Characterization of the thermolysis products of Nafion membrane: A potential source of perfluorinated compounds in the environment

Science.gov (United States)

Feng, Mingbao; Qu, Ruijuan; Wei, Zhongbo; Wang, Liansheng; Sun, Ping; Wang, Zunyao

2015-05-01

The thermal decomposition of Nafion N117 membrane, a typical perfluorosulfonic acid membrane that is widely used in various chemical technologies, was investigated in this study. Structural identification of thermolysis products in water and methanol was performed using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS). The fluoride release was studied using an ion-chromatography system, and the membrane thermal stability was characterized by thermogravimetric analysis. Notably, several types of perfluorinated compounds (PFCs) including perfluorocarboxylic acids were detected and identified. Based on these data, a thermolysis mechanism was proposed involving cleavage of both the polymer backbone and its side chains by attack of radical species. This is the first systematic report on the thermolysis products of Nafion by simulating its high-temperature operation and disposal process via incineration. The results of this study indicate that Nafion is a potential environmental source of PFCs, which have attracted growing interest and concern in recent years. Additionally, this study provides an analytical justification of the LC/ESI-MS/MS method for characterizing the degradation products of polymer electrolyte membranes. These identifications can substantially facilitate an understanding of their decomposition mechanisms and offer insight into the proper utilization and effective management on these membranes.

Properties of residual marine fuel produced by thermolysis from polypropylene waste

Directory of Open Access Journals (Sweden)

Linas Miknius

2015-06-01

Full Text Available Thermal degradation of waste plastics with the aim of producing liquid fuel is one of the alternative solutions to landfill disposal or incineration. The paper describes thermal conversion of polypropylene waste and analysis of produced liquid fuel that would satisfy ISO 8217-2012 requirements for a residual marine fuel. Single pass batch thermolysis processes were conducted at different own vapour pressures (20-80 barg that determined process temperature, residence time of intermediates what resulted in different yields of the liquid product. Obtained products were stabilized by rectification to achieve required standard flash point. Gas chromatography and 1H NMR spectrometry show aliphatic nature of the liquid product where majority of the compounds are isoalkanes and isoalkenes. Only lightest fractions boiling up to a temperature of 72 oC have significant amount of n-pentane. Distribution of aromatic hydrocarbons is not even along the boiling range. The fractions boiling at a temperature of 128 oC and 160 oC have the highest content of monocyclic arenes – 3.16 % and 4.09 % respectively. The obtained final liquid residual product meets all but one requirements of ISO 8217-2012 for residual marine fuels.DOI: http://dx.doi.org/10.5755/j01.ms.21.2.6105

Degradation reaction of Diazo reactive black 5 dye with copper (II) sulfate catalyst in thermolysis treatment.

Science.gov (United States)

Lau, Yen-Yie; Wong, Yee-Shian; Ang, Tze-Zhang; Ong, Soon-An; Lutpi, Nabilah Aminah; Ho, Li-Ngee

2018-03-01

The theme of present research demonstrates performance of copper (II) sulfate (CuSO 4 ) as catalyst in thermolysis process to treat reactive black 5 (RB 5) dye. During thermolysis without presence of catalyst, heat was converted to thermal energy to break the enthalpy of chemical structure bonding and only 31.62% of color removal. With CuSO 4 support as auxiliary agent, the thermally cleaved molecular structure was further destabilized and reacted with CuSO 4 . Copper ions functioned to delocalize the coordination of π of the lone paired electron in azo bond, C=C bond of the sp 2 carbon to form C-C of the sp 3 amorphous carbon in benzene and naphthalene. Further, the radicals of unpaired electrons were stabilized and RB 5 was thermally decomposed to methyl group. Zeta potential measurement was carried out to analyze the mechanism of RB 5 degradation and measurement at 0 mV verified the critical chemical concentration (CCC) (0.7 g/L copper (II) sulfate), as the maximum 92.30% color removal. The presence of copper (II) sulfate catalyst has remarkably increase the RB 5 dye degradation as the degradation rate constant without catalyst, k 1 is 6.5224 whereas the degradation rate constant with catalyst, k 2 is 25.6810. This revealed the correlation of conversion of thermal energy from heat to break the chemical bond strength, subsequent fragmentation of RB 5 dye molecular mediated by copper (II) sulfate catalyst. The novel framework on thermolysis degradation of molecular structure of RB 5 with respect to the bond enthalpy and interfacial intermediates decomposition with catalyst reaction were determined.

Synthesis of acid-base bifunctional mesoporous materials by oxidation and thermolysis

Energy Technology Data Exchange (ETDEWEB)

Yu, Xiaofang [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China); Zou, Yongcun [State Key Laboratory of Inoranic Synthesis and Preparative Chemistryg, College of Chemistry, Jilin University, Changchun 130012 (China); Wu, Shujie; Liu, Heng [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China); Guan, Jingqi, E-mail: guanjq@jlu.edu.cn [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China); Kan, Qiubin, E-mail: qkan@jlu.edu.cn [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China)

2011-06-15

Graphical abstract: A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst. The obtained sample of SO{sub 3}H-MCM-41-NH{sub 2} containing amine and sulfonic acids exhibits excellent catalytic activity in aldol condensation reaction. Research highlights: {yields} Synthesize acid-base bifunctional mesoporous materials SO{sub 3}H-MCM-41-NH{sub 2}. {yields} Oxidation and then thermolysis to generate acidic site and basic site. {yields} Exhibit good catalytic performance in aldol condensation reaction between acetone and various aldehydes. -- Abstract: A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst SO{sub 3}H-MCM-41-NH{sub 2}. This method was achieved by co-condensation of tetraethylorthosilicate (TEOS), 3-mercaptopropyltrimethoxysilane (MPTMS) and (3-triethoxysilylpropyl) carbamicacid-1-methylcyclohexylester (3TAME) in the presence of cetyltrimethylammonium bromide (CTAB), followed by oxidation and then thermolysis to generate acidic site and basic site. X-ray diffraction (XRD) and transmission electron micrographs (TEM) show that the resultant materials keep mesoporous structure. Thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), back titration, solid-state {sup 13}C CP/MAS NMR and solid-state {sup 29}Si MAS NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The bifunctional sample (SO{sub 3}H-MCM-41-NH{sub 2}) containing amine and sulfonic acids exhibits excellent acid-basic properties, which make it possess high activity in aldol condensation reaction between acetone and various aldehydes.

Thermolysis synthesis of pure phase NiO from novel sonochemical synthesized Ni(II) nano metal-organic supramolecular architecture.

Science.gov (United States)

Hanifehpour, Younes; Morsali, Ali; Mirtamizdoust, Babak; Joo, Sang Woo; Soltani, Behzad

2017-07-01

Nano-structures of a new supramolecular coordination compound of divalent nickel with the pyrazol (pzH) containing the terminal azide anions, [Ni(pzH) 2 (N 3 ) 2 ] (1), with discrete molecular architecture (DMA) in solid state was synthesized via sonochemical method. The new nanostructure was characterized by scanning electron microscopy, X-ray powder diffraction, IR, and elemental analysis. Compound 1 was structurally characterized by single crystal X-ray diffraction and the single-crystal X-ray data shows that the coordination number of Ni (II) ions is six, (NiN 6 ), with four N-donor atoms from neutral "pzH" ligands and two N-donors from two terminal azide anions. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The structure of the title complex was optimized by density functional theory calculations. Calculated structural parameters and IR spectra for the title complex are consistent with the crystal structure. The NiO nanoparticles were obtained by thermolysis of 1 at 180°C with oleic acid as a surfactant. Copyright © 2017 Elsevier B.V. All rights reserved.

Large-scale preparation of CdS quantum dots by direct thermolysis of a single-source precursor

Energy Technology Data Exchange (ETDEWEB)

Li Zhiguo; Cai Wei; Sui Jiehe [School of Material Science and Engineering, Harbin Institute of Technology, Harbin, Heilongjiang 150001 (China)

2008-01-23

CdS quantum dots (QDs) have been synthesized on a large scale, based on the direct thermolysis of one single-source precursor (Me{sub 4}N){sub 4}[S{sub 4}Cd{sub 10}(SPh){sub 16}], in hexadecylamine (HDA). Transmission electron microscopy (TEM) observations show that the CdS QDs are well-defined, nearly spherical particles. The clear lattice fringes in high-resolution TEM (HRTEM) images confirm the crystalline nature of the QDs. The broad diffraction in the x-ray diffraction (XRD) pattern and diffuse diffraction rings of the selected-area electron diffraction (SAED) pattern are typical of nanomeric-size particles and indicative of the hexagonal phase of CdS QDs. The absorption spectra confirm quantum confinement of CdS QDs. The synthesis process for CdS QDs was investigated by ultraviolet-visible (UV-vis) absorption spectroscopy. The results demonstrate that the nucleation and growth stages were separated automatically in a homogeneous system.

IR Laser-Induced Thermolysis and UV Laser-Induced Photolysis of 1,3-Diethyldisiloxane: Chemical Vapour Deposition of Nanotextured Hydridoalkylsilicones

Czech Academy of Sciences Publication Activity Database

Urbanová, Markéta; Bastl, Zdeněk; Šubrt, Jan; Pola, Josef

2001-01-01

Roč. 11, č. 6 (2001), s. 1557-1562 ISSN 0959-9428 R&D Projects: GA AV ČR IAA4072806 Keywords : thermolysis * UV laser photolysis * composition Subject RIV: CH - Nuclear ; Quantum Chemistry Impact factor: 2.736, year: 2001

Technological development report for fiscal 1993 on the woodwaste thermolysis/gasification technology and generated gas utilization technology; 1993 nendo mokushitsukei haikibutsu no netsubunkai gas ka gijutsu to seisei gas no riyo gijutsu kaihatsu hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1994-03-01

The project is a joint effort of Japan and the Philippines to develop a thermolysis/gasification system, in which woodwaste now remaining unexploited in the Philippines is subjected to thermolysis/gasification and the resulting gas is used in a gas engine for the generation of electric power, in a 5-year period beginning in fiscal 1990. In this fiscal year, element technology verification tests are conducted, components of a demonstration plant are manufactured, and procurement is made as required, which completes all the tasks allotted to this fiscal year. All the constituents of the said demonstration plant fabricated or procured since fiscal 1991 are packed up and forwarded to Industrial Technology Development Institute (ITDI) of the Philippines, and engineering guidance is extended and test operations are carried out at the site of plant installation. In line with the said endeavors, on-site investigations are performed and researches are conducted together with ITDI scientists concerning the construction work and element technology confirmation. On the other hand, the Philippine side performs the second phase of civil engineering and construction carried over from the first phase. The demonstration plant is completed, adjustment and test operations are carried out, which means that the project is in progress as initially scheduled. (NEDO)

Kinetic isotope effect in the thermolysis of methylenecyclobutane

International Nuclear Information System (INIS)

Chickos, J.S.

1979-01-01

The intramolecular kinetic isotope effect for the thermolysis of equilibrated methylenecyclobutane-d 2 was investigated at 515 0 C as a function of pressure. A high-pressure value of k/sub H/k/sub D/ (ethylene/ethylene-d 2 ) = 0.9 was obtained at 13 cm of N 2 pressure. This value decreased to 0.86 at 70 μm total pressure. No intermolecular kinetic isotope effect was measured for the formation of ethylene from labeled and unlabeled methylenecyclobutane. The pressure and temperature dependence of the intramolecular kinetic isotope effect was used as evidence in establishing the inverse nature of the effect. The isotope effect observed was explained in terms of competing equilibrium and kinetic isotope effects in which the equilibrium isotope effects dominate. It was concluded on the bases of these results that an acyclic intermediate is involved in the fragmentation of methylenecyclobutane to ethylene and allene. The results also support the notion that deuterium prefers to accumulate at the methylene group with the greatest p character in the carbon--hydrogen bond. 1 figure, 4 tables

Polyol-mediated thermolysis process for the synthesis of MgO nanoparticles and nanowires

Energy Technology Data Exchange (ETDEWEB)

Subramania, A; Kumar, G Vijaya; Priya, A R Sathiya; Vasudevan, T [Advanced Materials Research Lab, Department of Industrial Chemistry, Alagappa University, Karaikudi-630 003 (India)

2007-06-06

The main aim of this work is to prepare MgO nanoparticles and nanowires by a novel polyol-mediated thermolysis (PMT) process. The influence of different mole concentration of magnesium acetate, polyvinyl pyrrolidone (PVP; capping agent) and ethylene glycol (EG; solvent as well as reducing agent) on the formation of nanoparticles and nanowires and the effect of calcination on the crystalline size of the samples were also examined. The resultant oxide structure, thermal behaviour, size and shape have been studied using x-ray diffraction (XRD) studies, thermal (TG/DTA) analysis and scanning electron microscopy (SEM)/transmission electron microscopy (TEM) respectively.

Polyol-mediated thermolysis process for the synthesis of MgO nanoparticles and nanowires

Science.gov (United States)

Subramania, A.; Vijaya Kumar, G.; Sathiya Priya, A. R.; Vasudevan, T.

2007-06-01

The main aim of this work is to prepare MgO nanoparticles and nanowires by a novel polyol-mediated thermolysis (PMT) process. The influence of different mole concentration of magnesium acetate, polyvinyl pyrrolidone (PVP; capping agent) and ethylene glycol (EG; solvent as well as reducing agent) on the formation of nanoparticles and nanowires and the effect of calcination on the crystalline size of the samples were also examined. The resultant oxide structure, thermal behaviour, size and shape have been studied using x-ray diffraction (XRD) studies, thermal (TG/DTA) analysis and scanning electron microscopy (SEM)/transmission electron microscopy (TEM) respectively.

Polyol-mediated thermolysis process for the synthesis of MgO nanoparticles and nanowires

International Nuclear Information System (INIS)

Subramania, A; Kumar, G Vijaya; Priya, A R Sathiya; Vasudevan, T

2007-01-01

The main aim of this work is to prepare MgO nanoparticles and nanowires by a novel polyol-mediated thermolysis (PMT) process. The influence of different mole concentration of magnesium acetate, polyvinyl pyrrolidone (PVP; capping agent) and ethylene glycol (EG; solvent as well as reducing agent) on the formation of nanoparticles and nanowires and the effect of calcination on the crystalline size of the samples were also examined. The resultant oxide structure, thermal behaviour, size and shape have been studied using x-ray diffraction (XRD) studies, thermal (TG/DTA) analysis and scanning electron microscopy (SEM)/transmission electron microscopy (TEM) respectively

Surface phase transitions in cu-based solid solutions

Science.gov (United States)

Zhevnenko, S. N.; Chernyshikhin, S. V.

2017-11-01

We have measured surface energy in two-component Cu-based systems in H2 + Ar gas atmosphere. The experiments on solid Cu [Ag] and Cu [Co] solutions show presence of phase transitions on the surfaces. Isotherms of the surface energy have singularities (the minimum in the case of copper solid solutions with silver and the maximum in the case of solid solutions with cobalt). In both cases, the surface phase transitions cause deficiency of surface miscibility: formation of a monolayer (multilayer) (Cu-Ag) or of nanoscale particles (Cu-Co). At the same time, according to the volume phase diagrams, the concentration and temperature of the surface phase transitions correspond to the solid solution within the volume. The method permits determining the rate of diffusional creep in addition to the surface energy. The temperature and concentration dependence of the solid solutions' viscosity coefficient supports the fact of the surface phase transitions and provides insights into the diffusion properties of the transforming surfaces.

Tricyanomethane and Its Ketenimine Tautomer: Generation from Different Precursors and Analysis in Solution, Argon Matrix, and as a Single Crystal.

Science.gov (United States)

Banert, Klaus; Chityala, Madhu; Hagedorn, Manfred; Beckers, Helmut; Stüker, Tony; Riedel, Sebastian; Rüffer, Tobias; Lang, Heinrich

2017-08-01

Solutions of azidomethylidenemalononitrile were photolyzed at low temperatures to produce the corresponding 2H-azirine and tricyanomethane, which were analyzed by low-temperature NMR spectroscopy. The latter product was also observed after short thermolysis of the azide precursor in solution whereas irradiation of the azide isolated in an argon matrix did not lead to tricyanomethane, but to unequivocal detection of the tautomeric ketenimine by IR spectroscopy for the first time. When the long-known "aquoethereal" greenish phase generated from potassium tricyanomethanide, dilute sulfuric acid, and diethyl ether was rapidly evaporated and sublimed, a mixture of hydronium tricyanomethanide and tricyanomethane was formed instead of the previously claimed ketenimine tautomer. Under special conditions of sublimation, single crystals of tricyanomethane could be isolated, which enabled the analysis of the molecular structure by X-ray diffraction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Similarity solutions for phase-change problems

Science.gov (United States)

Canright, D.; Davis, S. H.

1989-01-01

A modification of Ivantsov's (1947) similarity solutions is proposed which can describe phase-change processes which are limited by diffusion. The method has application to systems that have n-components and possess cross-diffusion and Soret and Dufour effects, along with convection driven by density discontinuities at the two-phase interface. Local thermal equilibrium is assumed at the interface. It is shown that analytic solutions are possible when the material properties are constant.

Melting Behavior and Thermolysis of NaBH4−Mg(BH42 and NaBH4−Ca(BH42 Composites

Directory of Open Access Journals (Sweden)

Morten B. Ley

2015-04-01

Full Text Available The physical properties and the hydrogen release of NaBH4–Mg(BH42 and NaBH4−Ca(BH42 composites are investigated using in situ synchrotron radiation powder X-ray diffraction, thermal analysis and temperature programmed photographic analysis. The composite, xNaBH4–(1 − xMg(BH42, x = 0.4 to 0.5, shows melting/frothing between 205 and 220 °C. However, the sample does not become a transparent molten phase. This behavior is similar to other alkali-alkaline earth metal borohydride composites. In the xNaBH4–(1 − xCa(BH42 system, eutectic melting is not observed. Interestingly, eutectic melting in metal borohydrides systems leads to partial thermolysis and hydrogen release at lower temperatures and the control of sample melting may open new routes for obtaining high-capacity hydrogen storage materials.

Polymer solution phase separation: Microgravity simulation

Science.gov (United States)

Cerny, Lawrence C.; Sutter, James K.

1989-01-01

In many multicomponent systems, a transition from a single phase of uniform composition to a multiphase state with separated regions of different composition can be induced by changes in temperature and shear. The density difference between the phase and thermal and/or shear gradients within the system results in buoyancy driven convection. These differences affect kinetics of the phase separation if the system has a sufficiently low viscosity. This investigation presents more preliminary developments of a theoretical model in order to describe effects of the buoyancy driven convection in phase separation kinetics. Polymer solutions were employed as model systems because of the ease with which density differences can be systematically varied and because of the importance of phase separation in the processing and properties of polymeric materials. The results indicate that the kinetics of the phase separation can be performed viscometrically using laser light scattering as a principle means of following the process quantitatively. Isopycnic polymer solutions were used to determine the viscosity and density difference limits for polymer phase separation.

Network periodic solutions: patterns of phase-shift synchrony

International Nuclear Information System (INIS)

Golubitsky, Martin; Wang, Yunjiao; Romano, David

2012-01-01

We prove the rigid phase conjecture of Stewart and Parker. It then follows from previous results (of Stewart and Parker and our own) that rigid phase-shifts in periodic solutions on a transitive network are produced by a cyclic symmetry on a quotient network. More precisely, let X(t) = (x 1 (t), ..., x n (t)) be a hyperbolic T-periodic solution of an admissible system on an n-node network. Two nodes c and d are phase-related if there exists a phase-shift θ cd in [0, 1) such that x d (t) = x c (t + θ cd T). The conjecture states that if phase relations persist under all small admissible perturbations (that is, the phase relations are rigid), then for each pair of phase-related cells, their input signals are also phase-related to the same phase-shift. For a transitive network, rigid phase relations can also be described abstractly as a Z m permutation symmetry of a quotient network. We discuss how patterns of phase-shift synchrony lead to rigid synchrony, rigid phase synchrony, and rigid multirhythms, and we show that for each phase pattern there exists an admissible system with a periodic solution with that phase pattern. Finally, we generalize the results to nontransitive networks where we show that the symmetry that generates rigid phase-shifts occurs on an extension of a quotient network

Monte Carlo Solutions for Blind Phase Noise Estimation

Directory of Open Access Journals (Sweden)

Çırpan Hakan

2009-01-01

Full Text Available This paper investigates the use of Monte Carlo sampling methods for phase noise estimation on additive white Gaussian noise (AWGN channels. The main contributions of the paper are (i the development of a Monte Carlo framework for phase noise estimation, with special attention to sequential importance sampling and Rao-Blackwellization, (ii the interpretation of existing Monte Carlo solutions within this generic framework, and (iii the derivation of a novel phase noise estimator. Contrary to the ad hoc phase noise estimators that have been proposed in the past, the estimators considered in this paper are derived from solid probabilistic and performance-determining arguments. Computer simulations demonstrate that, on one hand, the Monte Carlo phase noise estimators outperform the existing estimators and, on the other hand, our newly proposed solution exhibits a lower complexity than the existing Monte Carlo solutions.

Phase coexistence in ferroelectric solid solutions: Formation of monoclinic phase with enhanced piezoelectricity

Directory of Open Access Journals (Sweden)

Xiaoyan Lu

2016-10-01

Full Text Available Phase morphology and corresponding piezoelectricity in ferroelectric solid solutions were studied by using a phenomenological theory with the consideration of phase coexistence. Results have shown that phases with similar energy potentials can coexist, thus induce interfacial stresses which lead to the formation of adaptive monoclinic phases. A new tetragonal-like monoclinic to rhombohedral-like monoclinic phase transition was predicted in a shear stress state. Enhanced piezoelectricity can be achieved by manipulating the stress state close to a critical stress field. Phase coexistence is universal in ferroelectric solid solutions and may provide a way to optimize ultra-fine structures and proper stress states to achieve ultrahigh piezoelectricity.

Regularity of solutions of a phase field model

KAUST Repository

Amler, Thomas

2013-01-01

Phase field models are widely-used for modelling phase transition processes such as solidification, freezing or CO2 sequestration. In this paper, a phase field model proposed by G. Caginalp is considered. The existence and uniqueness of solutions are proved in the case of nonsmooth initial data. Continuity of solutions with respect to time is established. In particular, it is shown that the governing initial boundary value problem can be considered as a dynamical system. © 2013 International Press.

Heterogeneous Ferroelectric Solid Solutions Phases and Domain States

CERN Document Server

Topolov, Vitaly

2012-01-01

The book deals with perovskite-type ferroelectric solid solutions for modern materials science and applications, solving problems of complicated heterophase/domain structures near the morphotropic phase boundary and applications to various systems with morphotropic phases. In this book domain state–interface diagrams are presented for the interpretation of heterophase states in perovskite-type ferroelectric solid solutions. It allows to describe the stress relief in the presence of polydomain phases, the behavior of unit-cell parameters of coexisting phases and the effect of external electric fields. The novelty of the book consists in (i) the first systematization of data about heterophase states and their evolution in ferroelectric solid solutions (ii) the general interpretation of heterophase and domain structures at changing temperature, composition or electric field (iii) the complete analysis of interconnection domain structures, unit-cell parameters changes, heterophase structures and stress relief.

Phase stability in wear-induced supersaturated Al-Ti solid solution

Energy Technology Data Exchange (ETDEWEB)

Watanabe, Y.; Yokoyama, K. [Dept. of Functional Machinery Mechanics Shinshu Univ., Ueda (Japan); Hosoda, H. [Precision and Intelligence Lab., Tokyo Inst. of Tech., Nagatsuta, Midori-ku, Yokohama (Japan)

2002-07-01

Al-Ti supersaturated solid solutions were introduced by wear testing and the rapid quenching of an Al/Al{sub 3}Ti composite (part of an Al/Al{sub 3}Ti functionally graded material) that was fabricated using the centrifugal method. The phase stability of the supersaturated solid solution was studied through systematic annealing of the supersaturated solid solution. It was found that the Al-Ti supersaturated solid solution decomposed into Al and Al{sub 3}Ti intermetallic compound phases during the heat treatment. The Al-Ti supersaturated solid solutions fabricated were, therefore, not an equilibrium phase, and thus decomposed into the equilibrium phases during heat treatment. It was also found that heat treatment leads to a significant hardness increase for the Al-Ti supersaturated solid solution. Finally, it was concluded that formation of the wear-induced supersaturated solid solution layer was a result of severe plastic deformation. (orig.)

Comparative solution and solid-phase glycosylations toward a disaccharide library

DEFF Research Database (Denmark)

Agoston, K.; Kröger, Lars; Agoston, Agnes

2009-01-01

A comparative study on solution-phase and solid-phase oligosaccharide synthesis was performed. A 16-member library containing all regioisomers of Glc-Glc, Glc-Gal, Gal-Glc, and Gal-Gal disaccharides was synthesized both in solution and on solid phase. The various reaction conditions for different...

Solutions without phase-slip for the Ginsburg-Landau equation

International Nuclear Information System (INIS)

Collet, P.; Eckmann, J.P.

1992-01-01

We consider the Ginsburg-Landau equation for a complex scalar field in one dimension and consider initial data which have two different stationary solutions as their limits in space as x→±∞. If these solutions are not very different, then we show that the initial data will evolve to a stationary solution by a 'phase melting' process which avoids 'phase slips,' i.e., which does not go through zero amplitude. (orig.)

Solution of a Complex Least Squares Problem with Constrained Phase.

Science.gov (United States)

Bydder, Mark

2010-12-30

The least squares solution of a complex linear equation is in general a complex vector with independent real and imaginary parts. In certain applications in magnetic resonance imaging, a solution is desired such that each element has the same phase. A direct method for obtaining the least squares solution to the phase constrained problem is described.

Imaginary eigenvalue solution in RPA and phase transition

International Nuclear Information System (INIS)

Yao Yujie; Jing Xiaogong; Zhao Guoquan; Wu Shishu

1993-01-01

The phase transition (PT) of a many-particle system with a close-shell configuration, the stability of the Hartree-Fock (HF) solution and the random phase approximation (RPA) are studied by means of a generalized three-level solvable model. The question whether the occurrence of an imaginary eigenvalue solution in RPA (OISA) may be considered as a signature of PT is explored in some detail. It is found that there is no close relation between OISA and PT. Generally, OISA shows that RPA becomes poor

Cerium(III) pivalate [Ce(Piv)3(HPiv)3]2: synthesis, crystal structure, and thermal stability

International Nuclear Information System (INIS)

Khudyakov, M.Yu.; Kuz'mina, N.P.; Pisarevskij, A.P.; Martynenko, L.I.

2002-01-01

Complex [Ce(Piv) 3 (HPiv) 3 ] 2 was prepared by precipitation of cerium(III) nitrate aqueous solution with salt NH 4 (Piv) (HPiv = pivalic acid) and subsequent recrystallization from 5% HPiv solution in hexane. According to data of X-ray diffraction analysis and IR spectroscopy crystal structure of the complex is built of centrally symmetric dimers, in which cerium atoms are bound by four bridge pivalate ligands. Thermal analysis suggests that heating of the complex in nitrogen atmosphere results first in splitting off six HPiv molecules in the range of 90-190 deg C and then in thermolysis of Ce(Piv) 3 formed at 290-450 deg C. Sublimation of Ce(Piv) 3 occurs in the range of 290-350 deg C along with thermolysis during heating in vacuum (0.01 mm Hg), which permits preparing CeO 2 films by the method of chemical precipitation from gaseous phase [ru

Impacts of glycolate and formate radiolysis and thermolysis on hydrogen generation rate calculations for the Savannah River Site tank farm

Energy Technology Data Exchange (ETDEWEB)

Crawford, C. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); King, W. D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2017-08-14

Savannah River Remediation (SRR) personnel requested that the Savannah River National Laboratory (SRNL) evaluate available data and determine its applicability to defining the impact of planned glycolate anion additions to Savannah River Site (SRS) High Level Waste (HLW) on Tank Farm flammability (primarily with regard to H₂ production). Flammability evaluations of formate anion, which is already present in SRS waste, were also needed. This report describes the impacts of glycolate and formate radiolysis and thermolysis on Hydrogen Generation Rate (HGR) calculations for the SRS Tank Farm.

Formation of the second organic phase during uranyl nitrate extraction from aqueous solution by 30% tributylphosphate solution in paraffin

International Nuclear Information System (INIS)

Yhrkin, V.G.

1996-01-01

For extraction systems aqueous solution of uranyl nitrate-30% solution of tributylphosphate in individual paraffins from C 13 to C 17 the influence of the second organic phase of uranyl nitrate concentration in aqueous and organic phases, the length of hydrocarbon chain of paraffin hydrocarbon and temperature from 25 to 50 deg C on formation conditions has been defected. A special method of achieving the conditions of organic phase stratification from three-phase region, involving definition of equilibrium phases composition by density and refractive index, has been elaborated for more precise definition of organic phase homogeneity region. It has been revealed that without addition of nitric acid to uranyl nitrate solution the organic phase homogeneity limits can be achieved solely on paraffins C 15 , C 16 and C 17 and only under conditions similar to equeous phase saturation in terms of uranyl nitrate. 16 refs., 2 figs

Crystallization of Trehalose in Frozen Solutions and its Phase Behavior during Drying

Energy Technology Data Exchange (ETDEWEB)

Sundaramurthi, Prakash; Patapoff, Thomas W.; Suryanarayanan, Raj (Genentech); (UMM)

2015-02-19

To study the crystallization of trehalose in frozen solutions and to understand the phase transitions during the entire freeze-drying cycle. Aqueous trehalose solution was cooled to -40 C in a custom-designed sample holder. The frozen solution was warmed to -18 C and annealed, and then dried in the sample chamber of the diffractometer. XRD patterns were continuously collected during cooling, annealing and drying. After cooling, hexagonal ice was the only crystalline phase observed. However, upon annealing, crystallization of trehalose dihydrate was evident. Seeding the frozen solution accelerated the solute crystallization. Thus, phase separation of the lyoprotectant was observed in frozen solutions. During drying, dehydration of trehalose dihydrate yielded a substantially amorphous anhydrous trehalose. Crystallization of trehalose, as trehalose dihydrate, was observed in frozen solutions. The dehydration of the crystalline trehalose dihydrate to substantially amorphous anhydrate occurred during drying. Therefore, analyzing the final lyophile will not reveal crystallization of the lyoprotectant during freeze-drying. The lyoprotectant crystallization can only become evident by continuous monitoring of the system during the entire freeze-drying cycle. In light of the phase separation of trehalose in frozen solutions, its ability to serve as a lyoprotectant warrants further investigation.

Fischer Indole Synthesis in the Gas Phase, the Solution Phase, and at the Electrospray Droplet Interface.

Science.gov (United States)

Bain, Ryan M; Ayrton, Stephen T; Cooks, R Graham

2017-07-01

Previous reports have shown that reactions occurring in the microdroplets formed during electrospray ionization can, under the right conditions, exhibit significantly greater rates than the corresponding bulk solution-phase reactions. The observed acceleration under electrospray ionization could result from a solution-phase, a gas-phase, or an interfacial reaction. This study shows that a gas-phase ion/molecule (or ion/ion) reaction is not responsible for the observed rate enhancement in the particular case of the Fischer indole synthesis. The results show that the accelerated reaction proceeds in the microdroplets, and evidence is provided that an interfacial process is involved. Graphical Abstract GRAPHICAL ABSTRACT TEXT HERE] -->.

Detection of various phases in liquids from the hypersound velocity and damping near closed phase-separation regions of solutions

International Nuclear Information System (INIS)

Kovalenko, K. V.; Krivokhizha, S. V.; Chaban, I. A.; Chaikov, L. L.

2008-01-01

Theoretical analysis revealed that experimental results obtained in our studies on hypersound propagation in a guaiacol-glycerol solution in the vicinity of the closed phase-separation region, double critical point, and special point, as well as the origin of these regions, can be explained by the presence of two different phases (I and II) of the solution with phase-transition temperature T 0 . Temperature T 0 coincides with the temperature at the center of closed phase-separation regions, as well as with the double critical point and with the special point. In (Frenkel) phase I, molecules are in potential wells whose depth exceeds the thermal energy of a molecule, while thermal energy in (gaslike) phase II is higher than the potential well depth. At the lower critical point, the thermodynamic potential of phase I is equal to the thermodynamic potential of the phase-separated solution. At the upper critical point, the thermodynamic potential of phase II is equal to the thermodynamic potential of the phase-separated solution. The observed broad dome of the hypersound absorption coefficient near T 0 can be explained by the contribution associated with fluctuations of the order parameter corresponding to the transition from phase I to phase II. The difference in the temperature coefficients of hypersound velocity on different sides of T 0 and some other effects are also explained

Preparation and characterization of CuO catalyst for the thermolysis treatment of distillery wastewater.

Science.gov (United States)

Sharma, Deepak; Prajapati, Abhinesh Kumar; Choudhary, Rumi; Kaushal, Rajesh Kumar; Pal, Dharm; Sawarkar, Ashish N

2017-08-16

CuO catalyst was prepared from copper sulfate by alkali precipitation method followed by drying and calcination. Characterization of CuO catalyst using X-ray diffraction, Brunauer-Emmett-Teller, and Barrett-Joyner-Halenda surface area analysis envisaged the effectiveness of CuO as a catalyst for the treatment of biodigester effluent (BDE) emanated from distilleries. The catalytic thermolysis is an efficient advance treatment method for distillery biodigester effluent (BDE). CT treatment of BDE was carried out in a 0.5 dm 3 thermolytic batch reactor using CuO as a catalyst at different pH (1-9), temperatures (80-110°C), and catalyst loadings (1-4 kg/m 3 ). With CuO catalyst, a temperature of 110°C, catalyst loading of 4 kg/m 3 , and pH of 2 was found to be optimal, providing a maximum reduction in chemical oxygen demand of 65%. The settling characteristics at different temperatures of CT-treated sludge were also presented.

Phase segregation in cerium-lanthanum solid solutions

NARCIS (Netherlands)

Belliere, V.; Joorst, G; Stephan, O; de Groot, FMF; Weckhuysen, BM

2006-01-01

Electron energy-loss spectroscopy (EELS) in combination with scanning transmission electron microscopy ( STEM) reveals that the La enrichment at the surface of cerium-lanthanum solid solutions is an averaged effect and that segregation occurs in a mixed oxide phase. This separation occurs within a

Pharmaceutical Perspective on Opalescence and Liquid-Liquid Phase Separation in Protein Solutions.

Science.gov (United States)

Raut, Ashlesha S; Kalonia, Devendra S

2016-05-02

Opalescence in protein solutions reduces aesthetic appeal of a formulation and can be an indicator of the presence of aggregates or precursor to phase separation in solution signifying reduced product stability. Liquid-liquid phase separation of a protein solution into a protein-rich and a protein-poor phase has been well-documented for globular proteins and recently observed for monoclonal antibody solutions, resulting in physical instability of the formulation. The present review discusses opalescence and liquid-liquid phase separation (LLPS) for therapeutic protein formulations. A brief discussion on theoretical concepts based on thermodynamics, kinetics, and light scattering is presented. This review also discusses theoretical concepts behind intense light scattering in the vicinity of the critical point termed as "critical opalescence". Both opalescence and LLPS are affected by the formulation factors including pH, ionic strength, protein concentration, temperature, and excipients. Literature reports for the effect of these formulation factors on attractive protein-protein interactions in solution as assessed by the second virial coefficient (B2) and the cloud-point temperature (Tcloud) measurements are also presented. The review also highlights pharmaceutical implications of LLPS in protein solutions.

