between aquifer minerals and MSWs, limiting our capabilities to monitor and predict. Here we combine flow-through experiments and process-based reactive transport modeling to understand mechanisms and quantify the retention of MSW chemicals in a quartz (Qtz) column, a calcite-rich (Cal) column, and a clay-rich (Vrm, vermiculite) column. These columns were used to represent sand, carbonate, and clay-rich aquifers. Results show that the types and extent of water-rock interactions differ significantly across columns. Although it is generally known that clay-rich media retard chemicals and that quartz media minimize water-rock interactions, results here have revealed insights that differ from previous thoughts. We found that the reaction mechanisms are much more complex than merely sorption and mineral precipitation. In clay rich media, trace metals participate in both ion exchange and mineral precipitation. In fact, the majority of metals (~50-90%) is retained in the solid via mineral precipitation, which is surprising because we typically expect the dominance of sorption in clay-rich aquifers. In the Cal column, trace metals are retained not only through precipitation but also solid solution partitioning, leading to a total of 75-99% retention. Even in the Qtz column, trace metals are retained at unexpectedly high percentages (~20-70%) due to precipitation. The reactive transport model developed here quantitatively differentiates the relative importance of individual processes, and bridges a limited number of experiments to a wide range of natural conditions. This is particularly useful where relatively limited knowledge and data prevent the prediction of complex rock-contaminant interactions and natural attenuation. Copyright © 2018 Elsevier B.V. All rights reserved.

THORIUM OXALATE-URANYL ACETATE COUPLED PROCEDURE FOR THE SEPARATION OF RADIOACTIVE MATERIALS

DOEpatents

Gofman, J.W.

1959-08-11

The recovery of fission products from neutronirradiated uranium is described. The neutron-irradiated uranium is dissolved in acid and thorium oxalate is precipitated in ihe solution formed, whereby the fission products are carried on the thorium oxalate. The separated thorium oxalate precipitate is then dissolved in an aqueous oxalate solution and the solution formed is acidified, limiting ihe excess acidity to a maximum of 2 N, whereby thorium oxalate precipitates and carries lanthanum-rareearth- and alkaline-earth-metal fission products while the zirconium-fission-product remains in solution. This precipitate, too, is dissolved in an aqaeous oxalate solution at elevated temperature, and lanthanum-rare-earth ions are added to the solution whereby lanthanum-rare-earth oxalate forms and the lanthanum-rare-earth-type and alkalineearth-metal-type fission products are carried on the oxalate. The precipitate is separated from the solution.

PROCESSING OF MONAZITE SAND

DOEpatents

Calkins, G.D.; Bohlmann, E.G.

1957-12-01

A process for the recovery of thorium, uranium, and rare earths from monazite sands is presented. The sands are first digested and dissolved in concentrated NaOH, and the solution is then diluted causing precipitation of uranium, thorium and rare earth hydroxides. The precipitate is collected and dissolved in HCl, and the pH of this solution is adjusted to about 6, precipitating the hydroxides of thorium and uranium but leaving the rare earths in solution. The rare earths are then separated from the solution by precipitation at a still higher pH. The thorium and uranium containing precipitate is redissolved in HNO/sub 3/ and the two elements are separated by extraction into tributyl phosphate and back extraction with a weakly acidic solution to remove the thorium.

URANIUM RECOVERY PROCESS

DOEpatents

Bailes, R.H.; Long, R.S.; Olson, R.S.; Kerlinger, H.O.

1959-02-10

A method is described for recovering uranium values from uranium bearing phosphate solutions such as are encountered in the manufacture of phosphate fertilizers. The solution is first treated with a reducing agent to obtain all the uranium in the tetravalent state. Following this reduction, the solution is treated to co-precipitate the rcduced uranium as a fluoride, together with other insoluble fluorides, thereby accomplishing a substantially complete recovery of even trace amounts of uranium from the phosphate solution. This precipitate usually takes the form of a complex fluoride precipitate, and after appropriate pre-treatment, the uranium fluorides are leached from this precipitate and rccovered from the leach solution.

URANIUM LEACHING AND RECOVERY PROCESS

DOEpatents

McClaine, L.A.

1959-08-18

A process is described for recovering uranium from carbonate leach solutions by precipitating uranium as a mixed oxidation state compound. Uranium is recovered by adding a quadrivalent uranium carbon;te solution to the carbonate solution, adjusting the pH to 13 or greater, and precipitating the uranium as a filterable mixed oxidation state compound. In the event vanadium occurs with the uranium, the vanadium is unaffected by the uranium precipitation step and remains in the carbonate solution. The uranium-free solution is electrolyzed in the cathode compartment of a mercury cathode diaphragm cell to reduce and precipitate the vanadium.

Solute mixing regulates heterogeneity of mineral precipitation in porous media: Effect of Solute Mixing on Precipitation

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

Cil, Mehmet B.; Xie, Minwei; Packman, Aaron I.

Synchrotron X-ray microtomography was used to track the spatiotemporal evolution of mineral precipitation and the consequent alteration of the pore structure. Column experiments were conducted by injecting CaCl2 and NaHCO3 solutions into granular porous media either as a premixed supersaturated solution (external mixing) or as separate solutions that mixed within the specimen (internal mixing). The two mixing modes produced distinct mineral growth patterns. While internal mixing promoted transverse heterogeneity with precipitation at the mixing zone, external mixing favored relatively homogeneous precipitation along the flow direction. The impact of precipitation on pore water flow and permeability was assessed via 3-D flowmore » simulations, which indicated anisotropic permeability evolution for both mixing modes. Under both mixing modes, precipitation decreased the median pore size and increased the skewness of the pore size distribution. Such similar pore-scale evolution patterns suggest that the clogging of individual pores depends primarily on local supersaturation state and pore geometry.« less

Polymer-encapsulated carbon capture liquids that tolerate precipitation of solids for increased capacity

DOEpatents

Aines, Roger D; Bourcier, William L; Spadaccini, Christopher M; Stolaroff, Joshuah K

2015-02-03

A system for carbon dioxide capture from flue gas and other industrial gas sources utilizes microcapsules with very thin polymer shells. The contents of the microcapsules can be liquids or mixtures of liquids and solids. The microcapsules are exposed to the flue gas and other industrial gas and take up carbon dioxide from the flue gas and other industrial gas and eventual precipitate solids in the capsule.

Interfacial Interaction in Anodic Aluminum Oxide Templates Modifies Morphology, Surface Area, and Crystallization of Polyamide-6 Nanofibers.

PubMed

Xue, Junhui; Xu, Yizhuang; Jin, Zhaoxia

2016-03-08

Here, we demonstrated that, when the precipitation process of polyamide-6 (PA6) solution happens in cylindrical channels of an anodized aluminum oxide membrane (AAO), interface interactions between a solid surface, solvent, non-solvent, and PA6 will influence the obtained polymer nanostructures, resulting in complex morphologies, increased surface area, and crystallization changes. With the enhancing interaction of PA6 and the AAO surface, the morphology of PA6 nanostructures changes from solid nanofibers, mesoporous, to bamboo-like, while at the same time, metastable γ-phase domains increase in these PA6 nanostructures. Brunauer-Emmett-Teller (BET) surface areas of solid, bamboo-like, and mesoporous PA6 nanofibers rise from 16, 20.9, to 25 m(2)/g. This study shows that interfacial interaction in AAO template fabrication can be used in manipulating the morphology and crystallization of one-dimensional polymer nanostructures. It also provides us a simple and novel method to create porous PA6 nanofibers with a large surface area.

Nondestructive ultrasonic characterization of engineering materials

NASA Technical Reports Server (NTRS)

Salama, K.

1985-01-01

The development of an ultrasonic method for the nondestructive characterization of mechanical properties of engineering material is described. The method utilizes the nonlinearity parameter measurement which describes the anharmonic behavior of the solid through measurements of amplitudes of the fundamental and of the generated second harmonic ultrasonic waves. The nonlinearity parameter is also directly related to the acoustoelastic constant of the solid which can be determined by measuring the linear dependence of ultrasonic velocity on stress. A major advantage of measurements of the nonlinearity parameter over that of the acoustoelastic constant is that it may be determined without the application of stress on the material, which makes it more applicable for in-service nondestructive characterization. The relationships between the nonlinearity parameter of second-harmonic generation and the percentage of solid solution phase in engineering materials such as heat treatable aluminum alloys was established. The acoustoelastic constants are measured on these alloys for comparison and confirmation. A linear relationship between the nonlinearity parameter and the volume fraction of second phase precipitates in the alloys is indicated.

Ground-water quality near the northwest 58th Street solid-waste disposal facility, Dade County, Florida

USGS Publications Warehouse

Mattraw, H.C.; Hull, John E.; Klein, Howard

1978-01-01

The Northwest 58th Street solid-waste disposal facility, 3 miles west of a major Dade County municipal water-supply well field, overlays the Biscayne aquifer, a permeable, solution-riddled limestone which transmits leachates eastward at a calculated rate of 2.9 feet per day. A discrete, identifiable leachate plume has been recognized under and downgradient from the waste disposal facility. Concentrations of sodium, ammonia, and dissolved solids decreased with depth beneath the disposal area and downgradient in response to an advective and convective dispersion. At a distance of about one-half downgradient, the rate of contribution of leachate from the source to the leading edge of the plume was about equal to the rate of loss of leachate from the leading edge of the plume by diffusion and dilution by rainfall infiltration during the period August 1973 - July 1975. Heavy metals and pesticides are filtered, adsorbed by aquifer materials, or are precipitated near the disposal area. (Woodard-USGS)

Advanced material and approach for metal ions removal from aqueous solutions

PubMed Central

Turhanen, Petri A.; Vepsäläinen, Jouko J.; Peräniemi, Sirpa

2015-01-01

A Novel approach to remove metals from aqueous solutions has been developed. The method is based on a resin free, solid, non-toxic, microcrystalline bisphosphonate material, which has very low solubility in water (59 mg/l to ion free Milli-Q water and 13 mg/l to 3.5% NaCl solution). The material has been produced almost quantitatively on a 1 kg scale (it has been prepared also on a pilot scale, ca. 7 kg) and tested successfully for its ability to collect metal cations from different sources, such as ground water and mining process waters. Not only was this material highly efficient at collecting several metal ions out of solution it also proved to be regenerable and reusable over a number of adsorption/desorption, which is crucial for environmental friendliness. This material has several advantages compared to the currently used approaches, such as no need for any precipitation step. PMID:25758924

RADIOMETRIC STUDY ON THE SUITABILITY OF CINCHONIN AS PRECIPITATION REAGENT FOR TUNGSTEN AND MOLYBDENUM (in German)

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

Merz, E.

1962-01-01

The precipitation of W and Mo with cinchonin was studied using P/sup 32/ , Mp/sup 99/, and W/sup 185/. The effects of the acid, acid concentration, solution volume, and precipitation time on the quantitative precipitation of the metals were determined. W was precipitated only from HCl and HNO/sub 3/, and no quantitative precipitation of Mo was obtained. No variation was found in the completeness of the precipitation using HCl concentrations of 1 to 6N, but precipitation is prevented or strongly inhibited in very strong solutions. The quantitative precipitation of W is very strongly dependent on the solution volume, but theremore » is no sharp time dependence. A study of the effectiveness of cinchonin and tannin as combined precipitation agents showed no advantage over the use of cinchonin alone, except in the removal of interferring elements in the precipitation. (J.S.R.)« less

PRECIPITATION OF PLUTONOUS PEROXIDE

DOEpatents

Barrick, J.G.; Manion, J.P.

1961-08-15

A precipitation process for recovering plutonium values contained in an aqueous solution is described. In the process for precipitating plutonium as plutonous peroxide, hydroxylamine or hydrazine is added to the plutoniumcontaining solution prior to the addition of peroxide to precipitate plutonium. The addition of hydroxylamine or hydrazine increases the amount of plutonium precipitated as plutonous peroxide. (AEC)

TEM Studies of Boron-Modified 17Cr-7Ni Precipitation-Hardenable Stainless Steel via Rapid Solidification Route

NASA Astrophysics Data System (ADS)

Gupta, Ankur; Bhargava, A. K.; Tewari, R.; Tiwari, A. N.

2013-09-01

Commercial grade 17Cr-7Ni precipitation-hardenable stainless steel has been modified by adding boron in the range 0.45 to 1.8 wt pct and using the chill block melt-spinning technique of rapid solidification (RS). Application of RS has been found to increase the solid solubility of boron and hardness of 17Cr-7Ni precipitation-hardenable stainless steel. The hardness of the boron-modified rapidly solidified alloys has been found to increase up to ~280 pct after isochronal aging to peak hardness. A TEM study has been carried out to understand the aging behavior. The presence of M23(B,C)6 and M2(B,C) borocarbides and epsilon-carbide in the matrix of austenite and ferrite with a change in heat treatment temperature has been observed. A new equation for Creq is also developed which includes the boron factor on ferrite phase stability. The study also emphasizes that aluminum only takes part in ferrite phase stabilization and remains in the solution.

Hafnium radioisotope recovery from irradiated tantalum

DOEpatents

Taylor, Wayne A.; Jamriska, David J.

2001-01-01

Hafnium is recovered from irradiated tantalum by: (a) contacting the irradiated tantalum with at least one acid to obtain a solution of dissolved tantalum; (b) combining an aqueous solution of a calcium compound with the solution of dissolved tantalum to obtain a third combined solution; (c) precipitating hafnium, lanthanide, and insoluble calcium complexes from the third combined solution to obtain a first precipitate; (d) contacting the first precipitate of hafnium, lanthanide and calcium complexes with at least one fluoride ion complexing agent to form a fourth solution; (e) selectively adsorbing lanthanides and calcium from the fourth solution by cationic exchange; (f) separating fluoride ion complexing agent product from hafnium in the fourth solution by adding an aqueous solution of ferric chloride to obtain a second precipitate containing the hafnium and iron; (g) dissolving the second precipitate containing the hafnium and iron in acid to obtain an acid solution of hafnium and iron; (h) selectively adsorbing the iron from the acid solution of hafnium and iron by anionic exchange; (i) drying the ion exchanged hafnium solution to obtain hafnium isotopes. Additionally, if needed to remove residue remaining after the product is dried, dissolution in acid followed by cation exchange, then anion exchange, is performed.

Mechanisms of iron-silica aqueous interaction and the genesis of Precambrian iron formation

NASA Astrophysics Data System (ADS)

Chemtob, S. M.; Catalano, J. G.; Moynier, F.; Pringle, E. A.

2015-12-01

Iron formations (IFs), Fe- and Si-rich chemical sediments common in Precambrian successions, preserve key information about the compositional, biological, and oxidative evolution of the Precambrian ocean. Stable Si isotopes (δ30Si) of IF have been used to infer paleo-oceanic composition, and secular variations in δ30Si may reflect ancient biogeochemical cycles. The δ30Si of primary Fe-Si precipitates that formed IF depends not only on the δ30Si of aqueous silica but also on the precipitation mechanism. Multiple formation mechanisms for these primary precipitates are plausible. Aqueous Si may have adsorbed on newly precipitated iron oxyhydroxide surfaces; alternatively, Fe and Si may have coprecipitated as a single phase. Here we explore variations in the Si isotope fractionation factor (ɛ) with Fe-Si aqueous interaction mechanism (adsorption vs. coprecipitation). In adsorption experiments, sodium silicate solutions (pH 8.1, 125-2000 µM Si) were reacted with iron oxide particles (hematite, ferrihydrite, goethite, and magnetite) for 24 to 72 hours. Resultant solutions had δ30Si between 0 and +6‰. Calculated ɛ varied significantly with oxide mineralogy and morphology. For ferrihydrite, ɛ = -1.7‰; for hematite, ɛ = -2 to -5‰, depending on particle morphology. Apparent ɛ decreased upon surface site saturation, implying a smaller isotope effect for polymeric Si adsorption than monomeric adsorption. In coprecipitation experiments, solutions of Na-silicate and Fe(II) chloride (0.4-10 mM) were prepared anaerobically, then air-oxidized for 3 days to induce precipitation. At low Si concentrations, magnetite formed; near silica saturation, lepidocrocite and ferrihydrite formed. The Si isotope fractionation factor for coprecipitation was within the range of ɛ observed for adsorption (ɛ = -2.3 ± 1.0‰). These results indicate that the mechanism of Fe-Si interaction affects ɛ, presumably due to varying silicate coordination environments. These isotopic analyses will be paired with Si K-edge and Fe K-edge X-ray absorption spectra of the solids to illustrate how Si bonding environment affects ɛ. Effective reconstruction of paleo-oceanic δ30Si may require additional constraints on the relative importance of Si adsorption and Fe-Si coprecipitation in the production of IF primary precipitates.

Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

2017-12-01

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr isotopes as environmental proxies in aquatic environments.

Spectroscopic studies of U(VI) sorption at the kaolinite-water interface. Final report

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

Thompson, H.A.; Parks, G.A.; Brown, G.E. Jr.

Efficient use of U as a resource and safe handling, recycling and disposal of U-containing wastes require an understanding of the factors controlling the fate of U, where fate refers to the destination of U, typically expressed as an environmental medium or a process phase. The sorption process constitutes a change in elemental fate. Partitioning of an element from solution to a solid phase, or sorption, can be divided into three broad categories: adsorption, surface precipitation, and absorption. Extended X-ray absorption fine structure (EXAFS), a type of X-ray absorption spectroscopy (XAS), offers the possibility for distinguishing among different modes ofmore » sorption by characterizing the atomic environment of the sorbing element. In this study, the authors use EXAFS to determine the structure of U(VI) sorption complexes at the kaolinite-water interface. In Chapter One, they present an overview of selected aspects of U structural chemistry as a basis for considering the structural environment of U at the solid-water interface. To evaluate the utility of XAS for characterization of the structural environment of U(VI) at the solid-water interface, they have carried out an in-depth analysis of XAS data from U(VI)-containing solid and solution model compounds, which they describe in Chapter Two. In Chapter three, they consider sorption of U by kaolinite as a means of effecting the removal of U from surface collection pond waters on the Rocky Flats Plant site in northern Colorado.« less

Caustic Precipitation of Plutonium and Uranium with Gadolinium as a Neutron Poison

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

VISSER, ANN E.; BRONIKOWSKI, MICHAEL G.; RUDISILL, TRACY S.

2005-10-18

The caustic precipitation of plutonium (Pu) and uranium (U) from Pu and U-containing waste solutions has been investigated to determine whether gadolinium (Gd) could be used as a neutron poison for precipitation with greater than a fissile mass containing both Pu and enriched U. Precipitation experiments were performed using both process solution samples and simulant solutions with a range of 2.6-5.16 g/L U and 0-4.3:1 U:Pu. Analyses were performed on solutions at intermediate pH to determine the partitioning of elements for accident scenarios. When both Pu and U were present in the solution, precipitation began at pH 4.5 and bymore » pH 7, 99% of Pu and U had precipitated. When complete neutralization was achieved at pH > 14 with 1.2 M excess OH{sup -}, greater than 99% of Pu, U, and Gd had precipitated. At pH > 14, the particles sizes were larger and the distribution was a single mode. The ratio of hydrogen:fissile atoms in the precipitate was determined after both settling and centrifuging and indicates that sufficient water was associated with the precipitates to provide the needed neutron moderation for Gd to prevent a criticality in solutions containing up to 4.3:1 U:Pu and up to 5.16 g/L U.« less

BIOLEACH: Coupled modeling of leachate and biogas production on solid waste landfills

NASA Astrophysics Data System (ADS)

Rodrigo-Clavero, Maria-Elena; Rodrigo-Ilarri, Javier

2015-04-01

One of the most important factors to address when performing the environmental impact assessment of urban solid waste landfills is to evaluate the leachate production. Leachate management (collection and treatment) is also one of the most relevant economical aspects to take into account during the landfill life. Leachate is formed as a solution of biological and chemical components during operational and post-operational phases on urban solid waste landfills as a combination of different processes that involve water gains and looses inside the solid waste mass. Infiltration of external water coming from precipitation is the most important component on this water balance. However, anaerobic waste decomposition and biogas formation processes play also a role on the balance as water-consuming processes. The production of leachate one biogas is therefore a coupled process. Biogas production models usually consider optimal conditions of water content on the solid waste mass. However, real conditions during the operational phase of the landfill may greatly differ from these optimal conditions. In this work, the first results obtained to predict both the leachate and the biogas production as a single coupled phenomenon on real solid waste landfills are shown. The model is applied on a synthetic case considering typical climatological conditions of Mediterranean catchments.

Superalloy for high-temperature hydrogen environmental applications

NASA Technical Reports Server (NTRS)

McKannan, Eugene C. (Inventor); McPherson, William B. (Inventor); Ahmed, Shaffiq (Inventor); Chandler, Shirley S. (Inventor)

1991-01-01

A nickel-based superalloy is provided which is resistant to deterioration in hydrogen at high operating temperatures and pressures, and which thus can be used in hydrogen-fueled spacecraft such as the Space Shuttle. The superalloy is characterized by a two-phase microstructure and consists of a gamma-prime precipitated phase in a gamma matrix. The gamma matrix phase is a primary solid solution and the gamma precipitated phase will be an intermetallic compound of the type A.sub.3 B, such as nickel aluminide or titanide. Both phases are coherent, ordered, and compatible, and thus will retain most of their strength at elevated temperatures. The alloy consists essentially of (by weight): Ni 50-60%, Cr 10-20%, Al 2-6%, Co 2-5%, Ti 3-8%, W 5-12%, Mo 5-10%, Nb 1-3%, wherein the ratio W/MO is approximately equal to 1, and Ti/Al ranges from about 1 to about 2.

Dissolution-Assisted Pattern Formation During Olivine Carbonation

NASA Astrophysics Data System (ADS)

Lisabeth, Harrison; Zhu, Wenlu; Xing, Tiange; De Andrade, Vincent

2017-10-01

Olivine and pyroxene-bearing rocks in the oceanic crust react with hydrothermal fluids producing changes in the physical characteristics and behaviors of the altered rocks. Notably, these reactions tend to increase solid volume, reducing pore volume, permeability, and available reactive surface area, yet entirely hydrated and/or carbonated rocks are commonly observed in the field. We investigate the evolution of porosity and permeability of fractured dunites reacted with CO2-rich solutions in laboratory experiments. The alteration of crack surfaces changes the mechanical and transport properties of the bulk samples. Analysis of three-dimensional microstructural data shows that although precipitation of secondary minerals causes the total porosity of the sample to decrease, an interconnected network of porosity is maintained through channelized dissolution and coupled carbonate precipitation. The observed microstructure appears to be the result of chemo-mechanical coupling, which may provide a mechanism of porosity maintenance without the need to invoke reaction-driven cracking.

Thermal Effects That Arise upon Different Heat Treatments in Austenitic Steels Alloyed with Titanium and Phosphorus

NASA Astrophysics Data System (ADS)

Arbuzov, V. L.; Berger, I. F.; Bobrovskii, V. I.; Voronin, V. I.; Danilov, S. E.; Kazantsev, V. A.; Kataev, N. V.; Sagaradze, V. V.

2018-04-01

Structural and microstructural changes that arise in the course of the heat treatment of Cr-Ni-Mo austenitic stainless steels with different concentrations of titanium and phosphorus have been studied. It has been found that the alloying with phosphorus decreases the lattice parameter of these steels. The phosphorus contribution to this effect is 0.015 ± 0.002 Å/at %. Aging at a temperature of 670 K for about 20 h leads to the precipitation of dispersed needle-like particles, which are most likely to be iron phosphides. In the temperature range of 700-800 K, in austenitic steels, the atomic separation of the solid solution occurs, the intensity of which decreases upon alloying with titanium or phosphorus at concentrations of 1.0 and 0.1 wt %, respectively. At higher temperatures (about 950 K), the formed precipitates of the Ni3Ti (γ') phase increase in size to 7-10 nm.

1300 K Creep Behavior of [001] Oriented Ni-49Al-1Hf (at.%) Single Crystals

NASA Technical Reports Server (NTRS)

Whittenberger, J. Daniel; Locci, I. E.; Darolia, Ram; Bowman, R.

1999-01-01

A study of the 1300 K compressive and tensile creep properties of [001]-oriented NiAl-1Hf (D209) single crystals has been undertaken. Neither post homogenization cooling treatment, minor chemical variations within an ingot or from ingot-to-ingot, nor testing procedure had a significant effect on mechanical behavior; however a heat treatment which dissolved the initial G-phase precipitates and promoted formation of Heusler particles led to a strength reduction. Little primary creep was found utilizing direct measurement of strain, and a misorientation of 18 deg from the [001] did not reduce the creep strength. The effects of heat treatments on properties and a comparison of the flow stress-strain rate data to those predicted by the Jaswon-Cottrell solid solution hardening model indicate that the 1300 K strength in NiAl-1Hf single crystals is mainly due to precipitation hardening mechanisms.