Transport of Liquid Phase Organic Solutes in Liquid Crystalline Membranes

OpenAIRE

Han, Sangil

2010-01-01

Porous cellulose nitrate membranes were impregnated with 8CB and PCH5 LCs (liquid crystals) and separations of solutes dissolved in aqueous phases were performed while monitoring solute concentration via UV-VIS spectrometry. The diffusing organic solutes, which consist of one aromatic ring and various functional groups, were selected to exclude molecular size effects on the diffusion and sorption. We studied the effects on solute transport of solute intra-molecular hydrogen bonding and so...

Solid-phase thermolysis of hexachlororuthenates (4) of onium type

Energy Technology Data Exchange (ETDEWEB)

Kukushkin, Yu N; Maslov, E I; Ryabkova, T P; Lobadyuk, V I [Leningradskij Tekhnologicheskij Inst. (USSR)

1982-10-01

Methods of thermogravimetry, infrared spectroscopy, electron absorption spectra and magnetic moment measurings were used to a study thermal solid-phase behaviour of onium hexachlororuthenates (4) of (AH)/sub 2/(RuCl/sub 6/) and (A'H/sub 2/)(RuCl/sub 6/) type, where A-benzimidazole (BAZ), pyridine (py), ammonia, A'-phenanthroline-ortho (o-phen), ethylenediamine (en). It was established that heating of solid (BAZH)/sub 2/(RuCl/sub 6/)x2H/sub 2/O and (o-phen H/sub 2/)(RuCl/sub 6/)xH/sub 2/O in 20-500 deg C range leads to separation of crystallization water and the following extraction of hydrogen chloride with formation of cis-(Ru(BAZ)/sub 2/Cl/sub 4/) and (Ru(o-phen)Cl/sub 4/). (pyH)/sub 2/(RuCl/sub 6/) heating causes initially the separation of two moles of hydrogen chloride with formation of cis-(Ru(py)/sub 2/Cl/sub 4/); further increase of temperature leads to reduction separation of chloride with formation of (Ru(py)/sub 2/Cl/sub 3/)/sub 2/ dimer. The mixture of ruthernium chlorides is prepared under conditions of isothermal heating of (NH/sub 4/)/sub 2/(RuCl/sub 6/) and (enH/sub 2/)(RuCl/sub 6/) compounds at temperatures close to the beginning of their decomposition. The separation of intermediate ruthenium compounds of diamine type with ammonia and ethylendiamine failed.

Lower critical solution temperature (LCST) phase separation of glycol ethers for forward osmotic control.

Science.gov (United States)

Nakayama, Daichi; Mok, Yeongbong; Noh, Minwoo; Park, Jeongseon; Kang, Sunyoung; Lee, Yan

2014-03-21

Lower critical solution temperature (LCST) phase transition of glycol ether (GE)-water mixtures induces an abrupt change in osmotic pressure driven by a mild temperature change. The temperature-controlled osmotic change was applied for the forward osmosis (FO) desalination. Among three GEs evaluated, di(ethylene glycol) n-hexyl ether (DEH) was selected as a potential FO draw solute. A DEH-water mixture with a high osmotic pressure could draw fresh water from a high-salt feed solution such as seawater through a semipermeable membrane at around 10 °C. The water-drawn DEH-water mixture was phase-separated into a water-rich phase and a DEH-rich phase at around 30 °C. The water-rich phase with a much reduced osmotic pressure released water into a low-salt solution, and the DEH-rich phase was recovered into the initial DEH-water mixture. The phase separation behaviour, the residual GE concentration in the water-rich phase, the osmotic pressure of the DEH-water mixture, and the osmotic flux between the DEH-water mixture and salt solutions were carefully analysed for FO desalination. The liquid-liquid phase separation of the GE-water mixture driven by the mild temperature change between 10 °C and 30 °C is very attractive for the development of an ideal draw solute for future practical FO desalination.

Pinning of phase separation of aqueous solution of hydroxypropylmethylcellulose by gelation

Science.gov (United States)

Kita, Rio; Kaku, Takeshi; Kubota, Kenji; Dobashi, Toshiaki

1999-08-01

Opalescence of the aqueous solution of hydroxypropylmethylcellulose (HPMC) induced by heating has been studied in terms of the phase diagram and the phase separation dynamics. The cloud point curve and the sol-to-gel transition curve intersected with each other at about 55 °C. Just above the cloud-point curve at which the spinodal curve has its minimum, a ring-like scattering pattern appeared corresponding to the spinodal decomposition. Temporal growth of the scattering function in the course of phase separation was studied by a time-resolved light scattering technique. The gelation pinned the phase separation (spinodal decomposition) of the aqueous HPMC solution.

Direct NMR Monitoring of Phase Separation Behavior of Highly Supersaturated Nifedipine Solution Stabilized with Hypromellose Derivatives.

Science.gov (United States)

Ueda, Keisuke; Higashi, Kenjirou; Moribe, Kunikazu

2017-07-03

We investigated the phase separation behavior and maintenance mechanism of the supersaturated state of poorly water-soluble nifedipine (NIF) in hypromellose (HPMC) derivative solutions. Highly supersaturated NIF formed NIF-rich nanodroplets through phase separation from aqueous solution containing HPMC derivative. Dissolvable NIF concentration in the bulk water phase was limited by the phase separation of NIF from the aqueous solution. HPMC derivatives stabilized the NIF-rich nanodroplets and maintained the NIF supersaturation with phase-separated NIF for several hours. The size of the NIF-rich phase was different depending on the HPMC derivatives dissolved in aqueous solution, although the droplet size had no correlation with the time for which NIF supersaturation was maintained without NIF crystallization. HPMC acetate and HPMC acetate succinate (HPMC-AS) effectively maintained the NIF supersaturation containing phase-separated NIF compared with HPMC. Furthermore, HPMC-AS stabilized NIF supersaturation more effectively in acidic conditions. Solution 1 H NMR measurements of NIF-supersaturated solution revealed that HPMC derivatives distributed into the NIF-rich phase during the phase separation of NIF from the aqueous solution. The hydrophobicity of HPMC derivative strongly affected its distribution into the NIF-rich phase. Moreover, the distribution of HPMC-AS into the NIF-rich phase was promoted at lower pH due to the lower aqueous solubility of HPMC-AS. The distribution of a large amount of HPMC derivatives into NIF-rich phase induced the strong inhibition of NIF crystallization from the NIF-rich phase. Polymer distribution into the drug-rich phase directly monitored by solution NMR technique can be a useful index for the stabilization efficiency of drug-supersaturated solution containing a drug-rich phase.

Thermolysis of (1R,2R)-1,2-dideuteriocyclobutane. An application of vibrational circular dichroism to kinetic analysis

International Nuclear Information System (INIS)

Chickos, J.S.; Annamalai, A.; Keiderling, T.A.

1986-01-01

The relative rates of geometric isomerization to racemization have been studied for the title compound by using a combination of infrared (IR) and vibrational circular dichroism (VCD) spectroscopies, respectively. The results are interpreted with a kinetic and mechanistic scheme which parallels that used by Berson, Pedersen, and Carpenter on a similar study of chiral cyclopropane-d 2 thermolysis. Relative rates of isomerization to stereomutation of 1.5 +/- 0.4 were obtained which can be interpreted to be consistent with a mechanism best described by random methylene rotation in tetramethylene-d 2 . This is the first application of VCD to kinetic analysis, and the advantages of IR techniques over the more usually employed UV spectroscopies to this type of basic mechanistic problem are illustrated

Glycine phases formed from frozen aqueous solutions: Revisited

Energy Technology Data Exchange (ETDEWEB)

Surovtsev, N. V. [Institute of Automation and Electrometry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Adichtchev, S. V.; Malinovsky, V. K. [Institute of Automation and Electrometry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Ogienko, A. G.; Manakov, A. Yu. [Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Drebushchak, V. A. [Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Institute of Geology and Mineralogy, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Ancharov, A. I.; Boldyreva, E. V. [Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Institute of Solid Chemistry and Mechanochemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Yunoshev, A. S. [Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Lavrentiev Institute of Hydrodynamics, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation)

2012-08-14

Glycine phases formed when aqueous solutions were frozen and subsequently heated under different conditions were studied by Raman scattering, x-ray diffraction, and differential scanning calorimetry (DSC) techniques. Crystallization of ice I{sub h} was observed in all the cases. On cooling at the rates of 0.5 K/min and 5 K/min, glassy glycine was formed as an intermediate phase which lived about 1 min or less only, and then transformed into {beta}-polymorph of glycine. Quench cooling of glycine solutions (15% w/w) in liquid nitrogen resulted in the formation of a mixture of crystalline water ice I{sub h} and a glassy glycine, which could be preserved at cryogenic temperatures (80 K) for an indefinitely long time. This mixture remained also quite stable for some time after heating above the cryogenic temperature. Subsequent heating under various conditions resulted in the transformation of the glycine glass into an unknown crystalline phase (glycine 'X-phase') at 209-216 K, which at 218-226 K transformed into {beta}-polymorph of glycine. The 'X-phase' was characterized by Raman spectroscopy; it could be obtained in noticeable amounts using a special preparation technique and tentatively characterized by x-ray powder diffraction (P2, a= 6.648 A, b= 25.867 A, c= 5.610 A, {beta}= 113.12 Masculine-Ordinal-Indicator ); the formation of 'X-phase' from the glycine glassy phase and its transformation into {beta}-polymorph were followed by DSC. Raman scattering technique with its power for unambiguous identification of the crystalline and glassy polymorphs without limitation on the crystallite size helped us to follow the phase transformations during quenching, heating, and annealing. The experimental findings are considered in relation to the problem of control of glycine polymorphism on crystallization.

Glycine phases formed from frozen aqueous solutions: Revisited

Science.gov (United States)

Surovtsev, N. V.; Adichtchev, S. V.; Malinovsky, V. K.; Ogienko, A. G.; Drebushchak, V. A.; Manakov, A. Yu.; Ancharov, A. I.; Yunoshev, A. S.; Boldyreva, E. V.

2012-08-01

Glycine phases formed when aqueous solutions were frozen and subsequently heated under different conditions were studied by Raman scattering, x-ray diffraction, and differential scanning calorimetry (DSC) techniques. Crystallization of ice Ih was observed in all the cases. On cooling at the rates of 0.5 K/min and 5 K/min, glassy glycine was formed as an intermediate phase which lived about 1 min or less only, and then transformed into β-polymorph of glycine. Quench cooling of glycine solutions (15% w/w) in liquid nitrogen resulted in the formation of a mixture of crystalline water ice Ih and a glassy glycine, which could be preserved at cryogenic temperatures (80 K) for an indefinitely long time. This mixture remained also quite stable for some time after heating above the cryogenic temperature. Subsequent heating under various conditions resulted in the transformation of the glycine glass into an unknown crystalline phase (glycine "X-phase") at 209-216 K, which at 218-226 K transformed into β-polymorph of glycine. The "X-phase" was characterized by Raman spectroscopy; it could be obtained in noticeable amounts using a special preparation technique and tentatively characterized by x-ray powder diffraction (P2, a = 6.648 Å, b = 25.867 Å, c = 5.610 Å, β = 113.12°); the formation of "X-phase" from the glycine glassy phase and its transformation into β-polymorph were followed by DSC. Raman scattering technique with its power for unambiguous identification of the crystalline and glassy polymorphs without limitation on the crystallite size helped us to follow the phase transformations during quenching, heating, and annealing. The experimental findings are considered in relation to the problem of control of glycine polymorphism on crystallization.

Hybrid vapor phase-solution phase growth techniques for improved CZT(S,Se) photovoltaic device performance

Energy Technology Data Exchange (ETDEWEB)

Chang, Liang-Yi; Gershon, Talia S.; Haight, Richard A.; Lee, Yun Seog

2016-12-27

A hybrid vapor phase-solution phase CZT(S,Se) growth technique is provided. In one aspect, a method of forming a kesterite absorber material on a substrate includes the steps of: depositing a layer of a first kesterite material on the substrate using a vapor phase deposition process, wherein the first kesterite material includes Cu, Zn, Sn, and at least one of S and Se; annealing the first kesterite material to crystallize the first kesterite material; and depositing a layer of a second kesterite material on a side of the first kesterite material opposite the substrate using a solution phase deposition process, wherein the second kesterite material includes Cu, Zn, Sn, and at least one of S and Se, wherein the first kesterite material and the second kesterite material form a multi-layer stack of the absorber material on the substrate. A photovoltaic device and method of formation thereof are also provided.

First-principles study of ternary fcc solution phases from special quasirandom structures

International Nuclear Information System (INIS)

Shin Dongwon; Wang Yi; Liu Zikui; Walle, Axel van de

2007-01-01

In the present work, ternary special quasirandom structures (SQSs) for a fcc solid solution phase are generated at different compositions, x A =x B =x C =(1/3) and x A =(1/2), x B =x C =(1/4), whose correlation functions are satisfactorily close to those of a random fcc solution. The generated SQSs are used to calculate the mixing enthalpy of the fcc phase in the Ca-Sr-Yb system. It is observed that first-principles calculations of all the binary and ternary SQSs in the Ca-Sr-Yb system exhibit very small local relaxation. It is concluded that the fcc ternary SQSs can provide valuable information about the mixing behavior of the fcc ternary solid solution phase. The SQSs presented in this work can be widely used to study the behavior of ternary fcc solid solutions

[Pd(NH{sub 3}){sub 4}]MoO{sub 4} as a precursor for Pd–Mo-containing catalysts: Thermal behavior, X-ray analysis of the thermolysis products and related catalytic studies

Energy Technology Data Exchange (ETDEWEB)

Gubanov, Alexander I., E-mail: gubanov@niic.nsc.su [Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Akad. Lavrentiev Prospekt 3, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Filatov, Eugeny Yu.; Semitut, Eugeny Yu.; Smolentsev, Anton I. [Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Akad. Lavrentiev Prospekt 3, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Snytnikov, Pavel V.; Potemkin, Dmitry I. [Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Akad. Lavrentiev Prospekt 5, 630090 Novosibirsk (Russian Federation); Korenev, Sergey V. [Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Akad. Lavrentiev Prospekt 3, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation)

2013-08-20

Highlights: • [Pd(NH{sub 3}){sub 4}]MoO{sub 4} as a precursor for Pd–Mo-containing catalysts. • Different products are formed depending on atmosphere of thermal decomposition. • Thermolysis in He atmosphere affords finely mixed two-phase nanosized system Pd–MoO{sub 2}. • Pd–MoO{sub 2} system can be a promising catalyst both in pure and supported form. - Abstract: Compound [Pd(NH{sub 3}){sub 4}]MoO{sub 4} (1) has been synthesized and characterized by IR spectroscopy, analytical data, powder and single-crystal X-ray crystallography. Thermal properties of 1 have been examined by thermogravimetry. Powder X-ray diffraction has been applied to investigate the nanosized products of thermal decomposition of the precursor in hydrogen (Pd–Mo) and helium (Pd–MoO{sub 2}) atmospheres. Pd–Mo catalysts supported with γ-Al{sub 2}O{sub 3} have been tested in oxidation of CO and H{sub 2} mixtures.

Retention of Halogenated Solutes on Stationary Phases Containing Heavy Atoms

Directory of Open Access Journals (Sweden)

Toshio Miwa

2013-05-01

Full Text Available To examine the effects of weak intermolecular interactions on solid-phase extraction (SPE and chromatographic separation, we synthesized some novel stationary phases with a heavy atom effect layer by immobilizing halogenated aromatic rings and hydroxyl groups onto the surface of a hydrophilic base polymer. Using SPE cartridges packed with the functionalized materials, we found that the heavy atom stationary phases could selectively retain halophenols in organic solvents, such as 1-propanol which blocks the hydrogen bonding, or acetonitrile which blocks the p-p interaction. The extraction efficiency of the materials toward the halophenols depended on the dipole moments of phenoxy groups present as functional groups. On the other hand, the extraction efficiency of solutes toward the functional group depended on their molar refractions, i.e., induced dipole moments. The retention of the solutes to the stationary phase ultimately depended on not only strong intermolecular interactions, but also the effects of weak interactions such as the dispersion force.

Thermodynamically Consistent Algorithms for the Solution of Phase-Field Models

KAUST Repository

Vignal, Philippe

2016-02-11

Phase-field models are emerging as a promising strategy to simulate interfacial phenomena. Rather than tracking interfaces explicitly as done in sharp interface descriptions, these models use a diffuse order parameter to monitor interfaces implicitly. This implicit description, as well as solid physical and mathematical footings, allow phase-field models to overcome problems found by predecessors. Nonetheless, the method has significant drawbacks. The phase-field framework relies on the solution of high-order, nonlinear partial differential equations. Solving these equations entails a considerable computational cost, so finding efficient strategies to handle them is important. Also, standard discretization strategies can many times lead to incorrect solutions. This happens because, for numerical solutions to phase-field equations to be valid, physical conditions such as mass conservation and free energy monotonicity need to be guaranteed. In this work, we focus on the development of thermodynamically consistent algorithms for time integration of phase-field models. The first part of this thesis focuses on an energy-stable numerical strategy developed for the phase-field crystal equation. This model was put forward to model microstructure evolution. The algorithm developed conserves, guarantees energy stability and is second order accurate in time. The second part of the thesis presents two numerical schemes that generalize literature regarding energy-stable methods for conserved and non-conserved phase-field models. The time discretization strategies can conserve mass if needed, are energy-stable, and second order accurate in time. We also develop an adaptive time-stepping strategy, which can be applied to any second-order accurate scheme. This time-adaptive strategy relies on a backward approximation to give an accurate error estimator. The spatial discretization, in both parts, relies on a mixed finite element formulation and isogeometric analysis. The codes are

The growth and tensile deformation behavior of the silver solid solution phase with zinc

International Nuclear Information System (INIS)

Wu, Jiaqi; Lee, Chin C.

2016-01-01

The growth of homogeneous silver solid solution phase with zinc are conducted at two different compositions. X-ray diffraction (XRD) and Scanning electron microscope/Energy dispersive X-ray spectroscopy (SEM/EDX) are carried out for phase identification and chemical composition verification. The mechanical properties of silver solid solution phase with zinc are evaluated by tensile test. The engineering and true stress vs. strain curves are presented and analyzed, with those of pure silver in comparison. According to the experimental results, silver solid solution phase with zinc at both compositions show tempered yield strength, high tensile strength and large uniform strain compared to those of pure silver. Fractography further confirmed the superior ductility of silver solid solution phase with zinc at both compositions. Our preliminary but encouraging results may pave the way for the silver based alloys to be applied in industries such as electronic packaging and structure engineering.

Two cloud-point phenomena in tetrabutylammonium perfluorooctanoate aqueous solutions: anomalous temperature-induced phase and structure transitions.

Science.gov (United States)

Yan, Peng; Huang, Jin; Lu, Run-Chao; Jin, Chen; Xiao, Jin-Xin; Chen, Yong-Ming

2005-03-24

This paper reported the phase behavior and aggregate structure of tetrabutylammonium perfluorooctanoate (TBPFO), determined by differential scanning calorimeter, electrical conductivity, static/dynamic light scattering, and rheology methods. We found that above a certain concentration the TBPFO solution showed anomalous temperature-dependent phase behavior and structure transitions. Such an ionic surfactant solution exhibits two cloud points. When the temperature was increased, the solution turned from a homogeneous-phase to a liquid-liquid two-phase system, then to another homogeneous-phase, and finally to another liquid-liquid two-phase system. In the first homogeneous-phase region, the aggregates of TBPFO were rodlike micelles and the solution was Newtonian fluid. While in the second homogeneous-phase region, the aggregates of TBPFO were large wormlike micelles, and the solution behaved as pseudoplastic fluid that also exhibited viscoelastic behavior. We thought that the first cloud point might be caused by the "bridge" effect of the tetrabutylammonium counterion between the micelles and the second one by the formation of the micellar network.

Insight into black hole phase transition from parametric solutions

Science.gov (United States)

Li, Dandan; Li, Shanshan; Mi, Li-Qin; Li, Zhong-Heng

2017-12-01

We consider the first-order phase transition of a charged anti-de Sitter black hole and introduce a new dimensionless parameter, ω =(Δ S /π Q2)2 . The parametric solutions of the two reduced volumes are obtained. Each volume is described by a piecewise analytic function. The demarcation point is located at ωd=12 (2 √{3 }-3 ). The volume function is smoothly connected at the point. We show that all properties of the coexistence curve can be studied from the two volume functions. In other words, an arbitrary reduced thermodynamic variable of the two coexisting phases is only a function of ω . Some phase diagrams are plotted by using parametric solutions. We find that, when the reduced pressure P ^>P^A (of order 7.4 ×10-4), the first-order phase transition of the black hole is similar to the van der Waals fluid. However, the similarity disappears when P ^≤P^A. At a van der Waals fluidlike stage, the values of the reduced Gibbs function and the reduced density average are equal. At a non-van der Waals fluid stage, the phase diagrams have extraordinarily rich structure. It is worth pointing out that the phase transition is very important for the low-pressure case since the pressure in essence is the cosmological constant, which is normally very small. Moreover, the thermodynamic behaviors as ω →0 are discussed, from which one can easily obtain some critical exponents and amplitudes for small-large black hole phase transitions.

Analytical solution of laminar-laminar stratified two-phase flows with curved interfaces

International Nuclear Information System (INIS)

Brauner, N.; Rovinsky, J.; Maron, D.M.

1995-01-01

The present study represents a complete analytical solution for laminar two-phase flows with curved interfaces. The solution of the Navier-Stokes equations for the two-phases in bipolar coordinates provides the 'flow monograms' describe the relation between the interface curvature and the insitu flow geometry when given the phases flow rates and viscosity ratios. Energy considerations are employed to construct the 'interface monograms', whereby the characteristic interfacial curvature is determined in terms of the phases insitu holdup, pipe diameter, surface tension, fluids/wall adhesion and gravitation. The two monograms are then combined to construct the system 'operational monogram'. The 'operational monogram' enables the determination of the interface configuration, the local flow characteristics, such as velocity profiles, wall and interfacial shear stresses distribution as well as the integral characteristics of the two-phase flow: phases insitu holdup and pressure drop

Analytical solution of laminar-laminar stratified two-phase flows with curved interfaces

Energy Technology Data Exchange (ETDEWEB)

Brauner, N.; Rovinsky, J.; Maron, D.M. [Tel-Aviv Univ. (Israel)

1995-09-01

The present study represents a complete analytical solution for laminar two-phase flows with curved interfaces. The solution of the Navier-Stokes equations for the two-phases in bipolar coordinates provides the `flow monograms` describe the relation between the interface curvature and the insitu flow geometry when given the phases flow rates and viscosity ratios. Energy considerations are employed to construct the `interface monograms`, whereby the characteristic interfacial curvature is determined in terms of the phases insitu holdup, pipe diameter, surface tension, fluids/wall adhesion and gravitation. The two monograms are then combined to construct the system `operational monogram`. The `operational monogram` enables the determination of the interface configuration, the local flow characteristics, such as velocity profiles, wall and interfacial shear stresses distribution as well as the integral characteristics of the two-phase flow: phases insitu holdup and pressure drop.

Phase transitions in solid Kr-CH4 solutions and rotational excitations in phase II

International Nuclear Information System (INIS)

Bagatskii, M.I.; Mashchenko, D.A.; Dudkin, V.V.

2007-01-01

The heat capacity C p of solid Kr-n CH 4 solutions with the CH 4 concentrations n=0.82, 0.86, 0.90 as well as solutions with n=0.90, 0.95 doped with 0.002 O 2 impurity has been investigated under equilibrium vapor pressure over the internal 1-24 K. The (T,n)-phase diagram was refined and the region of two-phase states was determined for Kr-n CH 4 solid solutions. The contribution of the rotational subsystem, C r ot, to the heat capacity of the solutions has been separated. Analysis of C r ot(T) at T 1 and E 2 between the tunnel levels of the A-, T- and A-, E--nuclear-spin species of CH 4 molecules in the orientationally ordered subsystem, and to determine the effective energy gaps E 1 between lowest levels of the A- and T- species. The relations τ(n) and E 1 (n) stem from changes of the effective potential field caused as the replacement of CH 4 molecules by Kr atoms at sites of the ordered sublattices. The effective gaps E L between a group of tunnel levels of the ground-state liberation state and the nearest group of excited levels of the liberation state of the ordered CH 4 molecules in the solutions with n=0.90 (E L =52 K) and 0.95 (E L =55 K) has been estimated

Influence of the extracted solute on the aggregation of malonamide extractant in organic phases: Consequences for phase stability

International Nuclear Information System (INIS)

Berthon, L.; Martinet, L.; Testard, F.; Madic, Ch.; Zem, Th.

2010-01-01

Due to their amphiphilic properties, malonamide molecules in alkane are organized in reverse micelle type aggregates, composed of a polar core formed by the malonamide polar heads and the extracted solutes, and surrounded by a hydrophobic shell made up of the extractant alkyl chains. The aggregates interact with one another through an attractive potential, leading to the formation of a third phase. This occurs with the splitting of the organic phase into a light phase composed mostly of diluent, and a heavy third phase containing highly concentrated extractant and solutes. In this article, we show that the aggregation (monomer concentration, domain of stability, and attractive potential between micelles) greatly depends on the nature of the extracted solute, whereas the size of aggregate (aggregation number) is only slightly influenced by this. We describe the extraction of water, nitric acid, neodymium nitrate and uranyl nitrate. Strongly polarizable species induce consistently large attraction potentials and a small stability domain for the dispersion of nano-droplets in the solvent. Highly polarizable ions such as lanthanides or uranyl induce more long-range attractive interactions than do protons. (authors)

Chemical vapor deposition growth of boron-carbon-nitrogen layers from methylamine borane thermolysis products

Science.gov (United States)

Leardini, Fabrice; Flores, Eduardo; Galvis E, Andrés R.; Ferrer, Isabel J.; Ramón Ares, José; Sánchez, Carlos; Molina, Pablo; van der Meulen, Herko P.; Gómez Navarro, Cristina; López Polin, Guillermo; Urbanos, Fernando J.; Granados, Daniel; García-García, F. Javier; Demirci, Umit B.; Yot, Pascal G.; Mastrangelo, Filippo; Grazia Betti, Maria; Mariani, Carlo

2018-01-01

This work investigates the growth of B-C-N layers by chemical vapor deposition using methylamine borane (MeAB) as the single-source precursor. MeAB has been synthesized and characterized, paying particular attention to the analysis of its thermolysis products, which are the gaseous precursors for B-C-N growth. Samples have been grown on Cu foils and transferred onto different substrates for their morphological, structural, chemical, electronic and optical characterizations. The results of these characterizations indicate a segregation of h-BN and graphene-like (Gr) domains. However, there is an important presence of B and N interactions with C at the Gr borders, and of C interacting at the h-BN-edges, respectively, in the obtained nano-layers. In particular, there is a significant presence of C-N bonds, at Gr/h-BN borders and in the form of N doping of Gr domains. The overall B:C:N contents in the layers is close to 1:3:1.5. A careful analysis of the optical bandgap determination of the obtained B-C-N layers is presented, discussed and compared with previous seminal works with samples of similar composition.

Selectivity of some basic solutes on a poly(methyltetradecylsiloxane)-silica stationary phase.

Science.gov (United States)

Borges, Endler M; Collins, Carol H

2011-11-01

Complex analyses of polar compounds, especially basic ones, require more selective stationary phases. The present paper describes a stationary phase prepared by thermal immobilization of poly(methyltetradecylsiloxane) onto chromatographic silica (PMTDS-SiO(2)). This stationary phase presents hydrophobic and ion-exchange interactions that confer both high retention and unique selectivities for basic solutes. The influence of ion-exchange interactions is confirmed by the increase in retention factors of basic solutes when the mobile-phase pH changes from acidic to neutral and by the decrease in retention factors when the mobile-phase pH changes from neutral to alkaline. The ion-exchange properties of the stationary phase are enriched in neutral mobile phase (pH 7-7.5) using soft Lewis bases such as tricine and tris as buffers but are suppressed in both acidic (pH 2.5-6) and highly alkaline mobile phases (pH≤10). Increasing both temperature and flow rate permits more rapid separations while maintaining the selectivity. The stability of the stationary phase is evaluated with acid, neutral and alkaline mobile phases. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solution processing of polymer semiconductor: Insulator blends-Tailored optical properties through liquid-liquid phase separation control

KAUST Repository

Hellmann, Christoph; Treat, Neil D.; Scaccabarozzi, Alberto D.; Razzell Hollis, Joseph; Fleischli, Franziska D.; Bannock, James H.; de Mello, John; Michels, Jasper J.; Kim, Ji-Seon; Stingelin, Natalie

2014-01-01

© 2014 Wiley Periodicals, Inc. It has been demonstrated that the 0-0 absorption transition of poly(3-hexylthiophene) (P3HT) in blends with poly(ethylene oxide) (PEO) could be rationally tuned through the control of the liquid-liquid phase separation process during solution deposition. Pronounced J-like aggregation behavior, characteristic for systems of a low exciton band width, was found for blends where the most pronounced liquid-liquid phase separation occurred in solution, leading to domains of P3HT and PEO of high phase purity. Since liquid-liquid phase separation could be readily manipulated either by the solution temperature, solute concentration, or deposition temperature, to name a few parameters, our findings promise the design from the out-set of semiconductor:insulator architectures of pre-defined properties by manipulation of the interaction parameter between the solutes as well as the respective solute:solvent system using classical polymer science principles.

Solution processing of polymer semiconductor: Insulator blends-Tailored optical properties through liquid-liquid phase separation control

KAUST Repository

Hellmann, Christoph

2014-12-17

© 2014 Wiley Periodicals, Inc. It has been demonstrated that the 0-0 absorption transition of poly(3-hexylthiophene) (P3HT) in blends with poly(ethylene oxide) (PEO) could be rationally tuned through the control of the liquid-liquid phase separation process during solution deposition. Pronounced J-like aggregation behavior, characteristic for systems of a low exciton band width, was found for blends where the most pronounced liquid-liquid phase separation occurred in solution, leading to domains of P3HT and PEO of high phase purity. Since liquid-liquid phase separation could be readily manipulated either by the solution temperature, solute concentration, or deposition temperature, to name a few parameters, our findings promise the design from the out-set of semiconductor:insulator architectures of pre-defined properties by manipulation of the interaction parameter between the solutes as well as the respective solute:solvent system using classical polymer science principles.

GaN Bulk Growth and Epitaxy from Ca-Ga-N Solutions, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — This SBIR proposal addresses the liquid phase epitaxy (LPE) of gallium nitride (GaN) films using nitrogen-enriched metal solutions. Growth of GaN from solutions...

A direct comparison of protein structure in the gas and solution phase: the Trp-cage

DEFF Research Database (Denmark)

Patriksson, Alexandra; Adams, Christopher M; Kjeldsen, Frank

2007-01-01

Molecular dynamics simulations of zwitterions of the Trp-cage protein in the gas phase show that the most stable ion in vacuo has preserved the charge locations acquired in solution. A direct comparison of the gas and solution-phase structures reveals that, despite the similarity in charge location...

A Photoelectron Spectroscopic Study of Di-t-butylphosphazene

DEFF Research Database (Denmark)

Elbel, S.; Ellis, A.; Niecke, E.

1985-01-01

Gaseous trans-ButPNBut, generated by mild gas-phase thermolysis of its more stable [2 + 1] cyclodimer, has been characterized by field-ionization mass spectrometry and U.V. photoelectron spectroscopy. The photoelectron spectrum has been assigned based on SCC-Xα model calculations for representat......Gaseous trans-ButPNBut, generated by mild gas-phase thermolysis of its more stable [2 + 1] cyclodimer, has been characterized by field-ionization mass spectrometry and U.V. photoelectron spectroscopy. The photoelectron spectrum has been assigned based on SCC-Xα model calculations...

[Nasal submicron emulsion of Scutellariae Radix extract preparation technology research based on phase transfer of solute technology].

Science.gov (United States)

Shi, Ya-jun; Shi, Jun-hui; Chen, Shi-bin; Yang, Ming

2015-07-01

Based on the demand of nasal drug delivery high drug loadings, using the unique phase transfer of solute, integrating the phospholipid complex preparation and submicron emulsion molding process of Scutellariae Radix extract, the study obtained the preparation of the high drug loadings submicron emulsion of Scutellariae Radix extract. In the study of drug solution dispersion method, the uniformity of drug dispersed as the evaluation index, the traditional mixing method, grinding, homogenate and solute phase transfer technology were investigated, and the solute phase transfer technology was adopted in the last. With the adoption of new technology, the drug loading capacity reached 1.33% (phospholipid complex was 4%). The drug loading capacity was improved significantly. The transfer of solute method and timing were studied as follows,join the oil phase when the volume of phospholipid complex anhydrous ethanol solution remaining 30%, the solute phase transfer was completed with the continued recycling of anhydrous ethanol. After drug dissolved away to oil phase, the preparation technology of colostrum was determined with the evaluation index of emulsion droplet form. The particle size of submicron emulsion, PDI and stability parameters were used as evaluation index, orthogonal methodology were adopted to optimize the submicron emulsion ingredient and main influential factors of high pressure homogenization technology. The optimized preparation technology of Scutellariae Radix extract nasal submicron emulsion is practical and stable.

Numerical simulation of solute trapping phenomena using phase-field solidification model for dilute binary alloys

Directory of Open Access Journals (Sweden)

Henrique Silva Furtado

2009-09-01

Full Text Available Numerical simulation of solute trapping during solidification, using two phase-field model for dilute binary alloys developed by Kim et al. [Phys. Rev. E, 60, 7186 (1999] and Ramirez et al. [Phys. Rev. E, 69, 05167 (2004] is presented here. The simulations on dilute Cu-Ni alloy are in good agreement with one dimensional analytic solution of sharp interface model. Simulation conducted under small solidification velocity using solid-liquid interface thickness (2λ of 8 nanometers reproduced the solute (Cu equilibrium partition coefficient. The spurious numerical solute trapping in solid phase, due to the interface thickness was negligible. A parameter used in analytical solute trapping model was determined by isothermal phase-field simulation of Ni-Cu alloy. Its application to Si-As and Si-Bi alloys reproduced results that agree reasonably well with experimental data. A comparison between the three models of solute trapping (Aziz, Sobolev and Galenko [Phys. Rev. E, 76, 031606 (2007] was performed. It resulted in large differences in predicting the solidification velocity for partition-less solidification, indicating the necessity for new and more acute experimental data.

Catalytic thermal treatment (catalytic thermolysis) of a rice grain-based biodigester effluent of an alcohol distillery plant.

Science.gov (United States)

Prajapati, Abhinesh Kumar; Chaudhari, Parmesh Kumar; Mazumdar, Bidyut; Choudhary, Rumi

2015-01-01

The catalytic thermolysis (CT) process is an effective and novel approach to treat rice grain-based biodigester effluent (BDE) of the distillery plant. CT treatment of rice grain-based distillery wastewater was carried out in a 0.5 dm(3) thermolytic batch reactor using different catalysts such as CuO, copper sulphate and ferrous sulphate. With the CuO catalyst, a temperature of 95°C, catalyst loading of 4 g/dm(3) and pH 5 were found to be optimal, obtaining a maximum chemical oxygen demand (COD) and colour removal of 80.4% and 72%, respectively. The initial pH (pHi) was an important parameter to remove COD and colour from BDE. At higher pHi (pH 9.5), less COD and colour reduction were observed. The settling characteristics of CT-treated sludge were also analysed at different temperatures. It was noted that the treated slurry at a temperature of 80°C gave best settling characteristics. Characteristics of residues are also analysed at different pH.

Solid solution and amorphous phase in Ti–Nb–Ta–Mn systems synthesized by mechanical alloying

Energy Technology Data Exchange (ETDEWEB)

Aguilar, C., E-mail: claudio.aguilar@usm.cl [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Guzman, P. [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Lascano, S. [Departamento de Ingeniería Mecánica, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Parra, C. [Departamento de Física, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Bejar, L. [Instituto de Investigaciones Metalúrgicas, Universidad Michoacana de San Nicolás de Hidalgo, Ciudad Universitaria, Morelia C.P. 58000, Michoacán (Mexico); Medina, A. [Facultad de Ingeniería Mecánica, Universidad Michoacana de San Nicolás de Hidalgo, Ciudad Universitaria, C.P. 58000, Michoacán (Mexico); Guzman, D. [Departamento de Metalurgia, Universidad de Atacama, Av. España 485, Copiapó (Chile)

2016-06-15

This work discusses the formation of Ti–30Nb–13Ta–xMn (x: 2, 4 and 6 wt%) solid solution by mechanical alloying using a shaker mill. A solid solution was formed after 15 h of milling and an amorphous phase was formed after 30 h of milling, according to X-ray diffraction results. Disappearance of strongest X-ray diffraction peaks of Nb, Ta and Mn indicated the formation of solid solution, while, X-ray diffraction patterns of powders milled for 30 h showed an amorphous hump with crystalline peaks in the angular range of 35–45° in 2θ. TEM image analysis showed the presence of nanocrystalline intermetallic compounds embedded in an amorphous matrix. Mn{sub 2}Ti, MnTi and NbTi{sub 4} intermetallic compounds were detected and revealed crystallites with size ranging from 3 to 20 nm. The Gibbs free energy for the formation of solid solution and amorphous phase of three ternary systems (Ti–Nb–Ta, Ti–Nb–Mn and Ti–Ta–Mn) was calculated using extended Miedema's model. Experimental and thermodynamic data confirmed that solid solution was first formed in the alloy with 6wt% Mn followed by the formation of an amorphous phase as milling time increases. The presence of Mn promoted the formation of amorphous phase because the atomic radius difference between Mn with Ti, Nb and Ta. - Highlights: • Thermodynamics analysis of extension of solid solution of the Ti–Nb–Ta–Mn system. • Formation of amorphous phase and intermetallic compounds were observed. • Nanocrystalline intermetallic compounds were formed with the sizes between 3 and 20 nm.

One-Step Thermolysis Synthesis of Divalent Transition Metal Ions Monodoped and Tridoped CdS and ZnS Luminescent Nanomaterials

Directory of Open Access Journals (Sweden)

S. E. Saeed

2014-01-01

Full Text Available Mn2+, Co2+, or Ni2+ monodoped CdS (or ZnS and Mn2+-Co2+-Ni2+ tridoped CdS (or ZnS have been successfully synthesized by novel one-step thermolysis method using thiourea as a sulphur source. The synthesized nanomaterials were characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, and scanning electron microscopy (SEM. It is found that the average diameter and morphology of the synthesized samples varied with the nature of dopant ion. The successful doping of Mn2+-Co2+-Ni2+ tridoped ions into the host CdS (or ZnS was proved by the EDX spectra. The luminescence of CdS is only enhanced when monodoped with Mn2+ whereas it is enhanced when ZnS is either monodoped with Mn2+, Co2+, or Ni2+ or tridoped with Mn2+-Co2+-Ni2+. The synthesized samples could therefore offer opportunities for further fundamental research and technological applications.

Phase relations and Gibbs energies of spinel phases and solid solutions in the system Mg-Rh-O

Energy Technology Data Exchange (ETDEWEB)

Jacob, K.T., E-mail: katob@materials.iisc.ernet.in [Department of Materials Engineering, Indian Institute of Science, Bangalore 560 012 (India); Prusty, Debadutta [Department of Materials Engineering, Indian Institute of Science, Bangalore 560 012 (India); Kale, G.M. [Institute for Materials Research, University of Leeds, Leeds, LS2 9JT (United Kingdom)

2012-02-05

Highlights: Black-Right-Pointing-Pointer Refinement of phase diagram for the system Mg-Rh-O and thermodynamic data for spinel compounds MgRh{sub 2}O{sub 4} and Mg{sub 2}RhO{sub 4} is presented. Black-Right-Pointing-Pointer A solid-state electrochemical cell is used for thermodynamic measurement. Black-Right-Pointing-Pointer An advanced design of the solid-state electrochemical cell incorporating buffer electrodes is deployed to minimize polarization of working electrode. Black-Right-Pointing-Pointer Regular solution model for the spinel solid solution MgRh{sub 2}O{sub 4} - Mg{sub 2}RhO{sub 4} based on ideal mixing of cations on the octahedral site is proposed. Black-Right-Pointing-Pointer Factors responsible for stabilization of tetravalent rhodium in spinel compounds are identified. - Abstract: Pure stoichiometric MgRh{sub 2}O{sub 4} could not be prepared by solid state reaction from an equimolar mixture of MgO and Rh{sub 2}O{sub 3} in air. The spinel phase formed always contained excess of Mg and traces of Rh or Rh{sub 2}O{sub 3}. The spinel phase can be considered as a solid solution of Mg{sub 2}RhO{sub 4} in MgRh{sub 2}O{sub 4}. The compositions of the spinel solid solution in equilibrium with different phases in the ternary system Mg-Rh-O were determined by electron probe microanalysis. The oxygen potential established by the equilibrium between Rh + MgO + Mg{sub 1+x}Rh{sub 2-x}O{sub 4} was measured as a function of temperature using a solid-state cell incorporating yttria-stabilized zirconia as an electrolyte and pure oxygen at 0.1 MPa as the reference electrode. To avoid polarization of the working electrode during the measurements, an improved design of the cell with a buffer electrode was used. The standard Gibbs energies of formation of MgRh{sub 2}O{sub 4} and Mg{sub 2}RhO{sub 4} were deduced from the measured electromotive force (e.m.f.) by invoking a model for the spinel solid solution. The parameters of the model were optimized using the measured

Phase field simulations of ice crystal growth in sugar solutions

NARCIS (Netherlands)

Sman, Van Der R.G.M.

2016-01-01

We present the first model ever, that describes explicitly ice crystal growth in a sugar solution during freezing. This 2-D model uses the phase field method, supplemented with realistic, and predictive theories on the thermodynamics and (diffusion) kinetics of this food system. We have to make

Linking photochemistry in the gas and solution phase: S-H bond fission in p-methylthiophenol following UV photoexcitation.

Science.gov (United States)

Oliver, Thomas A A; Zhang, Yuyuan; Ashfold, Michael N R; Bradforth, Stephen E

2011-01-01

Gas-phase H (Rydberg) atom photofragment translational spectroscopy and solution-phase femtosecond-pump dispersed-probe transient absorption techniques are applied to explore the excited state dynamics of p-methylthiophenol connecting the short time reactive dynamics in the two phases. The molecule is excited at a range of UV wavelengths from 286 to 193 nm. The experiments clearly demonstrate that photoexcitation results in S-H bond fission--both in the gas phase and in ethanol solution-and that the resulting p-methythiophenoxyl radical fragments are formed with significant vibrational excitation. In the gas phase, the recoil anisotropy of the H atom and the vibrational energy disposal in the p-MePhS radical products formed at the longer excitation wavelengths reveal the operation of two excited state dissociation mechanisms. The prompt excited state dissociation motif appears to map into the condensed phase also. In both phases, radicals are produced in both their ground and first excited electronic states; characteristic signatures for both sets of radical products are already apparent in the condensed phase studies after 50 fs. No evidence is seen for either solute ionisation or proton coupled electron transfer--two alternate mechanisms that have been proposed for similar heteroaromatics in solution. Therefore, at least for prompt S-H bond fissions, the direct observation of the dissociation process in solution confirms that the gas phase photofragmentation studies indeed provide important insights into the early time dynamics that transfer to the condensed phase.

Thermodynamic nonequilibrium phase change behavior and thermal properties of biological solutions for cryobiology applications.

Science.gov (United States)

Han, Bumsoo; Bischof, John C

2004-04-01

Understanding the phase change behavior of biomaterials during freezing/thawing including their thermal properties at low temperatures is essential to design and improve cryobiology applications such as cryopreservation and cryosurgery. However, knowledge of phase change behavior and thermal properties of various biomaterials is still incomplete, especially at cryogenic temperatures (solutions--either water-NaCl or phosphate buffered saline (PBS)--with various chemical additives were investigated. The chemical additives studied are glycerol and raffinose as CPAs, an AFP (Type III, molecular weight = 6500), and NaCl as a cryosurgical adjuvant. The phase change behavior was investigated using a differential scanning calorimeter (DSC) and a cryomicroscope. The specific and latent heat of these solutions were also measured with the DSC. The saline solutions have two distinct phase changes--water/ice and eutectic phase changes. During freezing, eutectic solidification of both water-NaCl and PBS are significantly supercooled below their thermodynamic equilibrium eutectic temperatures. However, their melting temperatures are close to thermodynamic equilibrium during thawing. These eutectic phase changes disappear when even a small amount (0.1 M glycerol) of CPA was added, but they are still observed after the addition of an AFP. The specific heats of these solutions are close to that of ice at very low temperatures (< or = -100 degrees C) regardless of the additives, but they increase between -100 degrees C and -30 degrees C with the addition of CPAs. The amount of latent heat, which is evaluated with sample weight, generally decreases with the addition of the additives, but can be normalized to approximately 300 J/g based on the weight of water which participates in the phase change. This illustrates that thermal properties, especially latent heat, of a biomaterial should be evaluated based on the understanding of its phase change behavior. The results of the present

Pattern Formation During Phase Separation of Polymer-Ionic Liquid Co-Solutions

Science.gov (United States)

Meng, Zhiyong; Osuji, Chinedum

2010-03-01

Co-solutions of polystyrene (PS) with a 1-butyl-3-methylimidazolium based ionic liquid (IL) in DMF phase separated into IL-rich and PS-rich domains on solvent evaporation. Over a limited range of polymer molecular weights and substrate temperatures, a variety of striped and cellular or polygonal structures were found on the resulting film surface, as visualized using bright-field and phase-contrast optical microscopy. This effect appears to be due to a Benard-Marangoni instability at the free surface of the liquid film as it undergoes evaporation, setting up convection rolls inside the fluid which become locked in place as the system vitrifies on solvent removal. Differential scanning calorimetry shows that the IL does not significantly plasticize the polymer, suggesting that the viscosity of the polystyrene solution itself controls the formation of this instability.

Numerical method for solution of transient, homogeneous, equilibrium, two-phase flows in one space dimension

International Nuclear Information System (INIS)

Shin, Y.W.; Wiedermann, A.H.

1979-10-01

A solution method is presented for transient, homogeneous, equilibrium, two-phase flows of a single-component fluid in one space dimension. The method combines a direct finite-difference procedure and the method of characteristics. The finite-difference procedure solves the interior points of the computing domain; the boundary information is provided by a separate procedure based on the characteristics theory. The solution procedure for boundary points requires information in addition to the physical boundary conditions. This additional information is obtained by a new procedure involving integration of characteristics in the hodograph plane. Sample problems involving various combinations of basic boundary types are calculated for two-phase water/steam mixtures and single-phase nitrogen gas, and compared with independent method-of-characteristics solutions using very fine characteristic mesh. In all cases, excellent agreement is demonstrated

Properties of solutions of Bloch-type equations for the paraelectric phase of KDP

Energy Technology Data Exchange (ETDEWEB)

Glowacki, M; Paszkiewicz, T [Wroclaw Univ. (Poland). Inst. Fyziki Teoretycznej

1979-10-01

Exact solutions for two sets of Bloch-like equations describing the paraelectric phase of the model of KDP were studied. The general properties of both solutions are the same. However, in numerical calculations they differ significantly. A modification of the decay law connected with the soft mode frequency fluctuations is considered.

Formation of soft magnetic high entropy amorphous alloys composites containing in situ solid solution phase

Science.gov (United States)

Wei, Ran; Sun, Huan; Chen, Chen; Tao, Juan; Li, Fushan

2018-03-01

Fe-Co-Ni-Si-B high entropy amorphous alloys composites (HEAACs), which containing high entropy solid solution phase in amorphous matrix, show good soft magnetic properties and bending ductility even in optimal annealed state, were successfully developed by melt spinning method. The crystallization phase of the HEAACs is solid solution phase with body centered cubic (BCC) structure instead of brittle intermetallic phase. In addition, the BCC phase can transformed into face centered cubic (FCC) phase with temperature rise. Accordingly, Fe-Co-Ni-Si-B high entropy alloys (HEAs) with FCC structure and a small amount of BCC phase was prepared by copper mold casting method. The HEAs exhibit high yield strength (about 1200 MPa) and good plastic strain (about 18%). Meanwhile, soft magnetic characteristics of the HEAs are largely reserved from HEAACs. This work provides a new strategy to overcome the annealing induced brittleness of amorphous alloys and design new advanced materials with excellent comprehensive properties.

A theory of phase separation in asphaltene-micellar solutions

Energy Technology Data Exchange (ETDEWEB)

Pacheco Sanchez, Juan H. [Instituto Mexicano del Petroleo, Mexico D.F. (Mexico)

2001-08-01

A theory of phase separation in micellar solutions of asphaltene in aromatic hydrocarbons was reported in this paper, based on both the approach of the phase behavior of amphiphile/water micelles, and the self-association of asphaltene in aromatic core. Several experimental techniques have been used by different investigators showing the existence of some kind of critical micellar concentration (CMC) on asphaltenes in aromatic solutions. So, at least asphaltene-monomer and asphaltene-micellar phases are experimentally demonstrated facts. These two phases are the main purpose in this report on a theoretical model. Some results show the temperature versus asphaltene concentration phase diagram. The phase diagram is examined against the limited critical micelle concentration data for asphaltenes-in-toluene systems. Such phase diagram is also qualitatively examined against an experimental demonstration of phase separation. The asphaltene-micelle growth depends on the parameter K responsible for the shape and size of it. At the same time, parameter K depends on both the number of asphaltene-monomer associated in the asphaltene-micelle, and the chemical potentials in the interior and in the periphery of the micelle. An expression for getting the number of asphaltene-monomers self-associated in the asphaltene-micelle was obtained. [Spanish] Se reporta una teoria de separacion de fases en soluciones micelares de asfalteno en hidrocarburos aromaticos, basada tanto en la conducta de fase de micelas formadas por anififilos en agua como en la autoasociacion de asfaltenos en nucleos aromaticos. Se han usado diversas tecnicas experimentales por diferentes investigadores que demuestran la existancia de algun tipo de concentracion micelar critica (CMC) de soluciones de asfaltenos en aromaticos. Entonces, al menos las fases de asfalteno-monomerico y de asfalteno-micelar son hechos experimentalmente demostrados. Esta dos fases son el principal proposito de este reporte en un modelo

NMR studies of phase behaviour in polyacrylonitrile solutions

International Nuclear Information System (INIS)

Golightly, J.A.

1998-10-01

The aim of the thesis was to study the phase behaviour of aqueous polyacrylonitrile/NaSCN solutions using a variety of nuclear magnetic resonance techniques. Polyacrylonitrile (PAN) is the basis of the acrylic fibre industry, as such fibres contain at least 85% PAN. Despite this industrial importance, the available literature describing the phase behaviour of PAN in solution is far from comprehensive. Bulk 1 H NMR relaxation measurements were carried out over a wide range of concentrations and temperatures to probe the molecular dynamics of the PAN and water molecules. The relaxation data was found to be biexponential decay for all samples, the relative amplitudes of which were shown to be equal to the ratio of PAN protons to water protons. Both species were found to be in the regime of rapid molecular motion. Bulk 1 H NMR self diffusion measurements, using the PFGSTE technique, exhibited a bi-exponential decay of the echo amplitudes. By careful selection of the observation time, Δ, it was possible to independently probe the water and PAN translational diffusion. A background gradient, resulting from inhomogeneities of the magnetic field, complicated the analysis of the data and a novel polynomial least squares fitting procedure was devised to overcome this effect. The measured attenuation of the water diffusion coefficients (D∼10 -6 -10 -5 cm 2 s -1 ) with increasing PAN volume fraction was modelled according to various theories, including free volume and scaling laws. The study of the PAN diffusion coefficient (D∼10 -7 -10 -6 cm 2 s -1 ) was limited by the experimental constraints of the NMR spectrometer. A 1 H NMR one-dimensional imaging technique was used to study the non-solvent induced phase separation (coagulation) of a PAN solution. The time dependence of the measured profiles allowed observation of the coagulation process. A diffusion model was developed to fit the experimental data using a semi-infinite diffusion framework. The fitting parameters

Phase-separation phenomena in solutions of poly(2,6-dimethyl-1,4 phenylene oxide). II. Differential scanning calorimetry of solutions in toluene

NARCIS (Netherlands)

Koenhen, D.M.; Smolders, C.A.

1977-01-01

The phase-separation phenomena observed in solutions of poly(2,6 dimethyl-1,4 phenylene oxide) in toluene have been investigated by differential scanning calorimetry. These measurements supplement the experimental evidence in favor of the concept that the phase transitions observed are

Travelling-wave amplitudes as solutions of the phase-field crystal equation

Science.gov (United States)

Nizovtseva, I. G.; Galenko, P. K.

2018-01-01

The dynamics of the diffuse interface between liquid and solid states is analysed. The diffuse interface is considered as an envelope of atomic density amplitudes as predicted by the phase-field crystal model (Elder et al. 2004 Phys. Rev. E 70, 051605 (doi:10.1103/PhysRevE.70.051605); Elder et al. 2007 Phys. Rev. B 75, 064107 (doi:10.1103/PhysRevB.75.064107)). The propagation of crystalline amplitudes into metastable liquid is described by the hyperbolic equation of an extended Allen-Cahn type (Galenko & Jou 2005 Phys. Rev. E 71, 046125 (doi:10.1103/PhysRevE.71.046125)) for which the complete set of analytical travelling-wave solutions is obtained by the method (Malfliet & Hereman 1996 Phys. Scr. 15, 563-568 (doi:10.1088/0031-8949/54/6/003); Wazwaz 2004 Appl. Math. Comput. 154, 713-723 (doi:10.1016/S0096-3003(03)00745-8)). The general solution of travelling waves is based on the function of hyperbolic tangent. Together with its set of particular solutions, the general solution is analysed within an example of specific task about the crystal front invading metastable liquid (Galenko et al. 2015 Phys. D 308, 1-10 (doi:10.1016/j.physd.2015.06.002)). The influence of the driving force on the phase-field profile, amplitude velocity and correlation length is investigated for various relaxation times of the gradient flow. This article is part of the theme issue `From atomistic interfaces to dendritic patterns'.

Semiclassical series solution of the generalized phase shift atom--diatom scattering equations

International Nuclear Information System (INIS)

Squire, K.R.; Curtiss, C.F.

1980-01-01

A semiclassical series solution of the previously developed operator form of the generalized phase shift equations describing atom--diatom scattering is presented. This development is based on earlier work which led to a double series in powers of Planck's constant and a scaling parameter of the anisotropic portion of the intermolecular potential. The present solution is similar in that it is a double power series in Planck's constant and in the difference between the spherical radial momentum and a first order approximation. The present series solution avoids difficulties of the previous series associated with the classical turning point

A novel solution-phase route for the synthesis of crystalline silver nanowires

International Nuclear Information System (INIS)

Liu Yang; Chu Ying; Yang Likun; Han Dongxue; Lue Zhongxian

2005-01-01

A unique solution-phase route was devised to synthesize crystal Ag nanowires with high aspect-ratio (8-10 nm in diameter and length up to 10 μm) by the reduction of AgNO 3 with Vitamin C in SDS/ethanol solution. The resultant nanoproducts were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD) and electron diffraction (ED). A soft template mechanism was put forward to interpret the formation of metal Ag nanowires

Thermal transformations of oxohalide complexes of rhenium(5) and molybdenum(5) with diazo-18-crown-6 in solid phase

International Nuclear Information System (INIS)

Ashurova, N.Kh.; Yakubov, K.G.

1992-01-01

Methods for synthesis and separation in solid state of the rhenium(5) and molybdenum(5) onium complexes with diaza-18-crown-6(L), the content of which according to the data of elementary analysis, IRS in the close and remote areas, thermogravimetry, conductometry and potentiometry corresponds to the (H 2 L)[EOX 5 ], where E = Re, Mo; X = Cl - , Br - . Thermotransformation of onium compounds is studied by methods of thermal methods (TG-DTG-DTA combined study). Their avility to be affected by solid-phase dehydrohalogenization, e.i. anderson regrouping. The thermolysis products, corresponding to the general formula (EOLX 3 ), are separated and studied

Travelling Wave Solutions to Stretched Beam's Equation: Phase Portraits Survey

International Nuclear Information System (INIS)

Betchewe, Gambo; Victor, Kuetche Kamgang; Thomas, Bouetou Bouetou; Kofane, Timoleon Crepin

2011-01-01

In this paper, following the phase portraits analysis, we investigate the integrability of a system which physically describes the transverse oscillation of an elastic beam under end-thrust. As a result, we find that this system actually comprises two families of travelling waves: the sub- and super-sonic periodic waves of positive- and negative-definite velocities, respectively, and the localized sub-sonic loop-shaped waves of positive-definite velocity. Expressing the energy-like of this system while depicting its phase portrait dynamics, we show that these multivalued localized travelling waves appear as the boundary solutions to which the periodic travelling waves tend asymptotically. (general)

Solution-Phase Synthesis of Cesium Lead Halide Perovskite Nanowires.

Science.gov (United States)

Zhang, Dandan; Eaton, Samuel W; Yu, Yi; Dou, Letian; Yang, Peidong

2015-07-29

Halide perovskites have attracted much attention over the past 5 years as a promising class of materials for optoelectronic applications. However, compared to hybrid organic-inorganic perovskites, the study of their pure inorganic counterparts, like cesium lead halides (CsPbX3), lags far behind. Here, a catalyst-free, solution-phase synthesis of CsPbX3 nanowires (NWs) is reported. These NWs are single-crystalline, with uniform growth direction, and crystallize in the orthorhombic phase. Both CsPbBr3 and CsPbI3 are photoluminescence active, with composition-dependent temperature and self-trapping behavior. These NWs with a well-defined morphology could serve as an ideal platform for the investigation of fundamental properties and the development of future applications in nanoscale optoelectronic devices based on all-inorganic perovskites.

Performance of metal compound on thermolysis and electrolysis on sugar industries waste water treatment: COD and color removal with sludge analysis (batch-experiment)

Science.gov (United States)

Sahu, Omprakash

2017-10-01

The sugar cane industry is one of the most water demanding industries. Sugar industries consume and generate excess amount of water. The generated water contains organic compounds, which would cause pollution. The aim of this research work is to study the effectiveness of metal compound for treatment of sugar industry waste water by thermolysis and electrolysis process. The result shows ferrous metal catalyst shows 80 and 85 % chemical oxygen demand and color removal at pH 6, optimum mass loading 4 kg/m3, treatment temperature 85 °C and treatment time 9 h. When ferrous material was used as electrode, maximum 81 % chemical oxygen demand and 84 % color removal at pH 6, current density 156 Am-2, treatment time 120 min and anode consumption 0.7 g for 1.5 L wastewater were obtained.

Convergence to stationary solutions for a parabolic-hyperbolic phase-field system

Czech Academy of Sciences Publication Activity Database

Grasselli, M.; Petzeltová, Hana; Schimperna, G.

2006-01-01

Roč. 5, č. 4 (2006), s. 827-838 ISSN 1534-0392 R&D Projects: GA AV ČR(CZ) IAA1019302 Institutional research plan: CEZ:AV0Z10190503 Keywords : phase-field models * convergence to stationary solutions * Łojasiewicz-Simon inequality Subject RIV: BA - General Mathematics Impact factor: 0.857, year: 2006

Fully synchronous solutions and the synchronization phase transition for the finite-N Kuramoto model

Science.gov (United States)

Bronski, Jared C.; DeVille, Lee; Jip Park, Moon

2012-09-01

We present a detailed analysis of the stability of phase-locked solutions to the Kuramoto system of oscillators. We derive an analytical expression counting the dimension of the unstable manifold associated to a given stationary solution. From this we are able to derive a number of consequences, including analytic expressions for the first and last frequency vectors to phase-lock, upper and lower bounds on the probability that a randomly chosen frequency vector will phase-lock, and very sharp results on the large N limit of this model. One of the surprises in this calculation is that for frequencies that are Gaussian distributed, the correct scaling for full synchrony is not the one commonly studied in the literature; rather, there is a logarithmic correction to the scaling which is related to the extremal value statistics of the random frequency vector.

Theoretical study on phase coexistence in ferroelectric solid solutions near the tricritical point

Energy Technology Data Exchange (ETDEWEB)

Lu, Xiaoyan, E-mail: luxy@hit.edu.cn, E-mail: dzk@psu.edu; Li, Hui [Key Lab of Structures Dynamic Behavior and Control of the Ministry of Education, School of Civil Engineering, Harbin Institute of Technology, Harbin 150001 (China); Zheng, Limei [Condensed Matter Science and Technology Institute, Harbin Institute of Technology, Harbin 150001 (China); Cao, Wenwu [Condensed Matter Science and Technology Institute, Harbin Institute of Technology, Harbin 150001 (China); Department of Mathematics and Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States)

2015-04-07

Phase coexistence in ferroelectric solid solutions near the tricritical point has been theoretically analyzed by using the Landau-Devonshire theory. Results revealed that different phases having similar potential wells could coexist in a narrow composition range near the tricritical point in the classical Pb(Zr{sub 1−x}Ti{sub x})O{sub 3} system. The potential barrier between potential wells increases with the decrease of temperature. Coexisting phases or different domains of the same phase can produce adaptive strains to maintain atomic coherency at the interfaces or domain walls. Such compatibility strains have influence on the energy potential as well as the stability of relative phases, leading to the appearance of energetically unfavorable monoclinic phases. Those competing and coexisting phases also construct an easy phase transition path with small energy barrier in between, so that very small stimuli can produce large response in compositions near the morphotropic phase boundary, especially near the tricritical point.

Theoretical study on phase coexistence in ferroelectric solid solutions near the tricritical point

International Nuclear Information System (INIS)

Lu, Xiaoyan; Li, Hui; Zheng, Limei; Cao, Wenwu

2015-01-01

Phase coexistence in ferroelectric solid solutions near the tricritical point has been theoretically analyzed by using the Landau-Devonshire theory. Results revealed that different phases having similar potential wells could coexist in a narrow composition range near the tricritical point in the classical Pb(Zr 1−x Ti x )O 3 system. The potential barrier between potential wells increases with the decrease of temperature. Coexisting phases or different domains of the same phase can produce adaptive strains to maintain atomic coherency at the interfaces or domain walls. Such compatibility strains have influence on the energy potential as well as the stability of relative phases, leading to the appearance of energetically unfavorable monoclinic phases. Those competing and coexisting phases also construct an easy phase transition path with small energy barrier in between, so that very small stimuli can produce large response in compositions near the morphotropic phase boundary, especially near the tricritical point

A stationary phase solution for mountain waves with application to mesospheric mountain waves generated by Auckland Island

Science.gov (United States)

Broutman, Dave; Eckermann, Stephen D.; Knight, Harold; Ma, Jun

2017-01-01

A relatively general stationary phase solution is derived for mountain waves from localized topography. It applies to hydrostatic, nonhydrostatic, or anelastic dispersion relations, to arbitrary localized topography, and to arbitrary smooth vertically varying background temperature and vector wind profiles. A simple method is introduced to compute the ray Jacobian that quantifies the effects of horizontal geometrical spreading in the stationary phase solution. The stationary phase solution is applied to mesospheric mountain waves generated by Auckland Island during the Deep Propagating Gravity Wave Experiment. The results are compared to a Fourier solution. The emphasis is on interpretations involving horizontal geometrical spreading. The results show larger horizontal geometrical spreading for nonhydrostatic waves than for hydrostatic waves in the region directly above the island; the dominant effect of horizontal geometrical spreading in the lower ˜30 km of the atmosphere, compared to the effects of refraction and background density variation; and the enhanced geometrical spreading due to directional wind in the approach to a critical layer in the mesosphere.

Phase separation in solution of worm-like micelles: a dilute ? spin-vector model

Science.gov (United States)

Panizza, Pascal; Cristobal, Galder; Curély, Jacques

1998-12-01

We show how the dilute 0953-8984/10/50/006/img2 spin vector model introduced originally by Wheeler and co-workers for describing the polymerization phenomenon in solutions of liquid sulphur and of living polymers may be conveniently adapted for studying phase separation in systems containing long flexible micelles. We draw an isomorphism between the coupling constant appearing in the exchange Hamiltonian and the surfactant energies in the micellar problem. We solve this problem within the mean-field approximation and compare the main results we have obtained with respect to polymer theory and previous theories of phase separation in micellar solutions. We show that the attractive interaction term 0953-8984/10/50/006/img3 between monomers renormalizes the aggregation energy and subsequently the corresponding size distribution. Under these conditions, we observe that the general aspect of the phase diagram in the 0953-8984/10/50/006/img4 plane (where 0953-8984/10/50/006/img5 is the surfactant concentration) is different from previous results. The spinodal line shows a re-entrant behaviour and, at low concentrations, we point out the possibility of specific nucleation phenomena related to the existence of a metastable transition line between a region composed of spherical micelles and another one corresponding to a dilute solution of long flexible micelles.

Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures

Science.gov (United States)

Kanno, H.; Kajiwara, K.; Miyata, K.

2010-05-01

Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for TH (homogeneous ice nucleation temperature) and Tm (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the TH curve for a DMSO solution of R =20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at Pc2=˜200 MPa and at Tc2pressure of SCP, Tc2: temperature of SCP). The presence of two TH peaks for DMSO solutions (R =15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R ≤15) at high pressures and low temperatures (pressure dependence of the two TH curves for DMSO solutions of R =10 and 12 indicates that the two phase-separated components in the DMSO solution of R =10 have different liquid water structures [LDL-like and HDL-like structures (LDL: low-density liquid water, HDL: high-density liquid water)] in the pressure range of 120-230 MPa.

Solid-Phase and Oscillating Solution Crystallization Behavior of (+)- and (-)-N-Methylephedrine.

Science.gov (United States)

Tulashie, Samuel Kofi; Polenske, Daniel; Seidel-Morgenstern, Andreas; Lorenz, Heike

2016-11-01

This work involves the study of the solid-phase and solution crystallization behavior of the N-methylephedrine enantiomers. A systematic investigation of the melt phase diagram of the enantiomeric N-methylephedrine system was performed considering polymorphism. Two monotropically related modifications of the enantiomer were found. Solubilities and the ternary solubility phase diagrams of N-methylephedrine enantiomers in 2 solvents [isopropanol:water, 1:3 (Vol) and (2R, 3R)-diethyl tartrate] were determined in the temperature ranges between 15°C and 25°C, and 25°C and 40°C, respectively. Preferential nucleation and crystallization experiments at higher supersaturation leading to an unusual oscillatory crystallization behavior as well as a successful preferential crystallization experiment at lower supersaturation are presented and discussed. Copyright © 2016. Published by Elsevier Inc.

Retention prediction of highly polar ionizable solutes under gradient conditions on a mixed-mode reversed-phase and weak anion-exchange stationary phase.

Science.gov (United States)

Balkatzopoulou, P; Fasoula, S; Gika, H; Nikitas, P; Pappa-Louisi, A

2015-05-29

In the present work the retention of three highly polar and ionizable solutes - uric acid, nicotinic acid and ascorbic acid - was investigated on a mixed-mode reversed-phase and weak anion-exchange (RP/WAX) stationary phase in buffered aqueous acetonitrile (ACN) mobile phases. A U-shaped retention behavior was observed for all solutes with respect to the eluent organic modifier content studied in a range of 5-95% (v/v). This retention behavior clearly demonstrates the presence of a HILIC-type retention mechanism at ACN-rich hydro-organic eluents and an RP-like retention at aqueous-rich hydro-organic eluents. Hence, this column should be promising for application under both RP and HILIC gradient elution modes. For this reason, a series of programmed elution runs were carried out with increasing (RP) and decreasing (HILIC) organic solvent concentration in the mobile phase. This dual gradient process was successfully modeled by two retention models exhibiting a quadratic or a cubic dependence of the logarithm of the solute retention factor (lnk) upon the organic modifier volume fraction (φ). It was found that both models produced by gradient retention data allow the prediction of solute retention times for both types of programmed elution on the mixed-mode column. Four, in the case of the quadratic model, or five, in the case of the cubic model, initial HILIC- and RP-type gradient runs gave satisfactory retention predictions of any similar kind elution program, even with different flow rate, with an overall error of only 2.5 or 1.7%, respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecular theory of chromatography for blocklike solutes in anisotropic stationary phases and its application

International Nuclear Information System (INIS)

Yan, Chao; Martire, D.E.

1992-01-01

DiMarzio's lattice model is successfully applied to describe the equilibrium partitioning of blocklike molecules between an isotropic mobile phase and an anisotropic stationary phase in various types of fluid chromatography to obtain a retention equation. A linear relationship between the logarithm of the solute distribution coefficient and minimum area is predicted. 44 refs., 8 figs., 2 tabs

Mechanistic analysis of solute transport in an in vitro physiological two-phase dissolution apparatus.

Science.gov (United States)

Mudie, Deanna M; Shi, Yi; Ping, Haili; Gao, Ping; Amidon, Gordon L; Amidon, Gregory E

2012-10-01

In vitro dissolution methodologies that adequately capture the oral bioperformance of solid dosage forms are critical tools needed to aid formulation development. Such methodologies must encompass important physiological parameters and be designed with drug properties in mind. Two-phase dissolution apparatuses, which contain an aqueous phase in which the drug dissolves (representing the dissolution/solubility component) and an organic phase into which the drug partitions (representing the absorption component), have the potential to provide meaningful predictions of in vivo oral bioperformance for some BCS II, and possibly some BCS IV drug products. Before such an apparatus can be evaluated properly, it is important to understand the kinetics of drug substance partitioning from the aqueous to the organic medium. A mass transport analysis was performed of the kinetics of partitioning of drug substance solutions from the aqueous to the organic phase of a two-phase dissolution apparatus. Major assumptions include pseudo-steady-state conditions, a dilute aqueous solution and diffusion-controlled transport. Input parameters can be measured or estimated a priori. This paper presents the theory and derivation of our analysis, compares it with a recent kinetic approach, and demonstrates its effectiveness in predicting in vitro partitioning profiles of three BCS II weak acids in four different in vitro two-phase dissolution apparatuses. Very importantly, the paper discusses how a two-phase apparatus can be scaled to reflect in vivo absorption kinetics and for which drug substances the two-phase dissolution systems may be appropriate tools for measuring oral bioperformance. Copyright © 2012 John Wiley & Sons, Ltd.