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

Lisabeth, Harrison; Zhu, Wenlu; Xing, Tiange

Olivine and pyroxene bearing rocks in the oceanic crust react with hydrothermal fluids producing changes in the physical characteristics and behaviors of the altered rocks. Notably, these reactions tend to increase solid volume, reducing pore volume, permeability and available reactive surface area; yet, entirely hydrated and/or carbonated rocks are commonly observed in the field. We investigate the evolution of porosity and permeability of fractured dunites reacted with CO 2-rich solutions in laboratory experiments. The alteration of crack surfaces changes the mechanical and transport properties of the bulk samples. Analysis of three-dimensional microstructural data shows that although precipitation of secondary mineralsmore » causes the total porosity of the sample to decrease, an interconnected network of porosity is maintained through channelized dissolution and coupled carbonate precipitation. Lastly, the observed microstructure appears to be the result of chemo-mechanical coupling, which may provide a mechanism of porosity maintenance without the need to invoke reaction-driven cracking.« less

Value recovery from spent alumina-base catalyst

DOEpatents

Hyatt, David E.

1987-01-01

A process for the recovery of aluminum and at least one other metal selected from the group consisting of molybdenum, nickel and cobalt from a spent hydrogenation catalyst comprising (1) adding about 1 to 3 parts H.sub.2 SO.sub.4 to each part of spent catalyst in a reaction zone of about 20.degree. to 200.degree. C. under sulfide gas pressure between about 1 and about 35 atmospheres, (2) separating the resultant Al.sub.2 (SO.sub.4).sub.3 solution from the sulfide precipitate in the mixture, (3) oxidizing the remaining sulfide precipitate as an aqueous slurry at about 20.degree. to 200.degree. C. in an oxygen-containing atmosphere at a pressure between about 1 and about 35 atmospheres, (4) separating the slurry to obtain solid molybdic acid and a sulfate liquor containing said at least one metal, and (5) recovering said at least one metal from the sulfate liquor in marketable form.

Dissolution-Assisted Pattern Formation During Olivine Carbonation

DOE PAGES

Lisabeth, Harrison; Zhu, Wenlu; Xing, Tiange; ...

2017-08-31

Olivine and pyroxene bearing rocks in the oceanic crust react with hydrothermal fluids producing changes in the physical characteristics and behaviors of the altered rocks. Notably, these reactions tend to increase solid volume, reducing pore volume, permeability and available reactive surface area; yet, entirely hydrated and/or carbonated rocks are commonly observed in the field. We investigate the evolution of porosity and permeability of fractured dunites reacted with CO 2-rich solutions in laboratory experiments. The alteration of crack surfaces changes the mechanical and transport properties of the bulk samples. Analysis of three-dimensional microstructural data shows that although precipitation of secondary mineralsmore » causes the total porosity of the sample to decrease, an interconnected network of porosity is maintained through channelized dissolution and coupled carbonate precipitation. Lastly, the observed microstructure appears to be the result of chemo-mechanical coupling, which may provide a mechanism of porosity maintenance without the need to invoke reaction-driven cracking.« less

Mechanism for enhanced absorption of a solid dispersion formulation of LY2300559 using the artificial stomach duodenum model.

PubMed

Polster, Christopher S; Wu, Sy-Juen; Gueorguieva, Ivelina; Sperry, David C

2015-04-06

An artificial stomach duodenum (ASD) model has been used to demonstrate the performance difference between two formulations of LY2300559, a low-solubility acidic developmental drug. The two formulations investigated were a conventional high-shear wet granulation (HSWG) formulation and a solid dispersion formulation. A pharmacokinetic study in humans demonstrated the enhanced performance of the solid dispersion formulation relative to the HSWG formulation. The Cmax and AUC of the solid dispersion was 2.6 and 1.9 times greater, respectively, compared to the HSWG formulation. In the ASD, the solid dispersion formulation performance was characterized by three main phases: (1) rapid release in the stomach, creating a supersaturated concentration of drug, (2) precipitation in the stomach, and (3) rapid redissolution of the precipitate in the duodenum to concentration levels that are supersaturated relative to crystalline drug. A series of complementary experiments were employed to describe this performance behavior mechanistically. Imaging experiments with a pH indicating dye showed that local pH gradients from meglumine in the solid dispersion formulation were responsible for creating a high initial supersaturation concentration in the stomach. Upon dissipation of meglumine, the drug precipitated in the stomach as an amorphous solid. Because the precipitated drug is in an amorphous form, it can then rapidly redissolve as it transits to the more neutral environment of the duodenum. This unexpected sequence of physical state changes gives a mechanistic explanation for the enhanced in vivo performance of the solid dispersion formulation relative to the HSWG formulation.

Sodium Lauryl Sulfate Competitively Interacts with HPMC-AS and Consequently Reduces Oral Bioavailability of Posaconazole/HPMC-AS Amorphous Solid Dispersion.

PubMed

Chen, Yuejie; Wang, Shujing; Wang, Shan; Liu, Chengyu; Su, Ching; Hageman, Michael; Hussain, Munir; Haskell, Roy; Stefanski, Kevin; Qian, Feng

2016-08-01

Sodium lauryl sulfate (SLS), as an effective surfactant, is often used as a solubilizer and/or wetting agent in various dosage forms for the purpose of improving the solubility and dissolution of lipophilic, poorly water-soluble drugs. This study aims to understand the impact of SLS on the solution behavior and bioavailability of hypromellose acetate succinate (HPMC-AS)-based posaconazole (PSZ) ASDs, and to identify the underlying mechanisms governing the optimal oral bioavailability of ASDs when surfactants such as SLS are used in combination. Fluorescence spectroscopy and optical microscopy showed that "oil-out" or "liquid-liquid phase separation (LLPS)" occurred in the supersaturated PSZ solution once drug concentration surpassed ∼12 μg/mL, which caused the formation of drug-rich oily droplets with initial size of ∼300-400 nm. Although FT-IR study demonstrated the existence of specific interactions between PSZ and HPMC-AS in the solid state, predissolved HPMC-AS was unable to delay LLPS of the supersaturated PSZ solution and PSZ-rich amorphous precipitates with ∼16-18% HPMC-AS were formed within 10 min. The coprecipitated HPMC-AS was found to be able to significantly delay the crystallization of PSZ in the PSZ-rich amorphous phase from less than 10 min to more than 4 h, yet coexistent SLS was able to negate this crystallization inhibition effect of HPMC-AS in the PSZ-rich amorphous precipitates and cause fast PSZ crystallization within 30 min. 2D-NOESY and the CMC/CAC results demonstrated that SLS could assemble around HPMC-AS and competitively interact with HPMC-AS in the solution, thus prevent HPMC-AS from acting as an effective crystallization inhibitor. In a crossover dog PK study, this finding was found to be correlating well with the in vivo bioavailability of PSZ ASDs formulated with or without SLS. The SLS containing PSZ ASD formulation demonstrated an in vivo bioavailability ∼30% of that without SLS, despite the apparently better in vitro dissolution, which only compared the dissolved drug in solution, a small fraction of the total PSZ dose. We conclude that the bioavailability of ASDs is highly dependent on the molecular interactions between drug, surfactant, and polymer, not only in the solution phase but also in the drug-rich "oily" phase caused by supersaturation.

In-situ generation of oxygen-releasing metal peroxides

DOEpatents

Looney, Brian B.; Denham, Miles E.

2007-01-09

A method for remediation of contaminants in soil and groundwater is disclosed. The method generates oxygen releasing solids in groundwater or soil by injecting an aqueous energetic oxidant solution containing free radicals, oxidative conditions can be created within or ahead of a contaminant plume. Some contaminants may be remediated directly by reaction with the free radicals. Additionally and more importantly, the free radicals create an oxidative condition whereby native or injected materials, especially metals, are converted to peroxides. These peroxides provide a long-term oxygen reservoir, releasing oxygen relatively slowly over time. The oxygen can enhance microbial metabolism to remediate contaminants, can react with contaminant metals either to form immobile precipitants or to mobilize other metals to permit remediation through leaching techniques. Various injection strategies for injecting the energetic oxidant solution are also disclosed.

Mass transfer and carbon isotope evolution in natural water systems

USGS Publications Warehouse

Wigley, T.M.L.; Plummer, Niel; Pearson, F.J.

1978-01-01

This paper presents a theoretical treatment of the evolution of the carbon isotopes C13 and C14 in natural waters and in precipitates which derive from such waters. The effects of an arbitrary number of sources (such as dissolution of carbonate minerals and oxidation of organic material) and sinks (such as mineral precipitation, CO2 degassing and production of methane), and of equilibrium fractionation between solid, gas and aqueous phases are considered. The results are expressed as equations relating changes in isotopic composition to changes in conventional carbonate chemistry. One implication of the equations is that the isotopic composition of an aqueous phase may approach a limiting value whenever there are simultaneous inputs and outputs of carbonate. In order to unambiguously interpret isotopic data from carbonate precipitates and identify reactants and products in reacting natural waters, it is essential that isotopic changes are determined chiefly by reactant and product stoichiometry, independent of reaction path. We demonstrate that this is so by means of quantitative examples. The evolution equations are applied to: 1. (1) carbon-14 dating of groundwaters; 2. (2) interpretation of the isotopic composition of carbonate precipitates, carbonate cements and diagenetically altered carbonates; and 3. (3) the identification of chemical reaction stoichiometry. These applications are illustrated by examples which show the variation of ??C13 in solutions and in precipitates formed under a variety of conditions involving incongruent dissolution, CO2 degassing, methane production and mineral precipitation. ?? 1978.

MANGANESE DIOXIDE METHOD FOR PREPARATION OF PROTACTINIUM

DOEpatents

Katzin, L.I.

1958-08-12

A method of obtaining U/sup 233/ is described. An aqueous solution of neutriln irradiated thoriunn is treated by forming tberein a precipitate of manganese dioxide which carries and thus separates the Pa/sup 233/ from the solution. The carrier precipitate so formed is then dissolved in an acidic solution containing a reducing agent sufficiently electronegative to reduce the tetravalent manganese to the divalent state. Further purification of the Pa/sup 233/ may be obtained by forming another manganese dioxide carrier precipitate and subsequently dissolving it. Ater a sufficient number of such cycles have brought the Pa/sup 233/ to the desired purity, the solution is aged, allowing the formation ot U/sup 233/ by radioaetive decay. A manganese dioxide precipitate is then formed in the U/sup 233/ containing solution. This precipitate carries down any remaining Pa/sup 233/ thus leaving the separated U/sup 233/solution, from whieh it may be easily recovered.

Model predictions of realgar precipitation by reaction of As(III) with synthetic mackinawite under anoxic conditions

USGS Publications Warehouse

Gallegos, T.J.; Han, Y.-S.; Hayes, K.F.

2008-01-01

This study investigates the removal of As(III) from solution using mackinawite, a nanoparticulate reduced iron sulfide. Mackinawite suspensions (0.1-40 g/L) effectively lower initial concentrations of 1.3 ?? 10 -5 M As(III) from pH 5-10, with maximum removal occurring under acidic conditions. Based on Eh measurements, it was found that the redox state of the system depended on the mackinawite solids concentration and pH. Higher initial mackinawite concentrations and alkaline pH resulted in a more reducing redox condition. Given this, the pH edge data were modeled thermodynamically using pe (-log[e-]) as a fitting parameter and linear pe-pH relationships within the range of measured Eh values as a function of pH and mackinawite concentration. The model predicts removal of As(III) from solution by precipitation of realgar with the formation of secondary oxidation products, greigite or a mixed-valence iron oxide phase, depending on pH. This study demonstrates that mackinawite is an effective sequestration agent for As(III) and highlights the importance of incorporating redox into models describing the As-Fe-S-H2O system. ?? 2008 American Chemical Society.

Determination of selenium at trace levels in geologic materials by energy-dispersive X-ray fluorescence spectrometry

USGS Publications Warehouse

Wahlberg, J.S.

1981-01-01

Low levels of selenium (0.1-500 ppm) in both organic and inorganic geologic materials can be semiquantitatively measured by isolating Se as a thin film for presentation to an energy-dispersive X-ray fluorescence spectrometer. Suitably pulverized samples are first digested by fusing with a mixture of Na2CO3 and Na2O2. The fusion cake is dissolved in distilled water, buffered with NH4Cl, and filtered to remove Si and the R2O3 group. A carrier solution of Na2TeO4, plus solid KI, hydrazine sulfate and Na2SO3, is added to the filtrate. The solution is then vacuum-filtered through a 0.45-??m pore-size filter disc. The filter, with the thin film of precipitate, is supported between two sheets of Mylar?? film for analysis. Good agreement is shown between data reported in this study and literature values reported by epithermal neutron-activation analysis and spectrofluorimetry. The method can be made quantitative by utilizing a secondary precipitation to assure complete recovery of the Se. The X-ray method offers fast turn-around time and a reasonably high production rate. ?? 1981.

An Integrated, Low Temperature Process to Capture and Sequester Carbon Dioxide from Industrial Emissions

NASA Astrophysics Data System (ADS)

Wendlandt, R. F.; Foremski, J. J.

2013-12-01

Laboratory experiments show that it is possible to integrate (1) the chemistry of serpentine dissolution, (2) capture of CO2 gas from the combustion of natural gas and coal-fired power plants using aqueous amine-based solvents, (3) long-term CO2 sequestration via solid phase carbonate precipitation, and (4) capture solvent regeneration with acid recycling in a single, continuous process. In our process, magnesium is released from serpentine at 300°C via heat treatment with ammonium sulfate salts or at temperatures as low as 50°C via reaction with sulfuric acid. We have also demonstrated that various solid carbonate phases can be precipitated directly from aqueous amine-based (NH3, MEA, DMEA) CO2 capture solvent solutions at room temperature. Direct precipitation from the capture solvent enables regenerating CO2 capture solvent without the need for heat and without the need to compress the CO2 off gas. We propose that known low-temperature electrochemical methods can be integrated with this process to regenerate the aqueous amine capture solvent and recycle acid for dissolution of magnesium-bearing mineral feedstocks and magnesium release. Although the direct precipitation of magnesite at ambient conditions remains elusive, experimental results demonstrate that at temperatures ranging from 20°C to 60°C, either nesquehonite Mg(HCO3)(OH)●2H2O or a double salt with the formula [NH4]2Mg(CO3)2●4H2O or an amorphous magnesium carbonate precipitate directly from the capture solvent. These phases are less desirable for CO2 sequestration than magnesite because they potentially remove constituents (water, ammonia) from the reaction system, reducing the overall efficiency of the sequestration process. Accordingly, the integrated process can be accomplished with minimal energy consumption and loss of CO2 capture and acid solvents, and a net generation of 1 to 4 moles of H2O/6 moles of CO2 sequestered (depending on the solid carbonate precipitate and amount of produced H2 and O2 gas reacted to produce heat and water). Features of the integrated process include the following: 1) the four separate processes have compatible chemistry, enabling design of an integrated, continuous process scheme for CO2 capture and sequestration; 2) all 4 stages of the process can be conducted at ambient or slightly elevated temperatures; 3) precipitating carbonate directly from the capture solvent eliminates the need for costly CO2 gas compression; and 4) recycling the acid used for serpentine dissolution and the solvent used for CO2 capture reduces feed stock costs.

PROCESS OF REMOVING PLUTONIUM VALUES FROM SOLUTION WITH GROUP IVB METAL PHOSPHO-SILICATE COMPOSITIONS

DOEpatents

Russell, E.R.; Adamson, A.W.; Schubert, J.; Boyd, G.E.

1957-10-29

A process for separating plutonium values from aqueous solutions which contain the plutonium in minute concentrations is described. These values can be removed from an aqueous solution by taking an aqueous solution containing a salt of zirconium, titanium, hafnium or thorium, adding an aqueous solution of silicate and phosphoric acid anions to the metal salt solution, and separating, washing and drying the precipitate which forms when the two solutions are mixed. The aqueous plutonium containing solution is then acidified and passed over the above described precipi-tate causing the plutonium values to be adsorbed by the precipitate.

Formation of metallic and metal hydrous oxide dispersions

NASA Technical Reports Server (NTRS)

Matijevic, E.; Sapieszko, R. S.

1979-01-01

The formation, via hydrothermally induced precipitation from homogeneous solution, of a variety of well-defined dispersions of metallic and hydrous metal in the conditions under which the particles are produced (e.g., pH and composition of the growth medium, aging temperature, rate of heating, or degree of agitation) can be readily discerned by following changes in the mass, composition, and morphology of the final solid phase. The generation of colloidal dispersions in the absence of gravity convection or sedimentation effects may result in the appearance of morphological modifications not previously observed in terrestrially formed hydrosols.

SEPARATION OF RADIOACTIVE COLUMBIUM TRACER

DOEpatents

Glendenin, L.E.; Gest, H.

1958-08-26

A process is presented for the recovery of radioactive columbium from solutions containing such columbium together with radioactive tellurium. The columbium and tellurium values are separated from such solutions by means of an inorganic oxide carrier precipitate, such as MnO/sub 2/. This oxide carrier precipitate and its associated columbium and telluriuan values are then dissolved in an aqueous acidic solution and nonradioactive tellurium, in an ionic form, is then introduced into such solution, for example in the form of H/sub 2/TeO/sub 3/. The tellurium present in the solution is then reduced to the elemental state and precipitates, and is then separated from the supernataat solution. A basic acetate precipitate is formed in the supernatant and carries the remaining columblum values therefrom. After separation, this basic ferric acetate precipitate is dissolved, and the ferric ions are removed by means of an organic solvent extraction process utilizing ether. The remaining solution contains carrier-free columbium as its only metal ion.

Effect of nitrogen on iron-manganese-based shape memory alloys

NASA Astrophysics Data System (ADS)

Ariapour, Azita

Shape memory effect is due to a reversible martensitic transformation. The major drawback in case of Fe-Mn-based shape memory alloys is their inferior shape memory effect compared to Ni-Ti and Cu-based shape memory alloys and their low strength and corrosion resistance compared to steel alloys. It is known that by increasing the alloy strength the shape memory effect can be improved. Nitrogen in solid solution can increase the strength of steels to a greater extent than other major alloying elements. However, its effect on shape memory effect of Fe-Mn-based alloys is ambiguous. In this work first we investigated the effect of nitrogen addition in solid solution on both shape memory effect (SME) and strength of a Fe-Mn-Cr-Ni-Si shape memory alloy (SMA). It was found that interstitial nitrogen suppressed the shape memory effect in these alloys. As an example addition of 0.24 wt % nitrogen in solid solution to the alloy system suppressed the SME by ˜80% and increased the strength by 20%. A reduction of martensitic phase formation was found to be the dominant factor in suppression of the SME. This was related, experimentally and theoretically to stacking fault energy of the alloy as well as the driving force and friction force during the transformation. The second approach was doping the alloy with both 0.36 wt% of nitrogen and 0.36 wt% of niobium. Niobium has great affinity for nitrogen and thus NbN dispersed particles can be produced in the alloy following hot rolling. Then particles prevent growth of the alloy and increase the strength of the alloy due to reduced grain size, and precipitation hardening. The improvement of SME in this alloy compared to the interstitial containing alloys was due to the large removal of the nitrogen from solid solution. In case of all the alloys studied in this work, the presence of nitrogen in solid solution improved the corrosion resistance of the alloy. This suggests that nitrogen can replace nickel in the alloy. One of the proposed applications for high strength Fe-Mn-based alloys is as tendon rods in prestressed concrete. The advantage of M alloys in this application is the possibility of producing curved structural prestressed concrete.

Phase behavior and reactive transport of partial melt in heterogeneous mantle model

NASA Astrophysics Data System (ADS)

Jordan, J.; Hesse, M. A.

2013-12-01

The reactive transport of partial melt is the key process that leads to the chemical and physical differentiation of terrestrial planets and smaller celestial bodies. The essential role of the lithological heterogeneities during partial melting of the mantle is increasingly recognized. How far can enriched melts propagate while interacting with the ambient mantle? Can the melt flow emanating from a fertile heterogeneity be localized through a reactive infiltration feedback in a model without exogenous factors or contrived initial conditions? A full understanding of the role of heterogeneities requires reactive melt transport models that account for the phase behavior of major elements. Previous work on reactive transport in the mantle focuses on trace element partitioning; we present the first nonlinear chromatographic analysis of reactive melt transport in systems with binary solid solution. Our analysis shows that reactive melt transport in systems with binary solid solution leads to the formation of two separate reaction fronts: a slow melting/freezing front along which enthalpy change is dominant and a fast dissolution/precipitation front along which compositional changes are dominated by an ion-exchange process over enthalpy change. An intermediate state forms between these two fronts with a bulk-rock composition and enthalpy that are not necessarily bounded by the bulk-rock composition and enthalpy of either the enriched heterogeneity or the depleted ambient mantle. The formation of this intermediate state makes it difficult to anticipate the porosity changes and hence the stability of reaction fronts. Therefore, we develop a graphical representation for the solution that allows identification of the intermediate state by inspection, for all possible bulk-rock compositions and enthalpies of the heterogeneity and the ambient mantle. We apply the analysis to the partial melting of an enriched heterogeneity. This leads to the formation of moving precipitation front that followes a stationary melting front which creates low porosity intermediate states. Therefore, localization of the melt flow is not observed because the precipitation front is stable and the melting front is always stationary under these conditions. This analysis illustrates the counterintuitive behavior that can arise when the phase behavior is taken into account and is a first step to understanding reactive melt transport and the reactive constraints on channelization in partial melts. ¬¬

Precipitation method for barium metaborate (BaB2O4) synthesis from borax solution

NASA Astrophysics Data System (ADS)

Akşener, Eymen; Figen, Aysel Kantürk; Pişkin, Sabriye

2013-12-01

In this study, barium metaborate (BaB2O4, BMB) synthesis from the borax solution was carried out. BMB currently is used in production of ceramic glazes, luminophors, oxide cathodes as well as additives to pigments for aqueous emulsion paints and also β-BaB2O4 single crystals are the best candidate for fabrication of solid-state UV lasers operating at a wavelength of 200 nm due to excellent nonlinear optical properties. In the present study, synthesis was carried out from the borax solution (Na2B4O7ṡ10H2O, BDH) and barium chloride (BaCI2ṡ2H2O, Ba) in the glass-batch reactor with stirring. The effect of, times (5-15 min), molar ratio [stoich.ration (1.0:2.0), 1.25:2.0, 1.5:2.0, 2.5:2:0, 3.0:2.0, 3.5:2.0,4.0:2.0, 5.0:2.0] and also crystallization time (2-6 hour) on the BMB yield (%) was investigated at 80 °C reaction temperature. It is found that, BMB precipitation synthesis with 90 % yield can be performed from 0.50 molar ration (BDH:Ba), under 80 °C, 15 minute, and 6 hours crystallization time. The structural properties of BMB powders were characterized by using XRD, FT-IR and DTA-TG instrumental analysis technique.

Lithium Carbonate Recovery from Cathode Scrap of Spent Lithium-Ion Battery: A Closed-Loop Process.

PubMed

Gao, Wenfang; Zhang, Xihua; Zheng, Xiaohong; Lin, Xiao; Cao, Hongbin; Zhang, Yi; Sun, Zhi

2017-02-07

A closed-loop process to recover lithium carbonate from cathode scrap of lithium-ion battery (LIB) is developed. Lithium could be selectively leached into solution using formic acid while aluminum remained as the metallic form, and most of the other metals from the cathode scrap could be precipitated out. This phenomenon clearly demonstrates that formic acid can be used for lithium recovery from cathode scrap, as both leaching and separation reagent. By investigating the effects of different parameters including temperature, formic acid concentration, H 2 O 2 amount, and solid to liquid ratio, the leaching rate of Li can reach 99.93% with minor Al loss into the solution. Subsequently, the leaching kinetics was evaluated and the controlling step as well as the apparent activation energy could be determined. After further separation of the remaining Ni, Co, and Mn from the leachate, Li 2 CO 3 with the purity of 99.90% could be obtained. The final solution after lithium carbonate extraction can be further processed for sodium formate preparation, and Ni, Co, and Mn precipitates are ready for precursor preparation for cathode materials. As a result, the global recovery rates of Al, Li, Ni, Co, and Mn in this process were found to be 95.46%, 98.22%, 99.96%, 99.96%, and 99.95% respectively, achieving effective resources recycling from cathode scrap of spent LIB.

DNAPL remediation with in situ chemical oxidation using potassium permanganate - Part I. Mineralogy of Mn oxide and its dissolution in organic acids

NASA Astrophysics Data System (ADS)

Li, X. David; Schwartz, Franklin W.

2004-01-01

Previous studies on in situ chemical oxidation of trichloroethylene (TCE) with potassium permanganate indicated that the solid reaction product, Mn oxide, could reduce the permeability of the porous medium and impact the success of dense non-aqueous phase liquid (DNAPL) removal. In order to address the issue of permeability reduction caused by precipitation, this study investigated the mineralogy of Mn oxides and the possibilities of removing the solid precipitates by dissolution. The solid reaction product from the oxidation of TCE by permanganate is semi-amorphous potassium-rich birnessite, which has a layered mineral structure with an interlayer spacing of 7.3 Å. The chemical formula is K 0.854Mn 1.786O 4·1.55H 2O. It has a relatively small specific surface area at 23.6±0.82 m 2/g. Its point of zero charge (pzc) was measured as 3.7±0.4. This birnessite is a relatively active species and could participate in various reactions with existing organic and inorganic matter. The dissolution kinetics of Mn oxide was evaluated in batch experiments using solutions of citric acid, oxalic acid, and ethylenediaminetetraacetic acid (EDTA). Initial dissolution rates were determined to be 0.126 mM/m 2/h for citric acid, 1.35 mM/m 2/h for oxalic acid, and 5.176 mM/m 2/h for EDTA. These rates compare with 0.0025 mM/m 2/h for nitric acid at pH=2. Organic acids dissolve Mn oxide quickly. Reaction rates increase with acid concentration, as tested with citric acid. The dissolution mechanism likely involves proton and ligand-promoted dissolution and reductive dissolution. Citric and oxalic acid can induce ligand-promoted dissolution, while EDTA can induce ligand-promoted and reductive dissolutions. At low pH, proton-promoted dissolution seems to occur with all the acids tested, but this process is not dominant. Reductive dissolution appears to be the most effective process in dissolving the solid, followed by ligand-promoted dissolution. These experiments indicate the significant potential in using these organic acids to remove precipitates formed during the oxidation reaction.