Metastable Phase Separation and Concomitant Solute Redistribution of Liquid Fe-Cu-Sn Ternary Alloy

International Nuclear Information System (INIS)

Xiao-Mei, Zhang; Wei-Li, Wang; Ying, Ruan; Bing-Bo, Wei

2010-01-01

Liquid Fe-Cu-Sn ternary alloys with lower Sn contents are usually assumed to display a peritectic-type solidification process under equilibrium condition. Here we show that liquid Fe 47.5 Cu 47.5 Sn 5 ternary alloy exhibits a metastable immiscibility gap in the undercooling range of 51–329 K (0.19T L ). Macroscopic phase separation occurs once undercooling exceeds 196 K and causes the formation of a floating Fe-rich zone and a descending Cu-rich zone. Solute redistribution induces the depletion of Sn concentration in the Fe-rich zone and its enrichment in the Cu-rich zone. The primary Fe phase grows dendritically and its growth velocity increases with undercooling until the appearance of notable macrosegregation, but will decrease if undercooling further increases beyond 236 K. The microsegregation degrees of both solutes in Fe and Cu phases vary only slightly with undercooling. (condensed matter: structure, mechanical and thermal properties)

The numerical solution of thawing process in phase change slab using variable space grid technique

Directory of Open Access Journals (Sweden)

Serttikul, C.

2007-09-01

Full Text Available This paper focuses on the numerical analysis of melting process in phase change material which considers the moving boundary as the main parameter. In this study, pure ice slab and saturated porous packed bed are considered as the phase change material. The formulation of partial differential equations is performed consisting heat conduction equations in each phase and moving boundary equation (Stefan equation. The variable space grid method is then applied to these equations. The transient heat conduction equations and the Stefan condition are solved by using the finite difference method. A one-dimensional melting model is then validated against the available analytical solution. The effect of constant temperature heat source on melting rate and location of melting front at various times is studied in detail.It is found that the nonlinearity of melting rate occurs for a short time. The successful comparison with numerical solution and analytical solution should give confidence in the proposed mathematical treatment, and encourage the acceptance of this method as useful tool for exploring practical problems such as forming materials process, ice melting process, food preservation process and tissue preservation process.

Synthesis and Gas Phase Thermochemistry of Germanium-Containing Compounds

Energy Technology Data Exchange (ETDEWEB)

Classen, Nathan Robert [Iowa State Univ., Ames, IA (United States)

2002-01-01

The driving force behind much of the work in this dissertation was to gain further understanding of the unique olefin to carbene isomerization observed in the thermolysis of 1,1-dimethyl-2-methylenesilacyclobutane by finding new examples of it in other silicon and germanium compounds. This lead to the examination of a novel phenylmethylenesilacyclobut-2-ene, which did not undergo olefin to carbene rearrangement. A synthetic route to methylenegermacyclobutanes was developed, but the methylenegermacyclobutane system exhibited kinetic instability, making the study of the system difficult. In any case the germanium system decomposed through a complex mechanism which may not include olefin to carbene isomerization. However, this work lead to the study of the gas phase thermochemistry of a series of dialkylgermylene precursors in order to better understand the mechanism of the thermal decomposition of dialkylgermylenes. The resulting dialkylgermylenes were found to undergo a reversible intramolecular β C-H insertion mechanism.

Early-Time Solution of the Horizontal Unconfined Aquifer in the Buildup Phase

Science.gov (United States)

Gravanis, Elias; Akylas, Evangelos

2017-10-01

We derive the early-time solution of the Boussinesq equation for the horizontal unconfined aquifer in the buildup phase under constant recharge and zero inflow. The solution is expressed as a power series of a suitable similarity variable, which is constructed so that to satisfy the boundary conditions at both ends of the aquifer, that is, it is a polynomial approximation of the exact solution. The series turns out to be asymptotic and it is regularized by resummation techniques that are used to define divergent series. The outflow rate in this regime is linear in time, and the (dimensionless) coefficient is calculated to eight significant figures. The local error of the series is quantified by its deviation from satisfying the self-similar Boussinesq equation at every point. The local error turns out to be everywhere positive, hence, so is the integrated error, which in turn quantifies the degree of convergence of the series to the exact solution.

Solution and solid-phase halogen and C-H hydrogen bonding to perrhenate.

Science.gov (United States)

Massena, Casey J; Riel, Asia Marie S; Neuhaus, George F; Decato, Daniel A; Berryman, Orion B

2015-01-28

(1)H NMR spectroscopic and X-ray crystallographic investigations of a 1,3-bis(4-ethynyl-3-iodopyridinium)benzene scaffold with perrhenate reveal strong halogen bonding in solution, and bidentate association in the solid state. A nearly isostructural host molecule demonstrates significant C-H hydrogen bonding to perrhenate in the same phases.

Transient phases during crystallization of solution-processed organic thin films

Science.gov (United States)

Wan, Jing; Li, Yang; Ulbrandt, Jeffery; Smilgies, Detlef-M.; Hollin, Jonathan; Whalley, Adam; Headrick, Randall

We report an in-situ study of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) organic semiconductor thin film deposition from solution via hollow pen writing, which exhibits multiple transient phases during crystallization. Under high writing speed (25 mm/s) the films have an isotropic morphology, although the mobilities range up to 3.0 cm2/V.s. To understand the crystallization in this highly non-equilibrium regime, we employ in-situ microbeam grazing incidence wide-angle X-ray scattering combined with optical video microscopy at different deposition temperatures. A sequence of crystallization was observed in which a layered liquid-crystalline (LC) phase of C8-BTBT precedes inter-layer ordering. For films deposited above 80ºC, a transition from LC phase to a transient crystalline state that we denote as Cr1 occurs after a temperature-dependent incubation time, which is consistent with classical nucleation theory. After an additional ~ 0.5s, Cr1 transforms to the final stable structure Cr2. Based on these results, we demonstrate a method to produce large crystalline grain size and high carrier mobility during high-speed processing by controlling the nucleation rate during the transformation from the LC phase. Nsf DMR-1307017, NSF DMR-1332208.

[Preparation and evaluation of stationary phase of high performance liquid chromatography for the separation of basic solutes].

Science.gov (United States)

Wang, P; Wang, J; Cong, R; Dong, B

1997-05-01

A bonded phase for high performance liquid chromatography (HPLC) has been prepared by the new reaction between silica and silicon ether. The ether was synthesized from alkylchlorosilane and pentane-2,4-dione in the presence of imidazole under inert conditions by using anhydrous tetrahydrofuran as solvent. The bonded phase thus obtained was characterized by elemental analysis, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and HPLC evaluation. The carbon content was 9.4% and the surface coverage almost attained 3.0micromol/m2 without end-capping. The silanol absorption peaks of the product cannot be observed from the DRIFT spectrum, which revealed that the silanization reaction proceeded thoroughly. The basic solutes, such as aniline, o-toluidine, p-toluidine, N,N-dimethylaniline and pyridine were used as the probe solutes to examine their interaction with the residual silanols on the surface of the products. No buffer or salt was used in the mobile phase for these experiments. In comparison with an acidic solute, such as, phenol, basic aniline eluted in front of phenol, and the ratio of asymmetry of aniline peak to that of the phenol peak was 1.1. Furthermore the relative k' value of p-toluidine to that of o-toluidine was also 1.1. All the results showed that the stationary phase has better quality and reproducibility and can be used for the separation of basic solutes efficiently.

Chemical evolution studies: the radiolysis and thermal decomposition of malonic acid

International Nuclear Information System (INIS)

Cruz-Castaneda, J.; Negron-Mendoza, A.; Heredia, A.; Ramos-Bernal, S.; Villafane-Barajas, S.; Frias, D.; Colin-Garcia, M.

2015-01-01

In the context of chemical evolution a simulation of a hydrothermal vent was performed. The thermolysis and radiolysis of malonic acid in aqueous solution were studied. The thermolysis was done by heating the samples (95 deg C) and radiolysis using gamma radiation. Products were identified by gas chromatography and gas chromatography-mass spectrometry. The thermal treatment produced acetic acid and CO 2 . The radiolysis experiments yield carbon dioxide, acetic acid, and di- and tricarboxylic acids. A theoretical model of the chemical process occurring under irradiation was developed; this was able to reproduce formation of products and the consumption of malonic acid. (author)

The phase equilibria of multicomponent gas hydrate in methanol/ethylene glycol solution based formation water

International Nuclear Information System (INIS)

Xu, Shurui; Fan, Shuanshi; Yao, Haiyuan; Wang, Yanhong; Lang, Xuemei; Lv, Pingping; Fang, Songtian

2017-01-01

Highlights: • The equilibrium data in THI solution based formation water is first investigated. • The 0.55 mass fraction concentration of EG 0.55 mass fraction fills the vacancy of this area. • The testing pressure range from 4.22 MPa to 34.72 MPa was rare in published data. - Abstract: In this paper, the three-phase coexistence points are generated for multicomponent gas hydrate in methanol (MeOH) solution for (0.05, 0.10, 0.15, and 0.35) mass fraction and ethylene glycol (EG) solution for (0.05, 0.10, 0.15, 0.35, 0.40 and 0.55) mass fraction. The phase equilibrium curves of different system were obtained by an isochoric pressure-search method on high pressure apparatus. The phase equilibrium regions of multicomponent gas hydrate were measured using the same composition of natural gas distributed in the South China Sea. And the different concentration solutions were prepared based formation water. The experimental data were measured in a wide range temperature from 267.74 to 298.53 K and a wide range pressure from 4.22 MPa to 34.72 MPa. The results showed that the hydrate phase equilibrium curves shifted to the inhibition region in accordance with the increased inhibitor concentration. In addition, the equilibrium temperature would decrease about 2.7 K when the concentration of MeOH increased 0.05 mass fraction. Besides, the suppression temperature was 1.25 K with the 0.05 mass fraction increase of EG concentration in the range of 0.05 mass fraction to 0.15 mass fraction. While in high EG concentration region, the suppression temperature was 3.3 K with the same increase of EG concentration (0.05 mass fraction).

A parallel solution-adaptive scheme for predicting multi-phase core flows in solid propellant rocket motors

International Nuclear Information System (INIS)

Sachdev, J.S.; Groth, C.P.T.; Gottlieb, J.J.

2003-01-01

The development of a parallel adaptive mesh refinement (AMR) scheme is described for solving the governing equations for multi-phase (gas-particle) core flows in solid propellant rocket motors (SRM). An Eulerian formulation is used to described the coupled motion between the gas and particle phases. A cell-centred upwind finite-volume discretization and the use of limited solution reconstruction, Riemann solver based flux functions for the gas and particle phases, and explicit multi-stage time-stepping allows for high solution accuracy and computational robustness. A Riemann problem is formulated for prescribing boundary data at the burning surface. Efficient and scalable parallel implementations are achieved with domain decomposition on distributed memory multiprocessor architectures. Numerical results are described to demonstrate the capabilities of the approach for predicting SRM core flows. (author)

Fundamental aspects of nucleation and growth in the solution-phase synthesis of germanium nanocrystals

KAUST Repository

Codoluto, Stephen C.; Baumgardner, William J.; Hanrath, Tobias

2010-01-01

Colloidal Ge nanocrystals (NCs) were synthesized via the solution phase reduction of germanium(ii) iodide. We report a systematic investigation of the nanocrystal nucleation and growth as a function of synthesis conditions including the nature

Exact solution to the Coulomb wave using the linearized phase-amplitude method

Directory of Open Access Journals (Sweden)

Shuji Kiyokawa

2015-08-01

Full Text Available The author shows that the amplitude equation from the phase-amplitude method of calculating continuum wave functions can be linearized into a 3rd-order differential equation. Using this linearized equation, in the case of the Coulomb potential, the author also shows that the amplitude function has an analytically exact solution represented by means of an irregular confluent hypergeometric function. Furthermore, it is shown that the exact solution for the Coulomb potential reproduces the wave function for free space expressed by the spherical Bessel function. The amplitude equation for the large component of the Dirac spinor is also shown to be the linearized 3rd-order differential equation.

Roentgenographic and derivatographic investigation of gallium and indium complexes with azo compounds on the base of pyrogallol

International Nuclear Information System (INIS)

Gambarov, D.G.; Rzaev, R.Z.; Musaev, F.N.; Musaeva, A.N.; Chyragov, F.M.

1985-01-01

Seven complexes of gallium and indium with N-donor ligands obtained on the base of pyrogallol are synthesized. Their chemical composition is established. Nitrogen-containing ligands and their complexes are investigated by the methods of roentgenographic and thermogravimetric analyses. It is shown that gallium and indium complexes are amorphous compounds. An assumption is made on the thermolysis character that complexes have a similar structure: structural complex nucleus constitutes a six-term chelate ring. Para-substitutors in the ligand do not participate in complexing, possibly they participate in H-bonds formation. It is established by spectrophotometric methods that in solutions stoichiometric ratio metal: ligand is the same as in the solid phase

Roentgenographic and derivatographic investigation of gallium and indium complexes with azo compounds on the base of pyrogallol

Energy Technology Data Exchange (ETDEWEB)

Gambarov, D G; Rzaev, R Z; Musaev, F N; Musaeva, A N; Chyragov, F M

1985-01-01

Seven complexes of gallium and indium with N-donor ligands obtained on the base of pyrogallol are synthesized. Their chemical composition is established. Nitrogen-containing ligands and their complexes are investigated by the methods of roentgenographic and thermogravimetric analyses. It is shown that gallium and indium complexes are amorphous compounds. An assumption is made on the thermolysis character that complexes have a similar structure: structural complex nucleus constitutes a six-term chelate ring. Para-substitutors in the ligand do not participate in complexing, possibly they participate in H-bonds formation. It is established by spectrophotometric methods that in solutions stoichiometric ratio metal: ligand is the same as in the solid phase.

Processes leading to yttrium-barium cuprates formation in synthesis using nitrates

International Nuclear Information System (INIS)

Kulakov, A.B.; Tesker, A.M.; Zalishchanskij, M.E.; Tret'yakov, Yu.D.; Gipius, A.A.

1989-01-01

An attempt to determine sequence and conditions for transformations occuring at heating both of mechanical mixture of copper, yttrium and barium nitrates and salt product of sublimated dehydration of quick frozen solution of nitrates in question of correlation which corresponds to YBa 2 Cu 3 O 7-σ final compounds is made. It is shown that unlike individual nitrates their thermolysis in the mixture occurs at lower temperatures with mechanism variation of decomposition separate stages. Specimens of superconducting ceramics with 4.3 g/cm 3 density phase composition and oxygen content which correspond to YBa 2 Cu 3 O 6.85±0.05 formula are obtaied

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

Science.gov (United States)

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.

Solution-phase parallel synthesis of a library of delta(2)-pyrazolines.

Science.gov (United States)

Manyem, Shankar; Sibi, Mukund P; Lushington, Gerald H; Neuenswander, Benjamin; Schoenen, Frank; Aubé, Jeffrey

2007-01-01

A parallel synthesis of a library (80 members) of 2-pyrazolines in solution phase is described. The 2-pyrazoline core was accessed through the [3 + 2] cycloaddition of nitrilimines with enoyl oxazolidinones. The cycloaddition provided two regioisomers, the major product being the C regioisomer. The oxazolidinone moiety was further reduced to the primary alcohol, producing another library of 5-hydroxymethyl-2-pyrazolines. The Lipinski profiles and calculated ADME properties of the compounds are also reported.

Localization of the solution of a one-dimensional one-phase Stefan problem

OpenAIRE

Cortazar, C.; Elgueta, M.; Primicerio, M.

1996-01-01

Studiamo la localizzazione, l'insieme dei punti di blow up ed alcuni aspetti della velocità di propagazione della frontiera libera di soluzioni di un problema di Stefan unidimensionale ad una fase. We study localization, the set of blow up points and some aspects of the speed of the free boundary of solutions of a one-dimensional, one-phase Stefan problem.

Phase transitions of single polymer chains and of polymer solutions: insights from Monte Carlo simulations

International Nuclear Information System (INIS)

Binder, K; Paul, W; Strauch, T; Rampf, F; Ivanov, V; Luettmer-Strathmann, J

2008-01-01

The statistical mechanics of flexible and semiflexible macromolecules is distinct from that of small molecule systems, since the thermodynamic limit can also be approached when the number of (effective) monomers of a single chain (realizable by a polymer solution in the dilute limit) is approaching infinity. One can introduce effective attractive interactions into a simulation model for a single chain such that a swollen coil contracts when the temperature is reduced, until excluded volume interactions are effectively canceled by attractive forces, and the chain conformation becomes almost Gaussian at the theta point. This state corresponds to a tricritical point, as the renormalization group theory shows. Below the theta temperature a fluid globule is predicted (at nonzero concentration then phase separation between dilute and semidilute solutions occurs), while at still lower temperature a transition to a solid phase (crystal or glass) occurs. Monte Carlo simulations have shown, however, that the fluid globule phase may become suppressed, when the range of the effective attractive forces becomes too short, with the result that a direct (ultimately first-order) transition from the swollen coil to the solid occurs. This behavior is analogous to the behavior of colloidal particles with a very short range of attractive forces, where liquid-vapor-type phase separation may be suppressed. Analogous first-order transitions from swollen coils to dense rodlike or toroidal structures occur for semiflexible polymers. Finally, the modifications of the behavior discussed when the polymers are adsorbed at surfaces are also mentioned, and possible relations to wetting behavior of polymer solutions are addressed.

Multiple Multidentate Halogen Bonding in Solution, in the Solid State, and in the (Calculated) Gas Phase.

Science.gov (United States)

Jungbauer, Stefan H; Schindler, Severin; Herdtweck, Eberhardt; Keller, Sandro; Huber, Stefan M

2015-09-21

The binding properties of neutral halogen-bond donors (XB donors) bearing two multidentate Lewis acidic motifs toward halides were investigated. Employing polyfluorinated and polyiodinated terphenyl and quaterphenyl derivatives as anion receptors, we obtained X-ray crystallographic data of the adducts of three structurally related XB donors with tetraalkylammonium chloride, bromide, and iodide. The stability of these XB complexes in solution was determined by isothermal titration calorimetry (ITC), and the results were compared to X-ray analyses as well as to calculated binding patterns in the gas phase. Density functional theory (DFT) calculations on the gas-phase complexes indicated that the experimentally observed distortion of the XB donors during multiple multidentate binding can be reproduced in 1:1 complexes with halides, whereas adducts with two halides show a symmetric binding pattern in the gas phase that is markedly different from the solid state structures. Overall, this study demonstrates the limitations in the transferability of binding data between solid state, solution, and gas phase in the study of complex multidentate XB donors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Visualizing phase transition behavior of dilute stimuli responsive polymer solutions via Mueller matrix polarimetry.

Science.gov (United States)

Narayanan, Amal; Chandel, Shubham; Ghosh, Nirmalya; De, Priyadarsi

2015-09-15

Probing volume phase transition behavior of superdiluted polymer solutions both micro- and macroscopically still persists as an outstanding challenge. In this regard, we have explored 4 × 4 spectral Mueller matrix measurement and its inverse analysis for excavating the microarchitectural facts about stimuli responsiveness of "smart" polymers. Phase separation behavior of thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) and pH responsive poly(N,N-(dimethylamino)ethyl methacrylate) (PDMAEMA) and their copolymers were analyzed in terms of Mueller matrix derived polarization parameters, namely, depolarization (Δ), diattenuation (d), and linear retardance (δ). The Δ, d, and δ parameters provided useful information on both macro- and microstructural alterations during the phase separation. Additionally, the two step action ((i) breakage of polymer-water hydrogen bonding and (ii) polymer-polymer aggregation) at the molecular microenvironment during the cloud point generation was successfully probed via these parameters. It is demonstrated that, in comparison to the present techniques available for assessing the hydrophobic-hydrophilic switch over of simple stimuli-responsive polymers, Mueller matrix polarimetry offers an important advantage requiring a few hundred times dilute polymer solution (0.01 mg/mL, 1.1-1.4 μM) at a low-volume format.

Tetragonal-cubic phase boundary in nanocrystalline ZrO2-Y2O3 solid solutions synthesized by gel-combustion

International Nuclear Information System (INIS)

Fabregas, Ismael O.; Craievich, Aldo F.; Fantini, Marcia C.A.; Millen, Ricardo P.; Temperini, Marcia L.A.; Lamas, Diego G.

2011-01-01

Research highlights: → Gel-combustion synthesis yields compositionally homogeneous, single-phased ZrO 2 -Y 2 O 3 nanopowders, that exhibit the presence at room temperature of three different phases depending on Y 2 O 3 content, namely two tetragonal forms (t' and t'') and the cubic phase. → Phase identification can be achieved by synchrotron XPD (SXPD) and Raman spectroscopy since the tetragonal forms and the cubic phase can be distinguished by these techniques. → The crystallographic features of ZrO 2 -Y 2 O 3 nanopowders were determined by SXPD. They are similar to those reported by Yashima and coworkers for compositionally homogeneous materials containing larger (micro)crystals. However, the lattice parameters are slightly different and the axial ratios c/a of our t' samples are smaller than those reported by these authors. → Compositional t'/t'' and t''/cubic phase boundaries are located at (9 ± 1) and (10.5 ± 0.5) mol% Y 2 O 3 , respectively. → For the whole series of nanocrystalline ZrO 2 -Y 2 O 3 solid solutions studied in the present work, no evidences of the presence of a mixture of phases - as reported by Yashima and coworkers for microcrystalline solid solutions - were detected. - Abstract: By means of synchrotron X-ray powder diffraction (SXPD) and Raman spectroscopy, we have detected, in a series of nanocrystalline and compositionally homogeneous ZrO 2 -Y 2 O 3 solid solutions, the presence at room temperature of three different phases depending on Y 2 O 3 content, namely two tetragonal forms and the cubic phase. The studied materials, with average crystallite sizes within the range 7-10 nm, were synthesized by a nitrate-citrate gel-combustion process. The crystal structure of these phases was also investigated by SXPD. The results presented here indicate that the studied nanocrystalline ZrO 2 -Y 2 O 3 solid solutions exhibit the same phases reported in the literature for compositionally homogeneous materials containing larger (micro

Phase Behaviour and Miscibility Studies of Collagen/Silk Fibroin Macromolecular System in Dilute Solutions and Solid State.

Science.gov (United States)

Ghaeli, Ima; de Moraes, Mariana A; Beppu, Marisa M; Lewandowska, Katarzyna; Sionkowska, Alina; Ferreira-da-Silva, Frederico; Ferraz, Maria P; Monteiro, Fernando J

2017-08-18

Miscibility is an important issue in biopolymer blends for analysis of the behavior of polymer pairs through the detection of phase separation and improvement of the mechanical and physical properties of the blend. This study presents the formulation of a stable and one-phase mixture of collagen and regenerated silk fibroin (RSF), with the highest miscibility ratio between these two macromolecules, through inducing electrostatic interactions, using salt ions. For this aim, a ternary phase diagram was experimentally built for the mixtures, based on observations of phase behavior of blend solutions with various ratios. The miscibility behavior of the blend solutions in the miscible zones of the phase diagram was confirmed quantitatively by viscosimetric measurements. Assessing the effects of biopolymer mixing ratio and salt ions, before and after dialysis of blend solutions, revealed the importance of ion-specific interactions in the formation of coacervate-based materials containing collagen and RSF blends that can be used in pharmaceutical, drug delivery, and biomedical applications. Moreover, the conformational change of silk fibroin from random coil to beta sheet, in solution and in the final solid films, was detected by circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR), respectively. Scanning electron microscopy (SEM) exhibited alterations of surface morphology for the biocomposite films with different ratios. Surface contact angle measurement illustrated different hydrophobic properties for the blended film surfaces. Differential scanning calorimetry (DSC) showed that the formation of the beta sheet structure of silk fibroin enhances the thermal stability of the final blend films. Therefore, the novel method presented in this study resulted in the formation of biocomposite films whose physico-chemical properties can be tuned by silk fibroin conformational changes by applying different component mixing ratios.

Solution mining process

International Nuclear Information System (INIS)

Showalter, W.E.

1984-01-01

A solution mining process which may be used for uranium, thorium, vanadium, copper, nickel, molybdenum, rhenium, and selenium is claimed. During a first injection-and-production phase of between 6 months and 5 years, a leaching solution is injected through at least one well into the formation to solubilize the mineral values and form a pregnant liquor. This liquor is recovered through another well. The leaching solution contains sulfuric acid, nitric acid, hydrochloric acid, carbonic acid, an alkali metal carbonate, an alkali metal bicarbonate, ammonium carbonate or ammonium bicarbonate. Subsequently during a first production-only phase of between about 2 weeks and one year, injection of the leaching solution is suspended but pregnant liquor is still recovered. This stage is followed by a second injection-and-production phase of between 6 months and 5 years and a second production-only phase. The mineral values are separated from the pregnant liquor to form a barren liquor. The leaching agent is introduced into this liquor, and the solution is recycled. In a second claim for the solution mining of uranium, dilute carbonic acid is used as the leaching solution. The solution has a pH less than 7 and a bicarbonate ion concentration between about 380 ppm and 1000 ppm. The injection-and-production phase lasts between one and two years and the production only phase takes between one and four months. Carbon dioxide is introduced into the barren liquor to form a dilute carbonic acid solution and the solution is recycled

Study of complex formation of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel

International Nuclear Information System (INIS)

Ismailova, M.M.; Egorova, L.A.; Khamidov, B.O.

1993-01-01

Present article is devoted to study of complex formation of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel. The condition of cobalt in various rate of oxidation in acrylamide aqueous solutions was studied. The concentration conditions of stability of system Co(II)-Co(III) were defined. The composition of coordination compounds of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel was determined.

Modelling of the effect of solute structure and mobile phase pH and composition on the retention of phenoxy acid herbicides in reversed-phase high-performance liquid chromatography

International Nuclear Information System (INIS)

Aschi, Massimiliano; D'Archivio, Angelo Antonio; Mazzeo, Pietro; Pierabella, Mirko; Ruggieri, Fabrizio

2008-01-01

A feed-forward artificial neural network (ANN) learned by error back-propagation is used to generate a retention predictive model for phenoxy acid herbicides in isocratic reversed-phase high-performance liquid chromatography. The investigated solutes (18 compounds), apart from the most common herbicides of this class, include some derivatives of benzoic acid and phenylacetic acid structurally related to phenoxy acids, as a whole covering a pK a range between 2.3 and 4.3. A mixed model in terms of both solute descriptors and eluent attributes is built with the aim of predicting retention in water-acetonitrile mobile phases within a large range of composition (acetonitrile from 30% to 70%, v/v) and acidity (pH of water before mixing with acetonitrile ranging between 2 and 5). The set of input variables consists of solute pK a and quantum chemical molecular descriptors of both the neutral and dissociated form, %v/v of acetonitrile in the mobile phase and pH of aqueous phase before mixing with acetonitrile. After elimination of redundant variables, a nine-dimensional model is identified and its prediction ability is evaluated by external validation based on three solutes not involved in model generation and by cross-validation. A multilinear counterpart in terms of the same descriptors is seen to provide a noticeably poorer retention prediction

Modelling of the effect of solute structure and mobile phase pH and composition on the retention of phenoxy acid herbicides in reversed-phase high-performance liquid chromatography

Energy Technology Data Exchange (ETDEWEB)

Aschi, Massimiliano [Dipartimento di Chimica, Ingegneria Chimica e Materiali, Universita degli Studi di L' Aquila, Via Vetoio, 67010 Coppito, L' Aquila (Italy); D' Archivio, Angelo Antonio [Dipartimento di Chimica, Ingegneria Chimica e Materiali, Universita degli Studi di L' Aquila, Via Vetoio, 67010 Coppito, L' Aquila (Italy)], E-mail: darchivi@univaq.it; Mazzeo, Pietro; Pierabella, Mirko; Ruggieri, Fabrizio [Dipartimento di Chimica, Ingegneria Chimica e Materiali, Universita degli Studi di L' Aquila, Via Vetoio, 67010 Coppito, L' Aquila (Italy)

2008-06-02

A feed-forward artificial neural network (ANN) learned by error back-propagation is used to generate a retention predictive model for phenoxy acid herbicides in isocratic reversed-phase high-performance liquid chromatography. The investigated solutes (18 compounds), apart from the most common herbicides of this class, include some derivatives of benzoic acid and phenylacetic acid structurally related to phenoxy acids, as a whole covering a pK{sub a} range between 2.3 and 4.3. A mixed model in terms of both solute descriptors and eluent attributes is built with the aim of predicting retention in water-acetonitrile mobile phases within a large range of composition (acetonitrile from 30% to 70%, v/v) and acidity (pH of water before mixing with acetonitrile ranging between 2 and 5). The set of input variables consists of solute pK{sub a} and quantum chemical molecular descriptors of both the neutral and dissociated form, %v/v of acetonitrile in the mobile phase and pH of aqueous phase before mixing with acetonitrile. After elimination of redundant variables, a nine-dimensional model is identified and its prediction ability is evaluated by external validation based on three solutes not involved in model generation and by cross-validation. A multilinear counterpart in terms of the same descriptors is seen to provide a noticeably poorer retention prediction.

Approximate solution of space and time fractional higher order phase field equation

Science.gov (United States)

Shamseldeen, S.

2018-03-01

This paper is concerned with a class of space and time fractional partial differential equation (STFDE) with Riesz derivative in space and Caputo in time. The proposed STFDE is considered as a generalization of a sixth-order partial phase field equation. We describe the application of the optimal homotopy analysis method (OHAM) to obtain an approximate solution for the suggested fractional initial value problem. An averaged-squared residual error function is defined and used to determine the optimal convergence control parameter. Two numerical examples are studied, considering periodic and non-periodic initial conditions, to justify the efficiency and the accuracy of the adopted iterative approach. The dependence of the solution on the order of the fractional derivative in space and time and model parameters is investigated.

All-Inorganic Colloidal Quantum Dot Photovoltaics Employing Solution-Phase Halide Passivation

KAUST Repository

Ning, Zhijun

2012-09-12

A new solution-phase halide passivation strategy to improve the electronic properties of colloidal quantum dot films is reported. We prove experimentally that the approach leads to an order-of-magnitude increase in mobility and a notable reduction in trap state density. We build solar cells having the highest efficiency (6.6%) reported using all-inorganic colloidal quantum dots. The improved photocurrent results from increased efficiency of collection of infrared-generated photocarriers. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

All-Inorganic Colloidal Quantum Dot Photovoltaics Employing Solution-Phase Halide Passivation

KAUST Repository

Ning, Zhijun; Ren, Yuan; Hoogland, Sjoerd; Voznyy, Oleksandr; Levina, Larissa; Stadler, Philipp; Lan, Xinzheng; Zhitomirsky, David; Sargent, Edward H.

2012-01-01

A new solution-phase halide passivation strategy to improve the electronic properties of colloidal quantum dot films is reported. We prove experimentally that the approach leads to an order-of-magnitude increase in mobility and a notable reduction in trap state density. We build solar cells having the highest efficiency (6.6%) reported using all-inorganic colloidal quantum dots. The improved photocurrent results from increased efficiency of collection of infrared-generated photocarriers. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Approximate Analytic Solutions for the Two-Phase Stefan Problem Using the Adomian Decomposition Method

Directory of Open Access Journals (Sweden)

Xiao-Ying Qin

2014-01-01

Full Text Available An Adomian decomposition method (ADM is applied to solve a two-phase Stefan problem that describes the pure metal solidification process. In contrast to traditional analytical methods, ADM avoids complex mathematical derivations and does not require coordinate transformation for elimination of the unknown moving boundary. Based on polynomial approximations for some known and unknown boundary functions, approximate analytic solutions for the model with undetermined coefficients are obtained using ADM. Substitution of these expressions into other equations and boundary conditions of the model generates some function identities with the undetermined coefficients. By determining these coefficients, approximate analytic solutions for the model are obtained. A concrete example of the solution shows that this method can easily be implemented in MATLAB and has a fast convergence rate. This is an efficient method for finding approximate analytic solutions for the Stefan and the inverse Stefan problems.

Contribution to the study of the thermodynamic properties of solutions using their phase diagrams (1961); Contribution au calcul des proprietes thermodynamiques des solutions a partir des diagrammes de phases (1961)

Energy Technology Data Exchange (ETDEWEB)

Hagege, R [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1961-10-15

The thermodynamic study of the behaviour of solutions is of great interest in applied metallurgical problems, since the use of physical phenomena (solubility or volatility, for example) makes it possible to effect chemical reactions which, would not take place if the products formed did not mix. It is interesting to be able to predict this behaviour, at least for binary systems, using a knowledge of the phase diagrams. After showing the theoretical impossibility of resolving this problem without further data, an attempt is made to show what can be calculated from a knowledge of the phase diagrams: on the one hand it is possible to study the coherence between different types of data (calorimetric or equilibrium); on the other hand can be calculated the 'model' parameters, whether they be empirical, or statistically derived, and their validity can be checked. (author) [French] L'etude thermodynamique du comportement des solutions presente un grand interet dans les problemes de metallurgie appliquee puisque l'emploi de phenomenes physiques (solubilite ou volatilisation par exemple) permet de realiser des reactions chimiques qui seraient irrealisables si les produits formes ne se melangeaient pas. Il semble tres interessant de pouvoir prevoir ce comportement, tout au moins dans le cas de systemes binaires, a partir de la connaissance des diagrammes de phases. Apres avoir montre l'impossibilite theorique de resoudre ce probleme sans autres donnees, on essaie de voir ce que permet de calculer la connaissance des diagrammes de phases: d'une part, on peut etudier la coherenc entre divers types de donnees (calorimetrique ou d'equilibre); d'autre-part, on peut calculer les parametres de 'modeles', qu'ils soient empiriques ou a base statistique, et verifier leur validite. (auteur)

Formation of metastable and equilibrium phases in the decomposition of the β solid solution in Zr alloys

International Nuclear Information System (INIS)

Zakharova, M.I.; Kirov, S.A.; Khundzhua, A.G.

1978-01-01

The decomposition of the β solid solution is studied in Zr-Nb alloys with adding Mo, Al, V, Fe by the methods of electron microscopy and X-ray diffraction on single crystals. The intermetallic compounds forming during crystallization of the alloys do not influence the precipitation of the ω- and α-phases during ageing. In the local regions of foils prepared by electropolishing after ageing the formation of the metastable f.c.c. phase and in some cases the inverse transformation of two phase state to the parent phase is observed. (author)

Spectral analysis and quantum chemical studies of chair and twist-boat conformers of cycloheximide in gas and solution phases

Science.gov (United States)

Tokatli, A.; Ucun, F.; Sütçü, K.; Osmanoğlu, Y. E.; Osmanoğlu, Ş.

2018-02-01

In this study the conformational behavior of cycloheximide in the gas and solution (CHCl3) phases has theoretically been investigated by spectroscopic and quantum chemical properties using density functional theory (wB97X-D) method with 6-31++G(d,p) basis set, for the first time. The calculated IR results reveal that in the ground state the molecule exits as a mixture of the chair and twist-boat conformers in the gas phase, while the calculated NMR results reveal that it only exits as the chair conformer in the solution phase. In order to obtain the contributions coming from intramolecular interactions to the stability of the conformers in the gas and solution phases, the quantum theory of atoms in molecules (QTAIM), noncovalent interactions (NCI) method, and natural bond orbital analysis (NBO) have been employed. The QTAIM and NCI methods indicated that by intramolecular interactions with bond critical point (BCP) the twist-boat conformer is more stabilized than the chair conformer, while by steric interactions it is more destabilized. Considering that these interactions balance each other, the stabilities of the conformers are understood to be dictated by the van der Waals interactions. The NBO analyses show that the hyperconjugative and steric effects play an important role in the stabilization in the gas and solution phases. Furthermore, to get a better understanding of the chemical behavior of this important antibiotic drug we have evaluated and, commented the global and local reactivity descriptors of the both conformers. Finally, the EPR analysis of γ-irradiated cycloheximide has been done. The comparison of the experimental and calculated data have showed the inducement of a radical structure of (CH2)2ĊCH2 in the molecule. The experimental EPR spectrum has also confirmed that the molecule simultaneously exists in the chair and twist-boat conformers in the solid phase.