Structural Characterization of Poorly-Crystalline Scorodite, Iron (III)-arsenate Co-precipitates and Uranium Millneutralized Raffinate Solids using X-ray Absorption Fine Structure Spectroscopy

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

Chen, N.; Jiang, D; Cutler, J

X-ray absorption fine structure (XAFS) is used to characterize the mineralogy of the iron(III)-arsenate(V) precipitates produced during the raffinate (aqueous effluent) neutralization process at the McClean Lake uranium mill in northern Saskatchewan, Canada. To facilitate the structural characterization of the precipitated solids derived from the neutralized raffinate, a set of reference compounds were synthesized and analyzed. The reference compounds include crystalline scorodite, poorly-crystalline scorodite, iron(III)-arsenate co-precipitates obtained under different pH conditions, and arsenate-adsorbed on goethite. The poorly-crystalline scorodite (prepared at pH 4 with Fe/As = 1) has similar As local structure as that of crystalline scorodite. Both As and Femore » K-edge XAFS of poorly-crystalline scorodite yield consistent results on As-Fe (or Fe-As) shell. From As K-edge analysis the As-Fe shell has an inter-atomic distance of 3.33 {+-} 0.02 A and coordination number of 3.2; while from Fe K-edge analysis the Fe-As distance and coordination number are 3.31 {+-} 0.02 A and 3.8, respectively. These are in contrast with the typical arsenate adsorption on bidentate binuclear sites on goethite surfaces, where the As-Fe distance is 3.26 {+-} 0.03 A and coordination number is close to 2. A similar local structure identified in the poorly-crystalline scorodite is also found in co-precipitation solids (Fe(III)/As(V) = 3) when precipitated at the same pH (pH = 4): As-Fe distance 3.30 {+-} 0.03 A and coordination number 3.9; while at pH = 8 the co-precipitate has As-Fe distance of 3.27 {+-} 0.03 A and coordination number about 2, resembling more closely the adsorption case. The As local structure in the two neutralized raffinate solid series (precipitated at pH values up to 7) closely resembles that in the poorly-crystalline scorodite. All of the raffinate solids have the same As-Fe inter-atomic distance as that in the poorly-crystalline scorodite, and a systematic decrease in the As-Fe coordination is observed when pH is progressively increased; the basic poorly-crystalline scorodite structural feature remains in the raffinate solid up to pH 7.« less

Structural characterization of poorly-crystalline scorodite, iron(III)-arsenate co-precipitates and uranium mill neutralized raffinate solids using X-ray absorption fine structure spectroscopy

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

Chen, N; Jiang, D T; Cutler, J

X-ray absorption fine structure (XAFS) is used to characterize the mineralogy of the iron(III)-arsenate(V) precipitates produced during the raffinate (aqueous effluent) neutralization process at the McClean Lake uranium mill in northern Saskatchewan, Canada. To facilitate the structural characterization of the precipitated solids derived from the neutralized raffinate, a set of reference compounds were synthesized and analyzed. The reference compounds include crystalline scorodite, poorly-crystalline scorodite, iron(III)-arsenate co-precipitates obtained under different pH conditions, and arsenate-adsorbed on goethite. The poorly-crystalline scorodite (prepared at pH 4 with Fe/As = 1) has similar As local structure as that of crystalline scorodite. Both As and Femore » K-edge XAFS of poorly-crystalline scorodite yield consistent results on As-Fe (or Fe-As) shell. From As K-edge analysis the As-Fe shell has an inter-atomic distance of 3.33 ± 0.02 Å and coordination number of 3.2; while from Fe K-edge analysis the Fe-As distance and coordination number are 3.31 ± 0.02 Å and 3.8, respectively. These are in contrast with the typical arsenate adsorption on bidentate binuclear sites on goethite surfaces, where the As-Fe distance is 3.26 ± 0.03 Å and coordination number is close to 2. A similar local structure identified in the poorly-crystalline scorodite is also found in co-precipitation solids (Fe(III)/As(V) = 3) when precipitated at the same pH (pH = 4): As-Fe distance 3.30 ± 0.03 Å and coordination number 3.9; while at pH = 8 the co-precipitate has As-Fe distance of 3.27 ± 0.03 Å and coordination number about 2, resembling more closely the adsorption case. The As local structure in the two neutralized raffinate solid series (precipitated at pH values up to 7) closely resembles that in the poorly-crystalline scorodite. All of the raffinate solids have the same As-Fe inter-atomic distance as that in the poorly-crystalline scorodite, and a systematic decrease in the As-Fe coordination is observed when pH is progressively increased; the basic poorly-crystalline scorodite structural feature remains in the raffinate solid up to pH 7.« less

Mechanisms of scale formation and carbon dioxide partial pressure influence. Part II. Application in the study of mineral waters of reference.

PubMed

Gal, Jean-Yves; Fovet, Yannick; Gache, Nathalie

2002-02-01

In the first part, we have designed a new model of evolution for the calco-carbonic system which includes the hydrated forms of CaCO3: CaCO3 amorphous, CaCO3 x 6H2O (ikaite) and CaCO3 x H2O (monohydrate) (J. Eur. Hydr. 30 (1999) 47). According to this model, it is the precipitation of one or other of these hydrated forms which could be responsible for the breakdown of the metastable state. After this first step, the precipitates evolve to dehydrated solid forms. Through the elaboration of computer programs in which the CaCO3(0) (aq) ion pair formation was considered, this model was compared to experimental data obtained by the critical pH method applied to synthetic solutions. In the present article, the same method was applied for four French mineral waters, at 25 degrees C under study. Three samples formed a precipitation during the sodium hydroxide addition. For these three cases, this precipitation began for the CaCO3 H2O saturation. The added volume of sodium hydroxide was more than what was required for neutralizing free CO2 initially in solution. These results indicate that during a spontaneous scaling phenomenon, the pH rises at the same time by loss of the initial free CO2 and of the one produced by the hydrogen carbonate ions decomposition. Then we calculated, at various temperatures for the three studied scaling waters: CO2 partial pressures and loss of total carbon corresponding to the solubility products of CaCO3 hydrated forms. The results show that the partial pressure monitoring of the carbon dioxide is important in managing the behavior of scaling waters.

Homogeneous and Heterogeneous (Fex, Cr1-x)(OH)3 Precipitation: Implications for Cr Sequestration

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

Dai, Chong; Zuo, Xiaobing; Cao, B

2016-02-16

The formation of (Fe, Cr)(OH)3 nanoparticles determines the fate of aqueous Cr in many aquatic environments. Using small angle X-ray scattering, precipitation rates of (Fe, Cr)(OH)3 nanoparticles in solution and on quartz were quantified from 0.1 mM Fe(III) solutions containing 0 – 0.25 mM Cr(III) at pH = 3.7 ± 0.2. Concentration ratio of aqueous Cr(III)/Fe(III) controlled the chemical composition (x) of (Fex, Cr1-x)(OH)3 precipitates, solutions’ supersaturation with respect to precipitates, and the surface charge of quartz. Therefore, aqueous Cr(III)/Fe(III) ratio affected homogeneous (in solution) and heterogeneous (on quartz) precipitation rates of (Fex, Cr1-x)(OH)3 through different mechanisms. The sequestration mechanismsmore » of Cr(III) in precipitates were also investigated. In solutions with high aqueous Cr(III)/Fe(III) ratios, surface enrichment of Cr(III) on the precipitates occurred, resulting in slower particle growth in solution. From solutions with 0 – 0.1 mM Cr(III), the particles on quartz grew from 2 to 4 nm within 1 h. Interestingly, from solution with 0.25 mM Cr(III), particles of two distinct sizes (2 and 6 nm) formed on quartz, and their sizes remained unchanged throughout the reaction. Our study provided new insights on homogeneous and heterogeneous precipitation of (Fex, Cr1-x)(OH)3 nanoparticles, which can help determine the fate of Cr in aquatic environments.« less

Preventing Precipitation in the ISS Urine Processor

NASA Technical Reports Server (NTRS)

Muirhead, Dean; Carter, Layne; Williamson, Jill; Chambers, Antja

2017-01-01

The ISS Urine Processor Assembly (UPA) was initially designed to achieve 85% recovery of water from pretreated urine on ISS. Pretreated urine is comprised of crew urine treated with flush water, an oxidant (chromium trioxide), and an inorganic acid (sulfuric acid) to control microbial growth and inhibit precipitation. Unfortunately, initial operation of the UPA on ISS resulted in the precipitation of calcium sulfate at 85% recovery. This occurred because the calcium concentration in the crew urine was elevated in microgravity due to bone loss. The higher calcium concentration precipitated with sulfate from the pretreatment acid, resulting in a failure of the UPA due to the accumulation of solids in the Distillation Assembly. Since this failure, the UPA has been limited to a reduced recovery of water from urine to prevent calcium sulfate from reaching the solubility limit. NASA personnel have worked to identify a solution that would allow the UPA to return to a nominal recovery rate of 85%. This effort has culminated with the development of a pretreatment based on phosphoric acid instead of sulfuric acid. By eliminating the sulfate associated with the pretreatment, the brine can be concentrated to a much higher concentration before calcium sulfate reach the solubility limit. This paper summarizes the development of this pretreatment and the testing performed to verify its implementation on ISS.

Phase transformations in a Cu−Cr alloy induced by high pressure torsion

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

Korneva, Anna, E-mail: a.korniewa@imim.pl; Straumal, Boris; Institut für Nanotechnologie, Karlsruher Institut für Technologie, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen

2016-04-15

Phase transformations induced by high pressure torsion (HPT) at room temperature in two samples of the Cu-0.86 at.% Cr alloy, pre-annealed at 550 °C and 1000 °C, were studied in order to obtain two different initial states for the HPT procedure. Observation of microstructure of the samples before HPT revealed that the sample annealed at 550 °C contained two types of Cr precipitates in the Cu matrix: large particles (size about 500 nm) and small ones (size about 70 nm). The sample annealed at 1000 °C showed only a little fraction of Cr precipitates (size about 2 μm). The subsequentmore » HPT process resulted in the partial dissolution of Cr precipitates in the first sample and dissolution of Cr precipitates with simultaneous decomposition of the supersaturated solid solution in another. However, the resulting microstructure of the samples after HPT was very similar from the standpoint of grain size, phase composition, texture analysis and hardness measurements. - Highlights: • Cu−Cr alloy with two different initial states was deformed by HPT. • Phase transformations in the deformed materials were studied. • SEM, TEM and X-ray diffraction techniques were used for microstructure analysis. • HPT leads to formation the same microstructure independent of the initial state.« less

Effects of drug-carrier interactions on drug dissolution from binary and ternary matrices

NASA Astrophysics Data System (ADS)

Iqbal, Zafar

For nearly five decades, pharmaceutical researchers have studied solid solutions of drugs in polymers as a potential means to enhance the dissolution of drugs with poor aqueous solubility. This has become of greater importance in recent years because most new potential drug compounds (new chemical entities) exhibit poor water solubility and present great challenges to scientists who must design dosage forms from which the drugs are bioavailable. During the formulation of a solid solution, the drug undergoes physical but not chemical alterations that increase its chemical potential in the formulation relative to that of the pure drug in its stable form. This increased chemical potential is responsible for enhanced dissolution as well as physical instabilities, such as amorphous to crystalline conversions and precipitation within the solid state. The chemical potential is derived from the Gibbs free energy, so it is reasonable to explain the behavior of solid solution systems in terms of thermodynamics. Solid solutions and dispersions have been extensively studied by pharmaceutical scientists, both with regard to manufacturing aspects and the proposal of various models in attempts to explain the physical bases for how these systems work. Recently, Dave and Bellantone proposed a model based on the thermodynamic changes resulting from the formulation of binary solid solutions of a drug in the polymer PVP. Their model introduced a modification of the F-H theory, which was used to quantify the drug-polymer interaction energies and calculate the entropy of mixing of the drug and polymer. In this work, the model of Dave and Bellantone was extended to include three-component systems, consisting of one drug mixed in a carrier matrix consisting of mixture of two polymers or a polymer and a surfactant. For this research, solid solutions were formed using various drug weight fractions in the formulations. The study focused on the following points: (1) Prepare solid solution formulations and perform appropriate physical characterizations. (2) Characterize the increase in drug dissolution rates resulting from solid solution formulations. (3) Relate the initial dissolution rates to the drug solubility. (4) Explain the solubility enhancement from solid solution dosage in terms of the drug polymer interactions using the extended thermodynamic model. Two poorly water soluble drugs, levonorgestrel (LEVO) and ethinyl estradiol (EE) were formulated in seven solid solution preparations comprised of four carrier systems. Materials used as carriers included various combinations of the polymers PVP K-30, Copovidone (COP), Poloxamer 182, and the surfactant TweenRTM 20. Additionally, ibuprofen (IBU) was used in three formulations consisting of various combinations of PVP K-30, Copovidone and TweenRTM 20. Formulations with various drug weight fractions (0.5%--30%) were prepared using the solvent evaporation technique. Each formulation was tested for dissolution using intrinsic dissolution apparatus (USP). The solid solutions were compressed into tablets into the sample die that maintained a constant surface area during the dissolution process. DSC, XRD and NIRS scans identified that the crystalline peaks of the drug disappeared with the addition of the polymer for all ratios of EE, indicating the formation of solid solutions (to within the limits of detection of the equipment). This was also observed for the LEVO dispersions up to 10% drug loading. At higher drug loading, solutions were formed but some small degree crystallinity was also present. For each experiment, the initial dissolution rates were obtained from the slope of the mass dissolved vs. time plots taken at early times, and volume normalized initial dissolution rates RV were calculated by dividing the initial dissolution rate by the volume fraction of the drug in the formulation. Comparison of the RV values for the various formulations with a reference RV (typically that of the pure drug or of the formulation with the highest polymer content) allowed calculation of relative volume normalized dissolution rates (RNV). The various RNV were used in the thermodynamic model for data analyses and to determine the interactions between the drug and carrier molecules. It was generally seen that RNV increased with decreased drug fraction, and was adequately modeled by the equations derived from the extended thermodynamic model. It was concluded that the model proposed for the binary and ternary systems successfully represented the mechanism of drug-polymer interaction and the energy changes taken place within the dispersion systems. The dissolution data analysis and subsequent understanding of physical modifications in the dispersion systems characterized by XRD, NIRS and DSC further substantiated the findings. The understanding of the fundamental physical might help scientists to predict the effects of mixing various drugs and polymers, and the effects of varying ratios.

The wash-out of emissions from the atmosphere by precipitation

Treesearch

Ladislav Hanu& #154; ka; Eva Nov& #225; kov& #225; ; Nov& #225; kov& #225; Eva NO-VALUE

1976-01-01

We investigated the mechanism and dynamics of solid particles, emissions, and the concentrations of sulphur dioxide as integral components of the contamination of atmosphere. The only way of decontamination is the wash-out by precipitation (solid - snow, liquid - rain). We started from the items of information acquired during the studies of snow acidity in mountain...

Effect of processing route for preparation of mullite from kaolinite and alumina

NASA Astrophysics Data System (ADS)

Behera, Pallavi Suhasinee; Bhattacharyya, Sunipa

2018-05-01

In current work, two different types of mullite ceramic powder were prepared using kaolinite and alumina by solid state and chemical precipitation route. The phases, bond types and microstructural evolution of the mullite powders were investigated by X-ray diffraction, infrared analysis, and field emission scanning electron microscopy to study the mullitisation behavior. The solid state method evident a pure mullite phase formation at 1550 °C. In case of chemical precipitation route small amount of alumina peak was noticed along with major phase of mullite which was also clearly apprehended from FESEM micrographs and IR spectra. Densification was more for the samples prepared by solid state process which may be correlated to the delayed mullitization process in chemical precipitation route.

Strengthening Mechanisms and Their Relative Contributions to the Yield Strength of Microalloyed Steels

NASA Astrophysics Data System (ADS)

Lu, Junfang; Omotoso, Oladipo; Wiskel, J. Barry; Ivey, Douglas G.; Henein, Hani

2012-09-01

Microalloyed steels are used widely in oil and gas pipelines. They are a class of high-strength, low-carbon steels that contain small additions (in amounts less than 0.1 wt pct) of Nb, Ti, and/or V. The steels may contain other alloying elements, such as Mo, in amounts exceeding 0.1 wt pct. Precipitation in these steels can be controlled through thermomechanical-controlled processing, leading to precipitates with sizes that range from several microns to a few nanometers. Microalloyed steels have good strength, good toughness, and excellent weldability, which are attributed in part to the presence of the nanosized carbide and carbonitride precipitates. Because of their fine sizes, wide particle size distribution, and low volume fractions, conventional microscopic methods are not satisfactory for quantifying these precipitates. Matrix dissolution is a promising alternative to extract the precipitates for quantification. Relatively large volumes of material can be analyzed so that statistically significant quantities of precipitates of different sizes are collected. In this article, the microstructure features of a series of microalloyed steels (X70, X80, and X100) as well as a Grade 100 steel are characterized using optical microscopy (OM) and scanning electron microscopy (SEM). A chemical dissolution technique is used to extract the precipitates from the steels. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) are combined to analyze the chemical composition of these precipitates. Rietveld refinement of the XRD patterns is used to quantify fully the relative amounts of these precipitates. The size distribution of the nanosized precipitates is quantified using dark-field imaging (DF) in the TEM. The effects of microalloying content, finish rolling temperature (FRT), and coiling temperature (CT)/interrupted cooling temperature (ICT) on the grain size and the amount of nanoprecipitation are discussed. Individual strengthening contributions from grain size effects, solid-solution strengthening, and precipitation strengthening are quantified to understand fully the strengthening mechanisms for these steels.

Inhibition of heparin precipitation, bacterial growth, and fungal growth with a combined isopropanol-ethanol locking solution for vascular access devices.

PubMed

Restrepo, Daniel; Laconi, Nicholas S; Alcantar, Norma A; West, Leigh A; Buttice, Audrey L; Patel, Saumil; Kayton, Mark L

2015-03-01

Clinical reports of ethanol-lock use for the prevention of catheter-related bloodstream infections have been marked by the occurrence of serious catheter occlusions, particularly among children with mediports. We hypothesized that precipitate forms when ethanol mixes with heparin at the concentrations relevant for vascular access devices, but that the use of a combination of two alcohols, ethanol and isopropanol, would diminish heparin-related precipitation, while retaining anti-bacterial and anti-fungal effects. Heparin (0-100units/mL) was incubated in ethanol-water solutions (30%-70% vol/vol) or in an aqueous solution containing equal parts (35% and 35% vol/vol) of isopropanol and ethanol. Precipitation at temperatures from 4 to 40°C was measured in nephelometric turbidity units using a benchtop turbidimeter. Growth of Escherichia coli, Staphylococcus aureus, and Candida albicans colonies were measured following exposure to solutions of ethanol or isopropanol-ethanol. Groupwise comparisons were performed using analysis of variance with Bonferroni-corrected, post-hoc T-testing. Seventy percent ethanol and heparin exhibit dose-dependent precipitation that is pronounced and significant at the concentrations typically used in mediports (p<0.05). Precipitate is significantly reduced by use of a combined 35% isopropanol-35% ethanol solution rather than 70% ethanol (p<0.05), while maintaining the solution's anti-bacterial and anti-fungal properties. On the other hand, although ethanol solutions under 70% form less precipitate with heparin, such concentrations are also less effective at bacterial colony inhibition than solutions of either 70% ethanol or 35% isopropanol-35% ethanol (p<0.05). A combined 35% isopropanol-35% ethanol locking solution inhibits bacterial and fungal growth similarly to 70% ethanol, but results in less precipitate than 70% ethanol when exposed to heparin. Further study of a combined isopropanol-ethanol locking solution for the prevention of catheter-related bloodstream infections should focus on the determination as to whether such a locking solution may reduce the rate of precipitation-related catheter occlusion, and whether it may be administered with low systemic toxicity. Copyright © 2015 Elsevier Inc. All rights reserved.

Dependence of particle concentration effect on pH and redox for arsenic removal by FeS-coated sand under anoxic conditions.

PubMed

Han, Young-Soo; Demond, Avery H; Gallegos, Tanya J; Hayes, Kim F

2015-09-01

FeS has been recognized as a good scavenger for arsenic under anoxic conditions. To create a suitable adsorbent for flow-through reactors such as permeable reactive barriers, it has been suggested that this material may be coated onto sand. However, previous work on FeS-coated sand has focused on batch reactors, while flow-through reactors usually have higher solid-solution ratios. To ascertain whether differences in the solid-solution ratio (SSR) are important in this system, batch sorption experiments were conducted as a function of pH using As(III) and FeS-coated sands at various solid-solution ratios. The results showed little variation in the distribution coefficient with SSR at pH 7 and 9. However, at pH 5, the results showed lower values of the distribution coefficient at lower SSRs, the reverse of typically reported SSR effects. Measured pe values showed a dependence on SSR, which, when coupled with chemical modeling of the Fe-As-S-H2O system, suggested a change in the removal mechanism with SSR, from adsorption to a reduced Fe(II) oxyhydroxide phase (represented by Fe2(OH)5) to precipitation as As2S3 or AsS. On the other hand, at pH 7 and 9, arsenite adsorption is the most probable removal mechanism regardless of the pe. Thus, this study identified variations in pH and redox conditions, and the removal mechanisms that these parameters govern, as the reason for the apparent SSR effect. Copyright © 2014 Elsevier Ltd. All rights reserved.

GADOLINIUM OXALATE SOLUBILITY MEASUREMENTS IN NITRIC ACID SOLUTIONS

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

Pierce, R. A.

2012-03-12

HB-Line will begin processing Pu solutions during FY2012 that will involve the recovery of Pu using oxalate precipitation and filtration. After the precipitation and filtration processes, the filtrate solution will be transferred from HB-Line to H-Canyon. The presence of excess oxalate and unfiltered Pu oxalate solids in these solutions create a criticality safety issue if they are sent to H-Canyon without controls in H-Canyon. One approach involves H-Canyon receiving the filtrate solution into a tank that is poisoned with soluble gadolinium (Gd). Decomposition of the oxalate will occur within a subsequent H-Canyon vessel. The receipt of excess oxalate into themore » H-Canyon receipt tanks has the potential to precipitate a portion of the Gd poison in the receipt tanks. Because the amount of Gd in solution determines the maximum amount of Pu solids that H-Canyon can receive, H-Canyon Engineering requested that SRNL determine the solubility of Gd in aqueous solutions of 4-10 M nitric acid (HNO{sub 3}), 4-12 g/L Gd, and 0.15-0.25 M oxalic acid (H{sub 2}C{sub 2}O{sub 4}) at 25 °C. The target soluble Gd concentration is 6 g/L. The data indicate that the target can be achieved above 6 M HNO{sub 3} and below 0.25 M H{sub 2}C{sub 2}O{sub 4}. At 25 °C, for 6 M HNO{sub 3}, 11 g/L and 7 g/L Gd are soluble in 0.15 M and 0.25 M H{sub 2}C{sub 2}O{sub 4}, respectively. In 4 M HNO{sub 3}, the Gd solubility drops significantly to 2.5 g/L and 0.8 g/L in 0.15 M and 0.25 M H{sub 2}C{sub 2}O{sub 4}, respectively. The solubility of Gd at 8-10 M HNO{sub 3} exceeds the solubility at 6 M HNO{sub 3}. The data for 4 M HNO{sub 3} showed good agreement with data in the literature. To achieve a target of 6 g/L soluble Gd in solution in the presence of 0.15-0.25 M oxalate, the HNO{sub 3} concentration must be maintained at or above 6 M HNO{sub 3}. The solubility of Gd in 4 M HNO{sub 3} with 0.15 M oxalate at 10 °C is about 1.5 g/L. For 6 M HNO{sub 3} with 0.15 M oxalate, the solubility of Gd at 10 °C is about 10 g/L. Gadolinium nitrate is very soluble in HNO{sub 3}. The solubility of Gd is linear as a function of HNO{sub 3} from 343 g/L Gd in 2.88 M HNO{sub 3} to 149 g/L in 8.16 M HNO{sub 3}. Below 2.88 M HNO{sub 3}, the solubility of Gd approaches a limit of about 360 g/L. However, there are no data available below 1.40 M HNO{sub 3}, which has a Gd solubility of 353 g/L.« less

Soluble 1:1 complexes and insoluble 3:2 complexes - Understanding the phase-solubility diagram of hydrocortisone and γ-cyclodextrin.