Solution-phase synthesis of chromium-functionalized single-walled carbon nanotubes

KAUST Repository

Kalinina, Irina V.; Al-Hadeethi, Yas Fadel; Bekyarova, Elena; Zhao, Chao; Wang, Qingxiao; Zhang, Xixiang; Al-Zahrani, Ali; Al-Agel, Faisal Abdulaziz M; Al-Marzouki, Fahad M.; Haddon, Robert C.

2015-01-01

The solution phase reactions of single-walled carbon nanotubes (SWNTs) with Cr(CO)6 and benzene-Cr(CO)3 can lead to the formation of small chromium clusters. The cluster size can be varied from less than 1 nm to about 4 nm by increasing the reaction time. TEM images suggest that the clusters are deposited predominantly on the exterior walls of the nanotubes. TGA analysis was used to obtain the Cr content and carbon to chromium ratio in the Cr-complexed SWNTs. It is suggested that the carbon nanotube benzenoid structure templates the condensation of chromium atoms and facilitates the loss of carbon monoxide leading to well defined metal clusters.

Solution-phase synthesis of chromium-functionalized single-walled carbon nanotubes

KAUST Repository

Kalinina, Irina V.

2015-03-01

The solution phase reactions of single-walled carbon nanotubes (SWNTs) with Cr(CO)6 and benzene-Cr(CO)3 can lead to the formation of small chromium clusters. The cluster size can be varied from less than 1 nm to about 4 nm by increasing the reaction time. TEM images suggest that the clusters are deposited predominantly on the exterior walls of the nanotubes. TGA analysis was used to obtain the Cr content and carbon to chromium ratio in the Cr-complexed SWNTs. It is suggested that the carbon nanotube benzenoid structure templates the condensation of chromium atoms and facilitates the loss of carbon monoxide leading to well defined metal clusters.

Precipitation kinetics and mechanical behavior in a solution treated and aged dual phase stainless steel

Energy Technology Data Exchange (ETDEWEB)

Badji, R., E-mail: riadbadji1@yahoo.fr [Welding and NDT Research Centre (CSC), B.P. 64, Cheraga (Algeria); Kherrouba, N.; Mehdi, B.; Cheniti, B. [Welding and NDT Research Centre (CSC), B.P. 64, Cheraga (Algeria); Bouabdallah, M. [LGSDS – ENP, 10, Avenue Hassan Badi, 16200 El Harrah, Alger (Algeria); Kahloun, C.; Bacroix, B. [LSPM – CNRS, Université Paris 13, 93430 Villetaneuse (France)

2014-12-15

The precipitation kinetics and the mechanical behavior in a solution treated and aged dual phase stainless steel (DSS) are investigated. X-ray diffraction, transmission and scanning electron microscopy techniques are used to characterize the microstructure and to identify its constituents. The precipitation kinetics analysis shows that the ferrite to σ phase transformation follows the modified Johnson Mehl Avrami (JMA) model containing an impingement parameter c that is adjusted to 0.3. Activation energies calculation leads to conclude that interface reaction is the main mechanism that controls the σ phase formation. Detailed analysis of the extent of the different tensile deformation domains reveals the significant contribution of both σ phase particles and dislocation accumulation to the strain hardening of the material. - Highlights: • The precipitation kinetics of the σ phase is affected by both soft and hard impingement phenomena. • Interface reaction is found to be the main mechanism that controls the ferrite to σ phase transformation. • Both σ phase particles and dislocation accumulation contribute to the strain hardening of the dual phase steel studied.

First-principles thermodynamics study of phase stability in inorganic halide perovskite solid solutions

Science.gov (United States)

Bechtel, Jonathon S.; Van der Ven, Anton

2018-04-01

Halide substitution gives rise to a tunable band gap as a function of composition in halide perovskite materials. However, photoinduced phase segregation, observed at room temperature in mixed halide A Pb (IxBr1-x) 3 systems, limits open circuit voltages and decreases photovoltaic device efficiencies. We investigate equilibrium phase stability of orthorhombic P n m a γ -phase CsM (XxY1-x) 3 perovskites where M is Pb or Sn, and X and Y are Br, Cl, or I. Finite-temperature phase diagrams are constructed using a cluster expansion effective Hamiltonian parameterized from first-principles density-functional-theory calculations. Solid solution phases for CsM (IxBr1-x) 3 and CsM (BrxCl1-x) 3 are predicted to be stable well below room temperature while CsM (IxCl1-x) 3 systems have miscibility gaps that extend above 400 K. The height of the miscibility gap correlates with the difference in volume between end members. Also layered ground states are found on the convex hull at x =2 /3 for CsSnBr2Cl ,CsPbI2Br , and CsPbBrCl2. The impact of these ground states on the finite temperature phase diagram is discussed in the context of the experimentally observed photoinduced phase segregation.

Investigation of electrochemical corrosion behavior in a 3.5 wt.% NaCl solution of boronized dual-phase steel

International Nuclear Information System (INIS)

Kayali, Yusuf; Anaturk, Bilal

2013-01-01

Highlights: ► Corrosion behaviors in a 3.5% NaCl solution of boronized Dual-Phase (DP) steels were examined. ► The martensite ratio increased with an increase in the intercritical annealing temperature. ► The corrosion resistance decreased with increase of the martensite ratio. ► The boride layer increased the corrosion resistance of DP steel 2–3-fold. ► The superior properties of DP steel as well as poor corrosion properties were improved by the boriding process. - Abstract: In this study, corrosion behaviors of boronized and non-boronized dual-phase steel were investigated with Tafel extrapolation and linear polarization methods in a 3.5 wt.% NaCl solution. Microstructure analyses show that the boride layer on the dual-phase steel surface had a flat and saw smooth morphology. It was detected by X-ray diffraction (XRD) analysis that the boride layer contained FeB and Fe 2 B phases. The amount of martensite increases with an increase in the intercritical annealing temperature. Both the amount of martensite and the morphology of the phase constituents have an influence on the corrosion behavior of dual-phase steel. A higher corrosion tendency was observed with an increased amount of martensite. The corrosion resistance of boronized dual-phase steel is higher compared with that of dual-phase steel

Analytic solution to verify code predictions of two-phase flow in a boiling water reactor core channel

International Nuclear Information System (INIS)

Chen, K.F.; Olson, C.A.

1983-01-01

One reliable method that can be used to verify the solution scheme of a computer code is to compare the code prediction to a simplified problem for which an analytic solution can be derived. An analytic solution for the axial pressure drop as a function of the flow was obtained for the simplified problem of homogeneous equilibrium two-phase flow in a vertical, heated channel with a cosine axial heat flux shape. This analytic solution was then used to verify the predictions of the CONDOR computer code, which is used to evaluate the thermal-hydraulic performance of boiling water reactors. The results show excellent agreement between the analytic solution and CONDOR prediction

The Effect of Al and V on Microstructure and Transformation of β Phase during Solution Treatments of Cast Ti-6Al-4V Alloy

Energy Technology Data Exchange (ETDEWEB)

Oh, Seong-Tak; Woo, Kee-Do; Kwak, Seung-Mi [Chonbuk National University, Jeonju (Korea, Republic of); Kim, Jae-Hwang [Korea Institute of Industrial Technology, Jeonju (Korea, Republic of)

2017-03-15

In this study, the effect of α and β those stabilizers on the microstructure and phase transformation of cast Ti-6wt%Al-4wt%V alloy at various solution treatment temperatures was investigated. The dependence of the transformation behavior of the β phase during the solution treatment and its dependence was determined by the partitioning of α and β stabilizing elements. Solution treatments were conducted at 850 ~ 1050 ℃ for 0.5 h and, followed by water quenching. Aging treatments at 550 ℃ for 24 h were then performed. The α' martensite was transformed from the β phase when the concentration of vanadium in the β phase was less than 4.27 at %, while the metastable β phase did not transform to α' martensite when the concentration of vanadium in the β phase was over 5.14 at.

Phase equilibria in a system of aqueous arginine with an octane solution of sulfonic acid

Science.gov (United States)

Kuvaeva, Z. I.; Koval'chuk, I. V.; Vodop'yanova, L. A.; Soldatov, V. S.

2013-05-01

The extraction of arginine (Arg) from aqueous salt (0.1 M NaCl) solutions with a sulfo extractant in a wide range of pH values and amino acid concentrations was studied. The 0.1 M solution of dinonylnaphthalenesulfonic acid (HD) in octane was used as an extractant. The degree of extraction was found to be high at pH 0.8-9.0. This can be explained by the effect of additional intermolecular interactions in the extractant phase involving the guanidine group of Arg.

Solution-phase synthesis of nanomaterials at low temperature

Science.gov (United States)

Zhu, Yongchun; Qian, Yitai

2009-01-01

This paper reviews the solution-phase synthesis of nanoparticles via some routes at low temperatures, such as room temperature route, wave-assisted synthesis (γ-irradiation route and sonochemical route), directly heating at low temperatures, and hydrothermal/solvothermal methods. A number of strategies were developed to control the shape, the size, as well as the dispersion of nanostructures. Using diethylamine or n-butylamine as solvent, semiconductor nanorods were yielded. By the hydrothermal treatment of amorphous colloids, Bi2S3 nanorods and Se nanowires were obtained. CdS nanowires were prepared in the presence of polyacrylamide. ZnS nanowires were obtained using liquid crystal. The polymer poly (vinyl acetate) tubule acted as both nanoreactor and template for the CdSe nanowire growth. Assisted by the surfactant of sodium dodecyl benzenesulfonate (SDBS), nickel nanobelts were synthesized. In addition, Ag nanowires, Te nanotubes and ZnO nanorod arrays could be prepared without adding any additives or templates.

Pupil size stability of the cubic phase mask solution for presbyopia

Science.gov (United States)

Almaguer, Citlalli; Acosta, Eva; Arines, Justo

2018-01-01

Presbyopia correction involves different types of studies such as lens design, clinical study, and the development of objective metrics, such as the visual Strehl ratio. Different contact lens designs have been proposed for presbyopia correction, but performance depends on pupil diameter. We will analyze the potential use of a nonsymmetrical element, a cubic phase mask (CPM) solution, to develop a contact or intraocular lens whose performance is nearly insensitive to changes in pupil diameter. We will show the through focus optical transfer function of the proposed element for different pupil diameters ranging from 3 to 7 mm. Additionally, we will show the images obtained through computation and experiment for a group of eye charts with different visual acuities. Our results show that a CPM shaped as 7.07 μm*(Z33-Z3-3)-0.9 μm Z20 is a good solution for a range of clear vision with a visual acuity of at least 0.1 logMar from 0.4 to 6 m for pupil diameters in the 3- to 7-mm range. Our results appear to be a good starting point for further development and study of this kind of CPM solution for presbyopia.

Synthesis and derivatographic investigation of potassium octacyanotungstate (4)

International Nuclear Information System (INIS)

Kovbashin, V.I.; Dovgej, V.V.; Chernyak, B.I.

1983-01-01

The interaction between the rated quantities of potassium cyanide and WO(OH) 3 hydroxide resulted in preparation of potassium dioxytetracyanotungstate (4), K 4 [WO 2 (CN) 4 ]X6H 2 O. The latter, while interacting with a saturated potassium cyanide solution in a carbon dioxide flow transforms to potassium octacyanotungstate (4). The process of K 4 [W(CH) 8 ]x2H 2 O compound thermolysis in argon atmosphere is studied. It is found that, after dehydration of the complex, there occurs thermal transformation of K 4 [W(CN) 8 ] to K 3 [W(CN) 7 ] and then to K 3 [W(CN) 6 ]. The thermolysis final product is tungsten carbide WC

CONDENSED MATTER: STRUCTURE, MECHANICAL AND THERMAL PROPERTIES: Molecular Dynamics Study of Stability of Solid Solutions and Amorphous Phase in the Cu-Al System

Science.gov (United States)

Yang, Bin; Lai, Wen-Sheng

2009-06-01

The relative stability of fcc and bcc solid solutions and amorphous phase with different compositions in the Cu-Al system is studied by molecular dynamics simulations with n-body potentials. For Cu1-xAlx alloys, the calculations show that the fcc solid solution has the lowest energies in the composition region with x 0.72, while the bee solid solution has the lowest energies in the central composition range, in agreement with the ball-milling experiments that a single bcc solid solution with 0.30 < x < 0.70 is obtained. The evolution of structures in solid solutions and amorphous phase is studied by the coordination number (CN) and bond-length analysis so as to unveil the underlying physics. It is found that the energy sequence among three phases is determined by the competition in energy change originating from the bond length and CNs (or the number of bonds).

Robustness of third family solutions for hybrid stars against mixed phase effects

Science.gov (United States)

Ayriyan, A.; Bastian, N.-U.; Blaschke, D.; Grigorian, H.; Maslov, K.; Voskresensky, D. N.

2018-04-01

We investigate the robustness of third family solutions for hybrid compact stars with a quark matter core that correspond to the occurrence of high-mass twin stars against a softening of the phase transition by means of a construction that mimics the effects of pasta structures in the mixed phase. We consider a class of hybrid equations of state that exploits a relativistic mean-field model for the hadronic as well as for the quark matter phase. We present parametrizations that correspond to branches of high-mass twin star pairs with maximum masses between 2.05 M⊙ and 1.48 M⊙ having radius differences between 3.2 and 1.5 km, respectively. When compared to a Maxwell construction with a fixed value of critical pressure Pc, the effect of the mixed phase construction consists in the occurrence of a region of pressures around Pc belonging to the coexistence of hadronic and quark matter phases between the onset pressure at PH and the end of the transition at PQ. The maximum broadening which would still allow mass-twin compact stars is found to be (PQ-PH)max≈Pc for all parametrizations within the present class of models. At least the heavier of the neutron stars of the binary merger GW170817 could have been a member of the third family of hybrid stars. We present the example of another class of hybrid star equations of state for which the appearance of the third family branch is not as robust against mixed phase effects as that of the present work.

Phase transition in Smsub(1-x)Gdsub(x)S and Smsub(1-x)Tmsub(x)S solid solutions under pressure

International Nuclear Information System (INIS)

Kaminskij, V.V.; Stepanov, N.N.; Romanova, M.V.

1985-01-01

Experiments are conducted on studying the effect of the n quantity on Psub(pt) (phase transition pressure) for SmS and systems of solid solutions Smsub(1-x)Gdsub(x)S and Smsub(1-x)Tmsub(x)S with conductivity electron concentrations approximately 10 19 -10 21 cm -3 corresponding to the semiconducting phase of these solutions. The investigated monocrystal samples have been prepared by the method of planar crystallization from the melt, have been chipped off over the cleavage planes [100], their characteristic sizes not exceeding 2 mm. Samples of the Smsub(1-x)Tmsub(x)S system were polycrystalline and they had characteristic dimensions of approximately 3mm. Concentration of conductivity electrons has been determined from measurements of the Hall constant. Hydrostatic compression of the samples has been exercised in a piston high-pressure chamber at T=300 K. The observed electric conductivity jump determined by the standard d.c. compensation technique was a criterion of the presence of the phase transition to the metal state. Dependences of Psub(pt) in SmS base solid solutions with approximately 10 19 -10 21 cm -3 concentration of conductivity electrons have similar tendency in behaviour: a certain increase in the phase transition pressure with n growth and then its drop at n approaching concentrations corresponding to compositions close to critical ones for the semiconductor-metal phase transition in any system of solid solutions. If the first mechanism prevails at small as then further on the second mechanism swelling by a power law with a high index plays the main role

Fourier phasing with phase-uncertain mask

International Nuclear Information System (INIS)

Fannjiang, Albert; Liao, Wenjing

2013-01-01

Fourier phasing is the problem of retrieving Fourier phase information from Fourier intensity data. The standard Fourier phase retrieval (without a mask) is known to have many solutions which cause the standard phasing algorithms to stagnate and produce wrong or inaccurate solutions. In this paper Fourier phase retrieval is carried out with the introduction of a randomly fabricated mask in measurement and reconstruction. Highly probable uniqueness of solution, up to a global phase, was previously proved with exact knowledge of the mask. Here the uniqueness result is extended to the case where only rough information about the mask’s phases is assumed. The exponential probability bound for uniqueness is given in terms of the uncertainty-to-diversity ratio of the unknown mask. New phasing algorithms alternating between the object update and the mask update are systematically tested and demonstrated to have the capability of recovering both the object and the mask (within the object support) simultaneously, consistent with the uniqueness result. Phasing with a phase-uncertain mask is shown to be robust with respect to the correlation in the mask as well as the Gaussian and Poisson noises. (paper)

Kinetics of a new phase formation in supersaturated solid solutions. 1. Dilute one-component systems

International Nuclear Information System (INIS)

Dubinko, V.I.

1991-07-01

A complete set of kinetic equations describing the diffusion decay of supersaturated solutions, as well as the formation of new-phase fluctuations in equilibrium systems, is derived. A novel method of determining forward and backward reaction rates entering the master equation is proposed which does not require the use of any reference cluster size distribution, either the constrained or the true equilibrium one, employed in all modifications of the classical nucleation theory. Instead, this reference distribution can be obtained as an equilibrium solution of the present master equation. The main advantage of this method is the possibility to take into account various factors affecting the diffusion decay, such as the reaction kinetics at the precipitate surfaces and the diffusion kinetics in the mother phase with account of elastic interaction between nucleating species and their clusters. The latter is of a key importance in the irradiation environment considered in the forthcoming second part of the article. (author). 3 refs

Solution of the equations for one-dimensional, two-phase, immiscible flow by geometric methods

Science.gov (United States)

Boronin, Ivan; Shevlyakov, Andrey

2018-03-01

Buckley-Leverett equations describe non viscous, immiscible, two-phase filtration, which is often of interest in modelling of oil production. For many parameters and initial conditions, the solutions of these equations exhibit non-smooth behaviour, namely discontinuities in form of shock waves. In this paper we obtain a novel method for the solution of Buckley-Leverett equations, which is based on geometry of differential equations. This method is fast, accurate, stable, and describes non-smooth phenomena. The main idea of the method is that classic discontinuous solutions correspond to the continuous surfaces in the space of jets - the so-called multi-valued solutions (Bocharov et al., Symmetries and conservation laws for differential equations of mathematical physics. American Mathematical Society, Providence, 1998). A mapping of multi-valued solutions from the jet space onto the plane of the independent variables is constructed. This mapping is not one-to-one, and its singular points form a curve on the plane of the independent variables, which is called the caustic. The real shock occurs at the points close to the caustic and is determined by the Rankine-Hugoniot conditions.

Attractive interactions between reverse aggregates and phase separation in concentrated malonamide extractant solutions

International Nuclear Information System (INIS)

Erlinger, C.; Belloni, L.; Zemb, T.; Madic, C.

1999-01-01

Using small angle X-ray scattering, conductivity, and phase behavior determination, the authors show that concentrated solutions of malonamide extractants, dimethyldibutyltetradecylmalonamide (DMDBTDMA), are organized in reverse oligomeric aggregates which have many features in common with reverse micelles. The aggregation numbers of these reverse globular aggregates as well as their interaction potential are determined from absolute scattering curves. An attractive interaction is responsible for the demixing of the oil phase when in equilibrium with excess oil. Prediction of conductivity as well as the formation conditions for the third phase is possible using standard liquid theory applied to the extractant aggregates. The interactions, modeled with the sticky sphere model proposed by Baster, are shown to be due to steric interactions resulting from the hydrophobic tails of the extractant molecule and van der Waals forces between the highly polarizable water core of the reverse micelles. The attractive interaction in the oil phase, equilibrated with water, is determined as a function of temperature, extractant molecule concentration, and proton and neodynium(III) cation concentration. It is shown that van der Waals interactions, with an effective Hamaker constant of 3kT, quantitatively explain the behavior of DMDBTDMA in n-dodecane in terms of scattering as well as phase stability limits

Solution-Phase Synthesis of SnSe Nanocrystals for Use in Solar Cells

KAUST Repository

Franzman, Matthew A.

2010-03-31

Nanocrystals of phase-pure tin(II) selenide (SnSe) were synthesized via a solution-phase route employing stoichiometric amounts of di-tert-butyl dlselenlde as a novel and facile selenium source. The direct band gap of the resulting nanocrystals (E8 = 1.71 eV) is significantly blue-shifted relative to the bulk value (E8 = 1.30 eV), a likely consequence of quantum confinement resulting from the relatively small average diameter of the nanocrystals (μD < 20 nm). Preliminary solar cell devices incorporating SnSe nanocrystals into a poly[2-methoxy5-(3\\',7\\'-d1methyloctyloxy)-1,4- phenylenev1nylene] matrix demonstrate a significant enhancement In quantum efficiency and short-circuit current density, suggesting that this earth-abundant material could be a valuable component In future photovoltaic devices. Copyright © 2010 American Chemical Society.

Phase Evolution of YBa2Cu3O7-x films by all-chemical solution deposition route for coated conductors

DEFF Research Database (Denmark)

Yue, Zhao; Tang, Xiao; Wu, Wei

2014-01-01

In order to understand the all-chemical-solution-deposition (CSD) processes for manufacturing coated conductors, we investigated the phase evolution of YBa2Cu3O7 (YBCO) films deposited by a low-fluorine metal-organic solution deposition (LF-MOD) method on CSD derived Ce0.9La0.1O2/Gd2Zr2O7/Ni......W. It is shown that the phase transition from the pyrolyzed film to fully converted YBCO film in the LF-MOD process is similar to that in typical trifluoroacetates-metal organic deposition (TFA-MOD) processes even though the amount of TFA in the solution is reduced by almost one half compared with typical TFA...

An ordered metallic glass solid solution phase that grows from the melt like a crystal

International Nuclear Information System (INIS)

Chapman, Karena W.; Chupas, Peter J.; Long, Gabrielle G.; Bendersky, Leonid A.; Levine, Lyle E.; Mompiou, Frédéric; Stalick, Judith K.; Cahn, John W.

2014-01-01

We report structural studies of an Al–Fe–Si glassy solid that is a solid solution phase in the classical thermodynamic sense. We demonstrate that it is neither a frozen melt nor nanocrystalline. The glass has a well-defined solubility limit and rejects Al during formation from the melt. The pair distribution function of the glass reveals chemical ordering out to at least 12 Å that resembles the ordering within a stable crystalline intermetallic phase of neighboring composition. Under isothermal annealing at 305 °C the glass first rejects Al, then persists for approximately 1 h with no detectable change in structure, and finally is transformed by a first-order phase transition to a crystalline phase with a structure that is different from that within the glass. It is possible that this remarkable glass phase has a fully ordered atomic structure that nevertheless possesses no long-range translational symmetry and is isotropic

Convergent solid-phase and solution approaches in the synthesis of the cysteine-rich Mdm2 RING finger domain.

Science.gov (United States)

Vasileiou, Zoe; Barlos, Kostas; Gatos, Dimitrios

2009-12-01

The RING finger domain of the Mdm2, located at the C-terminus of the protein, is necessary for regulation of p53, a tumor suppressor protein. The 48-residues long Mdm2 peptide is an important target for studying its interaction with small anticancer drug candidates. For the chemical synthesis of the Mdm2 RING finger domain, the fragment condensation on solid-phase and the fragment condensation in solution were studied. The latter method was performed using either protected or free peptides at the C-terminus as the amino component. Best results were achieved using solution condensation where the N-component was applied with the C-terminal carboxyl group left unprotected. The developed method is well suited for large-scale synthesis of Mdm2 RING finger domain, combining the advantages of both solid-phase and solution synthesis. (c) 2009 European Peptide Society and John Wiley & Sons, Ltd.

THE DECEPTIVELY SIMPLE THERMOLYSIS OF TRIVALENT PERMETHYLTITANOCENE DERIVATIVES (ETA-5-C5ME5)2TIR - FORMATION OF A TETRAMETHYLFULVENE TITANIUM COMPOUND (ETA-6-C5ME4CH2)(ETA-5-C5ME5)TI AND RH, CATALYZED BY PERMETHYLTITANOCENE HYDRIDE, (ETA-5-C5ME5)2TIH

NARCIS (Netherlands)

LUINSTRA, GA; TEUBEN, JH

1992-01-01

The complexes Cp*2TiR (Cp* = eta-5-C5Me5; R = Me, Et, n-Pr, C2H3, CH2CMe3, Ph) undergo thermolysis to yield the fulvene complex Cp*FvTi (Fv = eta-6-C5Me4CH2) and RH. Kinetic measurements and deuterium labeling studies show that the decomposition is catalyzed by Cp*2TiH, which is formed either by

The use of wavelet transforms in the solution of two-phase flow problems

International Nuclear Information System (INIS)

Moridis, G.J.; Nikolaou, M.; You, Yong

1994-10-01

In this paper we present the use of wavelets to solve the nonlinear Partial Differential.Equation (PDE) of two-phase flow in one dimension. The wavelet transforms allow a drastically different approach in the discretization of space. In contrast to the traditional trigonometric basis functions, wavelets approximate a function not by cancellation but by placement of wavelets at appropriate locations. When an abrupt chance, such as a shock wave or a spike, occurs in a function, only local coefficients in a wavelet approximation will be affected. The unique feature of wavelets is their Multi-Resolution Analysis (MRA) property, which allows seamless investigational any spatial resolution. The use of wavelets is tested in the solution of the one-dimensional Buckley-Leverett problem against analytical solutions and solutions obtained from standard numerical models. Two classes of wavelet bases (Daubechies and Chui-Wang) and two methods (Galerkin and collocation) are investigated. We determine that the Chui-Wang, wavelets and a collocation method provide the optimum wavelet solution for this type of problem. Increasing the resolution level improves the accuracy of the solution, but the order of the basis function seems to be far less important. Our results indicate that wavelet transforms are an effective and accurate method which does not suffer from oscillations or numerical smearing in the presence of steep fronts

Oriented growth of Sr n+1Ti n O3n+1 Ruddlesden-Popper phases in chemical solution deposited thin films

International Nuclear Information System (INIS)

Gutmann, Emanuel; Levin, Alexandr A.; Reibold, Marianne; Mueller, Jan; Paufler, Peter; Meyer, Dirk C.

2006-01-01

Oriented thin films of perovskite-related Sr n +1 Ti n O 3 n +1 Ruddlesden-Popper phases (n=1, 2, 3) were grown on (001) single-crystalline SrTiO 3 substrates. Preparation of the films was carried out by wet chemical deposition from metalorganic Sr-Ti solutions (rich in Sr) and subsequent conversion into the crystalline state by thermal treatment in air atmosphere at a maximum temperature of 700 deg. C. Solutions were prepared by a modified Pechini method. The films were investigated by wide-angle X-ray scattering and high-resolution transmission electron microscopy. The phase content of powders prepared from the dried solutions and annealed under similar conditions differed from that present in the films, i.e. only polycrystalline SrTiO 3 was detected together with oxides of Ti and Sr. - Graphical abstract: Cross-sectional image of an oriented chemical solution deposited thin film obtained by high-resolution transmission electron microscopy. Periodical spacings corresponding to SrTiO 3 substrate (right) and Sr 2 TiO 4 Ruddlesden-Popper phase (n=1) film region (left) are marked

Phase Relations in Ternary Systems in the Subsolidus Region: Methods to Formulate Solid Solution Equations and to Find Particular Compositions

Science.gov (United States)

Alvarez-Montan~o, Victor E.; Farías, Mario H.; Brown, Francisco; Mun~oz-Palma, Iliana C.; Cubillas, Fernando; Castillon-Barraza, Felipe F.

2017-01-01

A good understanding of ternary phase diagrams is required to advance and/or to reproduce experimental research in solid-state and materials chemistry. The aim of this paper is to describe the solutions to problems that appear when studying or determining ternary phase diagrams. A brief description of the principal features shown in phase diagrams…

Carbene Reactions

DEFF Research Database (Denmark)

Hoffmann, R. W.; Barth, W.; Carlsen, Lars

1983-01-01

The gas-phase thermolysis of the norbornadienespirodithiolane S-oxides (5) and (7) led to benzene, ethylene, and carbon disulphide as the major products, possibly involving carbon disulphide oxides as intermediates. Thermolyses of the related sulphones (9) or (14) led to completely different prod...

Exact Solution of the Six-Vertex Model with Domain Wall Boundary Conditions. Disordered Phase

CERN Document Server

Bleher, P M

2005-01-01

The six-vertex model, or the square ice model, with domain wall boundary conditions (DWBC) has been introduced and solved for finite $N$ by Korepin and Izergin. The solution is based on the Yang-Baxter equations and it represents the free energy in terms of an $N\\times N$ Hankel determinant. Paul Zinn-Justin observed that the Izergin-Korepin formula can be re-expressed in terms of the partition function of a random matrix model with a nonpolynomial interaction. We use this observation to obtain the large $N$ asymptotics of the six-vertex model with DWBC in the disordered phase. The solution is based on the Riemann-Hilbert approach and the Deift-Zhou nonlinear steepest descent method. As was noticed by Kuperberg, the problem of enumeration of alternating sign matrices (the ASM problem) is a special case of the the six-vertex model. We compare the obtained exact solution of the six-vertex model with known exact results for the 1, 2, and 3 enumerations of ASMs, and also with the exact solution on the so-called f...

A generalized volumetric dispersion model for a class of two-phase separation/reaction: finite difference solutions

Science.gov (United States)

Siripatana, Chairat; Thongpan, Hathaikarn; Promraksa, Arwut

2017-03-01

This article explores a volumetric approach in formulating differential equations for a class of engineering flow problems involving component transfer within or between two phases. In contrast to conventional formulation which is based on linear velocities, this work proposed a slightly different approach based on volumetric flow-rate which is essentially constant in many industrial processes. In effect, many multi-dimensional flow problems found industrially can be simplified into multi-component or multi-phase but one-dimensional flow problems. The formulation is largely generic, covering counter-current, concurrent or batch, fixed and fluidized bed arrangement. It was also intended to use for start-up, shut-down, control and steady state simulation. Since many realistic and industrial operation are dynamic with variable velocity and porosity in relation to position, analytical solutions are rare and limited to only very simple cases. Thus we also provide a numerical solution using Crank-Nicolson finite difference scheme. This solution is inherently stable as tested against a few cases published in the literature. However, it is anticipated that, for unconfined flow or non-constant flow-rate, traditional formulation should be applied.

Fabrication of γ-Fe2O3 Nanoparticles by Solid-State Thermolysis of a Metal-Organic Framework, MIL-100(Fe, for Heavy Metal Ions Removal

Directory of Open Access Journals (Sweden)

Shengtao Hei

2014-01-01

Full Text Available Porous γ-Fe2O3 nanoparticles were prepared via a solid-state conversion process of a mesoporous iron(III carboxylate crystal, MIL-100(Fe. First, the MIL-100(Fe crystal that served as the template of the metal oxide was synthesized by a low-temperature (<100°C synthesis route. Subsequently, the porous γ-Fe2O3 nanoparticles were fabricated by facile thermolysis of the MIL-100(Fe powders via a two-step calcination treatment. The obtained γ-Fe2O3 was characterized by X-ray diffraction (XRD, N2 adsorption, X-ray photoelectron spectroscopy (XPS, and scanning electron microscopy (SEM techniques, and then used as an adsorbent for heavy metal ions removal in water treatment. This study illustrates that the metal-organic frameworks may be suitable precursors for the fabrication of metal oxides nanomaterials with large specific surface area, and the prepared porous γ-Fe2O3 exhibits a superior adsorption performance for As(V and As(III ions removal in water treatment.

Three-Dimensional ZnO Hierarchical Nanostructures: Solution Phase Synthesis and Applications

Directory of Open Access Journals (Sweden)

Xiaoliang Wang

2017-11-01

Full Text Available Zinc oxide (ZnO nanostructures have been studied extensively in the past 20 years due to their novel electronic, photonic, mechanical and electrochemical properties. Recently, more attention has been paid to assemble nanoscale building blocks into three-dimensional (3D complex hierarchical structures, which not only inherit the excellent properties of the single building blocks but also provide potential applications in the bottom-up fabrication of functional devices. This review article focuses on 3D ZnO hierarchical nanostructures, and summarizes major advances in the solution phase synthesis, applications in environment, and electrical/electrochemical devices. We present the principles and growth mechanisms of ZnO nanostructures via different solution methods, with an emphasis on rational control of the morphology and assembly. We then discuss the applications of 3D ZnO hierarchical nanostructures in photocatalysis, field emission, electrochemical sensor, and lithium ion batteries. Throughout the discussion, the relationship between the device performance and the microstructures of 3D ZnO hierarchical nanostructures will be highlighted. This review concludes with a personal perspective on the current challenges and future research.

EXAFS Phase Retrieval Solution Tracking for Complex Multi-Component System: Synthesized Topological Inverse Computation

International Nuclear Information System (INIS)

Lee, Jay Min; Yang, Dong-Seok; Bunker, Grant B

2013-01-01

Using the FEFF kernel A(k,r), we describe the inverse computation from χ(k)-data to g(r)-solution in terms of a singularity regularization method based on complete Bayesian statistics process. In this work, we topologically decompose the system-matched invariant projection operators into two distinct types, (A + AA + A) and (AA + AA + ), and achieved Synthesized Topological Inversion Computation (STIC), by employing a 12-operator-closed-loop emulator of the symplectic transformation. This leads to a numerically self-consistent solution as the optimal near-singular regularization parameters are sought, dramatically suppressing instability problems connected with finite precision arithmetic in ill-posed systems. By statistically correlating a pair of measured data, it was feasible to compute an optimal EXAFS phase retrieval solution expressed in terms of the complex-valued χ(k), and this approach was successfully used to determine the optimal g(r) for a complex multi-component system.

Construction of solutions in certain differential games with phase constraints

International Nuclear Information System (INIS)

Grigor'eva, S V; Uspenskii, A A; Ushakov, V N; Pakhotinskikh, V Yu

2005-01-01

A differential approach-evasion game with fixed termination time is studied. It is assumed that the phase vector of the conflict-control system is subjected to constraints that form a closed set in the position space. The ideology of stable bridges is used for solving the problem. A method of convolution is proposed, which is used in several problems for constructing explicitly the stable absorption operator defining the stable bridges. A method of approximate construction of the maximal stable bridge in this game is suggested. The relations are written down that define a system of sets approximating the maximal stable bridge, and a control procedure with a guide is described, which can be used for obtaining an approximate solution of the approach problem.

Molecular theory of chromatography for blocklike solutes in isotropic stationary phases and its application to supercritical fluid chromatographic retention of PAHs

International Nuclear Information System (INIS)

Chao Yan; Martire, D.E.

1992-01-01

This report discusses a molecular theory of chromatography for blocklike solutes in isotropic stationary phases as an extension to the anisotopic phase approach. Its it applied to gas, liquid, and supercritical fluid chromatography

A facile route to shape controlled CdTe nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Mntungwa, Nhlakanipho; Rajasekhar, Pullabhotla V.S.R. [Department of Chemistry, University of Zululand, Private Bag X1001, KwaDlangezwa 3886, Empangeni, KZN (South Africa); Revaprasadu, Neerish, E-mail: nrevapra@pan.uzulu.ac.za [Department of Chemistry, University of Zululand, Private Bag X1001, KwaDlangezwa 3886, Empangeni, KZN (South Africa)

2011-04-15

Research highlights: {yields} A facile hybrid solution based/thermolysis route has been used for the synthesis of hexadecylamine capped CdTe nanoparticles. {yields} This method involves the reaction by the addition of an aqueous suspension of a cadmium salt to a freshly prepared NaHTe solution. {yields} The cadmium salt plays an important role in the growth mechanism of the particles and hence its final morphology. - Abstract: Hexadecylamine (HDA) capped CdTe nanoparticles have been synthesized using a facile hybrid solution based/thermolysis route. This method involves the reaction by the addition of an aqueous suspension or solution of a cadmium salt (chloride, acetate, nitrate or carbonate) to a freshly prepared NaHTe solution. The isolated CdTe was then dispersed in tri-octylphosphine (TOP) and injected into pre-heated HDA at temperatures of 190, 230 and 270 deg. C for 2 h. The particle growth and size distribution of the CdTe particles synthesized using cadmium chloride as the cadmium source were monitored using absorption and photoluminescence spectroscopy. The final morphology of the CdTe nanoparticles synthesized from the various cadmium sources was studied by transmission electron microscopy (TEM) and high resolution TEM. The cadmium source has an influence on the final morphology of the particles.

A facile route to shape controlled CdTe nanoparticles

International Nuclear Information System (INIS)

Mntungwa, Nhlakanipho; Rajasekhar, Pullabhotla V.S.R.; Revaprasadu, Neerish

2011-01-01

Research highlights: → A facile hybrid solution based/thermolysis route has been used for the synthesis of hexadecylamine capped CdTe nanoparticles. → This method involves the reaction by the addition of an aqueous suspension of a cadmium salt to a freshly prepared NaHTe solution. → The cadmium salt plays an important role in the growth mechanism of the particles and hence its final morphology. - Abstract: Hexadecylamine (HDA) capped CdTe nanoparticles have been synthesized using a facile hybrid solution based/thermolysis route. This method involves the reaction by the addition of an aqueous suspension or solution of a cadmium salt (chloride, acetate, nitrate or carbonate) to a freshly prepared NaHTe solution. The isolated CdTe was then dispersed in tri-octylphosphine (TOP) and injected into pre-heated HDA at temperatures of 190, 230 and 270 deg. C for 2 h. The particle growth and size distribution of the CdTe particles synthesized using cadmium chloride as the cadmium source were monitored using absorption and photoluminescence spectroscopy. The final morphology of the CdTe nanoparticles synthesized from the various cadmium sources was studied by transmission electron microscopy (TEM) and high resolution TEM. The cadmium source has an influence on the final morphology of the particles.

Specific features of concentrated phase under decomposition of weak solid /sup 3/He-/sup 4/He solution

Energy Technology Data Exchange (ETDEWEB)

Mikheev, V A; Majdamov, V A; Kal' noj, S E; Omelaenko, N I

1988-06-01

The decomposition of solid /sup 3/He-/sup 4/He solutuions is studied on the samples 0.54% /sup 3/He(V=20.55 cm/sup 3//mole) and 0.60% /sup 4/He (V=24.04-24.93 cm/sup 3//mole) using pulse NMR method. At T=100 mK the decomposition of a weak solution proceeds more than for 30 h, the decomposition rate and temperature being dependent on the sample prehistory. In the concentrated phase of the decomposed weak solution the spin diffraction of /sup 3/He is of the quasi-one-dimensional character with the diffusion coefficient D /similar to/ 10/sup -5/ cm/sup 2//sec typical of liquid /sup 3/He and exceeding that bulk solid /sup 3/He by two orders of magnitude. The longitudinal relaxation time in the quasi-one-dimensional phase (/similar to/ 1 sec) is characteristic of the solid state and coinsides with data for bulk /sup 3/He. The temperature behaviour of magnetization in the quasi-one-dimensional phase is well described by the Curie law.

Tetragonal-cubic phase boundary in nanocrystalline ZrO{sub 2}-Y{sub 2}O{sub 3} solid solutions synthesized by gel-combustion

Energy Technology Data Exchange (ETDEWEB)

Fabregas, Ismael O. [CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Pcia. de Buenos Aires (Argentina); Craievich, Aldo F.; Fantini, Marcia C.A. [Instituto de Fisica, Universidade de Sao Paulo, Travessa R da Rua do Matao, No. 187, Cidade Universitaria, 05508-900 Sao Paulo (Brazil); Millen, Ricardo P.; Temperini, Marcia L.A. [Instituto de Quimica, Universidade de Sao Paulo, Avenida Prof. Lineu Prestes 748, Cidade Universitaria, 05508-900 Sao Paulo (Brazil); Lamas, Diego G., E-mail: dlamas@uncoma.edu.ar [CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Pcia. de Buenos Aires (Argentina); Laboratorio de Caracterizacion de Materiales, Facultad de Ingenieria, Universidad Nacional del Comahue, Buenos Aires 1400, (8300) Neuquen Capital, Prov. de Neuquen (Argentina)

2011-04-21

Research highlights: > Gel-combustion synthesis yields compositionally homogeneous, single-phased ZrO{sub 2}-Y{sub 2}O{sub 3} nanopowders, that exhibit the presence at room temperature of three different phases depending on Y{sub 2}O{sub 3} content, namely two tetragonal forms (t' and t'') and the cubic phase. > Phase identification can be achieved by synchrotron XPD (SXPD) and Raman spectroscopy since the tetragonal forms and the cubic phase can be distinguished by these techniques. > The crystallographic features of ZrO{sub 2}-Y{sub 2}O{sub 3} nanopowders were determined by SXPD. They are similar to those reported by Yashima and coworkers for compositionally homogeneous materials containing larger (micro)crystals. However, the lattice parameters are slightly different and the axial ratios c/a of our t' samples are smaller than those reported by these authors. > Compositional t'/t'' and t''/cubic phase boundaries are located at (9 {+-} 1) and (10.5 {+-} 0.5) mol% Y{sub 2}O{sub 3}, respectively. > For the whole series of nanocrystalline ZrO{sub 2}-Y{sub 2}O{sub 3} solid solutions studied in the present work, no evidences of the presence of a mixture of phases - as reported by Yashima and coworkers for microcrystalline solid solutions - were detected. - Abstract: By means of synchrotron X-ray powder diffraction (SXPD) and Raman spectroscopy, we have detected, in a series of nanocrystalline and compositionally homogeneous ZrO{sub 2}-Y{sub 2}O{sub 3} solid solutions, the presence at room temperature of three different phases depending on Y{sub 2}O{sub 3} content, namely two tetragonal forms and the cubic phase. The studied materials, with average crystallite sizes within the range 7-10 nm, were synthesized by a nitrate-citrate gel-combustion process. The crystal structure of these phases was also investigated by SXPD. The results presented here indicate that the studied nanocrystalline ZrO{sub 2}-Y{sub 2}O{sub 3} solid

The Deceptively Simple Thermolysis of Trivalent Permethyltitanocene Derivatives (η5-C5Me5)2TiR. Formation of a Tetramethylfulvene Titanium Compound (η6-C5Me4CH2)(η5-C5Me5)Ti and RH, Catalyzed by Permethyltitanocene Hydride, (η5-C5Me5)2TiH

NARCIS (Netherlands)

Luinstra, Gerrit A.; Teuben, Jan H.

1992-01-01

The complexes Cp*2TiR (Cp* = η5-C5Me5; R = Me, Et, n-Pr, C2H3, CH2CMe3, Ph) undergo thermolysis to yield the fulvene complex Cp*FvTi (Fv = η6-C5Me4CH2) and RH. Kinetic measurements and deuterium labeling studies show that the decomposition is catalyzed by Cp*2TiH, which is formed either by

Theory of the thermodynamic influence of solution-phase additives in shape-controlled nanocrystal synthesis.

Science.gov (United States)

Qi, Xin; Fichthorn, Kristen A

2017-10-19

Though many experimental studies have documented that certain solution-phase additives can play a key role in the shape-selective synthesis of metal nanocrystals, the origins and mechanisms of this shape selectivity are still unclear. One possible role of such molecules is to thermodynamically induce the equilibrium shape of a nanocrystal by altering the interfacial free energies of the facets. Using a multi-scheme thermodynamic integration method that we recently developed [J. Chem. Phys., 2016, 145, 194108], we calculate the solid-liquid interfacial free energies γ sl and investigate the propensity to achieve equilibrium shapes in such syntheses. We first apply this method to Ag(100) and Ag(111) facets in ethylene glycol solution containing polyvinylpyrrolidone (PVP), to mimic the environment in polyol synthesis of Ag nanocrystals. We find that although PVP has a preferred binding to Ag(100), its selectivity is not sufficient to induce a thermodynamic preference for {100}-faceted nanocubes, as has been observed experimentally. This indicates that PVP promotes Ag nanocube formation kinetically rather than thermodynamically. We further quantify the thermodynamic influence of adsorbed solution-phase additives for generic molecules, by building a γ sl ratio/nanocrystal shape map as a function of zero-temperature binding energies. This map can be used to gauge the efficacy of candidate additive molecules for producing targeted thermodynamic nanocrystal shapes. The results indicate that only additives with a strong facet selectivity can impart significant thermodynamic-shape change. Therefore, many of the nanocrystals observed in experiments are likely kinetic products.

Exploring Poly(ethylene glycol-Polyzwitterion Diblock Copolymers as Biocompatible Smart Macrosurfactants Featuring UCST-Phase Behavior in Normal Saline Solution

Directory of Open Access Journals (Sweden)

Noverra M. Nizardo

2018-03-01

Full Text Available Nonionic-zwitterionic diblock copolymers are designed to feature a coil-to-globule collapse transition with an upper critical solution temperature (UCST in aqueous media, including physiological saline solution. The block copolymers that combine presumably highly biocompatible blocks are synthesized by chain extension of a poly(ethylene glycol (PEG macroinitiator via atom transfer radical polymerization (ATRP of sulfobetaine and sulfabetaine methacrylates. Their thermoresponsive behavior is studied by variable temperature turbidimetry and 1H NMR spectroscopy. While the polymers with polysulfobetaine blocks exhibit phase transitions in the physiologically interesting window of 30–50 °C only in pure aqueous solution, the polymers bearing polysulfabetaine blocks enabled phase transitions only in physiological saline solution. By copolymerizing a pair of structurally closely related sulfo- and sulfabetaine monomers, thermoresponsive behavior can be implemented in aqueous solutions of both low and high salinity. Surprisingly, the presence of the PEG blocks can affect the UCST-transitions of the polyzwitterions notably. In specific cases, this results in “schizophrenic” thermoresponsive behavior displaying simultaneously an UCST and an LCST (lower critical solution temperature transition. Exploratory experiments on the UCST-transition triggered the encapsulation and release of various solvatochromic fluorescent dyes as model “cargos” failed, apparently due to the poor affinity even of charged organic compounds to the collapsed state of the polyzwitterions.

The first preparative solution phase synthesis of melanotan II

Directory of Open Access Journals (Sweden)

2008-10-01

Full Text Available Melanotan II is a synthetic cyclic heptapeptide used to prevent a sunlight-induced skin cancer by stimulating the skin tanning process. In this paper we report the first solution phase synthesis of the title compound. The hexapeptide sequence has been assembled by [(2+2+1+1] scheme. After removing the orthogonal protection, a carbodiimide mediated lactamization, involving the ε-amino group of lysine and γ-carboxy group of aspartic acid, led to a cyclic intermediate. Appending N-acetylnorleucine concluded the assembly of melanotan II molecule. Protection of the lateral groups in arginine and tryptophan was omitted for atom and step economy reasons. The total synthesis of melanotan II was accomplished in 12 steps with 2.6% overall yield, affording >90% pure peptide without using preparative chromatography.

Linear analytical solution to the phase diversity problem for extended objects based on the Born approximation

NARCIS (Netherlands)

Andrei, R.M.; Smith, C.S.; Fraanje, P.R.; Verhaegen, M.; Korkiakoski, V.A.; Keller, C.U.; Doelman, N.J.

2012-01-01

In this paper we give a new wavefront estimation technique that overcomes the main disadvantages of the phase diversity (PD) algorithms, namely the large computational complexity and the fact that the solutions can get stuck in a local minima. Our approach gives a good starting point for an

Br2 production from the heterogeneous reaction of gas-phase OH with aqueous salt solutions: Impacts of acidity, halide concentration, and organic surfactants.

Science.gov (United States)

Frinak, Elizabeth K; Abbatt, Jonathan P D

2006-09-07

This study reports the first laboratory measurement of gas-phase Br2 production from the reaction between gas-phase hydroxyl radicals and aqueous salt solutions. Experiments were conducted at 269 K in a rotating wetted-wall flow tube coupled to a chemical-ionization mass spectrometer for analysis of gas-phase components. From both pure NaBr solutions and mixed NaCl/NaBr solutions, the amount of Br2 released was found to increase with increasing acidity, whereas it was found to vary little with increasing concentration of bromide ions in the sample. For mixed NaCl/NaBr solutions, Br2 was formed preferentially over Cl2 unless the Br- levels in the solution were significantly depleted by OH oxidation, at which point Cl2 formation was observed. Presence of a surfactant in solution, sodium dodecyl sulfate, significantly suppressed the formation of Br2; this is the first indication that an organic surfactant can affect the rate of interfacial mass transfer of OH to an aqueous surface. The OH-mediated oxidation of bromide may serve as a source of active bromine in the troposphere and contribute to the subsequent destruction of ozone that proceeds in marine-influenced regions of the troposphere.

Solution of the Cox-Thompson inverse scattering problem using finite set of phase shifts

CERN Document Server

Apagyi, B; Scheid, W

2003-01-01

A system of nonlinear equations is presented for the solution of the Cox-Thompson inverse scattering problem (1970 J. Math. Phys. 11 805) at fixed energy. From a given finite set of phase shifts for physical angular momenta, the nonlinear equations determine related sets of asymptotic normalization constants and nonphysical (shifted) angular momenta from which all quantities of interest, including the inversion potential itself, can be calculated. As a first application of the method we use input data consisting of a finite set of phase shifts calculated from Woods-Saxon and box potentials representing interactions with diffuse or sharp surfaces, respectively. The results for the inversion potentials, their first moments and asymptotic properties are compared with those provided by the Newton-Sabatier quantum inversion procedure. It is found that in order to achieve inversion potentials of similar quality, the Cox-Thompson method requires a smaller set of phase shifts than the Newton-Sabatier procedure.

Solution of the Cox-Thompson inverse scattering problem using finite set of phase shifts

International Nuclear Information System (INIS)

Apagyi, Barnabas; Harman, Zoltan; Scheid, Werner

2003-01-01

A system of nonlinear equations is presented for the solution of the Cox-Thompson inverse scattering problem (1970 J. Math. Phys. 11 805) at fixed energy. From a given finite set of phase shifts for physical angular momenta, the nonlinear equations determine related sets of asymptotic normalization constants and nonphysical (shifted) angular momenta from which all quantities of interest, including the inversion potential itself, can be calculated. As a first application of the method we use input data consisting of a finite set of phase shifts calculated from Woods-Saxon and box potentials representing interactions with diffuse or sharp surfaces, respectively. The results for the inversion potentials, their first moments and asymptotic properties are compared with those provided by the Newton-Sabatier quantum inversion procedure. It is found that in order to achieve inversion potentials of similar quality, the Cox-Thompson method requires a smaller set of phase shifts than the Newton-Sabatier procedure

Opalescence of an IgG2 monoclonal antibody solution as it relates to liquid-liquid phase separation.

Science.gov (United States)

Mason, Bruce D; Zhang, Le; Remmele, Richard L; Zhang, Jifeng

2011-11-01

Opalescence for a monoclonal antibody solution was systematically studied with respect to temperature, protein concentration, ionic strength (using KCl), and pH conditions. Multiple techniques, including measurement of light scattering at 90° and transmission, Tyndall test, and microscopy, were deployed to examine the opalescence behavior. Near the vicinity of the critical point on the liquid-liquid coexistence curve in the temperature-protein concentration phase diagram, the enhanced concentration fluctuations significantly contributed to the critical opalescence evidently by formation of small liquid droplets. Furthermore, our data confirm that away from the critical point, the opalescence behavior is related to the antibody self-association (agglomeration) caused by the attractive antibody-antibody interactions. As expected, at a pH near the pI of the antibody, the solution became less opalescent as the ionic strength increased. However, at a pH below the pI, the opalescence of the solution became stronger, reached a maximum, and then began to drop as the ionic strength further increased. The change in the opalescence correlated well with the trends of protein-protein interactions revealed by the critical temperature from the liquid-liquid phase separation. Copyright © 2011 Wiley-Liss, Inc.

Continued development of a semianalytical solution for two-phase fluid and heat flow in a porous medium

Energy Technology Data Exchange (ETDEWEB)

Doughty, C.; Pruess, K. [Lawrence Berkeley Lab., CA (United States)

1991-06-01

Over the past few years the authors have developed a semianalytical solution for transient two-phase water, air, and heat flow in a porous medium surrounding a constant-strength linear heat source, using a similarity variable {eta} = r/{radical}t. Although the similarity transformation approach requires a simplified geometry, all the complex physical mechanisms involved in coupled two-phase fluid and heat flow can be taken into account in a rigorous way, so that the solution may be applied to a variety of problems of current interest. The work was motivated by adverse to predict the thermohydrological response to the proposed geologic repository for heat-generating high-level nuclear wastes at Yucca Mountain, Nevada, in a partially saturated, highly fractured volcanic formation. The paper describes thermal and hydrologic conditions near the heat source; new features of the model; vapor pressure lowering; and the effective-continuum representation of a fractured/porous medium.

Modelling of retention of pesticides in reversed-phase high-performance liquid chromatography: Quantitative structure-retention relationships based on solute quantum-chemical descriptors and experimental (solvatochromic and spin-probe) mobile phase descriptors

International Nuclear Information System (INIS)

D'Archivio, Angelo Antonio; Ruggieri, Fabrizio; Mazzeo, Pietro; Tettamanti, Enzo

2007-01-01

A quantitative structure-retention relationship (QSRR) analysis based on multilinear regression (MLR) and artificial neural networks (ANNs) is carried out to model the combined effect of solute structure and eluent composition on the retention behaviour of pesticides in isocratic reversed-phase high-performance liquid chromatography (RP-HPLC). The octanol-water partition coefficient and four quantum chemical descriptors (the total dipole moment, the mean polarizability, the anisotropy of the polarizability and a descriptor of hydrogen-bonding based on the atomic charges on acidic and basic chemical functionalities) are considered as solute descriptors. In order to identify suitable mobile phase descriptors, encoding composition-dependent properties of both methanol- and acetonitrile-containing mobile phases, the Kamlet-Taft solvatochromic parameters (polarity-dipolarity, hydrogen-bond acidity and hydrogen-bond basicity, π * , α and β, respectively) and the 14 N hyperfine-splitting constant (a N ) of a spin-probe dissolved in the eluent are examined. A satisfactory description of mobile phase properties influencing the solute retention is provided by a N and β or alternatively π * and β. The two seven-parameter models resulting from combination of a N and β, or π * and β, with the solute descriptors were tested on a set of 26 pesticides representative of 10 different chemical classes in a wide range of mobile phase composition (30-60% (v/v) water-methanol and 30-70% (v/v) water-acetonitrile). Within the explored experimental range, the acidity of the eluent, as quantified by α, is almost constant, and this parameter is in fact irrelevant. The results reveal that a N and π * , that can be considered as interchangeable mobile phase descriptors, are the most influent variables in the respective models. The predictive ability of the proposed models, as tested on an external data set, is quite good (Q 2 close to 0.94) when a MLR approach is used, but the

Modelling of retention of pesticides in reversed-phase high-performance liquid chromatography: Quantitative structure-retention relationships based on solute quantum-chemical descriptors and experimental (solvatochromic and spin-probe) mobile phase descriptors

Energy Technology Data Exchange (ETDEWEB)

D' Archivio, Angelo Antonio [Dipartimento di Chimica, Ingegneria Chimica e Materiali, Universita degli Studi di L' Aquila, Via Vetoio, 67010 Coppito, L' Aquila (Italy)]. E-mail: darchivi@univaq.it; Ruggieri, Fabrizio [Dipartimento di Chimica, Ingegneria Chimica e Materiali, Universita degli Studi di L' Aquila, Via Vetoio, 67010 Coppito, L' Aquila (Italy); Mazzeo, Pietro [Dipartimento di Chimica, Ingegneria Chimica e Materiali, Universita degli Studi di L' Aquila, Via Vetoio, 67010 Coppito, L' Aquila (Italy); Tettamanti, Enzo [Dipartimento di Scienze Biomediche Comparate, Universita di Teramo, P.zzale A. Moro 45, 64100 Teramo (Italy)

2007-06-19

A quantitative structure-retention relationship (QSRR) analysis based on multilinear regression (MLR) and artificial neural networks (ANNs) is carried out to model the combined effect of solute structure and eluent composition on the retention behaviour of pesticides in isocratic reversed-phase high-performance liquid chromatography (RP-HPLC). The octanol-water partition coefficient and four quantum chemical descriptors (the total dipole moment, the mean polarizability, the anisotropy of the polarizability and a descriptor of hydrogen-bonding based on the atomic charges on acidic and basic chemical functionalities) are considered as solute descriptors. In order to identify suitable mobile phase descriptors, encoding composition-dependent properties of both methanol- and acetonitrile-containing mobile phases, the Kamlet-Taft solvatochromic parameters (polarity-dipolarity, hydrogen-bond acidity and hydrogen-bond basicity, {pi} {sup *}, {alpha} and {beta}, respectively) and the {sup 14}N hyperfine-splitting constant (a {sub N}) of a spin-probe dissolved in the eluent are examined. A satisfactory description of mobile phase properties influencing the solute retention is provided by a {sub N} and {beta} or alternatively {pi} {sup *} and {beta}. The two seven-parameter models resulting from combination of a {sub N} and {beta}, or {pi} {sup *} and {beta}, with the solute descriptors were tested on a set of 26 pesticides representative of 10 different chemical classes in a wide range of mobile phase composition (30-60% (v/v) water-methanol and 30-70% (v/v) water-acetonitrile). Within the explored experimental range, the acidity of the eluent, as quantified by {alpha}, is almost constant, and this parameter is in fact irrelevant. The results reveal that a {sub N} and {pi} {sup *}, that can be considered as interchangeable mobile phase descriptors, are the most influent variables in the respective models. The predictive ability of the proposed models, as tested on an

A Mass Conservative Numerical Solution for Two-Phase Flow in Porous Media With Application to Unsaturated Flow

DEFF Research Database (Denmark)

Celia, Michael A.; Binning, Philip John

1992-01-01

that the algorithm produces solutions that are essentially mass conservative and oscillation free, even in the presence of steep infiltrating fronts. When the algorithm is applied to the case of air and water flow in unsaturated soils, numerical results confirm the conditions under which Richards's equation is valid....... Numerical results also demonstrate the potential importance of air phase advection when considering contaminant transport in unsaturated soils. Comparison to several other numerical algorithms shows that the modified Picard approach offers robust, mass conservative solutions to the general equations...

Conformational Study of DNA Sugars: from the Gas Phase to Solution

Science.gov (United States)

Uriarte, Iciar; Vallejo-López, Montserrat; Cocinero, Emilio J.; Corzana, Francisco; Davis, Benjamin G.

2017-06-01

Sugars are versatile molecules that play a variety of roles in the organism. For example, they are important in energy storage processes or as structural scaffolds. Here, we focus on the monosaccharide present in DNA by addressing the conformational and puckering properties in the gas phase of α- and β-methyl-2-deoxy-ribofuranoside and α- and β-methyl-2-deoxy-ribopiranoside. Other sugars have been previously studied in the gas phase The work presented here stems from a combination of chemical synthesis, ultrafast vaporization methods, supersonic expansions, microwave spectroscopy (both chirped-pulsed and Balle-Flygare cavity-based spectrometers) and NMR spectroscopy. Previous studies in the gas phase had been performed on 2-deoxyribose, but only piranose forms were detected. However, thanks to the combination of these techniques, we have isolated and characterized for the first time the conformational landscape of the sugar present in DNA in its biologically relevant furanose form. Our gas phase study serves as a probe of the conformational preferences of these biomolecules under isolation conditions. Thanks to the NMR experiments, we can characterize the favored conformations in solution and extract the role of the solvent in the structure and puckering of the monosaccharides. E. J. Cocinero, A. Lesarri, P. Écija, F. J. Basterretxea, J.-U. Grabow, J. A. Fernández, F. Castaño, Angew. Chem. Int. Edit. 2012, 51, 3119. P. Écija, I. Uriarte, L. Spada, B. G. Davis, W. Caminati, F. J. Basterretxea, A. Lesarri, E. J. Cocinero, Chem. Commun. 2016, 52, 6241. I. Peña, E. J. Cocinero, C. Cabezas, A. Lesarri, S. Mata, P. Écija, A. M. Daly, Á. Cimas, C. Bermúdez, F. J. Basterretxea, S. Blanco, J. A. Fernández, J. C. López, F. Castaño, J. L. Alonso, Angew. Chem. Int. Edit. 2013, 52, 11840.

Liquid-Phase Packaging of a Glucose Oxidase Solution with Parylene Direct Encapsulation and an Ultraviolet Curing Adhesive Cover for Glucose Sensors

Directory of Open Access Journals (Sweden)

Seiichi Takamatsu

2010-06-01

Full Text Available We have developed a package for disposable glucose sensor chips using Parylene encapsulation of a glucose oxidase solution in the liquid phase and a cover structure made of an ultraviolet (UV curable adhesive. Parylene was directly deposited onto a small volume (1 μL of glucose oxidase solution through chemical vapor deposition. The cover and reaction chamber were constructed on Parylene film using a UV-curable adhesive and photolithography. The package was processed at room temperature to avoid denaturation of the glucose oxidase. The glucose oxidase solution was encapsulated and unsealed. Glucose sensing was demonstrated using standard amperometric detection at glucose concentrations between 0.1 and 100 mM, which covers the glucose concentration range of diabetic patients. Our proposed Parylene encapsulation and UV-adhesive cover form a liquid phase glucose-oxidase package that has the advantages of room temperature processing and direct liquid encapsulation of a small volume solution without use of conventional solidifying chemicals.

In-Situ Synchrotron X-ray Study of the Phase and Texture Evolution of Ceria and Superconductor Films Deposited by Chemical Solution Method

DEFF Research Database (Denmark)

Yue, Zhao; Grivel, Jean-Claude; He, Dong

2012-01-01

In situ synchrotron x-ray diffraction is used to study the phase and texture formation of ceria based films and superconductor films deposited by the chemical solution method on technical substrates. Combined analysis using in situ synchrotron x-ray diffraction, thermogravimetry/differential ther......In situ synchrotron x-ray diffraction is used to study the phase and texture formation of ceria based films and superconductor films deposited by the chemical solution method on technical substrates. Combined analysis using in situ synchrotron x-ray diffraction, thermogravimetry...

The salting-out effect and phase separation in aqueous solutions of tri-sodium citrate and 1-butyl-3-methylimidazolium bromide

International Nuclear Information System (INIS)

Sadeghi, Rahmat; Golabiazar, Roonak; Shekaari, Hemayat

2010-01-01

The aim of this work is to obtain further evidence about the salting-out effect produced by the addition of tri-sodium citrate to aqueous solutions of water miscible ionic liquid 1-butyl-3-methylimidazolium bromide ([C 4 mim][Br]) by evaluating the effect of tri-sodium citrate on the thermodynamic properties of aqueous solutions of this ionic liquid. Experimental measurements of density and sound velocity at different temperatures ranging from (288.15 to 308.15) K, the refractive index at 308.15 K and the liquid-liquid phase diagram at different temperatures ranging from (288.15 to 338.15) K for aqueous solutions containing 1-butyl-3-methylimidazolium bromide ([C 4 mim][Br]) and tri-sodium citrate (Na 3 Cit) are taken. The apparent molar volume of transfer of [C 4 mim][Br] from water to aqueous solutions of Na 3 Cit have positive values and it increases by increasing salt molality. Although at high IL molality, the apparent molar isentropic compressibility shows similar behaviour with that of the apparent molar volume. However at low concentrations of IL, the apparent molar isentropic compressibility of transfer of [C 4 mim][Br] from water to aqueous solutions of Na 3 Cit have negative values. The effects of temperature and the addition of Na 3 Cit and [C 4 mim][Br] on the liquid-liquid phase diagram of the investigated system have been studied. It was found that an increase in temperature caused the expansion of the one-phase region. The presence of Na 3 Cit triggers a salting-out effect, leading to significant upward shifts of the liquid-liquid de-mixing temperatures of the system. The effect of temperature on the phase-forming ability in the system investigated has been studied based on a salting-out coefficient obtained from fitting the binodal values to a Setschenow-type equation for each temperature. Based on cloud point values, the energetics of the clouding process have been estimated and it was found that both of entropy and enthalpy are the driving forces

Phase and Texture of Solution-Processed Copper Phthalocyanine Thin Films Investigated by Two-Dimensional Grazing Incidence X-Ray Diffraction

Directory of Open Access Journals (Sweden)

Lulu Deng

2011-07-01

Full Text Available The phase and texture of a newly developed solution-processed copper phthalocyanine (CuPc thin film have been investigated by two-dimensional grazing incidence X-ray diffraction. The results show that it has β phase crystalline structure, with crystallinity greater than 80%. The average size of the crystallites is found to be about 24 nm. There are two different arrangements of crystallites, with one dominating the diffraction pattern. Both of them have preferred orientation along the thin film normal. Based on the similarities to the vacuum deposited CuPc thin films, the new solution processing method is verified to offer a good alternative to vacuum process, for the fabrication of low cost small molecule based organic photovoltaics.

Solid-state transformation of Fe-rich intermetallic phases in Al–5.0Cu–0.6Mn squeeze cast alloy with variable Fe contents during solution heat treatment

International Nuclear Information System (INIS)

Lin, Bo; Zhang, Weiwen; Zhao, Yuliang; Li, Yuanyuan

2015-01-01

The Al–5.0 wt.% Cu–0.6 wt.% Mn alloys with a variable Fe content were prepared by squeeze casting. Optical microscopy (OM), Deep etching technique, scanning electron microscopy(SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to examine the solid-state transformation of Fe-rich intermetallics during the solution heat treatment. The results showed that the Chinese script-like α-Fe, Al 6 (FeMn) and needle-like Al 3 (FeMn) phases transform to a new Cu-rich β-Fe (Al 7 Cu 2 (FeMn)) phase during solution heat treatment. The possible reaction and overall transformation kinetics of the solid-state phase transformation for the Fe-rich intermetallics were investigated. - Graphical abstract: Display Omitted - Highlights: • The α-Fe, Al 6 (FeMn) and Al 3 (FeMn) phases change to the β-Fe phases. • Possible reactions of Fe phases during solution heat treatment are discussed. • The overall fractional transformation rate follows an Avrami curve

Direct formation of new, phase-stable, and photoactive anatase-type Ti1-2XNbXScXO2 solid solution nanoparticles by hydrothermal method

International Nuclear Information System (INIS)

Hirano, Masanori; Ito, Takaharu

2008-01-01

A new anatase phase of photoactive Ti 1-2X Nb X Sc X O 2 (X = 0-0.2) solid solutions was directly formed as nanoparticles from precursor solutions of TiOSO 4 , NbCl 5 , and Sc(NO 3 ) 3 under mild hydrothermal conditions at 180 deg. C for 5 h using the hydrolysis of urea. With the increase of the content of niobium and scandium from X = 0 to 0.2, the lattice parameters a 0 and c 0 , the crystallite size, and the optical band gap of anatase gradually increased. Their photocatalytic activity and adsorptivity were evaluated separately by the measurement of the concentration of methylene blue (MB) remained in the solution in the dark or under UV-light irradiation. The anatase-type Ti 1-2X Nb X Sc X O 2 (X = 0.05) showed approximately two times and three times as high photocatalytic activity as those of the hydrothermal anatase-type pure TiO 2 and commercially available reference pure TiO 2 (ST-01), respectively. The anatase phase of Ti 1-2X Nb X Sc X O 2 (X = 0-0.2) existed stably up to 900 deg. C during heat treatment in air. New rutile-type Ti 1-2X Nb X Sc X O 2 solid solutions are formed through the phase transformation. The starting temperature of anatase-to-rutile phase transformation for Ti 1-2X Nb X Sc X O 2 (X = 0-0.2) solid solutions was delayed but its completing temperature was accelerated

A solution phase fabrication of magnetic nanoparticles encapsulated in carbon

International Nuclear Information System (INIS)

Wei Xianwen; Zhu Guoxing; Xia Chuanjun; Ye Yin

2006-01-01

To avoid high energy consumption, intensive use of hardware and high cost in the manufacture of nanoparticles encapsulated in carbon, a simple, efficient and economical solution-phase method for the fabrication of FeNi at C nanostructures has been explored. The reaction to the magnetic metal at C structures here is conducted at a relatively low temperature (160 deg. C) and this strategy can be transferred to prepare other transition metal at C core-shell nanostructures. The saturation magnetization of metal in metal at C nanostructures is similar to those of the corresponding buck metals. Magnetic metal at C nanostructures with magnetic metal nanoparticles inside and a functionalized carbon surface outside may not only provide the opportunity to tailor the magnetic properties for magnetic storage devices and therapeutics but also make possible the loading of other functional molecules (e.g. enzymes, antigens) for clinic diagnostics, molecular biology, bioengineering, and catalysis

Spontaneous vesicle phase formation by pseudogemini surfactants in aqueous solutions.

Science.gov (United States)

Sun, Nan; Shi, Lijuan; Lu, Fei; Xie, Shuting; Zheng, Liqiang

2014-08-14

The phase behavior of a kind of pseudogemini surfactant in aqueous solutions, formed by the mixture of sodium dodecyl benzene sulfonate (SDBS) and butane-1,4-bis (methylimidazolium bromide) ([mim-C4-mim]Br2) or butane-1,4-bis(methylpyrrolidinium bromide) ([mpy-C4-mpy]Br2) in a molar ratio of 2 : 1, is reported in the present work. When [mim-C4-mim]Br2 or [mpy-C4-mpy]Br2 is mixed with SDBS in aqueous solutions, one cationic [mim-C4-mim]Br2 or [mpy-C4-mpy]Br2 molecule "bridges" two SDBS molecules by noncovalent interactions (e.g. electrostatic, π-π stacking, and σ-π interactions), behaving like a pseudogemini surfactant. Vesicles can be formed by this kind of pseudogemini surfactant, determined by freeze-fracture transmission electron microscopy (FF-TEM) or cryogenic-transmission electron microscopy (cryo-TEM) and dynamic light scattering (DLS). The mixed system of sodium dodecyl sulfate (SDS) with [mim-C4-mim]Br2 or [mpy-C4-mpy]Br2 was also constructed, and only micelles were observed. We infer that a pseudogemini surfactant is formed under the synergic effect of electrostatic, π-π stacking, and σ-π interactions in the SDBS/[mim-C4-mim]Br2/H2O system, while electrostatic attraction and hydrophobic interactions may provide the directional force for vesicle formation in the SDBS/[mpy-C4-mpy]Br2/H2O system.