PubMed

Schönbeck, Christian; Madsen, Tobias L; Peters, Günther H; Holm, René; Loftsson, Thorsteinn

2017-10-15

The molecular mechanisms underlying the drug-solubilizing properties of γ-cyclodextrin were explored using hydrocortisone as a model drug. The B S -type phase-solubility diagram of hydrocortisone with γ-cyclodextrin was thoroughly characterized by measuring the concentrations of hydrocortisone and γ-cyclodextrin in solution and the solid phase. The drug-solubilizer interaction was also studied by isothermal titration calorimetry from which a precise value of the 1:1 binding constant (K 11 =4.01mM -1 at 20°C) was obtained. The formation of water-soluble 1:1 complexes is responsible for the initial increase in hydrocortisone solubility while the precipitation of entities with a 3:2 ratio of γ-cyclodextrin:hydrocortisone is responsible for the plateau and the ensuing strong decrease in solubility once all solid hydrocortisone is used up. The complete phase-solubility diagram is well accounted for by a model employing the 1:1 binding constant and the solubility product of the precipitating 3:2 entity (K 32 S =5.51 mM 5 ). For such systems, a small surplus of γ-cyclodextrin above the optimum concentration may result in a significant decrease in drug solubility, and the implications for drug formulations are briefly discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Identification, size classification and evolution of Laves phase precipitates in high chromium, fully ferritic steels.

PubMed

Lopez Barrilao, Jennifer; Kuhn, Bernd; Wessel, Egbert

2017-10-01

To fulfil the new challenges of the German "Energiewende" more efficient, sustainable, flexible and cost-effective energy technologies are strongly needed. For a reduction of consumed primary resources higher efficiency steam cycles with increased operating parameters, pressure and temperature, are mandatory. Therefore advanced materials are needed. The present study focuses on a new concept of high chromium, fully ferritic steels. These steels, originally designed for solid oxide fuel cell applications, provide favourable steam oxidation resistance, creep and thermomechanical fatigue behaviour in comparison to conventional ferritic-martensitic steels. The strength of this type of steel is achieved by a combination of solid-solution hardening and precipitation strengthening by intermetallic Laves phase particles. The effect of alloy composition on particle composition was measured by energy dispersive X-ray spectroscopy and partly verified by thermodynamic modelling results. Generally the Laves phase particles demonstrated high thermodynamic stability during long-term annealing up to 40,000h at 600°C. Variations in chemical alloy composition influence Laves phase particle formation and consequently lead to significant changes in creep behaviour. For this reason particle size distribution evolution was analysed in detail and associated with the creep performance of several trial alloys. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Curious Case of the OZ439 Mesylate Salt: An Amphiphilic Antimalarial Drug with Diverse Solution and Solid State Structures.

PubMed

Clulow, Andrew J; Salim, Malinda; Hawley, Adrian; Gilbert, Elliot P; Boyd, Ben J

2018-05-07

Efforts to develop orally administered drugs tend to place an exceptional focus on aqueous solubility as this is an essential criterion for their absorption in the gastrointestinal tract. In this work we examine the solid state behavior and solubility of OZ439, a promising single-dose cure for malaria being developed as the highly water-soluble mesylate salt. The aqueous phase behavior of the OZ439 mesylate salt was determined using a combination of small angle neutron and X-ray scattering (SANS and SAXS, respectively). It was found that this salt has low solubility at low concentrations with the drug largely precipitated in free base aggregates. However, with increasing concentration these crystalline aggregates were observed to dissociate into cationic micelles and lamellar phases, effectively increasing the dissolved drug concentration. It was also found that the dissolved OZ439 spontaneously precipitated in the presence of biologically relevant anions, which we attribute to the high lattice energies of most of the salt forms of the drug. These findings show that aqueous solubility is not always what it seems in the context of amphiphilic drug molecules and highlights that its use as the principal metric in selecting drug candidates for development can be perilous.

Anisotropic layered Bi2Te3-In2Te3 composites: control of interface density for tuning of thermoelectric properties

PubMed Central

Liu, Dongmei; Li, Xinzhong; Borlido, Pedro Miguel de Castro; Botti, Silvana; Schmechel, Roland; Rettenmayr, Markus

2017-01-01

Layered (Bi1−xInx)2Te3-In2Te3 (x = 0.075) composites of pronounced anisotropy in structure and thermoelectric properties were produced by zone melting and subsequent coherent precipitation of In2Te3 from a (Bi1−xInx)2Te3 (x > 0.075) matrix. Employing solid state phase transformation, the Bi2Te3/In2Te3 interface density was tuned by modifying the driving force for In2Te3 precipitation. The structure-property relationship in this strongly anisotropic material is characterized thoroughly and systematically for the first time. Unexpectedly, with increasing Bi2Te3/In2Te3 interface density, an increase in electrical conductivity and a decrease in the absolute Seebeck coefficient were found. This is likely to be due to electron accumulation layers at the Bi2Te3/In2Te3 interfaces and the interplay of bipolar transport in Bi2Te3. Significantly improved thermoelectric properties of Bi2Te3-In2Te3 composites as compared to the single phase (Bi1−xInx)2Te3 solid solution are obtained. PMID:28272541

Retardation of iron-cyanide complexes in the soil of a former manufactured gas plant site.

PubMed

Sut, Magdalena; Repmann, Frank; Raab, Thomas

2015-01-01

The soil in the vicinities of former Manufactured Gas Plant (MGP) sites is commonly contaminated with iron-cyanide complexes (ferric ferrocyanide). The phenomenon of cyanide mobility in soil, according to the literature, is mainly governed by the dissolution and precipitation of ferric ferrocyanide, which is only slightly soluble (<1 mg L(-1)) under acidic conditions. In this paper, retention properties of the sandy loam soil and the potential vertical movement of the solid iron-cyanide complexes, co-existing with the dissolution, sorption and precipitation reactions were investigated. Preliminary research conducted on a former MGP site implied colloidal transport of ferric ferricyanide from the initial deposition in the wastes layer towards the sandy loam material (secondary accumulation), which possibly retarded the mobility of cyanide (CN). A series of batch and column experiments were applied in order to investigate the retardation of iron-cyanide complexes by the sandy loam soil. Batch experiments revealed that in circumneutral pH conditions sandy loam material decreases the potassium ferro- and ferricyanide concentration. In column experiments a minor reduction in CN concentration was observed prior to addition of iron sulfide (FeS) layer, which induced the formation of the Prussian blue colloids in circumneutral pH conditions. Precipitated solid iron-cyanide complexes were mechanically filtered by the coherent structure of the investigated soil. Additionally, the reduction of the CN concentration of the percolation solutions by the sandy loam soil was presumably induced due to the formation of potassium manganese iron-cyanide (K2Mn[Fe(CN)6]).

Sol-gel preparation of lead magnesium niobate (PMN) powders and thin films

DOEpatents

Boyle, T.J.

1999-01-12

A method of preparing a lead magnesium niobium oxide (PMN), Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}, precursor solution by a solvent method wherein a liquid solution of a lead-complex PMN precursor is combined with a liquid solution of a niobium-complex PMN precursor, the combined lead- and niobium-complex liquid solutions are reacted with a magnesium-alkyl solution, forming a PMN precursor solution and a lead-based precipitate, and the precipitate is separated from the reacted liquid PMN precursor solution to form a precipitate-free PMN precursor solution. This precursor solution can be processed to form both ferroelectric powders and thin films. 3 figs.

Sol-Gel Preparation Of Lead Magnesium Ni Obate (Pmn) Powdersand Thin Films

DOEpatents

Boyle, Timothy J.

1999-01-12

A method of preparing a lead magnesium niobium oxide (PMN), Pb(Mg.sub.1/3 Nb.sub.2/3)O.sub.3, precursor solution by a solvent method wherein a liquid solution of a lead-complex PMN precursor is combined with a liquid solution of a niobium-complex PMN precursor, the combined lead- and niobium-complex liquid solutions are reacted with a magnesium-alkyl solution, forming a PMN precursor solution and a lead-based precipitate, and the precipitate is separated from the reacted liquid PMN precursor solution to form a precipitate-free PMN precursor solution. This precursor solution can be processed to form both ferroelectric powders and thin films.

PROCESS FOR THE RECOVERY AND PURIFICATION OF URANIUM DEPOSITS

DOEpatents

Carter, J.M.; Kamen, M.D.

1958-10-14

A process is presented for recovering uranium values from UCl/sub 4/ deposits formed on calutrons. Such deposits are removed from the calutron parts by an aqueous wash solution which then contains the uranium values in addition to the following impurities: Ni, Cu, Fe, and Cr. This impurity bearing wash solution is treated with an oxidizing agent, and the oxidized solution is then treated with ammonia in order to precipitate the uranium as ammonium diuranate. The metal impurities of iron and chromium, which form insoluble hydroxides, are precipitated along with the uranium values. The precipitate is separated from the solution, dissolved in acid, and the solution again treated with ammonia and ammonium carbonate, which results in the precipitation of the metal impurities as hydroxides while the uranium values remain in solution.

Leaching of lead from computer printed wire boards and cathode ray tubes by municipal solid waste landfill leachates.

PubMed

Jang, Yong-Chul; Townsend, Timothy G

2003-10-15

The proper management of discarded electronic devices (E-waste) is an important issue for solid waste professionals because of the magnitude of the waste stream and because these devices often contain a variety of toxic metals (e.g., lead). While recycling of E-waste is developing, much of this waste stream is disposed in landfills. Leaching tests are frequently used to characterize the potential of a solid waste to leach when disposed in a landfill. In the United States, the Toxicity Characteristic Leaching Procedure (TCLP) is used to determine whether a solid waste is a hazardous waste by the toxicity characteristic. The TCLP is designed to simulate worse-case leaching in a landfill environment where the waste is co-disposed with municipal solid waste (MSW). While the TCLP is a required analysis from a regulatory perspective, the leachate concentrations measured may not accurately reflect the concentrations observed under typical landfill conditions. Another method that can be performed to assess the degree a pollutant might leach from a waste in a landfill is to use actual landfill leachate as the leaching solution. In this study, two lead-containing components found in electronic devices (printed wire boards from computers and cathode ray tubes from computers and televisions) were leached using the TCLP and leachates from 11 Florida landfills. California's Waste Extraction Test (WET) and the Synthetic Precipitation Leaching Procedure were also performed. The results indicated that the extractions using MSW landfill leachates resulted in lower lead concentrations than those by the TCLP. The pH of the leaching solution and the ability of the organic acids in the TCLP and WET to complex with the lead are factors that regulate the amount of lead leached.

Caustic Precipitation of Plutonium and Uranium with Gadolinium as a Neutron Poison

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

ANN, VISSER

2005-04-14

The caustic precipitation of plutonium (Pu) and uranium (U) from Pu and U containing waste solutions has been investigated to determine whether gadolinium (Gd) could be used as a neutron poison for precipitation with greater than a fissile mass containing both Pu and enriched U. Precipitation experiments were performed using both actual samples and simulant solutions with a range of 2.6-5.16 g/L U and 0-4.3 to 1 U to Pu. Analyses were performed on solutions at intermediate pH to determine the partitioning of elements for accident scenarios. When both Pu and U were present in the solution, precipitation began atmore » pH 4.5 and by pH 7, 99 percent of Pu and U had precipitated. When complete neutralization was achieved at pH greater than 14 with 1.2 M excess OH-, greater than 99 percent of Pu, U, and Gd had precipitated. At pH greater than 14, the particles sizes were larger and the distribution was a single mode. The ratio of hydrogen to fissile atoms in the precipitate was determined after both settling and centrifuging and indicates that sufficient water was associated with the precipitates to provide the needed neutron moderation for Gd to prevent a criticality in solutions containing up to 4.3 to 1 U to Pu and up to 5.16 g/L U.« less

Influence of Surfactants on Sodium Chloride Crystallization in Confinement

PubMed Central

2017-01-01

We study the influence of different surfactants on NaCl crystallization during evaporation of aqueous salt solutions. We found that at concentrations of sodium chloride close to saturation, only the cationic surfactant CTAB and the nonionic surfactant Tween 80 remain stable. For the nonionic surfactant, the high concentration of salt does not significantly change either the critical micellar concentration (CMC) or the surface tension at the CMC; for the cationic surfactant, the CMC is reduced by roughly 2 orders of magnitude upon adding the salt. The presence of both types of surfactants in the salt solution delays the crystallization of sodium chloride with evaporation. This, in turn, leads to high supersaturation which induces the rapid precipitation of a hopper crystal in the bulk. The crystallization inhibitor role of these surfactants is shown to be mainly due to the passivation of nucleation sites at both liquid/air and solid/liquid interfaces rather than a change in the evaporation rate which is found not to be affected by the presence of the surfactants. The adsorption of surfactants at the liquid/air interface prevents the crystallization at this location which is generally the place where the precipitation of sodium chloride is observed. Moreover, sum frequency generation spectroscopy measurements show that the surfactants are also present at the solid/liquid interface. The incorporation of the surfactants into the salt crystals is investigated using a novel, but simple, method based on surface tension measurements. Our results show that the nonionic surfactant Tween 80 is incorporated in the NaCl crystals but the cationic surfactant CTAB is not. Taken together, these results therefore allow us to establish the effect of the presence of surfactants on sodium chloride crystallization. PMID:28425711

Process for recovery of palladium from nuclear fuel reprocessing wastes

DOEpatents

Campbell, D.O.; Buxton, S.R.

1980-06-16

Palladium is selectively removed from spent nuclear fuel reprocessing waste by adding sugar to a strong nitric acid solution of the waste to partially denitrate the solution and cause formation of an insoluble palladium compound. The process includes the steps of: (a) adjusting the nitric acid content of the starting solution to about 10 M; (b) adding 50% sucrose solution in an amount sufficient to effect the precipitation of the palladium compound; (c) heating the solution at reflux temperature until precipitation is complete; and (d) centrifuging the solution to separate the precipitated palladium compound from the supernatant liquid.

Process for recovery of palladium from nuclear fuel reprocessing wastes

DOEpatents

Campbell, David O.; Buxton, Samuel R.

1981-01-01

Palladium is selectively removed from spent nuclear fuel reprocessing waste by adding sugar to a strong nitric acid solution of the waste to partially denitrate the solution and cause formation of an insoluble palladium compound. The process includes the steps of: (a) adjusting the nitric acid content of the starting solution to about 10 M, (b) adding 50% sucrose solution in an amount sufficient to effect the precipitation of the palladium compound, (c) heating the solution at reflux temperature until precipitation is complete, and (d) centrifuging the solution to separate the precipitated palladium compound from the supernatant liquid.

Theory of precipitation effects on dead cylindrical fuels

Treesearch

Michael A. Fosberg

1972-01-01

Numerical and analytical solutions of the Fickian diffusion equation were used to determine the effects of precipitation on dead cylindrical forest fuels. The analytical solution provided a physical framework. The numerical solutions were then used to refine the analytical solution through a similarity argument. The theoretical solutions predicted realistic rates of...

RECOVERY OF URANIUM AND THORIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Calkins, G.D.

1958-06-10

>A process is described for the recovery of uranium and thorium from monazite sand, which is frequently processed by treating it with a hot sodium hydroxide solution whereby a precipitate forms consisting mainly of oxides or hydroxides of the rare earths, thorium and uranium. The precipitate is dissolved in mineral acid, and the acid solution is then neutralized to a pH value of between 5.2 and 6.2 whereby both the uranium and thorium precipitate as the hydroxides, while substantially all the rare earth metal values present remain in the solution. The uranium and thoriunn can then be separated by dissolving the precipitate in a solution containing a mixture of alkali carbonate and alkali bicarbonate: and contacting the carbonate solution with a strong-base anion exchange resin whereby the uranium values are adsorbed on the resin while the thorium remains in solution.

Aqueous speciation is likely to control the stable isotopic fractionation of cerium at varying pH

NASA Astrophysics Data System (ADS)

Nakada, Ryoichi; Tanaka, Masato; Tanimizu, Masaharu; Takahashi, Yoshio

2017-12-01

Cerium (Ce) can be used as a plaeoredox proxy as shown by a recent study of stable isotopic fractionation of Ce during adsorption and precipitation. However, the experiments in that study were performed at pH conditions lower than that of natural seawater. In the current study, adsorption and precipitation experiments were performed at pH 6.80, 8.20, and 11.00 with 2.25 mM dissolved carbonate to simulate Ce isotopic fractionation in the natural environment and examine the relationship between isotopic fractionation and Ce speciation in the liquid phase. Mean isotopic fractionation factors between liquid and solid phases (αLq-So) of Ce adsorbed on ferrihydrite did not depend on pH conditions or dissolved Ce species. In the Ce/δ-MnO2 system,αLq-So values decreased from 1.000411 (±0.000079) to 1.000194 (±0.000067) with increasing pH or number of carbonate ions, from Ce3+ to Ce(CO3)2-. In the Ce/precipitation system at pH 8.20 and 11.00 where Ce(CO3)2- is present in solution, the αLq-So values were 0.999821 (±0.000071) and 0.999589 (±0.000074), respectively, meaning that lighter isotope enrichment was observed in the liquid phase, which is the contrary to those of the other systems. Extended X-ray absorption fine structure (EXAFS) analyses were also performed to investigate the coordination structure of the adsorbed or precipitated Ce species that control the isotopic fractionation during adsorption. Even at higher pH, where Ce(CO3)+ or Ce(CO3)2- are the dominant dissolved species, the first coordination sphere of Ce in the solid phase in the Ce/ferrihydrite and Ce/precipitation systems was similar to that observed at pH 5.00 where Ce3+ was the main species in solution. A slight elongation in the Cesbnd O bond length in the solid phase at pH 11.00, where negatively charged dissolved species are dominant in the liquid phase, may cause a decrease in isotopic fractionation in the Ce/δ-MnO2 system. The coordination environment of Ce may not change significantly during the adsorption onto ferrihydrite, because Ce binds to the neutral surface OH group on ferrihydrite at pH below 8.5-8.8 (i.e. the pH of the point of zero charge (PZC) for ferrihydrite), similar to other cations when the metal-O distance was similar in hydrated and adsorbed species. At pH above PZC, Ce bonds to the negatively charged surface OH group, while Ce also bonds with CO32- in dissolved species. The reduced partition functions (ln β) for dissolved species (ln βLq) and adsorbed species (ln βSo) with the same trends canceled each other, because ln β of hydrated cation was reduced by the binding anion, resulting in small isotope fractionations. Thus, isotope fractionations for Ce/ferrihydrite may be quite small at the entire pH conditions in this study. The direction of the isotopic fractionation was estimated based on density functional theory (DFT) calculations, which confirmed that lighter Ce is enriched in the liquid phase when Ce forms a complex with carbonate ions. Therefore, this study indicates that the dissolved species can control stable Ce isotopic fractionation during precipitation reactions.

Asphaltene Aggregation and Fouling Behavior

NASA Astrophysics Data System (ADS)

Derakhshesh, Marzie

This thesis explored the properties of asphaltene nano-aggregates in crude oil and toluene based solutions and fouling at process furnace temperatures, and the links between these two phenomena. The link between stability of asphaltenes at ambient conditions and fouling at the conditions of a delayed coker furnace, at over 450 °C, was examined by blending crude oil with an aliphatic diluent in different ratios. The stability of the blends were measured using a S-value analyzer, then fouling rates were measured on electrically heated stainless steel 316 wires in an autoclave reactor. The less stable the blend, the greater the rate and extent of fouling. The most severe fouling occurred with the unstable asphaltenes. SEM imaging of the foulant illustrates very different textures, with the structure becoming more porous with lower stability. Under cross-polarized light, the coke shows the presence of mesophase in the foulant layer. These data suggest a correlation between the fouling rate at high temperature furnace conditions and the stability index of the crude oil. Three organic polysulfides were introduced to the crude oil to examine their effect on fouling. The polysulfides are able to reduce coking and carbon monoxide generation in steam crackers. The fouling results demonstrated that polysulfide with more sulfur content increased the amount of corrosion-fouling of the wire. Various additives, solvents, ultrasound, and heat were employed to attempt to completely disaggregate the asphaltene nano-aggregates in solution at room temperature. The primary analytical technique used to monitor the nano-aggregation state of the asphaltenes in solution was the UV-visible spectroscopy. The results indicate that stronger solvents, such as pyridine and quinoline, combined with ionic liquids yield a slight reduction in the apparent absorbance at longer wavelengths, indicative of a decrease in the nano-aggregate size although the magnitude of the decrease is not significant. Analysis of the spectra of the whole asphaltene samples in toluene indicates that the absorbance of visible light with wavelengths > 600 nm follows a lambda--4 dependence. This functional dependence is consistent with Rayleigh scattering. Rayleigh scattering provides strong evidence that the apparent absorption of visible light by asphaltenes from 600-800 nm is not a molecular absorption phenomenon but rather a scattering mechanism. Rayleigh scattering equations were combined with experimental visible spectra to estimate the average nanoaggregate sizes, which were in a very good agreement with the sizes reported in the literature. The occlusion of two polynuclear aromatic hydrocarbons (PAHs) (pyrene and phenanthrene) in asphaltene precipitates was tested by adding PAHs to the asphaltene in toluene solutions, precipitating by n-pentane and determining the amount of PAHs in precipitates using simulated distillation instrument. Pyrene and phenanthrene, which are normally soluble in the toluene-n-pentane solutions, were detected in the asphaltene precipitates at up to 6 wt% concentration. Trapping of PAHs outside of the nanoaggregates during precipitation gave 7-14 times less of the PAHs in the solid precipitate. This study shows that asphaltene aggregates can interact significantly with PAHs. The results are consistent with the presence open porous asphaltene nanoaggregates in solutions such as toluene.

Alterations of thorium oxalate morphology by changing elementary precipitation conditions

NASA Astrophysics Data System (ADS)

Tyrpekl, V.; Beliš, M.; Wangle, T.; Vleugels, J.; Verwerft, M.

2017-09-01

Oxalates of actinide elements are widely used in research and industry mainly due to their low solubility in aqueous solution and easy conversion to oxide. Although thorium oxide is worldwide mostly produced by the oxalate precipitation and conversion route, the powder morphology obtained through this process is known to inhibit the packing and sintering step of the pellet production. The presented work investigates the effects of oxalate precipitation conditions on the final powder morphology. Among the precipitation conditions considered are: pH of the thorium feed solution, concentration, temperature and the order of addition (thorium solution in oxalic acid solution and vice versa) known as reverse/direct strike. Herein, we show that the morphology of the final oxalate depends significantly on the above mentioned precipitation parameters.

E-beam and UV induced fabrication of CeO2, Eu2O3 and their mixed oxides with UO2

NASA Astrophysics Data System (ADS)

Pavelková, Tereza; Vaněček, Vojtěch; Jakubec, Ivo; Čuba, Václav

2016-07-01

CeO2, Eu2O3 and mixed oxides of CeO2-UO2, Eu2O3-UO2 were fabricated. The preparative method was based on the irradiation of aqueous solutions containing cerium/europium (and uranyl) nitrates and ammonium formate. In the course of irradiation, the solid phase (precursor) was precipitated. The composition of irradiated solutions significantly affected the properties of precursor formed in the course of the irradiation. However, subsequent heat treatment of (amorphous) precursors at temperatures ≤650 °C invariably resulted in the formation of powder oxides with well-developed nanocrystals with linear crystallite size 13-27 nm and specific surface area 10-46 m2 g-1. The applicability of both ionizing (e-beam) and non-ionizing (UV) radiation was studied.

Development of spray-dried co-precipitate of amorphous celecoxib containing storage and compression stabilizers.

PubMed

Dhumal, Ravindra S; Shimpi, Shamkant L; Paradkar, Anant R

2007-09-01

The purpose of this study was to obtain an amorphous system with minimum unit operations that will prevent recrystallization of amorphous drugs since preparation, during processing (compression) and further storage. Amorphous celecoxib, solid dispersion (SD) of celecoxib with polyvinyl pyrrollidone (PVP) and co-precipitate with PVP and carrageenan (CAR) in different ratios were prepared by the spray drying technique and compressed into tablets. Saturation solubility and dissolution studies were performed to differentiate performance after processing. Differential scanning calorimetry and X-ray powder difraction revealed the amorphous form of celecoxib, whereas infrared spectroscopy revealed hydrogen bonding between celecoxib and PVP. The dissolution profile of the solid dispersion and co-precipitate improved compared to celecoxib and amorphous celecoxib. Amorphous celecoxib was not stable on storage whereas the solid dispersion and co-precipitate powders were stable for 3 months. Tablets of the solid dispersion of celecoxib with PVP and physical mixture with PVP and carrageenan showed better resistance to recrystallization than amorphous celecoxib during compression but recrystallized on storage. However, tablets of co-precipitate with PVP and carageenan showed no evidence of crystallinity during stability studies with comparable dissolution profiles. This extraordinary stability of spray-dried co-precipitate tablets may be attributed to the cushioning action provided by the viscoelastic polymer CAR and hydrogen bonding interaction between celecoxib and PVP. The present study demonstrates the synergistic effect of combining two types of stabilizers, PVP and CAR, on the stability of amorphous drug during compression and storage as compared to their effect when used alone.

PRECIPITATION OF ZIRCONIUM AND FLUORIDE IONS FROM SOLUTIONS

DOEpatents

Newby, B.J.

1963-06-11

A process is given for removing zirconium and fluorine ions from aqueous solutions also containing uranium(VI). The precipitation is carried out with sodium formate, and the uranium remains in solution. (AEC)

Elastic moduli and thermal expansion coefficients of medium-entropy subsystems of the CrMnFeCoNi high-entropy alloy

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

Laplanche, Guillaume; Gadaud, P.; Barsch, C.