Identification of liquid-phase decomposition species and reactions for guanidinium azotetrazolate

International Nuclear Information System (INIS)

Kumbhakarna, Neeraj R.; Shah, Kaushal J.; Chowdhury, Arindrajit; Thynell, Stefan T.

2014-01-01

Highlights: • Guanidinium azotetrazolate (GzT) is a high-nitrogen energetic material. • FTIR spectroscopy and ToFMS spectrometry were used for species identification. • Quantum mechanics was used to identify transition states and decomposition pathways. • Important reactions in the GzT liquid-phase decomposition process were identified. • Initiation of decomposition occurs via ring opening, releasing N 2 . - Abstract: The objective of this work is to analyze the decomposition of guanidinium azotetrazolate (GzT) in the liquid phase by using a combined experimental and computational approach. The experimental part involves the use of Fourier transform infrared (FTIR) spectroscopy to acquire the spectral transmittance of the evolved gas-phase species from rapid thermolysis, as well as to acquire spectral transmittance of the condensate and residue formed from the decomposition. Time-of-flight mass spectrometry (ToFMS) is also used to acquire mass spectra of the evolved gas-phase species. Sub-milligram samples of GzT were heated at rates of about 2000 K/s to a set temperature (553–573 K) where decomposition occurred under isothermal conditions. N 2 , NH 3 , HCN, guanidine and melamine were identified as products of decomposition. The computational approach is based on using quantum mechanics for confirming the identity of the species observed in experiments and for identifying elementary chemical reactions that formed these species. In these ab initio techniques, various levels of theory and basis sets were used. Based on the calculated enthalpy and free energy values of various molecular structures, important reaction pathways were identified. Initiation of decomposition of GzT occurs via ring opening to release N 2

Crystal structure and magnetic properties of the solid-solution phase Ca3Co2-v Sc v O6

International Nuclear Information System (INIS)

Hervoches, Charles H.; Fredenborg, Vivian Miksch; Kjekshus, Arne; Fjellvag, Helmer; Hauback, Bjorn C.

2007-01-01

The two crystallographically non-equivalent Co atoms of the quasi-one-dimensional crystal structure of Ca 3 Co 2 O 6 form chains with alternating, face-sharing polyhedra of Co2O 6 trigonal prisms and Co1O 6 octahedra. This compound forms a substitutional solid-solution phase with Sc, in which the Sc atoms enter the Co2 sublattice exclusively. The homogeneity range of Ca 3 Co 2- v Sc v O 6 (more specifically Ca 3 Co1Co2 1- v Sc v O 6 ) extends up to v∼0.55. The crystal structure belongs to space group R3-barc with lattice parameters (in hexagonal setting): 9.0846(3)≤a≤9.1300(2) A and 10.3885(4)≤c≤10.4677(4) A. The magnetic moment decreases rapidly with increasing amount of the non-magnetic Sc solute in the lattice. - Graphical abstract: The quasi-one-dimensional Ca 3 Co 2 O 6 phase forms a substitutional solid-solution system with Sc, in which the Sc atoms enter the Co2 sublattice exclusively. The homogeneity range of Ca 3 Co 2- v Sc v O 6 extends up to v∼0.55. The magnetic moment decreases rapidly with increasing amount of the non-magnetic Sc solute in the lattice

1D and 2D NMR Spectroscopy of Bonding Interactions within Stable and Phase-Separating Organic Electrolyte-Cellulose Solutions.

Science.gov (United States)

Clough, Matthew T; Farès, Christophe; Rinaldi, Roberto

2017-09-11

Organic electrolyte solutions (i.e. mixtures containing an ionic liquid and a polar, molecular co-solvent) are highly versatile solvents for cellulose. However, the underlying solvent-solvent and solvent-solute interactions are not yet fully understood. Herein, mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate, the co-solvent 1,3-dimethyl-2-imidazolidinone, and cellulose are investigated using 1D and 2D NMR spectroscopy. The use of a triply- 13 C-labelled ionic liquid enhances the signal-to-noise ratio for 13 C NMR spectroscopy, enabling changes in bonding interactions to be accurately pinpointed. Current observations reveal an additional degree of complexity regarding the distinct roles of cation, anion, and co-solvent toward maintaining cellulose solubility and phase stability. Unexpectedly, the interactions between the dialkylimidazolium ring C 2 -H substituent and cellulose become more pronounced at high temperatures, counteracted by a net weakening of acetate-cellulose interactions. Moreover, for mixtures that exhibit critical solution behavior, phase separation is accompanied by the apparent recombination of cation-anion pairs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of removing alkyl iodides or mixtures of iodine and alkyl iodides from a gas phase and an aqueous solution phase by utilizing ion exchange resins

International Nuclear Information System (INIS)

Shimizu, Hiroshi; Mizuuchi, Noboru; Yokoyama, Fumio.

1967-01-01

Alkyl iodides and mixtures of iodine and alkyl iodides are removed from a gas phase and an aquous solution phase by using solely an anion exchange resin containing a tertiary amine or together with an anion exchange resin containing quarternary ammonium compound. The resin containing the quarternary ammonium compound is employed mainly to remove iodine, and the resin containing the tertiary amine serves mainly to remove alkyl iodides. The method can be applied to collecting a majority of the methyl iodide as well as the radioactive iodine produced in the atmosphere of a reactor in case of a fuel accident. In embodiments, it is desirable to maintain the sufficient moisture content of the anion exchange resins at a sufficient moisture level so as not to reduce the migration speed of the iodine and alkyl iodides. The iodine and alkyl iodide can be produced with high efficiency and stability independently of the relative humidity of the gas phase. In examples, a solution which consists of 20.5 mg/l of iodine and 42.2mg/l of methyl iodide flew through a column of Amberite IRA-93 alone or blended with IRA-900 at a speed of 15 /hr. respectively. The resins were able to treat 400 times their equivalent in water. (Iwakiri, K.)

Comparative environmental and human health evaluations of thermolysis and solvolysis recycling technologies of carbon fiber reinforced polymer waste.

Science.gov (United States)

Khalil, Y F

2018-06-01

This quantitative research aims to compare environmental and human health impacts associated with two recycling technologies of CFRP waste. The 'baseline' recycling technology is the conventional thermolysis process via pyrolysis and the 'alternative' recycling technology is an emerging chemical treatment via solvolysis using supercritical water (SCW) to digest the thermoset matrix. Two Gate-to-Gate recycling models are developed using GaBi LCA platform. The selected functional unit (FU) is 1 kg CFRP waste and the geographical boundary of this comparative LCIA is defined to be within the U.S. The results of this comparative assessment brought to light new insights about the environmental and human health impacts of CFRP waste recycling via solvolysis using SCW and, therefore, helped close a gap in the current state of knowledge about sustainability of SCW-based solvolysis as compared to pyrolysis. Two research questions are posed to identify whether solvolysis recycling offers more environmental and human health gains relative to the conventional pyrolysis recycling. These research questions lay the basis for formulating two null hypotheses (H 0,1 and H 0,2 ) and their associated research hypotheses (H 1,1 and H 1,2 ). LCIA results interpretation included 'base case' scenarios, 'sensitivity studies,' and 'scenarios analysis.' The results revealed that: (a) recycling via solvolysis using SCW exhibits no gains in environmental and human health impacts relative to those impacts associated with recycling via pyrolysis and (b) use of natural gas in lieu of electricity for pyrolyzer's heating reduces the environmental and human health impacts by 37% (lowest) and up to 95.7% (highest). It is recommended that on-going experimental efforts that focus only on identifying the best solvent for solvolysis-based recycling should also consider quantification of the energy intensity as well as environmental and human health impacts of the proposed solvents. Copyright © 2018

Comprehensive Peptide Ion Structure Studies Using Ion Mobility Techniques: Part 3. Relating Solution-Phase to Gas-Phase Structures.

Science.gov (United States)

Kondalaji, Samaneh Ghassabi; Khakinejad, Mahdiar; Valentine, Stephen J

2018-06-01

Molecular dynamics (MD) simulations have been utilized to study peptide ion conformer establishment during the electrospray process. An explicit water model is used for nanodroplets containing a model peptide and hydronium ions. Simulations are conducted at 300 K for two different peptide ion charge configurations and for droplets containing varying numbers of hydronium ions. For all conditions, modeling has been performed until production of the gas-phase ions and the resultant conformers have been compared to proposed gas-phase structures. The latter species were obtained from previous studies in which in silico candidate structures were filtered according to ion mobility and hydrogen-deuterium exchange (HDX) reactivity matches. Results from the present study present three key findings namely (1) the evidence from ion production modeling supports previous structure refinement studies based on mobility and HDX reactivity matching, (2) the modeling of the electrospray process is significantly improved by utilizing initial droplets existing below but close to the calculated Rayleigh limit, and (3) peptide ions in the nanodroplets sample significantly different conformers than those in the bulk solution due to altered physicochemical properties of the solvent. Graphical Abstract ᅟ.

Theoretical study of phase behaviour of DLVO model for lysozyme and γ-crystalline aqueous electrolyte solutions

Directory of Open Access Journals (Sweden)

R. Melnyk

2015-03-01

Full Text Available Mean spherical approximation (MSA, second-order Barker-Henderson (BH perturbation theory and thermodynamic perturbation theory (TPT for associating fluids in combination with BH perturbation theory are applied to the study of the structural properties and phase behaviour of the Derjaguin-Landau-Verwey-Overbeek (DLVO model of lysozyme and γ-cristalline aqueous electrolyte solutions. Predictions of the MSA for the structure factors are in good agreement with the corresponding computer simulation predictions. The agreement between theoretical results for the liquid-gas phase diagram and the corresponding results of the experiment and computer simulation is less satisfactory, with predictions of the combined BH-TPT approach being the most accurate.

Comparative study of solute trapping and Gibbs free energy changes at the phase interface during alloy solidification under local nonequilibrium conditions

Energy Technology Data Exchange (ETDEWEB)

Sobolev, S. L., E-mail: sobolev@icp.ac.ru [Russian Academy of Sciences, Institute of Problems of Chemical Physics (Russian Federation)

2017-03-15

An analytical model has been developed to describe the influence of solute trapping during rapid alloy solidification on the components of the Gibbs free energy change at the phase interface with emphasis on the solute drag energy. For relatively low interface velocity V < V{sub D}, where V{sub D} is the characteristic diffusion velocity, all the components, namely mixing part, local nonequilibrium part, and solute drag, significantly depend on solute diffusion and partitioning. When V ≥ V{sub D}, the local nonequilibrium effects lead to a sharp transition to diffusionless solidification. The transition is accompanied by complete solute trapping and vanishing solute drag energy, i.e. partitionless and “dragless” solidification.

Investigation into isomolar series of Al(NO3)3, Na3VO4 solution mixture and composition of solid phases

International Nuclear Information System (INIS)

Chernysh, L.F.; Nakhodnova, A.P.; Makarova, R.A.

1979-01-01

Conducted is investigation of properties of isomolar series of aluminium nitrate and sodiUm vanadate solutions at pH of the latter 12.5; 10.0; 7.0 and the temperature of 25 deg C using the methods of pH-metry, conductometry, ''seeming'' volume of precipitations, residual concentration of aluminium and vanadium. It is shown, that the composition property diagram of the system investigated does not reflect the true composition of solid-phase products of the reaction, which depends on the component ratio in solution. Bottom phases of isomolar series are mainly heterogeneous. At the excess of sodium vanadate solution and its high pH values conditions for the basic salt formation are created. At pH of the Na 3 VO 4 solution of 12.5 and 10.0 and Al(NO 3 ) 3 : Na 3 VO 4 ratios 4:6 and 3:7 respectively obtained are the basic aluminium vanadates of the (AlOH) 3 (VO 4 ) 2 x 7.5H 2 O and (AlOH) 2 V 2 O 7 x5H 2 O composition, some of their physicochemical properties being investigated

Structural and phase transition changes of sodium dodecyl sulfate micellar solution in alcohols probed by small-angle neutron scattering (SANS)

Energy Technology Data Exchange (ETDEWEB)

Putra, Edy Giri Rachman [Neutron Scattering Laboratory, National Nuclear Energy Agency of Indonesia (BATAN), Gedung 40 BATAN, Kawasan Puspiptek Serpong, Tangerang 15314 (Indonesia); Patriati, Arum [Neutron Scattering Laboratory, National Nuclear Energy Agency of Indonesia (BATAN), Gedung 40 BATAN, Kawasan Puspiptek Serpong, Tangerang 15314 (Indonesia); Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of Gadjah Mada, Bulaksumur, Yogyakarta 55281, Indonesia giri@batan.go.id (Indonesia)

2015-04-16

Small-angle neutron scattering (SANS) measurements on 0.3M sodium dodecyl sulfate (SDS) micellar solutions have been performed in the presence of n-alcohols, from ethanol to decanol at different alcohol concentrations, 2–10 wt%. The ellipsoid micellar structure which occurred in the 0.3M SDS in aqueous solution with the size range of 30–50 Å has different behavior at various hydrocarbon chain length and concentration of alcohols. At low concentration and short chain-length of alcohols, such as ethanol, propanol, and butanol, the size of micelles reduced and had a spherical-like structure. The opposite effect occurred as medium to long chain alcohols, such as hexanol, octanol and decanol was added into the 0.3M SDS micellar solutions. The micelles structure changed to be more elongated in major axis and then crossed the critical phase transition from micellar solution into liquid crystal phase as lamellar structure emerged by further addition of alcohols. The inter-lamellar distances were also depending on the hydrocarbon chain length and concentration of alcohols. In the meantime, the persistent micellar structures occurred in addition of medium chain of n-alcohol, pentanol at all concentrations.

Structural and phase transition changes of sodium dodecyl sulfate micellar solution in alcohols probed by small-angle neutron scattering (SANS)

International Nuclear Information System (INIS)

Putra, Edy Giri Rachman; Patriati, Arum

2015-01-01

Small-angle neutron scattering (SANS) measurements on 0.3M sodium dodecyl sulfate (SDS) micellar solutions have been performed in the presence of n-alcohols, from ethanol to decanol at different alcohol concentrations, 2–10 wt%. The ellipsoid micellar structure which occurred in the 0.3M SDS in aqueous solution with the size range of 30–50 Å has different behavior at various hydrocarbon chain length and concentration of alcohols. At low concentration and short chain-length of alcohols, such as ethanol, propanol, and butanol, the size of micelles reduced and had a spherical-like structure. The opposite effect occurred as medium to long chain alcohols, such as hexanol, octanol and decanol was added into the 0.3M SDS micellar solutions. The micelles structure changed to be more elongated in major axis and then crossed the critical phase transition from micellar solution into liquid crystal phase as lamellar structure emerged by further addition of alcohols. The inter-lamellar distances were also depending on the hydrocarbon chain length and concentration of alcohols. In the meantime, the persistent micellar structures occurred in addition of medium chain of n-alcohol, pentanol at all concentrations

Polarographic behaviour and determination of uranium(VI) in alcoholic solutions from organic extraction phases

International Nuclear Information System (INIS)

Degueldre, C.; Taibi, K.

1996-01-01

The determination of U(VI) in organic extraction phases: hydrocarbon-diethyl-2-hexyl phosphoric acid-trioctylphosphine oxide and hydrocarbon-tri-n-octylamine, diluted by an alcohol has been studied by direct current polarography, as well as by differential pulse polarography (DPP). In order to optimise the analytical procedure, miscibility and conductivity studies of the mixtures hydrocarbon-alcohol (ethanol, n- and isopropanol and n- and isobutanol) were made after addition of sulphuric acid as a supporting electrolyte. In the solutions of sulphuric acid in the alcohol-extractant-hydrocarbon phases, U(VI) gives rise to well defined polarograms. Its electroreduction involves a single electron step in all cases. The DPP peak height is proportional to the U(VI) concentration between 2x10 -6 and 2x10 -3 M, and the 3σ detection limit is ca. 10 -6 M

Sample-averaged biexciton quantum yield measured by solution-phase photon correlation.

Science.gov (United States)

Beyler, Andrew P; Bischof, Thomas S; Cui, Jian; Coropceanu, Igor; Harris, Daniel K; Bawendi, Moungi G

2014-12-10

The brightness of nanoscale optical materials such as semiconductor nanocrystals is currently limited in high excitation flux applications by inefficient multiexciton fluorescence. We have devised a solution-phase photon correlation measurement that can conveniently and reliably measure the average biexciton-to-exciton quantum yield ratio of an entire sample without user selection bias. This technique can be used to investigate the multiexciton recombination dynamics of a broad scope of synthetically underdeveloped materials, including those with low exciton quantum yields and poor fluorescence stability. Here, we have applied this method to measure weak biexciton fluorescence in samples of visible-emitting InP/ZnS and InAs/ZnS core/shell nanocrystals, and to demonstrate that a rapid CdS shell growth procedure can markedly increase the biexciton fluorescence of CdSe nanocrystals.

Excited-state dynamics of a ruthenium(II) catalyst studied by transient photofragmentation in gas phase and transient absorption in solution

Energy Technology Data Exchange (ETDEWEB)

Imanbaew, D.; Nosenko, Y. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Kerner, C. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Chevalier, K.; Rupp, F. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Riehn, C., E-mail: riehn@chemie.uni-kl.de [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Thiel, W.R. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Diller, R. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany)

2014-10-17

Graphical abstract: - Highlights: • Ultrafast dynamics of new Ru(II) catalysts investigated in gas phase and solution. • Catalyst activation (HCl loss) achieved in ion trap by UV photoexcitation. • Electronic relaxation proceeds by IVR and IC followed by ground state dissociation. • No triplet formation in contrast to other Ru-polypyridine complexes. • Solvent prohibits catalyst activation in solution by fast vibrational cooling. - Abstract: We report studies on the excited state dynamics of new ruthenium(II) complexes [(η{sup 6}-cymene)RuCl(apypm)]PF{sub 6} (apypm=2-NR{sub 2}-4-(pyridine-2-yl)-pyrimidine, R=CH{sub 3} (1)/H (2)) which, in their active form [1{sup +}-HCl] and [2{sup +}-HCl], catalyze the transfer hydrogenation of arylalkyl ketones in the absence of a base. The investigations encompass femtosecond pump–probe transient mass spectrometry under isolated conditions and transient absorption spectroscopy in acetonitrile solution, both on the cations [(η{sup 6}-cymene)RuCl(apypm)]{sup +} (1{sup +}, 2{sup +}). Gas phase studies on mass selected ions were performed in an ESI ion trap mass spectrometer by transient photofragmentation, unambiguously proving the formation of the activated catalyst species [1{sup +}-HCl] or [2{sup +}-HCl] after photoexcitation being the only fragmentation channel. The primary excited state dynamics in the gas phase could be fitted to a biexponential decay, yielding time constants of <100 fs and 1–3 ps. Transient absorption spectroscopy performed in acetonitrile solution using femtosecond UV/Vis and IR probe laser pulses revealed additional deactivation processes on longer time scales (∼7–12 ps). However, the formation of the active catalyst species after photoexcitation could not be observed in solution. The results from both studies are compared to former CID investigations and DFT calculations concerning the activation mechanism.

Statistical solutions of the Navier endash Stokes equations on the phase space of vorticity and the inviscid limits

International Nuclear Information System (INIS)

Constantin, P.; Wu, J.

1997-01-01

Using the methods of Foias [Sem. Math. Univ. Padova 48, 219 endash 343 (1972); 49, 9 endash 123 (1973)] and Vishik endash Fursikov [Mathematical Problems of Statistical Hydromechanics (Kluwer, Dordrecht, 1988)], we prove the existence and uniqueness of both spatial and space endash time statistical solutions of the Navier endash Stokes equations on the phase space of vorticity. Here the initial vorticity is in Yudovich space and the initial measure has finite mean enstrophy. We show under further assumptions on the initial vorticity that the statistical solutions of the Navier endash Stokes equations converge weakly and the inviscid limits are the corresponding statistical solutions of the Euler equations. copyright 1997 American Institute of Physics

Theory and modeling of microstructural evolution in polycrystalline materials: Solute segregation, grain growth and phase transformations

Science.gov (United States)

Ma, Ning

2005-11-01

To accurately predict microstructure evolution and, hence, to synthesis metal and ceramic alloys with desirable properties involves many fundamental as well as practical issues. In the present study, novel theoretical and phase field approaches have been developed to address some of these issues including solute drag and segregation transition at grain boundaries and dislocations, grain growth in systems of anisotropic boundary properties, and precipitate microstructure development in polycrystalline materials. The segregation model has allowed for the prediction of a first-order segregation transition, which could be related to the sharp transition of solute concentration of grain boundary as a function of temperature. The incorporating of interfacial energy and mobility as functions of misorientation and inclination in the phase field model has allowed for the study of concurrent grain growth and texture evolution. The simulation results were analyzed using the concept of local grain boundary energy density, which simplified significantly the development of governing equations for texture controlled grain growth in Ti-6Al-4V. Quantitative phase field modeling techniques have been developed by incorporating thermodynamic and diffusivity databases. The models have been validated against DICTRA simulations in simple 1D problems and applied to simulate realistic microstructural evolutions in Ti-6Al-4V, including grain boundary a and globular a growth and sideplate development under both isothermal aging and continuous cooling conditions. The simulation predictions agree well with experimental observations.

Solid-state transformation of Fe-rich intermetallic phases in Al–5.0Cu–0.6Mn squeeze cast alloy with variable Fe contents during solution heat treatment

Energy Technology Data Exchange (ETDEWEB)

Lin, Bo [School of Mechanical and Automotive Engineering, South China University of Technology, Guangzhou 510640 (China); School of Mechanical Engineering, Gui Zhou University, Guiyang 550000 (China); Zhang, Weiwen, E-mail: mewzhang@scut.edu.cn [School of Mechanical and Automotive Engineering, South China University of Technology, Guangzhou 510640 (China); Zhao, Yuliang; Li, Yuanyuan [School of Mechanical and Automotive Engineering, South China University of Technology, Guangzhou 510640 (China)

2015-06-15

The Al–5.0 wt.% Cu–0.6 wt.% Mn alloys with a variable Fe content were prepared by squeeze casting. Optical microscopy (OM), Deep etching technique, scanning electron microscopy(SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to examine the solid-state transformation of Fe-rich intermetallics during the solution heat treatment. The results showed that the Chinese script-like α-Fe, Al{sub 6}(FeMn) and needle-like Al{sub 3}(FeMn) phases transform to a new Cu-rich β-Fe (Al{sub 7}Cu{sub 2}(FeMn)) phase during solution heat treatment. The possible reaction and overall transformation kinetics of the solid-state phase transformation for the Fe-rich intermetallics were investigated. - Graphical abstract: Display Omitted - Highlights: • The α-Fe, Al{sub 6}(FeMn) and Al{sub 3}(FeMn) phases change to the β-Fe phases. • Possible reactions of Fe phases during solution heat treatment are discussed. • The overall fractional transformation rate follows an Avrami curve.

Liquid-phase epitaxy of InGaAsP solid solutions on profiled substrates of InP(100)

International Nuclear Information System (INIS)

Dvoryankin, V.F.; Kaevitser, L.R.; Komarov, A.A.; Telegin, A.A.; Khusid, L.B.; Chernushin, M.D.

1990-01-01

Peculiarities of selective growth of InGaAsP solid solutions under liquid-phase epitaxy in shallow grooves are considered. InGaAsP crystals grown in grooves oriented along crystallografic [110] and [011] directions are determined to trend to equilibrium form under two-phase epitaxy, while wedge-shaped form of In 0.77 Ga 0.23 As 0.53 P 0.45 and In 0.53 P o.45 and IN 0.59 Ga 0.41 As 0.83 P 0.12 epitaxial layers obtained in grooves is determined by their composition only and does not depend on groove configuration

The use of linear expressions of solute boiling point versus retention to indicate special interactions with the molecular rings of modified cyclodextrin phases in gas chromatography

Science.gov (United States)

Betts

2000-08-01

The boiling points (degrees C, 1 x 10) of diverse C10 polar solutes from volatile oils are set against their relative retention times versus n-undecane to calculate linear equations for 12 commercial modified cyclodextrin (CD) capillary phases. Ten data points are considered for each CD, then solutes are rejected until 5 or more remain that give an expression with a correlation coefficient of at least 0.990 and a standard deviation of less than 5.5. Three phases give almost perfect correlation, and 3 other CDs have difficulty complying. Solutes involved in the equations (most frequently cuminal, linalol, and carvone) are presumed to have a 'standard' polar transient interaction with the molecular rings of the CDs concerned. Several remaining solutes (mostly citral, fenchone, and menthol) exhibit extra retention over the calculated standard (up to 772%), which is believed to indicate a firm 'host' CD or 'guest' solute molecular fit in some cases. Other solutes show less retention than calculated (mostly citronellal, citronellol, estragole, and pulegone). This suggests rejection by the CD, which behaves merely as a conventional stationary phase to them. The intercept constant in the equation for each phase is suggested to be a numerical relative polarity indicator. These b values indicate that 3 hydroxypropyl CDs show the most polarity with values from 28 to 43; and CDs that are fully substituted with inert groups fall in the range of 15 to 20.

The salting-out effect and phase separation in aqueous solutions of tri-sodium citrate and 1-butyl-3-methylimidazolium bromide

Energy Technology Data Exchange (ETDEWEB)

Sadeghi, Rahmat, E-mail: rsadeghi@uok.ac.i [Department of Chemistry, University of Kurdistan, Sanandaj (Iran, Islamic Republic of); Golabiazar, Roonak [Department of Chemistry, University of Kurdistan, Sanandaj (Iran, Islamic Republic of); Shekaari, Hemayat [Department of Chemistry, Faculty of Science, University of Mohaghegh Ardabili, Ardabil (Iran, Islamic Republic of)

2010-04-15

The aim of this work is to obtain further evidence about the salting-out effect produced by the addition of tri-sodium citrate to aqueous solutions of water miscible ionic liquid 1-butyl-3-methylimidazolium bromide ([C{sub 4}mim][Br]) by evaluating the effect of tri-sodium citrate on the thermodynamic properties of aqueous solutions of this ionic liquid. Experimental measurements of density and sound velocity at different temperatures ranging from (288.15 to 308.15) K, the refractive index at 308.15 K and the liquid-liquid phase diagram at different temperatures ranging from (288.15 to 338.15) K for aqueous solutions containing 1-butyl-3-methylimidazolium bromide ([C{sub 4}mim][Br]) and tri-sodium citrate (Na{sub 3}Cit) are taken. The apparent molar volume of transfer of [C{sub 4}mim][Br] from water to aqueous solutions of Na{sub 3}Cit have positive values and it increases by increasing salt molality. Although at high IL molality, the apparent molar isentropic compressibility shows similar behaviour with that of the apparent molar volume. However at low concentrations of IL, the apparent molar isentropic compressibility of transfer of [C{sub 4}mim][Br] from water to aqueous solutions of Na{sub 3}Cit have negative values. The effects of temperature and the addition of Na{sub 3}Cit and [C{sub 4}mim][Br] on the liquid-liquid phase diagram of the investigated system have been studied. It was found that an increase in temperature caused the expansion of the one-phase region. The presence of Na{sub 3}Cit triggers a salting-out effect, leading to significant upward shifts of the liquid-liquid de-mixing temperatures of the system. The effect of temperature on the phase-forming ability in the system investigated has been studied based on a salting-out coefficient obtained from fitting the binodal values to a Setschenow-type equation for each temperature. Based on cloud point values, the energetics of the clouding process have been estimated and it was found that both of

Solution and gas phase evidence of anion binding through the secondary bonding interactions of a bidentate bis-antimony(iii) anion receptor.

Science.gov (United States)

Qiu, J; Song, B; Li, X; Cozzolino, A F

2017-12-20

The solution and gas phase halide binding to a bis-antimony(iii) anion receptor was studied. This new class of anion receptors utilizes the strong Sb-centered secondary bonding interactions (SBIs) that are formed opposite to the polar Sb-O primary bond. 1 H NMR titration data were fitted statistically to binding models and solution-phase binding energetics were extracted, while the formation of anion-to-receptor complexes was observed using ESI-MS. Density functional theory calculations suggest that their affinity towards binding halide anions is mitigated by the strong explicit solvation effect in DMSO, which gives insights into future designs that circumvent direct solvent binding and are anticipated to yield tighter and perhaps more selectivity in anion binding.

Hydro-dynamic Solute Transport under Two-Phase Flow Conditions.

Science.gov (United States)

Karadimitriou, Nikolaos K; Joekar-Niasar, Vahid; Brizuela, Omar Godinez

2017-07-26

There are abundant examples of natural, engineering and industrial applications, in which "solute transport" and "mixing" in porous media occur under multiphase flow conditions. Current state-of-the-art understanding and modelling of such processes are established based on flawed and non-representative models. Moreover, there is no direct experimental result to show the true hydrodynamics of transport and mixing under multiphase flow conditions while the saturation topology is being kept constant for a number of flow rates. With the use of a custom-made microscope, and under well-controlled flow boundary conditions, we visualized directly the transport of a tracer in a Reservoir-on-Chip (RoC) micromodel filled with two immiscible fluids. This study provides novel insights into the saturation-dependency of transport and mixing in porous media. To our knowledge, this is the first reported pore-scale experiment in which the saturation topology, relative permeability, and tortuosity were kept constant and transport was studied under different dynamic conditions in a wide range of saturation. The critical role of two-phase hydrodynamic properties on non-Fickian transport and saturation-dependency of dispersion are discussed, which highlight the major flaws in parametrization of existing models.

Synthetic study on cystinyl peptides using solution and solid phase metodology: human IgG1 hinge region

Czech Academy of Sciences Publication Activity Database

Niederhafner, Petr; Gut, Vladimír; Ježek, Jan; Buděšínský, Miloš; Kašička, Václav; Wünsch, Erich; Hlaváček, Jan

2010-01-01

Roč. 39, č. 3 (2010), s. 641-650 ISSN 0939-4451 R&D Projects: GA ČR GA203/03/1362; GA ČR GA203/07/1517 Institutional research plan: CEZ:AV0Z40550506 Keywords : hinge region * immunoglobulin * prion protein * solution synthesis * solid phase synthesis Subject RIV: CC - Organic Chemistry Impact factor: 4.106, year: 2010

Facile room-temperature solution-phase synthesis of a spherical covalent organic framework for high-resolution chromatographic separation.

Science.gov (United States)

Yang, Cheng-Xiong; Liu, Chang; Cao, Yi-Meng; Yan, Xiu-Ping

2015-08-07

A simple and facile room-temperature solution-phase synthesis was developed to fabricate a spherical covalent organic framework with large surface area, good solvent stability and high thermostability for high-resolution chromatographic separation of diverse important industrial analytes including alkanes, cyclohexane and benzene, α-pinene and β-pinene, and alcohols with high column efficiency and good precision.

Opalescence in monoclonal antibody solutions and its correlation with intermolecular interactions in dilute and concentrated solutions.

Science.gov (United States)

Raut, Ashlesha S; Kalonia, Devendra S

2015-04-01

Opalescence indicates physical instability of a formulation because of the presence of aggregates or liquid-liquid phase separation in solution and has been reported for monoclonal antibody (mAb) formulations. Increased solution opalescence can be attributed to attractive protein-protein interactions (PPIs). Techniques including light scattering, AUC, or membrane osmometry are routinely employed to measure PPIs in dilute solutions, whereas opalescence is seen at relatively higher concentrations, where both long- and short-range forces contribute to overall PPIs. The mAb molecule studied here shows a unique property of high opalescence because of liquid-liquid phase separation. In this study, opalescence measurements are correlated to PPIs measured in diluted and concentrated solutions using light scattering (kD ) and high-frequency rheology (G'), respectively. Charges on the molecules were calculated using zeta potential measurements. Results indicate that high opalescence and phase separation are a result of the attractive interactions in solution; however, the presence of attractive interactions do not always imply phase separation. Temperature dependence of opalescence suggests that thermodynamic contribution to opalescence is significant and Tcloud can be utilized as a potential tool to assess attractive interactions in solution. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

High temperature aqueous potassium and sodium phosphate solutions: two-liquid-phase boundaries and critical phenomena, 275-4000C; potential applications for steam generators

International Nuclear Information System (INIS)

Marshall, W.L.

1981-12-01

Two-liquid-phase boundaries at temperatures between 275 and 400 0 C were determined for potassium phosphate and sodium phosphate aqueous solutions for compositions from 0 to 60 wt % dissolved salt. The stoichiometric mole ratios, K/PO 4 or Na/PO 4 , were varied from 1.00 to 2.12 and from 1.00 to 2.16 for the potassium and sodium systems, respectively. Liquid-vapor critical temperatures were also determined for most of the dilute liquid phases that formed. The minimum temperatures (below which a single solution existed) of two-liquid-phase formation were 360 0 C for the potassium system and 279 0 C for the sodium system at mole ratios of 2.00 and 2.16, respectively. For the sodium system at mole ratios greater than 2.16, solids crystallized at lower temperatures as expected from earlier studies. In contrast, potassium solutions that were explored at mole ratios from 2.12 to 3.16 and at temperatures below 360 0 C did not produce solid phases nor liquid-liquid immiscibilities. Aside from the generally unusual observations of two immiscible liquids in an aqueous inorganic salt system, the results could possibly be applied to the use of phosphate additives in steam power generators. 16 refs

Liquid-phase and vapor-phase dehydration of organic/water solutions

Science.gov (United States)

Huang, Yu [Palo Alto, CA; Ly, Jennifer [San Jose, CA; Aldajani, Tiem [San Jose, CA; Baker, Richard W [Palo Alto, CA

2011-08-23

Processes for dehydrating an organic/water solution by pervaporation or vapor separation using fluorinated membranes. The processes are particularly useful for treating mixtures containing light organic components, such as ethanol, isopropanol or acetic acid.

Ultrafast excited-state relaxation of a binuclear Ag(i) phosphine complex in gas phase and solution.