Elastic moduli of a set of equiatomic alloys (CrFeCoNi, CrCoNi, CrFeNi, FeCoNi, MnCoNi, MnFeNi, and CoNi), which are medium-entropy subsystems of the CrMnFeCoNi high-entropy alloy were determined as a function of temperature over the range 293 K–1000 K. Thermal expansion coefficients were determined for these alloys over the temperature range 100 K–673 K. All alloys were single-phase and had the face-centered cubic (FCC) crystal structure, except CrFeNi which is a two-phase alloy containing a small amount of body-centered cubic (BCC) precipitates in a FCC matrix. The temperature dependences of thermal expansion coefficients and elastic moduli obtained here are useful for quantifying fundamental aspects suchmore » as solid solution strengthening, and for structural analysis/design. Furthermore, using the above results, the yield strengths reported in literature for these alloys were normalized by their shear moduli to reveal the influence of shear modulus on solid solution strengthening.« less

Investigation of in situ gelling alginate formulations as a sustained release vehicle for co-precipitates of dextromethrophan and Eudragit S 100.

PubMed

El Maghraby, Gamal Mohamed; Elzayat, Ehab Mostafa; Alanazi, Fars Kaed

2014-03-01

Alginate vehicles are capable of forming a gel matrix in situ when they come into contact with gastric medium in the presence of calcium ions. However, the gel structure is pH dependent and can break after gastric emptying, leading to dose dumping. The aim of this work was to develop modified in situ gelling alginate formulations capable of sustaining dextromethorphan release throughout the gastrointestinal tract. Alginate solution (2 %, m/m) was used as a vehicle for the tested formulations. Solid matrix of the drug and Eudragit S 100 was prepared by dissolving the drug and polymer in acetone. The organic solvent was then evaporated and the deposited solid matrix was micronized, sieved and dispersed in alginate solution to obtain candidate formulations. The release behavior of dextromethorphan was monitored and evaluated in a medium simulating the gastric and intestinal pH. Drug-polymer compatibility and possible solid-state interactions suggested physical interaction through hydrogen bonding between the drug and the polymer. A significant decrease in the rate and extent of dextromethorphan release was observed with increasing Eudragit S 100 concentration in the prepared particles. Most formulations showed sustained release profiles similar to that of a commercial sustained-release liquid based on ion exchange resin. The release pattern indicated strict control of drug release both under gastric and intestinal conditions, suggesting the potential advantage of using a solid dispersion of drug-Eudragit S 100 to overcome the problem of dose dumping after the rupture of the pH dependent alginate gels.

Effect of solution annealing temperature on precipitation in 2205 duplex stainless steel

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

Kashiwar, A., E-mail: akashiwar@gmail.com; Vennela, N. Phani, E-mail: phanivennela@gmail.com; Kamath, S.L., E-mail: kamath@iitb.ac.in

2012-12-15

In the present study, effect of solution annealing temperature (1050 Degree-Sign C and 1100 Degree-Sign C) and isothermal ageing (700 Degree-Sign C: 15 min to 6 h) on the microstructural changes in 2205 duplex stainless steel has been investigated systematically. Scanning electron microscopy and X-ray diffraction were adopted to follow the microstructural evolution, while an energy dispersive spectrometer attached to scanning electron microscope was used to obtain localised chemical information of various phases. The ferritic matrix of the two phase 2205 duplex stainless steel ({approx} 45% ferrite and {approx} 55% austenite) undergoes a series of metallurgical transformations during ageing-formation ofmore » secondary austenite ({gamma}{sub 2}) and precipitation of Cr and Mo rich intermetallic (chi-{chi} and sigma-{sigma}) phases. For solution annealing at 1050 Degree-Sign C, significant amount of carbides were observed in the ferrite grains after 1 h of ageing at 700 Degree-Sign C. {chi} Phase precipitated after the precipitation of carbides-preferentially at the ferrite-ferrite and also at the ferrite-austenite boundaries. {sigma} Phase was not observed in significant quantity even after 6 h of ageing. The sequence of precipitation in samples solution annealed at 1050 Degree-Sign C was found to be carbides {yields} {chi} {yields} {sigma}. On the contrary, for samples solution annealed at 1100 Degree-Sign C, the precipitation of {chi} phase was negligible. {chi} Phase precipitated before {sigma} phase, preferentially along the ferrite-ferrite grain boundaries and was later consumed in the {sigma} phase precipitation. The {sigma} phase precipitated via the eutectoid transformation of ferrite to yield secondary austenite {gamma}{sub 2} and {sigma} phase in the ferrite and along the ferrite-austenite grain boundaries. An increase in the volume fraction of {gamma}{sub 2} and {sigma} phase with simultaneous decrease in the ferrite was evidenced with ageing. - Highlights: Black-Right-Pointing-Pointer Effect of solution annealing temperature on microstructural evolution is studied. Black-Right-Pointing-Pointer {chi} Phase precipitated preferentially in the samples solution annealed at 1050 Degree-Sign C. Black-Right-Pointing-Pointer {sigma} Phase precipitated preferentially in the samples solution annealed at 1100 Degree-Sign C. Black-Right-Pointing-Pointer For SA at 1050 Degree-Sign C, the sequence of precipitation was carbides {yields} {chi} phase {yields} {sigma} phase. Black-Right-Pointing-Pointer For SA at 1100 Degree-Sign C, {sigma} phase precipitated via the eutectoid reaction: ferrite (F) {yields} {sigma} + {gamma}{sub 2}.« less

CESIUM RECOVERY FROM AQUEOUS SOLUTIONS

DOEpatents

Schneider, R.A.

1961-06-20

Cesium may be precipitated from an aqueous solution whose acidity ranges between a pH of 1.5 and a molarity of 5 on cobaltous, zinc, cadmium, nickel, or ferrous cobalticyanide. This precipitation brings about a separation from most fission products. Ruthenium which coprecipitates to a great degree can be removed by dissolving in sulfuric acid and boiling the solution in the presence of periodic acid for volatilization; other coprecipitated fission products can then be precipitated from the sulfuric acid solution with a ferric hydroxide carrier.

Solutions Network Formulation Report. The Potential Contributions of the Global Precipitation Measurement Mission to Phosphorus Reduction Efforts in the Florida Everglades

NASA Technical Reports Server (NTRS)

Anderson, Daniel; Hilbert, Kent; Lewis, David

2009-01-01

This candidate solution suggests the use of GPM precipitation observations to enhance the CERP. Specifically, GPM measurements could augment in situ precipitation data that are used to model agricultural phosphorus discharged into the Everglades. This solution benefits society by aiding water resource managers in identifying effective phosphorus reduction scenarios and thereby returning the Everglades to a more natural state. This solution supports the Water Management, Coastal Management, and Ecological Forecasting National Applications.

STRONTIUM PRECIPITATION

DOEpatents

McKenzie, T.R.

1960-09-13

A process is given for improving the precipitation of strontium from an aqueous phosphoric-acid-containing solution with nickel or cobalt ferrocyanide by simultaneously precipitating strontium or calcium phosphate. This is accomplished by adding to the ferrocyanide-containing solution calcium or strontium nitrate in a quantity to yield a concentration of from 0.004 to 0.03 and adjusting the pH of the solution to a value of above 8.

Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries

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

Sun Liang; Key Laboratory of Resources Chemistry of Nonferrous Metals, Central South University, Ministry of Education of the People's Republic of China; Qiu Keqiang, E-mail: qiuwhs@sohu.com

2012-08-15

Graphical abstract: Display Omitted Highlights: Black-Right-Pointing-Pointer Vacuum pyrolysis as a pretreatment was used to separate cathode material from aluminum foils. Black-Right-Pointing-Pointer Cobalt and lithium can be leached using oxalate while cobalt can be directly precipitated as cobalt oxalate. Black-Right-Pointing-Pointer Cobalt and lithium can be separated efficiently from each other only in the oxalate leaching process. Black-Right-Pointing-Pointer High reaction efficiency of LiCoO{sub 2} was obtained with oxalate. - Abstract: Spent lithium-ion batteries containing lots of strategic resources such as cobalt and lithium are considered as an attractive secondary resource. In this work, an environmentally compatible process based on vacuum pyrolysis, oxalatemore » leaching and precipitation is applied to recover cobalt and lithium from spent lithium-ion batteries. Oxalate is introduced as leaching reagent meanwhile as precipitant which leaches and precipitates cobalt from LiCoO{sub 2} and CoO directly as CoC{sub 2}O{sub 4}{center_dot}2H{sub 2}O with 1.0 M oxalate solution at 80 Degree-Sign C and solid/liquid ratio of 50 g L{sup -1} for 120 min. The reaction efficiency of more than 98% of LiCoO{sub 2} can be achieved and cobalt and lithium can also be separated efficiently during the hydrometallurgical process. The combined process is simple and adequate for the recovery of valuable metals from spent lithium-ion batteries.« less

[Study on focusing chromatographic simultaneous determinations of 226Ra and its daughter nuclides by means of solid state alpha-tracks detection and beta-autoradiography (author's transl)].

PubMed

Furushima, K; Shinagawa, M

1980-09-01

In order to detect to radioactive band on the paper strip developed by focusing chromatography, plate-making-film was used for the autoradiography and beta-spots were photographed. Thereafter the film was etched with sodium hydroxide solution to find the alpha-tracks. Paper strip used for the sample was prepared by the precipitation focusing chromatography of 226Ra and its daughter nuclides using HCl-KF solution as a developer. The film used was not high in its beta-sensitivity, but because of its high resolution good photographic results were obtained according to the intensity of beta-activity when the proper conditions of photographic development were fulfilled. The simple alpha-spectrometry was made possible by counting the numbers of tracks according to the etching depth of the film. The film was hard and thick enough for etching with 6M sodium hydroxide solution at 50 degrees C for more than 50 hrs to measure the depth of tracks.

Thermomechanical deformation behavior of a dynamic strain aging alloy, Hastelloy X

NASA Technical Reports Server (NTRS)

Castelli, Michael G.; Miner, Robert V.; Robinson, David N.

1992-01-01

An experimental study was performed to identify the effects of dynamic strain aging (solute drag) and metallurgical instabilities under thermomechanical loading conditions. The study involved a series of closely controlled thermomechanical deformation tests on the solid-solution-strenghened nickel-base superalloy, Hastelloy X. This alloy exhibits a strong isothermal strain aging peak at approximately 600 C, promoted by the effects of solute drag and precipitation hardening. Macroscopic thermomechanical hardening trends are correlated with microstructural characteristics through the use of transmission electron microscopy. These observations are compared and contrasted with isothermal conditions. Thermomechanical behavior unique to the isothermal database is identified and discussed. The microstructural characteristics were shown to be dominated by effects associated with the highest temperature of the thermomechanical cycle. Results indicate that the deformation behavior of Hastelloy X is thermomechanically path dependent. In addition, guidance is given pertaining to deformation modeling in the context of macroscopic unified theory. An internal state variable is formulated to qualitatively reflect the isotropic hardening trends identified in the TMD experiments.

PROCESS OF RECOVERING URANIUM FROM ITS ORES

DOEpatents

Galvanek, P. Jr.

1959-02-24

A process is presented for recovering uranium from its ores. The crushed ore is mixed with 5 to 10% of sulfuric acid and added water to about 5 to 30% of the weight of the ore. This pugged material is cured for 2 to 3 hours at 100 to 110 deg C and then cooled. The cooled mass is nitrate-conditioned by mixing with a solution equivalent to 35 pounds of ammunium nitrate and 300 pounds of water per ton of ore. The resulting pulp containing 70% or more solids is treated by upflow percolation with a 5% solution of tributyl phosphate in kerosene at a rate equivalent to a residence time of about one hour to extract the solubilized uranium. The uranium is recovered from the pregnant organic liquid by counter-current washing with water. The organic extractant may be recycled. The uranium is removed from the water solution by treating with ammonia to precipitate ammonium diuranate. The filtrate from the last step may be recycled for the nitrate-conditioning treatment.

Quantitative assessment of carbon allocation anomalies in low temperature bainite

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

Rementeria, Rosalia

Low temperature bainite is a mixture of ferrite and austenite with a high dislocation density and nanoscale precipitates produced by isothermal transformation of the austenite in high-carbon high-silicon steels. The mass balance for carbon is systematically unsuitable when considering only ferrite and austenite forming the structure, but no attempt has been made to evaluate the amount of carbon located at linear defects and precipitates. Additionally, bainitic ferrite has been recently shown to have a tetragonal crystal structure, allowing greater amounts of carbon in solid solution than those expected by the paraequilibrium phase boundaries. In order to quantify the contribution ofmore » all the carbon sinks, we have followed the evolution of carbon in ferrite and austenite, along with the precipitation of cementite and η–carbide, during the isothermal bainitic transformation at 220 and 250 °C by means of in-situ synchrotron high energy X-ray diffraction and complementary transmission electron microscopy (TEM) and atom probe tomography (APT) analyses. Furthermore, this is the first time that the mass balance for carbon is successfully achieved by considering all the transformation products together with an estimation of the carbon segregated to linear defects.« less

Quantitative assessment of carbon allocation anomalies in low temperature bainite

DOE PAGES

Rementeria, Rosalia

2017-05-24

Low temperature bainite is a mixture of ferrite and austenite with a high dislocation density and nanoscale precipitates produced by isothermal transformation of the austenite in high-carbon high-silicon steels. The mass balance for carbon is systematically unsuitable when considering only ferrite and austenite forming the structure, but no attempt has been made to evaluate the amount of carbon located at linear defects and precipitates. Additionally, bainitic ferrite has been recently shown to have a tetragonal crystal structure, allowing greater amounts of carbon in solid solution than those expected by the paraequilibrium phase boundaries. In order to quantify the contribution ofmore » all the carbon sinks, we have followed the evolution of carbon in ferrite and austenite, along with the precipitation of cementite and η–carbide, during the isothermal bainitic transformation at 220 and 250 °C by means of in-situ synchrotron high energy X-ray diffraction and complementary transmission electron microscopy (TEM) and atom probe tomography (APT) analyses. Furthermore, this is the first time that the mass balance for carbon is successfully achieved by considering all the transformation products together with an estimation of the carbon segregated to linear defects.« less

Preparation and characterization of host-guest system between inosine and β-cyclodextrin through inclusion mode

NASA Astrophysics Data System (ADS)

Prabu, Samikannu; Sivakumar, Krishnamurty; Swaminathan, Meenakshisundaram; Rajamohan, Rajaram

2015-08-01

Inosine is a nucleoside that is formed when hypoxanthine is attached to a ribose ring (also known as a ribofuranose) via a β-N9-glycosidic bond. Inosine is commonly found in tRNAs. Inosine (INS) has been used widely as an antiviral drug. The inclusion complex of INS with β-CDx in solution phase is studied by ground and excited state with UV-visible and fluorescence spectroscopy, respectively. A binding constant and stoichiometric ratio between INS and β-CDx are calculated by BH equation. The lifetime and relative amplitude of INS is increases with increasing the concentrations of β-CDx, confirms the formation of inclusion complex in liquid state. The solid complexes are prepared by kneading method (KM) and co-precipitation method (CP). The solid complex is characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and differential scanning colorimetry (DSC). CP method gives the solid product with good yield than that of physical mixture and KM method. The structure of complex is proposed based on the study of Patch - Dock server.

Processing of spent Ni-MH batteries for the recovery of cobalt, nickel and rare earth elements bearing materials by means of a chemical and electrochemical sequential process

NASA Astrophysics Data System (ADS)

Delvasto, P.; Orta Rodríguez, R.; Blanco, S.

2016-02-01

Rechargeable Ni-MH batteries contain strategic metal values which are worth to be recovered. In the present work, a preliminary sequential chemical and electrochemical procedure is proposed, in order to reclaim materials bearing Ni, Co and rare earth elements (REE) from Ni-MH spent batteries. Initially, spent batteries are disassembled to separate the electrode materials (anode and cathode), which are then leached with an aqueous solution of 5w% sulphuric acid. The metal content of this solution is checked by atomic absorption spectrometry techniques. The obtained solution is pH-adjusted (with NaOH), until pH is between 4.0 and 4.3; then, it is heated up to 70°C to precipitate a rare earth elements sulphate (Nd, La, Pr, Ce), as determined by means of x-ray fluorescence techniques. The solids-free solution is then electrolyzed, in order to recover a Ni-Co alloy. The electrolysis conditions were established through a cyclic voltammetry technique.

Application of precipitation methods for the production of water-insoluble drug nanocrystals: production techniques and stability of nanocrystals.

PubMed

Xia, Dengning; Gan, Yong; Cui, Fude

2014-01-01

This review focuses on using precipitation (bottom-up) method to produce water-insoluble drug nanocrystals, and the stability issues of nanocrystals. The precipitation techniques for production of ultra-fine particles have been widely researched for last few decades. In these techniques, precipitation of solute is achieved by addition of a non-solvent for solute called anti-solvent to decrease the solvent power for the solute dissolved in a solution. The anti-solvent can be water, organic solvents or supercritical fluids. In this paper, efforts have been made to review the precipitation techniques involving the anti-solvent precipitation by simple mixing, impinging jet mixing, multi-inlet vortex mixing, the using of high-gravity, ultrasonic waves and supercritical fluids. The key to the success of yielding stable nanocrystals in these techniques is to control the nucleation kinetics and particle growth through mixing during precipitation based on crystallization theories. The stability issues of the nanocrystals, such as sedimentation, Ostwald ripening, agglomeration and cementing of crystals, change of crystalline state, and the approaches to stabilizing nanocrystals are also discussed in detail.

Effect of cryogenic treatment on the fracture toughness of aircraft aluminum alloy 7075

NASA Astrophysics Data System (ADS)

Ermishkin, V. A.; Soloveva, Y. B.

2018-04-01

Influence of three types of the treatment on fracture toughness of the Al-7075 alloy was investigated in this study. Commercial Al-7075 alloy in the solid solution heat-treated condition was processed by hardening with post-cryogenic deformation treatment and PVD deposition titanium and copper coatings. The fracture toughness was estimated with using macroscopic and microscopic approaches. The conditions for the coincidence of the fracture toughness estimates between brittle fracture mechanics and the photometric analysis of structural images (PHASI) methods were achieved. The highest fracture toughness was obtained by applying hardening, cryogenic compression, ageing and deposition of the Ti-coating, leading to dispersion particles precipitation.

Kinetics of radiation-induced precipitation at the alloy surface

NASA Astrophysics Data System (ADS)

Lam, N. Q.; Nguyen, T.; Leaf, G. K.; Yip, S.

1988-05-01

Radiation-induced precipitation of a new phase at the surface of an alloy during irradiation at elevated temperatures was studied with the aid of a kinetic model of segregation. The preferential coupling of solute atoms with the defect fluxes gives rise to a strong solute enrichment at the surface, which, if surpassing the solute solubility limit, leads to the formation of a precipitate layer. The moving precipitate/matrix interface was accommodated by means of a mathematical scheme that transforms spatial coordinates into a reference frame in which the boundaries are immobile. Sample calculations were performed for precipitation of the γ'-Ni 3Si layer on Ni-Si alloys undergoing electron irradiation. The dependences of the precipitation kinetics on the defect-production rate, irradiation temperature, internal defect sink concentration and alloy composition were investigated systematically.

METHOD OF PREPARING PROTACTINIUM VALUES

DOEpatents

Katzin, L.I.; Larson, R.G.; Thompson, R.C.; Van Winkle, Q.

1959-05-19

Separation and purification from initial acid leaches of pitchblende of Pa is described. This supernatant acid solution is treated with alkali metal carbonates to precipitate Pa. Silica is removed from the precipitate by hydroxide treatment. The Pa residue is dissolved in HNO/sub 3/ and Pa is concentrated by cyclic precipitations with MnO/sub 2/. The last solution is hydrolyzed to precipitate Pa. The Pa precipitate contains Ti and Zr which are removed by ion exchange. (T.R.H.)

CONCENTRATION OF Pu USING OXALATE TYPE CARRIER

DOEpatents

Ritter, D.M.; Black, R.P.S.

1960-04-19

A method is given for dissolving and reprecipitating an oxalate carrier precipitate in a carrier precipitation process for separating and recovering plutonium from an aqueous solution. Uranous oxalate, together with plutonium being carried thereby, is dissolved in an aqueous alkaline solution. Suitable alkaline reagents are the carbonates and oxulates of the alkali metals and ammonium. An oxidizing agent selected from hydroxylamine and hydrogen peroxide is then added to the alkaline solution, thereby oxidizing uranium to the hexavalent state. The resulting solution is then acidified and a source of uranous ions provided in the acidified solution, thereby forming a second plutoniumcarrying uranous oxalate precipitate.

Study of continuous precipitation of ADU for the implantation in the pilot installation at the Atomic Energy Institute, Brazil. Estudo de precipitacao continua de DUA para a implantacao na instalacao piloto CEQ-IEA (in Portuguese)

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

Araujo, Jose Adroalado de

1974-05-15

The paper deals with the ammonium diuranate continuous precipitation with a high chemical purity degree from uranyl nitrate solutions, using 1.2 and 2.4 ammonium hydroxide solutions and gaseous NH{sub 3} as a precipitating agent. The precipitations were carried out in a continuous procedure with one and two stages. The variables studied were the NH[sub 4}OH solutions concentration, ADU precipitation curve, the flow rate of reactants, the temperature of the precipitation, pH of the suspended ADU, and ammonium diuranate filtrability. The experimental work performed and the data obtained permitted the design of a chemical reactor for the continuous nuclear grade ADUmore » precipitation at the Chemical Engineering Department of the Atomic Energy Institute of Sao Paulo.« less

Measuring precipitation with a geolysimeter

NASA Astrophysics Data System (ADS)

Smith, Craig D.; van der Kamp, Garth; Arnold, Lauren; Schmidt, Randy

2017-10-01

Using the relationship between measured groundwater pressures in deep observation wells and total surface loading, a geological weighing lysimeter (geolysimeter) has the capability of measuring precipitation event totals independently of conventional precipitation gauge observations. Correlations between groundwater pressure change and event precipitation were observed at a co-located site near Duck Lake, SK, over a multi-year and multi-season period. Correlation coefficients (r2) varied from 0.99 for rainfall to 0.94 for snowfall. The geolysimeter was shown to underestimate rainfall by 7 % while overestimating snowfall by 9 % as compared to the unadjusted gauge precipitation. It is speculated that the underestimation of rainfall is due to unmeasured run-off and evapotranspiration within the response area of the geolysimeter during larger rainfall events, while the overestimation of snow is at least partially due to the systematic undercatch common to most precipitation gauges due to wind. Using recently developed transfer functions from the World Meteorological Organization's (WMO) Solid Precipitation Intercomparison Experiment (SPICE), bias adjustments were applied to the Alter-shielded, Geonor T-200B precipitation gauge measurements of snowfall to mitigate wind-induced errors. The bias between the gauge and geolysimeter measurements was reduced to 3 %. This suggests that the geolysimeter is capable of accurately measuring solid precipitation and can be used as an independent and representative reference of true precipitation.

Precipitation method for barium metaborate (BaB{sub 2}O{sub 4}) synthesis from borax solution

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

Akşener, Eymen; Figen, Aysel Kantürk; Pişkin, Sabriye

2013-12-16

In this study, barium metaborate (BaB{sub 2}O{sub 4}, BMB) synthesis from the borax solution was carried out. BMB currently is used in production of ceramic glazes, luminophors, oxide cathodes as well as additives to pigments for aqueous emulsion paints and also β−BaB{sub 2}O{sub 4} single crystals are the best candidate for fabrication of solid-state UV lasers operating at a wavelength of 200 nm due to excellent nonlinear optical properties. In the present study, synthesis was carried out from the borax solution (Na{sub 2}B{sub 4}O{sub 7⋅}10H{sub 2}O, BDH) and barium chloride (BaCI{sub 2⋅}2H{sub 2}O, Ba) in the glass-batch reactor with stirring.more » The effect of, times (5-15 min), molar ratio [stoich.ration (1.0:2.0), 1.25:2.0, 1.5:2.0, 2.5:2:0, 3.0:2.0, 3.5:2.0,4.0:2.0, 5.0:2.0] and also crystallization time (2-6 hour) on the BMB yield (%) was investigated at 80 °C reaction temperature. It is found that, BMB precipitation synthesis with 90 % yield can be performed from 0.50 molar ration (BDH:Ba), under 80 °C, 15 minute, and 6 hours crystallization time. The structural properties of BMB powders were characterized by using XRD, FT-IR and DTA-TG instrumental analysis technique.« less

Reactive Precipitation of Anhydrous Alkali Sulfide Nanocrystals with Concomitant Abatement of Hydrogen Sulfide and Cogeneration of Hydrogen.

PubMed

Li, Xuemin; Zhao, Yangzhi; Brennan, Alice; McCeig, Miranda; Wolden, Colin A; Yang, Yongan

2017-07-21

Anhydrous alkali sulfide (M 2 S, M=Li or Na) nanocrystals (NCs) are important materials central to the development of next generation cathodes and solid-state electrolytes for advanced batteries, but not commercially available at present. This work reports an innovative method to directly synthesize M 2 S NCs through alcohol-mediated reactions between alkali metals and hydrogen sulfide (H 2 S). In the first step, the alkali metal is complexed with alcohol in solution, forming metal alkoxide (ROM) and releasing hydrogen (H 2 ). Next, H 2 S is bubbled through the ROM solution, where both chemicals are completely consumed to produce phase-pure M 2 S NC precipitates and regenerate alcohol that can be recycled. The M 2 S NCs morphology may be tuned through the choice of the alcohol and solvent. Both synthetic steps are thermodynamically favorable (ΔG m o <-100 kJ mol -1 ), proceeding rapidly to completion at ambient temperature with almost 100 % atom efficiency. The net result, H 2 S+2 m→M 2 S+H 2 , makes good use of a hazardous chemical (H 2 S) and delivers two value-added products that naturally phase separate for easy recovery. This scalable approach provides an energy-efficient and environmentally benign solution to the production of nanostructured materials required in emerging battery technologies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Prosviryakov, A.S., E-mail: pro.alex@mail.ru; Shch

Ground chips of as-cast Al-10 wt.% Zr alloy were subjected to mechanical alloying (MA) with 5 vol.% of nanodiamond addition in a high energy planetary ball-mill. The aim of this work was to investigate the microstructure, phase transformation and mechanical properties of the material both after MA and after subsequent annealing. Optical and transmission electron microscopes were used for morphological and microstructural analysis. The effect of milling time on powder microhardness, Al lattice parameter, lattice microstrain and crystallite size was determined. It was shown that mechanical alloying of as-cast Al-10wt.%Zr alloy during 20 h leads to a complete dissolution ofmore » the primary tetragonal Al{sub 3}Zr crystals in aluminum. At the same time, the powder microhardness increases to 370 HV. Metastable cubic Al{sub 3}Zr phase nanoparticles precipitate from the Al solution due to its decomposition after annealing, however, the Al solid solution remains supersaturated and nanocrystalline. Compression tests at room temperature and at 300 °C showed that the strength values of the hot-pressed samples reach 822 MPa and 344 MPa, respectively. - Highlights: •As-cast Al-10 wt.% Zr alloy was mechanically alloyed with 5 vol.% nanodiamond. •The primary tetragonal Al{sub 3}Zr crystals were completely dissolved in Al after 20 h. •Cubic Al{sub 3}Zr phase nanoparticles precipitated from Al solution after aging. •The aged bulk material showed a high strength at room and elevated temperatures.« less

From Drought to Flood: An Analysis of the Water Balance of the Tuolumne River Basin During Extreme Conditions (2015 - 2017)

NASA Astrophysics Data System (ADS)

Hedrick, A. R.; Marks, D. G.; Havens, S.; Robertson, M.; Johnson, M.; Sandusky, M.; Bormann, K. J.; Painter, T. H.

2017-12-01

Closing the water balance of a snow-dominated mountain basin has long been a focal point of the hydrologic sciences. This study attempts to more precisely quantify the solid precipitation inputs to a basin using the iSnobal energy balance snowmelt model and assimilated snow depth information from the Airborne Snow Observatory (ASO). Throughout the ablation seasons of three highly dissimilar consecutive water years (2015 - 2017), the ASO captured high resolution snow depth snapshots over the Tuolumne River Basin in California's Central Sierra Nevada. These measurements were used to periodically update the snow depth state variable of iSnobal, thereby nudging the estimates of water storage (snow water equivalent, or SWE) and melt (surface water input, or SWI) toward a more accurate solution. Once precipitation inputs and streamflow outputs are better constrained, the additional loss terms of the water mass balance equation (i.e. groundwater recharge and evapotranspiration) can be estimated with less uncertainty.

Electrolytic Deposition and Diffusion of Lithium onto Magnesium-9 Wt Pct Yttrium Bulk Alloy in Low-Temperature Molten Salt of Lithium Chloride and Potassium Chloride

NASA Astrophysics Data System (ADS)

Dong, Hanwu; Wu, Yaoming; Wang, Lidong; Wang, Limin

2009-10-01

The electrolytic deposition and diffusion of lithium onto bulk magnesium-9 wt pct yttrium alloy cathode in molten salt of 47 wt pct lithium chloride and 53 wt pct potassium chloride at 693 K were investigated. Results show that magnesium-yttrium-lithium ternary alloys are formed on the surface of the cathodes, and a penetration depth of 642 μm is acquired after 2 hours of electrolysis at the cathodic current density of 0.06 A·cm-2. The diffusion of lithium results in a great amount of precipitates in the lithium containing layer. These precipitates are the compound of Mg41Y5, which arrange along the grain boundaries and hinder the diffusion of lithium, and solid solution of yttrium in magnesium. The grain boundaries and the twins of the magnesium-9 wt pct yttrium substrate also have negative effects on the diffusion of lithium.

Eutectic superalloys strengthened by sigma, Ni3CB lamellae and gamma prime, Ni3Al precipitates

NASA Technical Reports Server (NTRS)

Lemkey, F. D.

1973-01-01

By means of a screening and solidification optimization study of certain alloys located on the gamma-sigma liquidus surface within the Ni-Cb-Cr-Al system, alloys with high temperature properties superior to those of all known superalloys were defined. One alloy, Ni - 19.7w/o Cb - 6.0w/o Cr - 2.5w/o Al, directionally solidified at 3 cm/hr met or exceeded each program goal. A second alloy, Ni-21.75 w/o Cb-2.55 w/o Al, although deficient in its inherent oxidation resistance, met the other program goals and combined a remarkable insensitivity of composite microstructure to solidification parameters with excellent low temperature toughness. This investigation demonstrated that useful properties for gas turbine airfoil application have been achieved by reinforcing a strong and tough gamma solid solution matrix containing precipitated gamma prime by a lamellar intermetallic compound Ni3 Cb having greater strength at elevated temperature.

Long-term leaching behavior of phenol in cement/activated-carbon solidified/stabilized hazardous waste.

PubMed

Liu, Jianguo; Nie, Xiaoqin; Zeng, Xianwei; Su, Zhaoji

2013-01-30

The long-term leaching behavior of phenol in solidified/stabilized (S/S) hazardous wastes cured for 28 d with different amounts of activated carbon (AC) was investigated using synthetic inorganic acid (H(2)SO(4):HNO(3) = 2:1, pH = 3.2), acetic acid buffer (HAc/NaAc, pH = 4.93), and deionized water as leachants to simulate the leaching of phenol in three exposure scenarios: acid-precipitation, co-disposal, and neutral-precipitation. Phenol immobilization was enhanced by AC adsorption and impaired by the growth of micropores with increasing amount of AC; thus the optimal added amount of AC to be to added S/S wastes was 2%. The leaching behavior of phenol in co-disposal scenario was unpredictable due to inadequate ionization of HAc in the HAc-NaAc buffer solution. The findings indicated that S/S products should be disposed of in hazardous waste landfills rather than municipal solid waste landfills. Copyright © 2012 Elsevier Ltd. All rights reserved.

Recycling of Ammonia Wastewater During Vanadium Extraction from Shale

NASA Astrophysics Data System (ADS)

Shi, Qihua; Zhang, Yimin; Liu, Tao; Huang, Jing

2018-03-01

In the vanadium metallurgical industry, massive amounts of ammonia hydroxide or ammonia salt are added during the precipitation process to obtain V2O5; therefore, wastewater containing a high level of NH4 + is generated, which poses a serious threat to environmental and hydrologic safety. In this article, a novel process was developed to recycle ammonia wastewater based on a combination of ammonia wastewater leaching and crystallization during vanadium extraction from shale. The effects of the NH4 + concentration, temperature, time and liquid-to-solid ratio on the leaching efficiencies of vanadium, aluminum and potassium were investigated, and the results showed that 93.2% of vanadium, 86.3% of aluminum and 96.8% of potassium can be leached from sulfation-roasted shale. Subsequently, 80.6% of NH4 + was separated from the leaching solution via cooling crystallization. Vanadium was recovered via a combined method of solvent extraction, precipitation and calcination. Therefore, ammonia wastewater was successfully recycled during vanadium extraction from shale.

Disintegration of the net-shaped grain-boundary phase by multi-directional forging and its influence on the microstructure and properties of Cu-Ni-Si alloy

NASA Astrophysics Data System (ADS)

Zhang, Jinlong; Lu, Zhenlin; Zhao, Yuntao; Jia, Lei; Xie, Hui; Tao, Shiping

2017-09-01

Cu-Ni-Si alloys with 90% Cu content and Ni to Si ratios of 5:1 were fabricated by fusion casting, and severe plastic deformation of the Cu-Ni-Si alloy was carried out by multi-direction forging (MDF). The results showed that the as-cast and homogenized Cu-Ni-Si alloys consisted of three phases, namely the matrix phase α-Cu (Ni, Si), the reticular grain boundary phase Ni31Si12 and the precipitated phase Ni2Si. MDF significantly destroyed the net-shaped grain boundary phase, the Ni31Si12 phase and refined the grain size of the Cu matrix, and also resulted in the dissolving of Ni2Si precipitates into the Cu matrix. The effect of MDF on the conductivity of the solid solution Cu-Ni-Si alloy was very significant, with an average increase of 165.16%, and the hardness of the Cu-Ni-Si alloy also increased obviously.

Iron oxide and hydroxide precipitation from ferrous solutions and its relevance to Martian surface mineralogy

NASA Technical Reports Server (NTRS)

Posey-Dowty, J.; Moskowitz, B.; Crerar, D.; Hargraves, R.; Tanenbaum, L.

1986-01-01

Experiments were performed to examine if the ubiquitousness of a weak magnetic component in all Martian surface fines tested with the Viking Landers can be attributed to ferric iron precipitation in aqueous solution under oxidizing conditions at neutral pH. Ferrous solutions were mixed in deionized water and various minerals were added to separate liquid samples. The iron-bearing additives included hematite, goethite, magnetite, maghemite, lepidocrocite and potassium bromide blank at varying concentrations. IR spectroscopic scans were made to identify any precipitates resulting from bubbling oxygen throughout the solutions; the magnetic properties of the precipitates were also examined. The data indicated that the lepidocrocite may have been preferentially precipitated, then aged to maghemite. The process would account for the presumed thin residue of maghemite on the present Martian surface, long after abundant liquid water on the Martian surface vanished.

CARBONATE METHOD OF SEPARATION OF TETRAVALENT PLUTONIUM FROM FISSION PRODUCT VALUES

DOEpatents

Duffield, R.B.; Stoughton, R.W.

1959-02-01

It has been found that plutonium forms an insoluble precipitate with carbonate ion when the carbonate ion is present in stoichiometric proportions, while an excess of the carbonate ion complexes plutonium and renders it soluble. A method for separating tetravalent plutonium from lanthanum-group rare earths has been based on this discovery, since these rare earths form insoluble carbonates in approximately neutral solutions. According to the process the pH is adjusted to between 5 and 7, and approximately stoichiometric amounts of carbonate ion are added to the solution causing the formation of a precipitate of plutonium carbonate and the lanthanum-group rare earth carbonates. The precipitate is then separated from the solution and contacted with a carbonate solution of a concentration between 1 M and 3 M to complex and redissolve the plutonium precipitate, and thus separate it from the insoluble rare earth precipitate.

Solutions Network Formulation Report. The Potential Contributions of the Global Precipitation Measurement Mission to Estuary Management in Acadia National Park

NASA Technical Reports Server (NTRS)

Anderson, Daniel; Hilbert, Kent; Lewis, David

2007-01-01

This candidate solution suggests the use of GPM precipitation observations to enhance the Acadia National Park NLERDSS. Simulated GPM data should provide measurements that would enable analysis of how precipitation affects runoff and nutrient load in the park?s wetlands. This solution benefits society by aiding park and resource managers in making predictions based on hypothetical changes and in identifying effective mitigation scenarios. This solution supports the Coastal Management, Water Management, and Ecological Forecasting National Applications.

SULFIDE METHOD PLUTONIUM SEPARATION

DOEpatents

Duffield, R.B.

1958-08-12

A process is described for the recovery of plutonium from neutron irradiated uranium solutions. Such a solution is first treated with a soluble sullide, causing precipitation of the plutoniunn and uraniunn values present, along with those impurities which form insoluble sulfides. The precipitate is then treated with a solution of carbonate ions, which will dissolve the uranium and plutonium present while the fission product sulfides remain unaffected. After separation from the residue, this solution may then be treated by any of the usual methods, such as formation of a lanthanum fluoride precipitate, to effect separation of plutoniunn from uranium.

A model for osmium isotopic evolution of metallic solids at the core-mantle boundary

NASA Astrophysics Data System (ADS)

Humayun, Munir

2011-03-01

Some plumes are thought to originate at the core-mantle boundary, but geochemical evidence of core-mantle interaction is limited to Os isotopes in samples from Hawaii, Gorgona (89 Ma), and Kostomuksha (2.7 Ga). The Os isotopes have been explained by physical entrainment of Earth's liquid outer core into mantle plumes. This model has come into conflict with geophysical estimates of the timing of core formation, high-pressure experimental determinations of the solid metal-liquid metal partition coefficients (D), and the absence of expected 182W anomalies. A new model is proposed where metallic liquid from the outer core is partially trapped in a compacting cumulate pile of Fe-rich nonmetallic precipitates (FeO, FeS, Fe3Si, etc.) at the top of the core and undergoes fractional crystallization precipitating solid metal grains, followed by expulsion of the residual metallic liquid back to the outer core. The Os isotopic composition of the solids and liquids in the cumulate pile is modeled as a function of the residual liquid remaining and the emplacement age using 1 bar D values, with variable amounts of oxygen (0-10 wt %) as the light element. The precipitated solids evolve Os isotope compositions that match the trends for Hawaii (at an emplacement age of 3.5-4.5 Ga; 5%-10% oxygen) and Gorgona (emplacement age < 1.5 Ga; 0%-5% oxygen). The Fe-rich matrix of the cumulate pile dilutes the precipitated solid metal decoupling the Fe/Mn ratio from Os and W isotopes. The advantages to using precipitated solid metal as the Os host include a lower platinum group element and Ni content to the mantle source region relative to excess iron, miniscule anomalies in 182W (<0.1 ɛ), and no effects for Pb isotopes, etc. A gradual thermomechanical erosion of the cumulate pile results in incorporation of this material into the base of the mantle, where mantle plumes subsequently entrain it. Fractional crystallization of metallic liquids within the CMB provides a consistent explanation of both Os isotope correlations, Os-W isotope systematics, and Fe/Mn evidence for core-mantle interaction over the entire Hawaiian source.

PROCESSES OF RECLAIMING URANIUM FROM SOLUTIONS

DOEpatents

Zumwalt, L.R.

1959-02-10

A process is described for reclaiming residual enriched uranium from calutron wash solutions containing Fe, Cr, Cu, Ni, and Mn as impurities. The solution is adjusted to a pH of between 2 and 4 and is contacted with a metallic reducing agent, such as iron or zinc, in order to reduce the copper to metal and thereby remove it from the solution. At the same time the uranium present is reduced to the uranous state The solution is then contacted with a precipitate of zinc hydroxide or barium carbonate in order to precipitate and carry uranium, iron, and chromium away from the nickel and manganese ions in the solution. The uranium is then recovered fronm this precipitate.

Mesoscale modeling of solute precipitation and radiation damage

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

Zhang, Yongfeng; Schwen, Daniel; Ke, Huibin

2015-09-01

This report summarizes the low length scale effort during FY 2014 in developing mesoscale capabilities for microstructure evolution in reactor pressure vessels. During operation, reactor pressure vessels are subject to hardening and embrittlement caused by irradiation-induced defect accumulation and irradiation-enhanced solute precipitation. Both defect production and solute precipitation start from the atomic scale, and manifest their eventual effects as degradation in engineering-scale properties. To predict the property degradation, multiscale modeling and simulation are needed to deal with the microstructure evolution, and to link the microstructure feature to material properties. In this report, the development of mesoscale capabilities for defect accumulationmore » and solute precipitation are summarized. Atomic-scale efforts that supply information for the mesoscale capabilities are also included.« less

Incompatibility of Contrast Medium and Trisodium Citrate

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

Delcour, Christian, E-mail: christian.delcour@chu-charleroi.be; Bruninx, Guy

2013-02-15

To test the compatibility of trisodium citrate, a catheter lock solution, with iodinated contrast medium. Iohexol, iobitridol, iodixanol, ioxaglate, ioxithalamate, iomeprol, and iopromide were tested. In all tests, 2 ml of contrast medium were mixed with 2 ml of trisodium citrate solution. Iodixanol and ioxaglate provoked a highly viscous gluelike precipitation when mixed with trisodium citrate. A brief transient precipitate was observed with iohexol, iomeprol, and ioxithalamate. Permanent precipitation occurred with iobitridol and iopromide. One must be aware of the potential for precipitation when contrast medium is mixed with trisodium citrate solution. Before trisodium citrate solution is injected, the cathetermore » should be thoroughly flushed with saline if a contrast medium has previously been injected through it.« less

Effect of Al Addition on Microstructure of AZ91D

NASA Astrophysics Data System (ADS)

Joshi, Utsavi; Babu, Nadendla Hari

Casting is a net shape or near net shape forming process so work-hardening will not be applicable for improving properties of magnesium cast alloys. Grain refinement, solid-solution strengthening, precipitation hardening and specially designed heat treatment are the techniques used to enhance the properties of these alloys. This research focusses on grain refinement of magnesium alloy AZ91D, which is a widely used commercial cast alloy. Recently, Al-B based master alloys have shown potential in grain refining AZ91D. A comparative study of the grain refinement of AZ91D by addition of 0.02wt%B, 0.04wt%B, 0.1wt%B, 0.5wt%B and 1.0wt%B of A1-5B master alloy and equivalent amount of solute element aluminium is described in this paper. Hardness profile of AZ91D alloyed with boron and aluminium is compared.

A physicochemical research of the Dy-Sn-O system

NASA Astrophysics Data System (ADS)

Malinovskaya, Tatyana; Lysak, Ilya; Zhek, Valentina; Kuznetsova, Svetlana

2017-11-01

A physicochemical research of the processes of phase composition formation in the materials of the Dy-Sn-O system was performed. Phase composition was taking place in the course of thermal treatment of dysprosium (III) and tin (IV) codeposition products. These were codeposited from nitrate solutions at pH 7, and 25% ammonia water was used as the precipitant. Using thermal and X-ray diffraction analysis, it was found that in the above system at 90 wt. % of Dy2O3 and 10 wt. % of SnO2, when the precursors were heated above 600°C there are no solid solutions. In the meanwhile, at temperatures below 1000°C there is only one phase, Dy2O3. At temperatures above 1000°C, the system becomes bi-phase and includes Dy2O3 and Dy2Sn2O7.

Aluminum Target Dissolution in Support of the Pu-238 Program

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

McFarlane, Joanna; Benker, Dennis; DePaoli, David W

2014-09-01

Selection of an aluminum alloy for target cladding affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the caustic dissolution step, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. We present a study to maximize dissolution of aluminum metal alloy, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as a function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. These datamore » have been compared with published calculations of aluminum phase diagrams. Temperature logging during the transients has been investigated as a means to generate kinetic and mass transport data on the dissolution process. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.« less

Dissolution and Separation of Aluminum and Aluminosilicates

DOE PAGES

McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; ...

2015-12-19

The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as amore » function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.« less

2DCOS and PCMW2D analysis of FT-IR/ATR spectra measured at variable temperatures on-line to a polyurethane polymerization

NASA Astrophysics Data System (ADS)

Schuchardt, Patrick; Unger, Miriam; Siesler, Heinz W.

2018-01-01

In the present communication the potential of 2DCOS analysis and the spin-off technique perturbation-correlation moving window 2D (PCMW2D) analysis is illustrated with reference to spectroscopic changes observed in a data set recorded by in-line fiber-coupled FT-IR spectroscopy in the attenuated total reflection (ATR) mode during a polyurethane solution polymerization at different temperatures. In view of the chemical functionalities involved, hydrogen bonding plays an important role in this polymerization reaction. Based on the 2DCOS and PCMW2D analysis, the sequence of hydrogen bonding changes accompanying the progress of polymerization and precipitation of solid polymer can be determined. Complementary to the kinetic data derived from the original variable-temperature spectra in a previous publication the results provide a more detailed picture of the investigated solution polymerization.

A new approach for the recovery of precious metals from solution and from leachates derived from electronic scrap.

PubMed

Macaskie, L E; Creamer, N J; Essa, A M M; Brown, N L

2007-03-01

A new approach is described for the recovery of precious metals (PMs: Au, Pd and Ag) with >99% efficiency from aqueous solution utilising biogas produced during the aerobic growth of Klebsiella pneumoniae. Gold was recovered from electronic scrap leachate ( approximately 95%) by this method, with some selectivity against Cu. The recovered PM solids all contained metal and sulphur as determined by energy dispersive X-ray microanalysis (EDX). X-ray powder diffraction analysis (XRD) showed no crystalline metal sulphur compounds but a crystalline palladium amine was recorded. Silver was recovered as a sulphide (found by EDX), carbonate and oxide (found by XRD). EDX analysis of the Au-precipitate showed mainly gold and sulphur, with some metallic Au(0) detected by XRD. The gold compound was shock-sensitive; upon grinding it detonated to leave a sooty black deposit.

Phase-field simulations of coherent precipitate morphologies and coarsening kinetics

NASA Astrophysics Data System (ADS)

Vaithyanathan, Venugopalan

2002-09-01

The primary aim of this research is to enhance the fundamental understanding of coherent precipitation reactions in advanced metallic alloys. The emphasis is on a particular class of precipitation reactions which result in ordered intermetallic precipitates embedded in a disordered matrix. These precipitation reactions underlie the development of high-temperature Ni-base superalloys and ultra-light aluminum alloys. Phase-field approach, which has emerged as the method of choice for modeling microstructure evolution, is employed for this research with the focus on factors that control the precipitate morphologies and coarsening kinetics, such as precipitate volume fractions and lattice mismatch between precipitates and matrix. Two types of alloy systems are considered. The first involves L1 2 ordered precipitates in a disordered cubic matrix, in an attempt to model the gamma' precipitates in Ni-base superalloys and delta' precipitates in Al-Li alloys. The effect of volume fraction on coarsening kinetics of gamma' precipitates was investigated using two-dimensional (2D) computer simulations. With increase in volume fraction, larger fractions of precipitates were found to have smaller aspect ratios in the late stages of coarsening, and the precipitate size distributions became wider and more positively skewed. The most interesting result was associated with the effect of volume fraction on the coarsening rate constant. Coarsening rate constant as a function of volume fraction extracted from the cubic growth law of average half-edge length was found to exhibit three distinct regimes: anomalous behavior or decreasing rate constant with volume fraction at small volume fractions ( ≲ 20%), volume fraction independent or constant behavior for intermediate volume fractions (˜20--50%), and the normal behavior or increasing rate constant with volume fraction for large volume fractions ( ≳ 50%). The second alloy system considered was Al-Cu with the focus on understanding precipitation of metastable tetragonal theta'-Al 2Cu in a cubic Al solid solution matrix. In collaboration with Chris Wolverton at Ford Motor Company, a multiscale model, which involves a novel combination of first-principles atomistic calculations with a mesoscale phase-field microstructure model, was developed. Reliable energetics in the form of bulk free energy, interfacial energy and parameters for calculating the elastic energy were obtained using accurate first-principles calculations. (Abstract shortened by UMI.)

Mineral dissolution and secondary precipitation on quartz sand in simulated Hanford tank solutions affecting subsurface porosity

NASA Astrophysics Data System (ADS)

Wang, Guohui; Um, Wooyong

2012-11-01

Highly alkaline nuclear waste solutions have been released from underground nuclear waste storage tanks and pipelines into the vadose zone at the US Department of Energy's Hanford Site in Washington, causing mineral dissolution and re-precipitation upon contact with subsurface sediments. High pH caustic NaNO3 solutions with and without dissolved Al were reacted with quartz sand through flow-through columns stepwise at 45, 51, and 89 °C to simulate possible reactions between leaked nuclear waste solution and primary subsurface mineral. Upon reaction, Si was released from the dissolution of quartz sand, and nitrate-cancrinite [Na8Si6Al6O24(NO3)2] precipitated on the quartz surface as a secondary mineral phase. Both steady-state dissolution and precipitation kinetics were quantified, and quartz dissolution apparent activation energy was determined. Mineral alteration through dissolution and precipitation processes results in pore volume and structure changes in the subsurface porous media. In this study, the column porosity increased up to 40.3% in the pure dissolution column when no dissolved Al was present in the leachate, whereas up to a 26.5% porosity decrease was found in columns where both dissolution and precipitation were observed because of the presence of Al in the input solution. The porosity change was also confirmed by calculation using the dissolution and precipitation rates and mineral volume changes.

pH-Dependent Liquid-Liquid Phase Separation of Highly Supersaturated Solutions of Weakly Basic Drugs.

PubMed

Indulkar, Anura S; Box, Karl J; Taylor, Robert; Ruiz, Rebeca; Taylor, Lynne S

2015-07-06

Supersaturated solutions of poorly aqueous soluble drugs can be formed both in vivo and in vitro. For example, increases in pH during gastrointestinal transit can decrease the aqueous solubility of weakly basic drugs resulting in supersaturation, in particular when exiting the acidic stomach environment. Recently, it has been observed that highly supersaturated solutions of drugs with low aqueous solubility can undergo liquid-liquid phase separation (LLPS) prior to crystallization, forming a turbid solution such that the concentration of the drug in the continuous solution phase corresponds to the amorphous solubility while the colloidal phase is composed of a disordered drug-rich phase. Although it is well established that the equilibrium solubility of crystalline weakly basic drugs follows the Henderson-Hasselbalch relationship, the impact of pH on the LLPS phenomenon or the amorphous solubility has not been explored. In this work, the LLPS concentration of three weakly basic compounds-clotrimazole, nicardipine, and atazanavir-was determined as a function of pH using three different methods and was compared to the predicted amorphous solubility, which was calculated from the pH-dependent crystalline solubility and by estimating the free energy difference between the amorphous and crystalline forms. It was observed that, similar to crystalline solubility, the experimental amorphous solubility at any pH follows the Henderson-Hasselbalch relation and can be predicted if the amorphous solubility of the free base is known. Excellent agreement between the LLPS concentration and the predicted amorphous solubility was observed. Dissolution studies of amorphous drugs showed that the solution concentration can reach the corresponding LLPS concentration at that pH. Solid-state analysis of the precipitated material confirmed the amorphous nature. This work provides insight into the pH-dependent precipitation behavior of poorly water-soluble compounds and provides a fundamental basis with which to understand the performance of supersaturating dosage forms.

Tank 26F-2F Evaporator Study

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

Adu-Wusu, K.

2012-12-19

Tank 26F supernate sample was sent by Savannah River Remediation to Savannah River National Laboratory for evaporation test to help understand the underlying cause of the recent gravity drain line (GDL) pluggage during operation of the 2F Evaporator system. The supernate sample was characterized prior to the evaporation test. The evaporation test involved boiling the supernate in an open beaker until the density of the concentrate (evaporation product) was between 1.4 to 1.5 g/mL. It was followed by filtering and washing of the precipitated solids with deionized water. The concentrate supernate (or concentrate filtrate), the damp unwashed precipitated solids, andmore » the wash filtrates were characterized. All the precipitated solids dissolved during water washing. A semi-quantitative X-ray diffraction (XRD) analysis on the unwashed precipitated solids revealed their composition. All the compounds with the exception of silica (silicon oxide) are known to be readily soluble in water. Hence, their dissolution during water washing is not unexpected. Even though silica is a sparingly water-soluble compound, its dissolution is also not surprising. This stems from its small fraction in the solids as a whole and also its relative freshness. Assuming similar supernate characteristics, flushing the GDL with water (preferably warm) should facilitate dissolution and removal of future pluggage events as long as build up/aging of the sparingly soluble constituent (silica) is limited. On the other hand, since the amount of silica formed is relatively small, it is quite possible dissolution of the more soluble larger fraction will cause disintegration or fragmentation of the sparingly soluble smaller fraction (that may be embedded in the larger soluble solid mass) and allow its removal via suspension in the flushing water.« less

The effect of heat treatment on microfissuring in alloy 718

NASA Technical Reports Server (NTRS)

Thompson, R. G.; Dobbs, J. R.; Mayo, D. E.

1986-01-01

Changes in the microfissuring susceptibility of alloy 718 due to solution annealing and age hardening are studied. The effects of Ni3Nb (delta) precipitation during solution annealing and gamma-prime + gamma-double-prime precipitation during age hardening on microfissuring are investigated. It is observed that solution annealing reduces microfissuring and age hardening increases it, and the two precipitates do not affect microfissuring susceptibility. Potential causes for the detected intergranular segregation of the alloy are discussed.

SEPARATION OF FISSION PRODUCT VALUES FROM THE HEXAVALENT PLUTONIUM BY CARRIER PRECIPITATION

DOEpatents

Davies, T.H.

1959-12-15

An improved precipitation of fission products on bismuth phosphate from an aqueous mineral acid solution also containing hexavalent plutonium by incorporating, prior to bismuth phosphate precipitation, from 0.05 to 2.5 grams/ liter of zirconium phosphate, niobium oxide. and/or lanthanum fluoride is described. The plutonium remains in solution.

Inter-comparison of Precipitation Estimation Derived from GPM Dual-frequency Radar and CSU-CHILL Radar

NASA Astrophysics Data System (ADS)

Chen, S.; Chen, H.; Hu, J.; Zhang, A.; Min, C.

2017-12-01

It is more than 3 years since the launch of Global Precipitation Measurement (GPM) core satellite on February 27 2014. This satellite carries two core sensors, i.e. dual-frequency precipitation radar (DPR) and microwave imager (GMI). These two sensors are of the state-of- the-art sensors that observe the precipitation over the globe. The DPR level-2 product provides both precipitation rates and phases. The precipitation phase information can help advance global hydrological cycle modeling, particularly crucial for high-altitude and high latitude regions where solid precipitation is the dominated source of water. However, people are still in short of the reliability and accuracy of DPR level-2 product. Assess the performance and uncertainty of precipitation retrievals derived from the core sensor dual-frequency precipitation radar (DPR) on board the satellite is needed for the precipitation algorithm developers and the end users in hydrology, weather, meteorology, and hydro-related communities. In this study, the precipitation estimation derived from DPR is compared with that derived from CSU-CHILL National Weather Radar from March 2014 to October 2017. The CSU-CHILL radar is located in Greeley, CO, and is an advanced, transportable dual-polarized dual-wavelength (S- and X-band) weather radar. The system and random errors of DPR in measuring precipitation will be analyzed as a function of the precipitation rate and precipitation type (liquid and solid). This study is expected to offer insights into performance of the most advanced sensor and thus provide useful feedback to the algorithm developers as well as the GPM data end users.

Preparation of the polyelectrolyte complex hydrogel of biopolymers via a semi-dissolution acidification sol-gel transition method and its application in solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Zhao, Jian; Chen, Yu; Yao, Ying; Tong, Zong-Rui; Li, Pu-Wang; Yang, Zi-Ming; Jin, Shao-Hua

2018-02-01

Hydrogels have drawn many attentions as the solid-state electrolytes in flexible solid-state supercapacitors (SCs) recently. Among them, the polyelectrolyte complex hydrogel (PECH) electrolytes of natural polymers are more competitive because of their environmentally friendly property and low cost. However, while mixing two biopolymer solutions with opposite charges, the strong electrostatic interactions between the cationic and anionic biopolymers may result in precipitates instead of hydrogels. Here we report a novel method, semi-dissolution acidification sol-gel transition (SD-A-SGT), for the preparation of the PECH of chitosan (CTS) and sodium alginate (SA), with the controllable sol-gel transition and uniform composition and successfully apply it as the hydrogel electrolyte of solid-state supercapacitors (SCs). The CTS-SA PECH exhibits an extremely high ionic conductivity of 0.051 S·cm-1 and reasonable mechanical properties with a tensile strength of 0.29 MPa and elongation at break of 109.5%. The solid-state SC fabricated with the CTS-SA PECH and conventional polyaniline (PANI) nanowire electrodes provided a high specific capacitance of 234.6 F·g-1 at 5 mV·s-1 and exhibited excellent cycling stability with 95.3% capacitance retention after 1000 cycles. Our work may pave a novel avenue to the preparation of biodegradable PECHs of full natural polymers, and promote the development of environmentally friendly electronic devices.

Hydrodynamic Fingering Instability Induced by a Precipitation Reaction

NASA Astrophysics Data System (ADS)

Nagatsu, Y.; Ishii, Y.; Tada, Y.; De Wit, A.

2014-07-01

We experimentally demonstrate that a precipitation reaction at the miscible interface between two reactive solutions can trigger a hydrodynamic instability due to the buildup of a locally adverse mobility gradient related to a decrease in permeability. The precipitate results from an A +B→C type of reaction when a solution containing one of the reactants is injected into a solution of the other reactant in a porous medium or a Hele-Shaw cell. Fingerlike precipitation patterns are observed upon displacement, the properties of which depend on whether A displaces B or vice versa. A mathematical modeling of the underlying mobility profile confirms that the instability originates from a local decrease in mobility driven by the localized precipitation. Nonlinear simulations of the related reaction-diffusion-convection model reproduce the properties of the instability observed experimentally. In particular, the simulations suggest that differences in diffusivity between A and B may contribute to the asymmetric characteristics of the fingering precipitation patterns.

URANOUS IODATE AS A CARRIER FOR PLUTONIUM

DOEpatents

Miller, D.R.; Seaborg, G.T.; Thompson, S.G.

1959-12-15

A process is described for precipitating plutonium on a uranous iodate carrier from an aqueous acid solution conA plutonium solution more concentrated than the original solution can then be obtained by oxidizing the uranium to the hexavalent state and dissolving the precipitate, after separating the latter from the original solution, by means of warm nitric acid.

Insights into the discrepant luminescence for BaSiO3 :Eu2+ phosphors prepared by solid-state reaction and precipitation reaction methods.

PubMed

Xu, Jiao; Zhao, Yang; Chen, Jingjing; Mao, Zhiyong; Yang, Yanfang; Wang, Dajian

2017-09-01

Two synthesis routes, solid-state reaction and precipitation reaction, were employed to prepare BaSiO 3 :Eu 2+ phosphors in this study. Discrepancies in the luminescence green emission at 505 nm for the solid-state reaction method sample and in the yellow emission at 570 nm for the sample prepared by the precipitation reaction method, were observed respectively. A detail investigation about the discrepant luminescence of BaSiO 3 :Eu 2+ phosphors was performed by evaluation of X-ray diffraction (XRD), photoluminescence (PL)/photoluminescence excitation (PLE), decay time and thermal quenching properties. The results showed that the yellow emission was generated from the BaSiO 3 :Eu 2+ phosphor, while the green emission was ascribed to a small amount of Ba 2 SiO 4 :Eu 2+ compound that was present in the solid-state reaction sample. This work clarifies the luminescence properties of Eu 2+ ions in BaSiO 3 and Ba 2 SiO 4 hosts. Copyright © 2017 John Wiley & Sons, Ltd.

Binary ferrihydrite catalysts

DOEpatents

Huffman, Gerald P.; Zhao, Jianmin; Feng, Zhen

1996-01-01

A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered.

Variable diffusion rates during exsolution coarsening in the presence of fluids.

NASA Astrophysics Data System (ADS)

Putnis, Andrew; Prent, Alexander

2017-04-01

The scale of exsolution textures in mineral solid solutions has long been used as an indicator of thermal history during cooling. The theory of spinodal decomposition in an anisotropic solid and subsequent coarsening of exsolution textures as a function of temperature and cooling rate is well developed (see Petrishcheva et al., 2009 and Abart et al., 2009 for a review of the Cahn-Hilliard theory). For the case of exsolution in the alkali feldspar solid solution [(Na,K)AlSi3O8] the characteristic texture shows compositional fluctuations in Na,K with a wavelength that depends on the cooling rate. The cooling rate is determined from knowledge of the Na-K interdiffusion coefficient, assuming that the unmixing is simply due to the interdiffusion of Na and K in an otherwise fixed tetrahedral Al,Si framework. Cryptoperthites and mesoperthites with a periodic lamellar microstructure are considered to be the end-result of such a solid-state exsolution process. Later-stage fluid infiltration results in patch perthites that are formed at a sharp replacement front by a dissolution-precipitation mechanism (Parsons et al., 2015). Patch perthites have an easily recognizable texture and are clear indicators of a reaction with an aqueous solution. The distinction is thus drawn between crypto- and meso-perthite showing periodic lamellae, associated with a solid-state exsolution process, and the patch perthite showing irregular domains of Na-rich and K-rich feldspars associated with a fluid mediated reprecipitation process. However, the presence of fluids can also enhance the coarsening of lamellar exsolution textures, retaining an apparently solid-state microstructure but with a length scale that is dependent on local recrystallization driven by fluid infiltration. Examples will be given from alkali feldspars in granitic rocks where it is clearly demonstrable that cooling rates cannot be inferred from such exsolution textures. The variability in Na,K diffusion rates and thus different length scales of exsolution are likely to be due to the efficiency of diffusional transport through a fluid phase, which is influenced by differences in fluid-induced micro- and nano-porosity. Abart R. et al. (2009) Am. J. Sci. 309, 450-475. Petrishcheva E. and Abart R. (2009) Am. J. Sci, 309, 431-449. Parsons I. et al., (2015) Am. Min. 100, 1277-1303.

Control of silicification by genetically engineered fusion proteins: silk-silica binding peptides.

PubMed

Zhou, Shun; Huang, Wenwen; Belton, David J; Simmons, Leo O; Perry, Carole C; Wang, Xiaoqin; Kaplan, David L

2015-03-01

In the present study, an artificial spider silk gene, 6mer, derived from the consensus sequence of Nephila clavipes dragline silk gene, was fused with different silica-binding peptides (SiBPs), A1, A3 and R5, to study the impact of the fusion protein sequence chemistry on silica formation and the ability to generate a silk-silica composite in two different bioinspired silicification systems: solution-solution and solution-solid. Condensed silica nanoscale particles (600-800 nm) were formed in the presence of the recombinant silk and chimeras, which were smaller than those formed by 15mer-SiBP chimeras, revealing that the molecular weight of the silk domain correlated to the sizes of the condensed silica particles in the solution system. In addition, the chimeras (6mer-A1/A3/R5) produced smaller condensed silica particles than the control (6mer), revealing that the silica particle size formed in the solution system is controlled by the size of protein assemblies in solution. In the solution-solid interface system, silicification reactions were performed on the surface of films fabricated from the recombinant silk proteins and chimeras and then treated to induce β-sheet formation. A higher density of condensed silica formed on the films containing the lowest β-sheet content while the films with the highest β-sheet content precipitated the lowest density of silica, revealing an inverse correlation between the β-sheet secondary structure and the silica content formed on the films. Intriguingly, the 6mer-A3 showed the highest rate of silica condensation but the lowest density of silica deposition on the films, compared with 6mer-A1 and -R5, revealing antagonistic crosstalk between the silk and the SiBP domains in terms of protein assembly. These findings offer a path forward in the tailoring of biopolymer-silica composites for biomaterial related needs. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

PROCESSES FOR SEPARATING AND RECOVERING CONSTITUENTS OF NEUTRON IRRADIATED URANIUM

DOEpatents

Connick, R.E.; Gofman, J.W.; Pimentel, G.C.

1959-11-10

Processes are described for preparing plutonium, particularly processes of separating plutonium from uranium and fission products in neutron-irradiated uraniumcontaining matter. Specifically, plutonium solutions containing uranium, fission products and other impurities are contacted with reducing agents such as sulfur dioxide, uranous ion, hydroxyl ammonium chloride, hydrogen peroxide, and ferrous ion whereby the plutoninm is reduced to its fluoride-insoluble state. The reduced plutonium is then carried out of solution by precipitating niobic oxide therein. Uranium and certain fission products remain behind in the solution. Certain other fission products precipitate along with the plutonium. Subsequently, the plutonium and fission product precipitates are redissolved, and the solution is oxidized with oxidizing agents such as chlorine, peroxydisulfate ion in the presence of silver ion, permanganate ion, dichromate ion, ceric ion, and a bromate ion, whereby plutonium is oxidized to the fluoride-soluble state. The oxidized solution is once again treated with niobic oxide, thus precipitating the contamirant fission products along with the niobic oxide while the oxidized plutonium remains in solution. Plutonium is then recovered from the decontaminated solution.

Precipitated Silica from Pumice and Carbon Dioxide Gas (Co2) in Bubble Column Reactor

NASA Astrophysics Data System (ADS)

Dewati, R.; Suprihatin, S.; Sumada, K.; Muljani, S.; Familya, M.; Ariani, S.

2018-01-01

Precipitated silica from silica and carbon dioxide gas has been studied successfully. The source of silica was obtained from pumice stone while precipitation process was carried out with carbon dioxide gas (CO2). The sodium silicate solution was obtained by extracting the silica from pumice stone with sodium hydroxide (NaOH) solution and heated to 100 °C for 1 h. The carbon dioxide gas is injected into the aqueous solution of sodium silicate in a bubble column reactor to form precipitated silica. m2/g. The results indicate that the products obtained are precipitate silica have surface area in the range of 100 - 227 m2/g, silica concentration more than 80%, white in appearance, and silica concentration reached 90% at pH 7.

PRECIPITATION METHOD OF SEPARATION OF NEPTUNIUM

DOEpatents

Magnusson, L.B.

1958-07-01

A process is described for the separation of neptunium from plutonium in an aqueous solution containing neptunium ions in a valence state not greater than +4, plutonium ioms in a valence state not greater than +4, and sulfate ions. The Process consists of adding hypochlorite ions to said solution in order to preferentially oxidize the neptunium and then adding lanthanum ions and fluoride ions to form a precipitate of LaF/sub 3/ carrying the plutonium, and thereafter separating the supernatant solution from the precipitate.

CONCENTRATION AND DECONTAMINATION OF SOLUTIONS CONTAINING PLUTONIUM VALUES BY BISMUTH PHOSPHATE CARRIER PRECIPITATION METHODS

DOEpatents

Seaborg, G.T.; Thompson, S.G.

1960-08-23

A process is given for isolating plutonium present in the tetravalent state in an aqueous solution together with fission products. First, the plutonium and fission products are coprecipitated on a bismuth phosphate carrier. The precipitate obtained is dissolved, and the plutonium in the solution is oxidized to the hexavalent state (with ceric nitrate, potassium dichromate, Pb/ sub 3/O/sub 4/, sodium bismuthate and/or potassium dichromate). Thereafter a carrier for fission products is added (bismuth phosphate, lanthanum fluoride, ceric phosphate, bismuth oxalate, thorium iodate, or thorium oxalate), and the fission-product precipitation can be repeated with one other of these carriers. After removal of the fission-product-containing precipitate or precipitates. the plutonium in the supernatant is reduced to the tetravalent state (with sulfur dioxide, hydrogen peroxide. or sodium nitrate), and a carrier for tetravalent plutonium is added (lanthanum fluoride, lanthanum hydroxide, lanthanum phosphate, ceric phosphate, thorium iodate, thorium oxalate, bismuth oxalate, or niobium pentoxide). The plutonium-containing precipitate is then dissolved in a relatively small volume of liquid so as to obtain a concentrated solution. Prior to dissolution, the bismuth phosphate precipitates first formed can be metathesized with a mixture of sodium hydroxide and potassium carbonate and plutonium-containing lanthanum fluorides with alkali-metal hydroxide. In the solutions formed from a plutonium-containing lanthanum fluoride carrier the plutonium can be selectively precipitated with a peroxide after the pH was adjusted preferably to a value of between 1 and 2. Various combinations of second, third, and fourth carriers are discussed.

Fe hydroxyphosphate precipitation and Fe(II) oxidation kinetics upon aeration of Fe(II) and phosphate-containing synthetic and natural solutions

NASA Astrophysics Data System (ADS)

van der Grift, B.; Behrends, T.; Osté, L. A.; Schot, P. P.; Wassen, M. J.; Griffioen, J.

2016-08-01

Exfiltration of anoxic Fe-rich groundwater into surface water and the concomitant oxidative precipitation of Fe are important processes controlling the transport of phosphate (PO4) from agricultural areas to aquatic systems. Here, we explored the relationship between solution composition, reaction kinetics, and the characteristics of the produced Fe hydroxyphosphate precipitates in a series of aeration experiments with anoxic synthetic water and natural groundwater. A pH stat device was used to maintain constant pH and to record the H+ production during Fe(II) oxidation in the aeration experiments in which the initial aqueous P/Fe ratios ((P/Fe)ini), oxygen concentration and pH were varied. In general, Fe(II) oxidation proceeded slower in the presence of PO4 but the decrease of the PO4 concentration during Fe(II) oxidation due to the formation of Fe hydroxyphosphates caused additional deceleration of the reaction rate. The progress of the reaction could be described using a pseudo-second-order rate law with first-order dependencies on PO4 and Fe(II) concentrations. After PO4 depletion, the Fe(II) oxidation rates increased again and the kinetics followed a pseudo-first-order rate law. The first-order rate constants after PO4 depletion, however, were lower compared to the Fe(II) oxidation in a PO4-free solution. Hence, the initially formed Fe hydroxyphosphates also affect the kinetics of continuing Fe(II) oxidation after PO4 depletion. Presence of aqueous PO4 during oxidation of Fe(II) led to the formation of Fe hydroxyphosphates. The P/Fe ratios of the precipitates ((P/Fe)ppt) and the recorded ratio of H+ production over decrease in dissolved Fe(II) did not change detectably throughout the reaction despite a changing P/Fe ratio in the solution. When (P/Fe)ini was 0.9, precipitates with a (P/Fe)ppt ratio of about 0.6 were formed. In experiments with (P/Fe)ini ratios below 0.6, the (P/Fe)ppt decreased with decreasing (P/Fe)ini and pH value. Aeration experiments with natural groundwater showed no principal differences in Fe(II) oxidation kinetics and in PO4 immobilisation dynamics compared with synthetic solutions with corresponding P/Fe ratio, pH and oxygen pressure. However, aeration of groundwater with relative high DOC concentrations and a low salinity lead to P-rich Fe colloids that were colloidally stable. The formation of a Fe hydroxyphosphate phase with a molar P/Fe ratio of 0.6 can be used for predictive modelling of PO4 immobilisation upon aeration of pH-neutral natural groundwater with an (P/Fe)ini ratio up to 1.5. These findings provide a solid basis for further studies on transport and bioavailability of phosphorus in streams, ditches and channels that receive anoxic Fe-rich groundwater.

Monoclinic structure of hydroxylpyromorphite Pb10(PO4)6(OH)2 - hydroxylmimetite Pb10(AsO4)6(OH)2 solid solution series

NASA Astrophysics Data System (ADS)

Giera, Alicja; Manecki, Maciej; Borkiewicz, Olaf; Zelek, Sylwia; Rakovan, John; Bajda, Tomasz; Marchlewski, Tomasz

2016-04-01

Seven samples of hydroxyl analogues of pyromorphite-mimetite solid solutions series were synthesized from aqueous solutions at 80° C in a computer-controlled chemistate: 200 mL aqueous solutions of 0.05M Pb(NO3)2 and 0.03M KH2AsO4 and/or KH2PO4 were dosed with a 0.25 mL/min rate to a glass beaker, which initially contained 100 mL of distilled water. Constant pH of 8 was maintained using 2M KOH. The syntheses yielded homogeneous fine-grained white precipitates composition of which was close to theoretical Pb10[(PO4)6-x(AsO4)x](OH)2, where x = 0, 1, 2, 3, 4, 5, 6. High-resolution powder X-ray diffraction data were obtained in transmission geometry at the beamline 11-BM at the Advanced Photon Source (Argonne National Laboratory in Illinois, USA). The structure Rietveld refinements based on starting parameters of either hexagonal hydroxylpyromorphite or monoclinic mimetite-M were performed using GSAS+EXPGUI software. Apatite usually crystallizes in the hexagonal crystal system with the space group P63/m. For the first time, however, the lowering of the hexagonal to monoclinic crystal symmetry was observed in the hydroxyl variety of pyromorphite-mimetite solid solution series. This is indicated by better fitting of the modeled monoclinic structure to the experimental data. The same is not the case for analogous calcium hydroxylapatite series Ca5(PO4)3OH - Ca5(AsO4)3OH (Lee et al. 2009). Systematical linear increase of unit cell parameters is observed with As substitution from a=9.88, b=19.75, and c=7.43 for Pb10(PO4)6(OH)2 to a=10.23, b=20.32, and c=7.51 for Pb10(AsO4)6(OH)2. A strong pseudohexagonal character (γ ≈ 120° and b ≈ 2a) of the analyzed monoclinic phases was established. This work is partially funded by AGH research grant no 11.11.140.319 and partially by Polish NCN grant No 2011/01/M/ST10/06999. Lee Y.J., Stephens P.W., Tang Y., Li W., Philips B.L., Parise J.B., Reeder R.J., 2009. Arsenate substitution in hydroxylapatite: Structural characterization of the Ca5(PxAs1-xO4)3OH solid solution. American Mineralogist, 94, 666-675.

ELECTROLYTIC REDUCTION OF NITRIC ACID SOLUTIONS

DOEpatents

Alter, H.W.; Barney, D.L.

1958-09-30

A process is presented for the treatment of radioactivc waste nitric acid solutions. The nitric acid solution is neutralized with an alkali metal hydroxide in an amount sufficient to precipitate insoluble hydroxides, and after separation of the precipitate the solution is electrolyzed to convert the alkali nitrate formed, to alkali hydroxide, gaseous ammonla and oxygen. The solution is then reusable after reducing the volume by evaporating the water and dissolved ammonia.

Influence of lysozyme on the precipitation of calcium carbonate: a kinetic and morphologic study

NASA Astrophysics Data System (ADS)

Jimenez-Lopez, Concepcion; Rodriguez-Navarro, Alejandro; Dominguez-Vera, Jose M.; Garcia-Ruiz, Juan M.

2003-05-01

Several mechanisms have been proposed to explain the interactions between proteins and mineral surfaces, among them a combination of electrostatic, stereochemical interactions and molecular recognition between the protein and the crystal surface. To identify the mechanisms of interaction in the lysozyme-calcium carbonate model system, the effect of this protein on the precipitation kinetics and morphology of calcite crystals was examined. The solution chemistry and morphology of the solid were monitored over time in a set of time-series free-drift experiments in which CaCO 3 was precipitated from solution in a closed system at 25°C and 1 atm total pressure, in the presence and absence of lysozyme. The precipitation of calcite was preceded by the precipitation of a metastable phase that later dissolved and gave rise to calcite as the sole phase. With increasing lysozyme concentration, the nucleation of both the metastable phase and calcite occurred at lower Ω calcite, indicating that lysozyme favored the nucleation of both phases. Calcite growth rate was not affected by the presence of lysozyme, at least at protein concentrations ranging from 0 mg/mL to 10 mg/mL. Lysozyme modified the habit of calcite crystals. The degree of habit modification changed with protein concentration. At lower concentrations of lysozyme, the typical rhombohedral habit of calcite crystals was modified by the expression of {110} faces, which resulted from the preferential adsorption of protein on these faces. With increasing lysozyme concentration, the growth of {110}, {100}, and finally {001} faces was sequentially inhibited. This adsorption sequence may be explained by an electrostatic interaction between lysozyme and calcite, in which the inhibition of the growth of {110}, {100}, and {001} faces could be explained by a combined effect of the density of carbonate groups in the calcite face and the specific orientation (perpendicular) of these carbonate groups with respect to the calcite surface. Overgrowth of calcite in the presence of lysozyme demonstrated that the protein favored and controlled the nucleation on the calcite substrate. Overgrowth crystals nucleated epitaxially in lines which run diagonal to rhombohedral {104} faces.

PRECIPITATION OF PROTACTINIUM

DOEpatents

Moore, R.L.

1958-07-15

An lmprovement in the separation of protactinium from aqueous nitric acid solutions is described. 1t covers the use of lead dioxide and tin dioxide as carrier precipitates for the protactinium. In carrying out the process, divalent lead or divalent tin is addcd to the solution and oxidized, causing formation of a carrier precipitate of lead dioxide or stannic oxide, respectively.

Precipitate resolution in an electron irradiated ni-si alloy

NASA Astrophysics Data System (ADS)

Watanabe, H.; Muroga, T.; Yoshida, N.; Kitajima, K.

1988-09-01

Precipitate resolution processes in a Ni-12.6 at% Si alloy under electron irradiation have been observed by means of HVEM. Above 400°C, growth and resolution of Ni 3Si precipitates were observed simultaneously. The detail stereoscopic observation showed that the precipitates close to free surfaces grew, while those in the middle of a specimen dissolved. The critical dose when the precipitates start to shrink increases with increasing the depth. This depth dependence of the precipitate behavior under irradiation has a close relation with the formation of surface precipitates and the growth of solute depleted zone beneath them. The temperature and dose dependence of the resolution rate showed that the precipitates in the solute depleted zone dissolved by the interface controlled process of radiation-enhanced diffusion.

Cupric oxide inclusions in cuprous oxide crystals grown by the floating zone method

NASA Astrophysics Data System (ADS)

Frazer, Laszlo; Chang, Kelvin B.; Poeppelmeier, Kenneth R.; Ketterson, John B.

2015-06-01

Phase-pure cuprous oxide (Cu2O) crystals are difficult to grow since cupric oxide can form within the crystal as the crystal is cooled to ambient conditions. Vacancies are the solute which causes precipitation of macroscopic defects. Therefore, even when a mostly phase-pure single crystal is used as a feed rod, cupric oxide inclusions persist in the recrystallized solid. Control of the thermal profile during crystal growth, however, can improve phase-purity; a slow counter-rotation rate of the feed and seed rods results in fewer inclusions. Cupric oxide can be removed by annealing, which produces a factor of 540 ± 70 increase in phase-purity.

Development of a Thin Gauge Metallic Seal for Gas Turbine Engine Applications to 1700 F

NASA Technical Reports Server (NTRS)

England, Raymond O.

2006-01-01

The goal of doubling thrust-to-weight ratio for gas turbine engines has placed significant demands on engine component materials. Operating temperatures for static seals in the transition duct and turbine sections for instance, may well reach 2000 F within the next ten years. At these temperatures conventional age-hardenable superalloys lose their high strength via overaging and eventual dissolution of the gamma precipitate, and are well above their oxidation stability limit. Conventional solid-solution-strengthened alloys offer metallurgical stability, but suffer from rapid oxidation and little useful load bearing strength. Ceramic materials can theoretically be used at these temperatures, but manufacturing processes are in the developmental stages.

Phase Composition and Hardening of Castable Al - Ca - Ni - Sc Alloys Containing 0.3% Sc

NASA Astrophysics Data System (ADS)

Belov, N. A.; Naumova, E. A.; Bazlova, T. A.; Doroshenko, V. V.

2017-05-01

The phase composition of aluminum alloys of the Al - Ca - Ni - Sc system containing 0.3 wt.% Sc is studied. It is shown that the aluminum solid solution may be in equilibrium not only with binary phases (Al4Ca, Al3Sc and Al3Ni) but also with a ternary Al9NiCa compound. The temperature of attainment of maximum hardening due to precipitation of nanoparticles of phase Al3Sc is determined for all the alloys studied. Principal possibility of creation of castable alloys based on an (Al) + Al4Ca + Al9NiCa eutectic, the hardening heat treatment of which does not require quenching, is substantiated.

Cupric oxide inclusions in cuprous oxide crystals grown by the floating zone method

PubMed Central

Frazer, Laszlo; Chang, Kelvin B; Poeppelmeier, Kenneth R; Ketterson, John B

2015-01-01

Phase-pure cuprous oxide (Cu2O) crystals are difficult to grow since cupric oxide can form within the crystal as the crystal is cooled to ambient conditions. Vacancies are the solute which causes precipitation of macroscopic defects. Therefore, even when a mostly phase-pure single crystal is used as a feed rod, cupric oxide inclusions persist in the recrystallized solid. Control of the thermal profile during crystal growth, however, can improve phase-purity; a slow counter-rotation rate of the feed and seed rods results in fewer inclusions. Cupric oxide can be removed by annealing, which produces a factor of 540 ± 70 increase in phase-purity. PMID:27877798

Mechanical properties and grindability of experimental Ti-Au alloys.

PubMed

Takahashi, Masatoshi; Kikuchi, Masafumi; Okuno, Osamu

2004-06-01

Experimental Ti-Au alloys (5, 10, 20 and 40 mass% Au) were made. Mechanical properties and grindability of the castings of the Ti-Au alloys were examined. As the concentration of gold increased to 20%, the yield strength and the tensile strength of the Ti-Au alloys became higher without markedly deteriorating their ductility. This higher strength can be explained by the solid-solution strengthening of the a titanium. The Ti-40%Au alloy became brittle because the intermetallic compound Ti3Au precipitated intensively near the grain boundaries. There was no significant difference in the grinding rate and grinding ratio among all the Ti-Au alloys and the pure titanium at any speed.

Synthesis and stability of hetaerolite, ZnMn2O4, at 25°C

USGS Publications Warehouse

Hem, J.D.; Roberson, C.E.; Lind, C.J.

1987-01-01

A precipitate of nearly pure hetaerolite, ZnMn2O4, a spinel-structured analog of hausmannite, Mn3O4, was prepared by an irreversible wprecipitation of zinc with manganese at 25°C. The synthesis technique entailed constant slow addition of a dilute solution of Mn2+ and Zn2+ chlorides having a Mn/Zn ratio of 2:1 to a reaction vessel that initially contained distilled deionized water, maintained at a pH of 8.50 by addition of dilute NaOH by an automated pH stat, with continuous bubbling of CO2-free air. The solid was identified by means of X-ray diffraction and transmission electron microscopy and consisted of bipyramidal crystals generally less than 0.10 μm in diameter. Zn2+ ions are able to substitute extensively for Mn2+ ions that occupy tetrahedral sites in the hausmannite structure.Hetaerolite appears to be more stable than hausmannite with respect to spontaneous conversion to γMnOOH. The value of the standard free energy of formation of hetaerolite was estimated from the experimental data to be −289.4 ± 0.8 kcal per mole. Solids intermediate in composition between hetaerolite and hausmannite can be prepared by altering the Mn/Zn ratio in the feed solution.

Effect of Strengthening Mechanism on Strain-Rate Related Tensile Properties of Low-Carbon Sheet Steels for Automotive Application

NASA Astrophysics Data System (ADS)

Das, Anindya; Biswas, Pinaki; Tarafder, S.; Chakrabarti, D.; Sivaprasad, S.

2018-05-01

In order to ensure crash resistance of the steels used in automotive components, the ensile deformation behavior needs to be studied and predicted not only under quasi-static condition, but also under dynamic loading rates. In the present study, tensile tests have been performed on four different automobile grade sheet steels, namely interstitial free steel, dual-phase 600 and 800, and a carbon manganese steel over the strain rate regime of 0.001-800/s. Apart from the variation in strength (which always increased with strain rate), the effect of strengthening mechanism on strain rate sensitivity and strain hardening behavior has been evaluated. Strain rate sensitivity was found to increase at high-strain rate regime for all the steels. Contribution of solid solution hardening on strain rate sensitivity at lower plastic strains was found to be higher compared to dislocation strengthening and second-phase hardening. However, precipitation hardening coupled with solid solution hardening produced the highest strain rate sensitivity, in C-Mn-440 steel at high strain rates. Different strain-rate-sensitive models which take into account the change in yield stress and strain hardening behavior with strain rate for ductile materials were used to predict the flow behavior of these sheet steels at strain rates up to 800/s.

Study of accuracy of precipitation measurements using simulation method

NASA Astrophysics Data System (ADS)

Nagy, Zoltán; Lajos, Tamás; Morvai, Krisztián

2013-04-01

Hungarian Meteorological Service1 Budapest University of Technology and Economics2 Precipitation is one of the the most important meteorological parameters describing the state of the climate and to get correct information from trends, accurate measurements of precipitation is very important. The problem is that the precipitation measurements are affected by systematic errors leading to an underestimation of actual precipitation which errors vary by type of precipitaion and gauge type. It is well known that the wind speed is the most important enviromental factor that contributes to the underestimation of actual precipitation, especially for solid precipitation. To study and correct the errors of precipitation measurements there are two basic possibilities: · Use of results and conclusion of International Precipitation Measurements Intercomparisons; · To build standard reference gauges (DFIR, pit gauge) and make own investigation; In 1999 at the HMS we tried to achieve own investigation and built standard reference gauges But the cost-benefit ratio in case of snow (use of DFIR) was very bad (we had several winters without significant amount of snow, while the state of DFIR was continously falling) Due to the problem mentioned above there was need for new approximation that was the modelling made by Budapest University of Technology and Economics, Department of Fluid Mechanics using the FLUENT 6.2 model. The ANSYS Fluent package is featured fluid dynamics solution for modelling flow and other related physical phenomena. It provides the tools needed to describe atmospheric processes, design and optimize new equipment. The CFD package includes solvers that accurately simulate behaviour of the broad range of flows that from single-phase to multi-phase. The questions we wanted to get answer to are as follows: · How do the different types of gauges deform the airflow around themselves? · Try to give quantitative estimation of wind induced error. · How does the use of wind shield improve the accuracy of precipitation measurements? · Try to find the source of the error that can be detected at tipping bucket raingauge in winter time because of use of heating power? On our poster we would like to present the answers to the questions listed above.

Enhancement of Thermoelectric Properties in SnTe with (Ag, In) Co-Doping

NASA Astrophysics Data System (ADS)

Li, J. Q.; Yang, N.; Li, S. M.; Li, Y.; Liu, F. S.; Ao, W. Q.

2018-01-01

A lead-free SnTe compound shows good electrical property but high thermal conductivity, resulting in a low figure-of-merit ZT. We present a significant enhancement of the thermoelectric properties of p-type SnTe with (Ag, In) co-doping. The Ag and In co-doped Sn1-2 x Ag x In x Te ( x = 0.00, 0.01, 0.02, 0.03, 0.04 and 0.05) are prepared by melting, quenching and spark plasma sintering. A homogeneous NaCl-type SnTe-based solid solution forms in the alloys at low Ag and In content ( x ≤ 0.02), while a AgInTe2 minor secondary phase precipitates for higher x. Similar to In doping, the introduction of Ag and In at Sn sites in SnTe considerably increases the Seebeck coefficient and power factor by creating resonant levels near the Fermi energy. In addition, the Ag and In solute atoms in the SnTe-based solid solution and the minor secondary phase AgInTe2 enhance phonon scattering and thus significantly reduce the carrier and lattice thermal conductivity. Ag and In co-doping shows a collective advantage on the overall thermoelectric performance of SnTe or In-doped SnTe. A maximum ZT of 1.23 at 873 K and average ZT of 0.58 can be obtained in the alloy Sn1-2 x Ag x In x Te with x = 0.03.

Aqueous two-phase extraction of nickel dimethylglyoximato complex and its application to spectrophotometric determination of nickel in stainless steel.

PubMed

Yoshikuni, Nobutaka; Baba, Takayuki; Tsunoda, Natsuki; Oguma, Koichi

2005-03-31

A polyethylene glycol (PEG)-based aqueous two-phase system has been established for the extraction of Ni-dimethylglyoximato complex. Appropriate amounts of PEG solution and solid (NH(4))(2)SO(4) were added to the Ni-dimethylglyoximato complex which had been formed in the presence of sodium tartrate and K(2)S(2)O(8) at pH 12 in a separatory funnel and shaken vigorously for about 1min. The mixture was allowed to stand for 10min and then the absorbance of the extracted complex in the upper PEG-rich phase was measured at 470nm. Beer's law was obeyed over the range of 0.26-2.1ppm Ni. The proposed extraction method has been applied to the determination of Ni in steel. A steel sample was decomposed with an appropriate acid mixture. An aliquot of the sample solution was taken, treated with H(3)PO(4) and most of the iron and copper were removed by hydroxide precipitation using solid BaCO(3) to control the pH of the sample solution in advance of the extraction of Ni. The analytical results obtained for Ni in steel certified reference material JSS 650-10 (The Japan Iron and Steel Federation), BCS 323 (Bureau of Analysed Samples Ltd.) and NIST SRM 361 and 362 (National Institute of Standards and Technology) were in good agreement with certified values.

Heterogeneous Catalysts for VOC Oxidation from Red Mud and Bagasse Ash Carbon

NASA Astrophysics Data System (ADS)

Pande, Gaurav

A range of VOC oxidation catalysts have been prepared in this study from agricultural and industrial waste as the starting point. The aim is to prepare catalysts with non-noble metal oxides as the active catalytic component (iron in red mud). The same active component was also supported on activated carbon obtained from unburned carbon in bagasse ash. Red mud which is an aluminum industry waste and rich in different phases of iron as oxide and hydroxide is used as the source for the catalytically active species. It is our aim to enhance the catalytic performance of red mud which though high in iron concentration has a low surface area and may not have the properties of an ideal catalyst by itself. In one of the attempts to enhance the catalytic performance, we have tried to leach red mud for which we have explored a range of leaching acids for effecting the leaching most efficiently and then precipitated the iron from the leachate as its hydroxide by precipitating with alkali solution followed by drying and calcination to give high surface area metal oxide material. Extensive surface characterization and VOC oxidation catalytic testing were performed for these solids. In a step to further enhance the catalytic activity towards oxidation, copper was introduced by taking another industrial waste from the copper tubing industry viz. the pickling acid. Copper has a more favourable redox potential making it catalytically more effective than iron. To make the mixed metal oxide, red mud leachate was mixed with the pickling acid in a pre-decided ratio before precipitating with alkali solution followed by drying and calcination as was done with the red mud leachate. The results from these experiments are encouraging. The temperature programmed reduction (TPR) of the solids show that the precipitate of red mud leachates show hydrogen uptake peak at a lower temperature than for just the calcined red mud. This could be due to the greatly enhanced surface area of the prepared solids. The highest surface area of 311 m2/g was for the sample prepared from oxalic acid and l-ascorbic acid as the leaching acid; as received red mud has a surface area of 11.5 m2/g. This sample showed better catalytic performance than the ones made from hydrochloric acid as the leaching acid in spite of a similar increase in surface area. High temperature XRD shows the reason for this difference in catalytic properties could be due to both the solids reducing in a different way to give different phases though they are both derived from red mud as the starting material. Also, the sample prepared with oxalic acid leachate had higher surface iron concentration. For the best catalyst (oxalic acid derived) the light off temperature is about 300 °C for toluene oxidation. For solids prepared from red mud leachate for iron source and pickling acid for copper source, it was seen that the TPR gave hydrogen absorption at temperatures even lower than that for red mud leachate precipitates. In another set of experiments, iron oxide impregnated on activated carbon supports were prepared. Activated carbon is known for its adsorption properties which could give a better access of the impregnated metal oxide catalyst to perform the catalytic oxidation on the adsorbed substrate. Unburned carbon in bagasse ash which is a sugar industry agricultural waste was used to get the activated carbon. This material was separated from the ash and further modified to enhance the activity and increase the porosity. To this effect steam activation was performed. To impart thermal stability for oxidation reaction, the carbon was impregnated by phosphoric acid at activated at high temperatures in inert atmosphere. These carbons were thermally stable due to the surface C--O--P groups. Toluene adsorption studies were also performed for both the steam activated as well as phosphoric acid activated carbon and it was found that the steam activated carbons with less surface oxygen had reasonable adsorption attributes. For iron impregnation onto the prepared bagasse ash carbons, two different methods of impregnation viz. incipient wetness method as well as impregnation by precipitation of the red mud leachate by adding alkali to a slurry of carbon and leachate (Pratt method) was used. It was found that impregnation by precipitation led to better butanol oxidation performing catalyst than the one prepared by impregnating by incipient wetness method. The best performing catalyst amongst the iron impregnated on carbon types was found to give 100% butanol conversion at 200 °C. It was also observed that red mud leachate precipitated catalyst performed well for toluene oxidation and not for butanol oxidation while carbon supported iron oxide catalysts worked better for butanol oxidation than for toluene oxidation.

Mineral Dissolution and Secondary Precipitation on Quartz Sand in Simulated Hanford Tank Solutions Affecting Subsurface Porosity

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

Wang, Guohui; Um, Wooyong

2012-11-23

Highly alkaline nuclear waste solutions have been released from underground nuclear waste storage tanks and pipelines into the vadose zone at the U.S. Department of Energy’s Hanford Site in Washington, causing mineral dissolution and re-precipitation upon contact with subsurface sediments. High pH caustic NaNO3 solutions with and without dissolved Al were reacted with quartz sand through flow-through columns stepwise at 45, 51, and 89°C to simulate possible reactions between leaked nuclear waste solution and primary subsurface mineral. Upon reaction, Si was released from the dissolution of quartz sand, and nitrate-cancrinite [Na8Si6Al6O24(NO3)2] precipitated on the quartz surface as a secondary mineralmore » phase. Both steady-state dissolution and precipitation kinetics were quantified, and quartz dissolution apparent activation energy was determined. Mineral alteration through dissolution and precipitation processes results in pore volume and structure changes in the subsurface porous media. In this study, the column porosity increased up to 40.3% in the pure dissolution column when no dissolved Al was present in the leachate, whereas up to a 26.5% porosity decrease was found in columns where both dissolution and precipitation were observed because of the presence of Al in the input solution. The porosity change was also confirmed by calculation using the dissolution and precipitation rates and mineral volume changes.« less

Calcite Precipitation and Trace Metal Partitioning in Groundwater and the Vadose Zone: Remediation of Strontium-90 and Other Divalent Metals and Radionuclides in Arid Western Environments

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

F. Grant Ferris

2003-04-12

In situ remediation is an emerging technology that will play an important role in DOE's environmental restoration program, and is an area where enhancement in fundamental understanding will lead to significantly improved cleanup tools. In situ remediation technologies have inherent advantages because they do not require the costly removal, transport, and disposal of contamination. In addition, these technologies minimize worker exposure because contaminated materials are not brought to the surface. Finally, these technologies will minimize the generation of secondary waste streams with their associated treatment and disposal. A particularly promising in situ remediation technology is bioremediation. For inorganic contaminants suchmore » as radionuclides and metals, in situ bioremediation can be used to alter the mobility or reduce the toxicity of radionuclides and metals by changing the valence state of the radionuclides and metals, degrading or producing complexing ligands, or facilitating partitioning on to or off of solid phases. The purpose of the research presented here was to explore microbially facilitated partitioning of metal and radionuclides by their co-precipitation with calcium carbonate. Although this approach is a very attractive cleanup alternative, its practical implementation requires improved scientific understanding of the geochemical and biological mechanisms involved, particularly with respect to rates and mechanisms of microbially facilitated calcite precipitation. Of interest for this investigation is the in situ manipulation of calcite precipitation by the microbially catalyzed hydrolysis of urea. The production of ammonia during microbial decomposition of urea tends to drive pH upwards, and results in formation of alkaline conditions. When solution concentrations of Ca2+ and HCO3- are high enough, calcium carbonate precipitation may occur. A series of water samples collected from four wells tapping the aquifer underlying Eastern Snake River Plain (ESRP) in the vicinity of the Idaho National Engineering and Environmental Laboratory (INEEL) all tested positively for the presence of urea degrading bacteria. Calcite precipitation experiments were conducted with isolated ESRP urea degrading bacteria and B. pasteurii (ATCC 11859), a known urea hydrolyzer. In all of the experiments, visible white precipitates developed within the first thirty minutes after inoculation. The identity of the precipitates as calcite was confirmed by X-ray diffraction. Scanning electron micrographs of the solids revealed both spherical and amorphous precipitates, with microbes in close association with the minerals. The kinetics of calcite precipitation at 10 to 20 C was subsequently investigated using an artificial groundwater (AGW) medium based on the aqueous chemistry of the ESRP aquifer. Experimental data was fit using unconstrained nonlinear regression and optimization to determine rate constants and points of critical supersaturation (Scritical i.e., calcite nucleation). The highest rates of calcite precipitation (ca. 0.8 mmole L-1 day-1) occurred near Scritical. While unique time course trajectories of dissolved Ca2+ concentrations were observed at the different experimental temperatures, the calcite precipitation rates all followed the same asymptotic profile decreasing progressively with saturation state regardless of temperature. This emphasizes the fundamental kinetic dependence of calcite precipitation on saturation state, which connects the otherwise dissimilar temporal patterns of calcite precipitation that evolved under the different temperature and biogeochemical regimes of the experiments.« less

Binary ferrihydrite catalysts

DOEpatents

Huffman, G.P.; Zhao, J.; Feng, Z.

1996-12-03

A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered. 3 figs.

RECOVERY OF THORIUM AND URANIUM VALUES FROM AQUEOUS SOLUTIONS

DOEpatents

Calkins, G.D.

1958-02-18

This patent deals with the separation and recovery of uranium from monazite sand. After initial treatment of the sand with sodium hydroxide, a precipitate is obtuined which contains the uranium, thorium, rare earths and some phosphorus. This precipitate is then dissolved in nitric acid. The bulk of the rare earths are removed from thls soiution by adding aa excess of alkali carbonate, causing precipitation of the rare earths together with part of the thorium present. The solution still contains a considerable amount of thorium, some rare earths, and practically all of the uranium originally present. Thorium and rare earth values are readily precipitated from such solution, and the uranium values thus isolated, by the addition of an excess hydrogen peroxide. The pH value of the solution is preferably adjusted to at least 9 prior to the addition of the peroxide.

Solid-State Cloud Radar System (CRS) Upgrade and Deployment

NASA Technical Reports Server (NTRS)

McLinden, Matt; Heymsfield, Gerald; Li, Lihua; Racette, Paul; Coon, Michael; Venkatesh, Vijay

2015-01-01

The recent decade has brought rapid development in solid-state power amplifier (SSPA) technology. This has enabled the use of solid-state precipitation radar in place of high-power and high-voltage systems such as those that use Klystron or Magnetron transmitters. The NASA Goddard Space Flight Center has recently completed a comprehensive redesign of the 94 gigahertz Cloud Radar System (CRS) to incorporate a solid-state transmitter. It is the first cloud radar to achieve sensitivity comparable to that of a high-voltage transmitter using solid-state. The NASA Goddard Space Flight Center's Cloud Radar System (CRS) is a 94 gigahertz Doppler radar that flies on the NASA ER-2 high-altitude aircraft. The upgraded CRS system utilizes a state-of-the-art solid-state 94 gigahertz power amplifier with a peak transmit power of 30 watts. The modernized CRS system is detailed here with data results from its deployment during the 2014 Integrated Precipitation and Hydrology Experiment (IPHEX).

PRECIPITATION METHOD OF SEPARATING PLUTONIUM FROM CONTAMINATING ELEMENTS

DOEpatents

Sutton, J.B.

1958-02-18

This patent relates to an improved method for the decontamination of plutonium. The process consists broadly in an improvement in a method for recovering plutonium from radioactive uranium fission products in aqueous solutions by decontamination steps including byproduct carrier precipitation comprising the step of introducing a preformed aqueous slurry of a hydroxide of a metal of group IV B into any aqueous acidic solution which contains the plutonium in the hexavalent state, radioactive uranium fission products contaminant and a by-product carrier precipitate and separating the metal hydroxide and by-product precipitate from the solution. The process of this invention is especially useful in the separation of plutonium from radioactive zirconium and columbium fission products.