Science.gov (United States)

Kruppa, S V; Bäppler, F; Klopper, W; Walg, S P; Thiel, W R; Diller, R; Riehn, C

2017-08-30

The binuclear complex [Ag 2 (dcpm) 2 ](PF 6 ) 2 (dcpm = bis(dicyclohexylphosphino)methane) exhibits a structure with a close silver-silver contact mediated by the bridging ligand and thus a weak argentophilic interaction. Upon electronic excitation this cooperative effect is strongly increased and determines the optical and luminescence properties of the compound. We have studied here the ultrafast electronic dynamics in parallel in gas phase by transient photodissociation and in solution by transient absorption. In particular, we report the diverse photofragmentation pathways of isolated [Ag 2 (dcpm) 2 ] 2+ in an ion trap and its gas phase UV photodissociation spectrum. By pump-probe fragmentation action spectroscopy (λ ex = 260 nm) in the gas phase, we have obtained fragment-specific transients which exhibit a common ultrafast multiexponential decay. This is fitted to four time constants (0.6/5.8/100/>1000 ps), highlighting complex intrinsic photophysical processes. Remarkably, multiexponential dynamics (0.9/8.5/73/604 ps) are as well found for the relaxation dynamics in acetonitrile solution. Ab initio calculations at the level of approximate coupled-cluster singles-doubles (CC2) theory of ground and electronically excited states of the reduced model system [Ag 2 (dmpm) 2 ] 2+ (dmpm = bis(dimethylphosphino)methane) indicate a shortening of the Ag-Ag distance upon excitation by 0.3-0.4 Å. In C 2 geometry two close-lying singlet states S 1 ( 1 MC(dσ*-pπ), 1 B, 4.13 eV) and S 2 ( 1 MC(dσ*-pσ), 1 A, 4.45 eV) are found. The nearly dark S 1 state has not been reported so far. The excitation of the S 2 state carries a large oscillator strength for the calculated vertical transition (266 nm). Two related triplets are calculated at T 1 (3.87 eV) and T 2 (3.90 eV). From these findings we suggest possible relaxation pathways with the two short time constants ascribed to ISC/IVR and propose from the obtained similar values in gas phase that the fast solution dynamics

Liquid-liquid phase separation in dilute solutions of poly(styrene sulfonate) with multivalent cations: Phase diagrams, chain morphology, and impact of temperature

Science.gov (United States)

Hansch, Markus; Hämisch, Benjamin; Schweins, Ralf; Prévost, Sylvain; Huber, Klaus

2018-01-01

The dilute solution behavior of sodium poly(styrene sulfonate) is studied in the presence of trivalent Al3+ and bivalent Ba2+ cations at various levels of excess NaCl. The study evaluates the phase behavior and the morphology of the polyelectrolyte chains with increasing extent of decoration with the Al3+ and Ba2+ cations and analyses the effect of temperature on these decorated chains. The phase behavior is presented in the form of the cation concentration versus the respective poly(styrene sulfonate) concentration, recorded at the onset of precipitation. Whereas poly(styrene sulfonate) with Al3+ exhibits a linear phase boundary, denoted as the "threshold line," which increases with increasing poly(styrene sulfonate) concentration, Ba2+ cations show a threshold line which is independent of the poly(styrene sulfonate) concentration. An additional re-entrant phase, at considerably higher cation content than those of the threshold lines, is observed with Al3+ cations but not with Ba2+ cations. The threshold line and the re-entrant phase boundary form parts of the liquid-liquid phase boundary observed at the limit of low polymer concentration. The dimensions of the polyelectrolyte chains shrink considerably while approaching the respective threshold lines on increase of the Al3+ and Ba2+ cation content. However, subtle differences occur between the morphological transformation induced by Al3+ and Ba2+. Most strikingly, coils decorated with Al3+ respond very differently to temperature variations than coils decorated with Ba2+ do. As the temperature increases, the poly(styrene sulfonate) chains decrease their size in the presence of Al3+ cations but increase in size in the presence of Ba2+ cations.

Relating hydrogen-bonding interactions with the phase behavior of naproxen/PVP K 25 solid dispersions: evaluation of solution-cast and quench-cooled films.

Science.gov (United States)

Paudel, Amrit; Nies, Erik; Van den Mooter, Guy

2012-11-05

In this work, we investigated the relationship between various intermolecular hydrogen-bonding (H-bonding) interactions and the miscibility of the model hydrophobic drug naproxen with the hydrophilic polymer polyvinylpyrrolidone (PVP) across an entire composition range of solid dispersions prepared by quasi-equilibrium film casting and nonequilibrium melt quench cooling. The binary phase behavior in solid dispersions exhibited substantial processing method dependence. The solid state solubility of crystalline naproxen in PVP to form amorphous solid dispersions was 35% and 70% w/w naproxen in solution-cast films and quench-cooled films, respectively. However, the presence of a single mixed phase glass transition indicated the amorphous miscibility to be 20% w/w naproxen for the films, beyond which amorphous-amorphous and/or crystalline phase separations were apparent. This was further supported by the solution state interactions data such as PVP globular size distribution and solution infrared spectral profiles. The borderline melt composition showed cooling rate dependence of amorphization. The glass transition and melting point depression profiles of the system were treated with the analytical expressions based on Flory-Huggins mixing theory to interpolate the equilibrium solid solubility. FTIR analysis and subsequent spectral deconvolution revealed composition and miscibility dependent variations in the strength of drug-polymer intermolecular H-bonding. Two types of H-bonded populations were evidenced from 25% w/w and 35% w/w naproxen in solution-cast films and quench-cooled films, respectively, with the higher fraction of strongly H-bonded population in the drug rich domains of phase separated amorphous film compositions and highly drug loaded amorphous quench-cooled dispersions.

XI International conference Problems of solvation and complex formation in solutions, and VI Conference of young scientists Theoretical and experimental chemistry of liquid-phase systems (Krestovsky readings). Summary of reports

International Nuclear Information System (INIS)

2011-01-01

The collection contains materials of plenary, sectional and poster sessions, presented at the XI International conference Problems of solvation and complex formation in solutions, and VI Conference of young scientists Theoretical and experimental chemistry of liquid-phase systems (Krestovsky readings). Theoretical questions and new experimental methods of chemistry of solutions, structure and dynamics of molecular and ion-molecular systems in solution and at the phase boundary; modern aspects of applied chemistry of solutions are discussed [ru

Crystal phase evolution of TiO2 nanoparticles with reaction time in acidic solutions studied via freeze-drying method

International Nuclear Information System (INIS)

Shin, Hyunho; Jung, Hyun Suk; Hong, Kug Sun; Lee, Jung-Kun

2005-01-01

The crystal phase evolution of TiO 2 nanoparticles, during hydrolysis and condensation of titanium tetraisopropoxide, was quenched at various reaction times by a freeze-drying method, followed by various characterizations. Three types of solutions with different acid input times were studied: (1) addition in infinite time (no addition) (2) addition at 24h after the hydrolysis/condensation reaction started, and (3) addition from the beginning of the reaction. The acid-free solution yielded amorphous TiO 2 , which transformed to anatase very slowly. The acid input in 24h resulted in a fast transformation of amorphous to a metastable anatase having a highly distorted atomic arrangement: thereby its transformation to a more stable phase, rutile, was suitable. The acid addition from the beginning of the reaction yielded the formation of a relatively stable anatase from the hydrolysis seed, thereby the subsequent transformation to rutile was sluggish

Discovery of a thermally persistent h.c.p. solid-solution phase in the Ni-W system

International Nuclear Information System (INIS)

Kurz, S. J. B.; Leineweber, A.; Maisel, S. B.; Höfler, M.; Müller, S.; Mittemeijer, E. J.

2014-01-01

Although the accepted Ni-W phase diagram does not reveal the existence of h.c.p.-based phases, h.c.p.-like stacking sequences were observed in magnetron-co-sputtered Ni-W thin films at W contents of 20 to 25 at. %, by using transmission electron microscopy and X-ray diffraction. The occurrence of this h.c.p.-like solid-solution phase could be rationalized by first-principles calculations, showing that the vicinity of the system's ground-state line is populated with metastable h.c.p.-based superstructures in the intermediate concentration range from 20 to 50 at. % W. The h.c.p.-like stacking in Ni-W films was observed to be thermally persistent, up to temperatures as high as at least 850 K, as evidenced by extensive X-ray diffraction analyses on specimens before and after annealing treatments. The tendency of Ni-W for excessive planar faulting is discussed in the light of these new findings

Efficient and Safe Chemical Gas Generators with Nanocomposite Reactive Materials

Science.gov (United States)

2015-11-30

thermolysis and hydrolysis . This reaction also releases hydrogen from water, thus increasing the total hydrogen yield. The investigation of iodine...for AB thermolysis and hydrolysis . This reaction also releases hydrogen from water, thus increasing the total hydrogen yield. Experiments have... hydrogen yield. The isotopic tests have shown that AB participates in two parallel processes − thermolysis and hydrolysis . Because of this, as much as 88

Closed-form solution for the Wigner phase-space distribution function for diffuse reflection and small-angle scattering in a random medium.

Science.gov (United States)

Yura, H T; Thrane, L; Andersen, P E

2000-12-01

Within the paraxial approximation, a closed-form solution for the Wigner phase-space distribution function is derived for diffuse reflection and small-angle scattering in a random medium. This solution is based on the extended Huygens-Fresnel principle for the optical field, which is widely used in studies of wave propagation through random media. The results are general in that they apply to both an arbitrary small-angle volume scattering function, and arbitrary (real) ABCD optical systems. Furthermore, they are valid in both the single- and multiple-scattering regimes. Some general features of the Wigner phase-space distribution function are discussed, and analytic results are obtained for various types of scattering functions in the asymptotic limit s > 1, where s is the optical depth. In particular, explicit results are presented for optical coherence tomography (OCT) systems. On this basis, a novel way of creating OCT images based on measurements of the momentum width of the Wigner phase-space distribution is suggested, and the advantage over conventional OCT images is discussed. Because all previous published studies regarding the Wigner function are carried out in the transmission geometry, it is important to note that the extended Huygens-Fresnel principle and the ABCD matrix formalism may be used successfully to describe this geometry (within the paraxial approximation). Therefore for completeness we present in an appendix the general closed-form solution for the Wigner phase-space distribution function in ABCD paraxial optical systems for direct propagation through random media, and in a second appendix absorption effects are included.

Stability of Naturally Relevant Ternary Phases in the Cu–Sn–S system in Contact with an Aqueous Solution

Directory of Open Access Journals (Sweden)

Andrea Giaccherini

2016-07-01

Full Text Available A relevant research effort is devoted to the synthesis and characterization of phases belonging to the ternary system Cu–Sn–S, mainly for their possible applications in semiconductor technology. Among all ternary phases, kuramite, Cu3SnS4, mohite, Cu2SnS3, and Cu4Sn7S16 have attracted the highest interest. Numerous studies were carried out claiming for the description of new phases in the ternary compositional field. In this study, we revise the existing literature on this ternary system, with a special focus on the phases stable in a temperature range at 25 °C. The only two ternary phases observed in nature are mohite and kuramite. Their occurrence is described as very rare. A numerical modelling of the stable solid phases in contact with a water solution was underwent to define stability relationships of the relevant phases of the system. The numerical modelling of the Eh-pH diagrams was carried out through the phreeqc software with the lnll.dat thermodynamic database. Owing to the complexity of this task, the subsystems Cu–O–H, Sn–O–H, Cu–S–O–H and Sn–S–O–H were firstly considered. The first Pourbaix diagram for the two naturally relevant ternary phases is then proposed.

Classical solutions for a one phase osmosis model

NARCIS (Netherlands)

Lippoth, F.; Prokert, G.

2011-01-01

For a moving boundary problem modelling the motion of a semipermeable membrane by osmotic pressure and surface tension we prove the existence and uniqueness of classical solutions on small time intervals. Moreover, we construct solutions existing on arbitrary long time intervals, provided the

Thermotropic phase transition in aqueous polymer solutions and gels as studied by .sup.1./sup.H NMR methods

Czech Academy of Sciences Publication Activity Database

Spěváček, Jiří; Hanyková, L.; Starovoytova, L.; Ilavský, Michal

2002-01-01

Roč. 2, č. 3 (2002), s. 36-43 ISSN 1335-8243 R&D Projects: GA AV ČR IAA4050209 Grant - others:GA UK(XC) 164/2001B Institutional research plan: CEZ:AV0Z4050913 Keywords : thermotropic phase transition * collapse * D 2 O solutions and gels Subject RIV: CD - Macromolecular Chemistry

Application of Surfactant Micellar Solutions as Extractants and Mobile Phases for TLC-Determination of Purine Bases and Doping Agents in Biological Liquids

Directory of Open Access Journals (Sweden)

Daria Victorovna Yedamenko

2015-04-01

Full Text Available Separation of caffeine and its metabolites (theophylline and theobromine and doping agents (spironolactone, propranolol, and ephedrine and determination of caffeine in serum sample and propranolol and ephedrine in urine were studied on normal-phase thin layers (“Sorbfil-UV-254”. Aqueous organic solvents and aqueous micellar surfactant solutions were compared as the mobile phases for separation. The acceptable separation of purine bases and doping agents was achieved by micellar Thin Layer Chromatography and normal-phase Thin Layer Chromatography. Anionic surfactant solution with added 1-propanol was the best eluent as for caffeine, theophylline, and theobromine separation, as for doping agents. The best characteristics of caffeine extraction from serum, and propranolol and ephedrine from urine were achieved when micellar eluent based on non-ionic Tween-80 surfactant was used. DOI: http://dx.doi.org/10.17807/orbital.v7i1.632

Thermogravimetric analysis of phase transitions in cement compositions mixed by sodium silicate solution

Directory of Open Access Journals (Sweden)

Fedosov Sergey Viktorovich

2014-01-01

Full Text Available This paper presents a study of the capability to modify cement by mechanical activation of sodium silicate water solution. Admixtures or blends of binding agents were employed for modifying concrete properties. The liquid glass is applied to protect from chemically or physically unfavorable environmental impacts, such as acidic medium and high temperature. The sodium silicate is a high-capacity setting accelerator. The increasing of the liquid glass proportion in the mix leads to the degradation of the cement paste plasticity and for this reason it is necessary to reduce the amount of liquid glass in the cement paste. The activation of dilute water solution of sodium silicate into rotary pulsating apparatus directly before tempering of the cement paste is an effective way to decrease mass fraction of liquid glass in the cement paste. The results of the combined influence of liquid glass and mechanical activation on physicochemical processes taking place in cement stone are represented in this research. Thermogravimetric analysis was used in order to study cement blends. Thermogravimetric analysis of modified cement stone assays was performed by thermo analyzer SETARAM TGA 92-24. The results of the analysis of phase transition taking place under high-temperature heating of cement stone modified by the mechanical activation of the water solution of the sodium silicate were introduced. Thermograms of cement stone assays were obtained at different hardening age. The comparison of these thermograms allows us to come to a conclusion on the formation and the retention during long time of a more dense structure of the composite matrix mixed by the mechanical activation of sodium silicate water solution. The relation between the concrete composition and its strength properties was stated. Perhaps, the capability of modified concrete to keep calcium ions in sparingly soluble hydrosilicates leads to the increase in its durability and corrosion resistance.

The phase diagram and magnetic properties of Co and Ti co-doped (1−x)BiFeO_3–xLaFeO_3 solid solutions

International Nuclear Information System (INIS)

Wu, Jiangtao; Xu, Jun; Li, Nan; Jiang, Yaqi; Xie, Zhaoxiong

2015-01-01

Single phase Co and Ti co-doped Bi_1_−_xFeO_3−La_xFeO_3 (x = 0–1) solid solutions were prepared by the sol–gel method. Room temperature x-ray powder diffraction (XRD) patterns showed that the structures of as-prepared Bi_1_−_xLa_xFe_0_._9_0Co_0_._0_5Ti_0_._0_5O_3 solid solutions transformed from rhombohedral R3c to tetragonal P4mm and then to orthorhombic Pnma, with increasing La concentration from 0 to 1. In situ high-temperature XRD (HTXRD) analysis further revealed that rhombohedral structure R3c (x ≤ 0.16) and tetragonal structure P4mm (0.17 ≤ x ≤ 0.40) changed to orthorhombic Pnma along with increasing temperature, and the phase transition temperature decreased with the increase of La doping concentration. However, the orthorhombic structure Pnma (x ≥ 0.41) kept stable even when the temperature reached 850 °C. The phase diagram of as-prepared binary solid solutions of Bi_1_−_xLa_xFe_0_._9_0Co_0_._0_5Ti_0_._0_5O_3(x = 0–1) was drawn on the basis of XRD and HTXRD analysis. Magnetic measurement revealed that the magnetic properties are greatly enhanced with the increase of La content. - Highlights: • Single phase Co and Ti co-doped (1−x)BiFeO_3–xLaFeO_3 (x = 0–1) solid solutions were synthesized. • The phase transitions were investigated by tuning composition and temperature. • Phase diagram was constructed according to the results of XRD for the first time. • The magnetization of solid solution can be enhanced when increasing La content.

Directly relating gas-phase cluster measurements to solution-phase hydrolysis, the absolute standard hydrogen electrode potential, and the absolute proton solvation energy.

Science.gov (United States)

Donald, William A; Leib, Ryan D; O'Brien, Jeremy T; Williams, Evan R

2009-06-08

Solution-phase, half-cell potentials are measured relative to other half-cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline-earth or transition-metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M(H(2)O)(24)(2+)(g) + e(-)(g)-->M(H(2)O)(24)(+)(g) and 2) M(H(2)O)(24)(2+)(g) + e(-)(g)-->MOH(H(2)O)(23)(+)(g) + H(g) and the hydrogen atom affinities of MOH(H(2)O)(23)(+)(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29 V vs. e(-)(g) (standard deviation of 0.02 V) and a real proton solvation free energy of -265 kcal mol(-1) are obtained. With this method, the absolute SHE potential can be obtained from a one-electron reduction of nanodrops containing divalent ions that are not observed to undergo one-electron reduction in aqueous solution.

Nanoscale phase transition behavior of shape memory alloys — closed form solution of 1D effective modelling

Science.gov (United States)

Li, M. P.; Sun, Q. P.

2018-01-01

We investigate the roles of grain size (lg) and grain boundary thickness (lb) on the stress-induced phase transition (PT) behaviors of nanocrystalline shape memory alloys (SMAs) by using a Core-shell type "crystallite-amorphous composite" model. A non-dimensionalized length scale lbarg(=lg /lb) is identified as the governing parameter which is indicative of the energy competition between the crystallite and the grain boundary. Closed form analytical solutions of a reduced effective 1D model with embedded microstructure length scales of lg and lb are presented in this paper. It is shown that, with lbarg reduction, the energy of the elastic non-transformable grain boundary will gradually become dominant in the phase transition process, and eventually bring fundamental changes of the deformation behaviors: breakdown of two-phase coexistence and vanishing of superelastic hysteresis. The predictions are supported by experimental data of nanocrystalline NiTi SMAs.

Ions, solutes and solvents, oh my!

Energy Technology Data Exchange (ETDEWEB)

Kemp, Daniel David [Iowa State Univ., Ames, IA (United States)

2009-08-01

Modern methods in ab initio quantum mechanics have become efficient and accurate enough to study many gas-phase systems. However, chemists often work in the solution phase. The presence of solvent molecules has been shown to affect reaction mechanisms1, lower reaction energy barriers2, participate in energy transfer with the solute3 and change the physical properties of the solute4. These effects would be overlooked in simple gas phase calculations. Careful study of specific solvents and solutes must be done in order to fully understand the chemistry of the solution phase. Water is a key solvent in chemical and biological applications. The properties of an individual water molecule (a monomer) and the behavior of thousands of molecules (bulk solution) are well known for many solvents. Much is also understood about aqueous microsolvation (small clusters containing ten water molecules or fewer) and the solvation characteristics when bulk water is chosen to solvate a solute. However, much less is known about how these properties behave as the cluster size transitions from the microsolvated cluster size to the bulk. This thesis will focus on species solvated with water clusters that are large enough to exhibit the properties of the bulk but small enough to consist of fewer than one hundred solvent molecules. New methods to study such systems will also be presented.

Solubility and phase separation of 4-morpholinepropanesulfonic acid (MOPS), and 3-morpholino-2-hydroxypropanesulfonic acid (MOPSO) in aqueous 1,4-dioxane and ethanol solutions

International Nuclear Information System (INIS)

Taha, Mohamed; Lee, Ming-Jer

2011-01-01

Highlights: → Solubilities of MOPS and MOPSO buffers in aqueous 1,4-dioxane and ethanol solutions. → We found that MOPS-induced phase separation of aqueous solution of 1,4-dioxane. → The phase diagram of (MOPS + water + 1,4-dioxane) system at 298.15 K is documented. → The tie-lines within the two-liquid phase region were also determined at 298.15 K. → The effective excluded volume theory was applied to correlate the binodal LLE data. - Abstract: The buffers 4-morpholinepropanesulfonic acid (MOPS) and 3-morpholino-2-hydroxypropanesulfonic acid (MOPSO) are useful biological zwitterionic buffers within the pH range of 6.5 to 7.9 and 6.2 to 7.6, respectively. The solubilities of these buffers were determined in binary mixtures (1,4-dioxane + water) and (ethanol + water) at T = 298.15 K by using the results of density measurements. It has been observed that MOPS induced liquid-liquid phase splitting for the mixtures of 40% to 90% (w/w) 1,4-dioxane in water. The two-liquid phase formation was visualized with disperse orange 25. The phase equilibrium boundaries, including the regions of one liquid, two liquids, (one liquid + one solid) and (two liquids + one solid), for the (MOPS + water + 1,4-dioxane) system have been determined experimentally at T = 298.15 K. The tie lines of the (liquid + liquid) equilibrium were also measured. The Othmer-Tobias and Bancroft equation were used to evaluate the reliability of the tie-line data. The binodal curve was fitted to an empirical equation and the effective excluded volume (EEV) model. The apparent free energies of transfer (ΔG tr ' ) of MOPS and MOPSO from water to 1,4-dioxane and ethanol solutions have been calculated from the solubility data. These ΔG tr ' values were compared with those of some related biological buffers (TRIS, TAPS, TAPSO, and TABS). Furthermore, we also calculated the contribution of transfer free energies (Δg tr ' ) of -OH group from water to 1,4-dioxane and ethanol solutions.

Defect and phase stability of solid solutions of Mg2X with an antifluorite structure: An ab initio study

International Nuclear Information System (INIS)

Viennois, Romain; Jund, Philippe; Colinet, Catherine; Tédenac, Jean-Claude

2012-01-01

First principles calculations are done for Mg 2 X (X=Si, Ge or Sn) antifluorite compounds and their solid solutions in order to investigate their pseudo-binary phase diagram. The formation energies of the end-member compounds agree qualitatively with the experiments. For X=Si and Ge, there is a complete solubility, but we observe a miscibility gap in the pseudo-binary phase diagram Mg 2 Si–Mg 2 Sn. This agrees with the most recent experiments and phase diagram assessments. Calculated electronic properties of Mg 2 Si 1−x Sn x alloys qualitatively agree with experiments and in particular the energy bandgap decreases when Si is substituted by Sn. Supercell calculations are also done in order to determine the most stable defects and the doping induced by these defects in the three end-member compounds. We find that the intrinsic n-doping in pure Mg 2 Si can be attributed to the presence of magnesium atoms in interstitial positions. In Mg 2 Ge and Mg 2 Sn, since other defects are stable, they can be also of p-type. - Graphical abstract: Evidence of a miscibility gap from the plot of the formation energy vs x Si (silicon content) for the solid solutions Mg 2 Si–Mg 2 Sn. Highlights: ► First-principles study of the stability of Mg 2 Si–Mg 2 X alloys (X=Ge or Sn) and their defects. ► Mg 2 Si–Mg 2 Ge alloys form a complete series of solid solutions. ► Miscibility gap is found in Mg 2 Si–Mg 2 Sn alloys. ► Interstitial defects are more stable in Mg 2 Si and induce n-doping.

Layout and Optics Solution for the LHC Insertion Upgrade Phase I

CERN Document Server

Fartoukh, S

2010-01-01

The main guidelines of the LHC IR upgrade Phase I project are the development of wider aperture (120 mm) and lower gradient (120 T/m) quadrupoles using the wellcharacterized Nb-Ti technology in order to build new inner triplets (IT) for the ATLAS and CMS experimental insertions, while minimizing the hardware modifications in the other parts of these insertions, in particular leaving unchanged the so-called "matching section" (MS) and "dispersion suppressor" (DS). While one of the initial goal was to squeeze the optics down to a B* of 25 cm, optics solutions with a B* of 30 cm are already at the edge of feasibility, both in terms of the IT and MS mechanical acceptance, gradients of the MS and DS quadrupole magnets, and correctability by the arc sextupoles of the huge chromatic aberrations generated at low B*. The layout of the new inner triplet and the corresponding injection and collision optics will be presented and analyzed in terms of aperture and chromatic correction.

Novel chemistry of alpha-tosyloxy ketones: applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries

DEFF Research Database (Denmark)

Nicolaou, K C; Montagnon, T; Ulven, T

2002-01-01

New synthetic technologies for the preparation and elaboration of alpha-tosyloxy ketones in solution- and on solid-phase are described. Both olefins and ketones serve as precursors to these relatively stable chemical entities: olefins via a novel one-pot epoxidation, arylsulfonic acid displacemen...

Fundamental aspects of nucleation and growth in the solution-phase synthesis of germanium nanocrystals

KAUST Repository

Codoluto, Stephen C.

2010-01-01

Colloidal Ge nanocrystals (NCs) were synthesized via the solution phase reduction of germanium(ii) iodide. We report a systematic investigation of the nanocrystal nucleation and growth as a function of synthesis conditions including the nature of coordinating solvents, surface bound ligands, synthesis duration and temperature. NC synthesis in reaction environments with weakly bound phosphine surface ligand led to the coalescence of nascent particles leading to ensembles with broad lognormal particle diameter distributions. Synthesis in the presence of amine or alkene ligands mitigated particle coalescence. High-resolution transmission electron micrographs revealed that NCs grown in the presence of weak ligands had a high crystal defect density whereas NCs grown in amine solutions were predominantly defect-free. We applied infrared spectroscopy to study the NC surface chemistry and showed that alkene ligands project the NCs from surface oxidation. Photoluminescence spectroscopy measurements showed that alkene ligands passivate surface traps, as indicated by infrared fluorescence, conversely oxidized phosphine and amine passivated NCs did not fluoresce. © 2010 The Royal Society of Chemistry.

Investigation of Processes Controlling Elution of Solutes from Nonaqueous Phase Liquid (NAPL) Pools into Groundwater

Science.gov (United States)

Seyedabbasi, M.; Pirestani, K.; Holland, S. B.; Imhoff, P. T.

2005-12-01

Two major processes influencing the elution of solutes from porous media contaminated with nonaqueous phase liquids (NAPLs) are external mass transfer between the NAPL and groundwater and internal diffusion through NAPL ganglia and pools. There is a relatively large body of literature on the dissolution of single-species NAPLs. Less is known about the rates of elution of compounds dissolving from multicomponent NAPLs. We examined the mass transfer of one solute, 2,3-dimethyl-2-butanol (DMB) - a partitioning tracer, between groundwater and a dense NAPL - trichloroethylene (TCE). Diffusion cell experiments were used to measure the molecular diffusion coefficient of DMB in pure TCE and in porous media contaminated with a TCE pool. Measured diffusion coefficients were compared with empirical correlations (pure TCE) and a parallel resistance model (TCE pool). Based on the results from these analyses, a dimensionless Biot number was derived to express the ratio of the external rate of mass transfer from a NAPL pool to the internal rate of diffusion within the pool, which varies with NAPL saturation and NAPL-water partition coefficient. Biot numbers were then estimated for several laboratory scale experiments involving DMB transport between NAPL pools and groundwater. The estimated Biot numbers were in good agreement with experimental results. The expression for the Biot number developed here may be used to assess the processes controlling the elution of solutes from NAPL pools, which has implications on long-term predictions of solute dissolution from NAPLs in the field.

Mixture-mixture design for the fingerprint optimization of chromatographic mobile phases and extraction solutions for Camellia sinensis.

Science.gov (United States)

Borges, Cleber N; Bruns, Roy E; Almeida, Aline A; Scarminio, Ieda S

2007-07-09

A composite simplex centroid-simplex centroid mixture design is proposed for simultaneously optimizing two mixture systems. The complementary model is formed by multiplying special cubic models for the two systems. The design was applied to the simultaneous optimization of both mobile phase chromatographic mixtures and extraction mixtures for the Camellia sinensis Chinese tea plant. The extraction mixtures investigated contained varying proportions of ethyl acetate, ethanol and dichloromethane while the mobile phase was made up of varying proportions of methanol, acetonitrile and a methanol-acetonitrile-water (MAW) 15%:15%:70% mixture. The experiments were block randomized corresponding to a split-plot error structure to minimize laboratory work and reduce environmental impact. Coefficients of an initial saturated model were obtained using Scheffe-type equations. A cumulative probability graph was used to determine an approximate reduced model. The split-plot error structure was then introduced into the reduced model by applying generalized least square equations with variance components calculated using the restricted maximum likelihood approach. A model was developed to calculate the number of peaks observed with the chromatographic detector at 210 nm. A 20-term model contained essentially all the statistical information of the initial model and had a root mean square calibration error of 1.38. The model was used to predict the number of peaks eluted in chromatograms obtained from extraction solutions that correspond to axial points of the simplex centroid design. The significant model coefficients are interpreted in terms of interacting linear, quadratic and cubic effects of the mobile phase and extraction solution components.

Process for removing a mixture containing iodine and alkyl iodine compounds from a gas phase or aqueous solution with ion-exchange resins

Energy Technology Data Exchange (ETDEWEB)

Shimizu, H; Mizuuchi, A; Yokoyama, F

1968-10-04

Iodine and alkyl iodine compounds are removed from a gas phase or aqueous solution containing salts, iodine and iodine compounds, such as the ambient gas in a reactor, if an accident should occur. The process comprises contacting the phase or solution: (a) with a hydrogen type strongly acidic cationic exchange resin, (b) with an anionic exchange resin containing quarternary ammonium and (c) with an anionic exchange resin containing free basic type tertiary amine, in this order or by reversing the order of the two anionic exchange resins. Although no problems arise in the liquid phase reaction, the ion-exchange resins in the gas phase reaction are desired in the moist state in order to stable maintain the migration speed of the materials to be removed regardless of the relative humidity of the amibent gas. In example I, Amberlite IRA-900 of 200 mm thickness as the lowermost bed, Amberlite IRA93 of 200 mm thickness as the middle bed and Amberlite 200 of 200 mm thickness as the uppermost bed were filled respectively, in a methacrylate resin cylinder with an inner diameter of 25 mm. A solution containing 15.9 mg/1 of iodine, 41.2 mg/1 of methyl iodide and 550 mg/1 of sodium carbonate flows at a rate of 15 liter/hr downward through the beds. As a result of testing, no iodine, iodine ions, iodic acid ions and methyl iodine were detected. The amount of water the beds could treat was 60 times the total quantity of the filled resins.

Phases of Kaluza-Klein Black Holes

DEFF Research Database (Denmark)

Harmark, Troels; Obers, N. A.

2005-01-01

We review the latest progress in understanding the phase structure of static and neutral Kaluza-Klein black holes, i.e. static and neutral solutions of pure gravity with an event horizon that asymptote to a d-dimensional Minkowski-space times a circle. We start by reviewing the (mu,n) phase diagram...... and the split-up of the phase structure into solutions with an internal SO(d-1) symmetry and solutions with Kaluza-Klein bubbles. We then discuss the uniform black string, non-uniform black string and localized black hole phases, and how those three phases are connected, involving issues such as classical...... instability and horizon-topology changing transitions. Finally, we review the bubble-black hole sequences, their place in the phase structure and interesting aspects such as the continuously infinite non-uniqueness of solutions for a given mass and relative tension....

Liquid-Phase Packaging of a Glucose Oxidase Solution with Parylene Direct Encapsulation and an Ultraviolet Curing Adhesive Cover for Glucose Sensors

OpenAIRE

Seiichi Takamatsu; Hisanori Takano; Nguyen Binh-Khiem; Tomoyuki Takahata; Eiji Iwase; Kiyoshi Matsumoto; Isao Shimoyama

2010-01-01

We have developed a package for disposable glucose sensor chips using Parylene encapsulation of a glucose oxidase solution in the liquid phase and a cover structure made of an ultraviolet (UV) curable adhesive. Parylene was directly deposited onto a small volume (1 μL) of glucose oxidase solution through chemical vapor deposition. The cover and reaction chamber were constructed on Parylene film using a UV-curable adhesive and photolithography. The package was processed at room temperature to ...

Solute segregation during irradiation

International Nuclear Information System (INIS)

Wiedersich, H.; Okamoto, P.R.; Lam, N.Q.

1977-01-01

Irradiation at elevated temperature induces redistribution of the elements in alloys on a microstructural level. This phenomenon is caused by differences in the coupling of the various alloy constituents to the radiation-induced defect fluxes. A simple model of the segregation process based on coupled reaction-rate and diffusion equations is discussed. The model gives a good description of the experimentally observed consequences of radiation-induced segregation, including enrichment or depletion of solute elements near defect sinks such as surfaces, voids and dislocations; precipitation of second phases in solid solutions; precipitate redistribution in two-phase alloys; and effects of defect-production rates on void-swelling rates in alloys with minor solute additions

Scalable solution-phase epitaxial growth of symmetry-mismatched heterostructures on two-dimensional crystal soft template.

Science.gov (United States)

Lin, Zhaoyang; Yin, Anxiang; Mao, Jun; Xia, Yi; Kempf, Nicholas; He, Qiyuan; Wang, Yiliu; Chen, Chih-Yen; Zhang, Yanliang; Ozolins, Vidvuds; Ren, Zhifeng; Huang, Yu; Duan, Xiangfeng

2016-10-01

Epitaxial heterostructures with precisely controlled composition and electronic modulation are of central importance for electronics, optoelectronics, thermoelectrics, and catalysis. In general, epitaxial material growth requires identical or nearly identical crystal structures with small misfit in lattice symmetry and parameters and is typically achieved by vapor-phase depositions in vacuum. We report a scalable solution-phase growth of symmetry-mismatched PbSe/Bi 2 Se 3 epitaxial heterostructures by using two-dimensional (2D) Bi 2 Se 3 nanoplates as soft templates. The dangling bond-free surface of 2D Bi 2 Se 3 nanoplates guides the growth of PbSe crystal without requiring a one-to-one match in the atomic structure, which exerts minimal restriction on the epitaxial layer. With a layered structure and weak van der Waals interlayer interaction, the interface layer in the 2D Bi 2 Se 3 nanoplates can deform to accommodate incoming layer, thus functioning as a soft template for symmetry-mismatched epitaxial growth of cubic PbSe crystal on rhombohedral Bi 2 Se 3 nanoplates. We show that a solution chemistry approach can be readily used for the synthesis of gram-scale PbSe/Bi 2 Se 3 epitaxial heterostructures, in which the square PbSe (001) layer forms on the trigonal/hexagonal (0001) plane of Bi 2 Se 3 nanoplates. We further show that the resulted PbSe/Bi 2 Se 3 heterostructures can be readily processed into bulk pellet with considerably suppressed thermal conductivity (0.30 W/m·K at room temperature) while retaining respectable electrical conductivity, together delivering a thermoelectric figure of merit ZT three times higher than that of the pristine Bi 2 Se 3 nanoplates at 575 K. Our study demonstrates a unique epitaxy mode enabled by the 2D nanocrystal soft template via an affordable and scalable solution chemistry approach. It opens up new opportunities for the creation of diverse epitaxial heterostructures with highly disparate structures and functions.

Simultaneous Extraction, Enrichment and Removal of Dyes from Aqueous Solutions Using a Magnetic Aqueous Micellar Two-Phase System

Directory of Open Access Journals (Sweden)

Shuanggen Wu

2017-12-01

Full Text Available The magnetic aqueous micellar two-phase system (MAMTPS has the advantages combined of magnetic solid phase extraction (MSPE and aqueous micellar two-phase system (AMTPS. Thus, MAMTPS based on Fe3O4 magnetic nanoparticles (MNPs and a nonionic surfactant Triton X-114 (TX-114 was developed for the extraction, enrichment and removal of three dyes (Congo red, methyl blue, and methyl violet from aqueous solutions in this study. The MNPs Fe3O4@NH2 was screened as the optimal MNPs benefiting the extraction. Then, the influencing factors of MNPs amount, TX-114 concentration, vibration time, and extraction temperature were investigated in detail. The results showed that the extraction efficiencies of three dyes almost reached 100% using MAMTPS under the optimal conditions; MAMTPS had higher extraction ability than the individual MSPE or AMTPS. Thus, MAMTPS had the advantages of simple operation, high extraction ability, easy recycling of MNPs, and short phase-separation time, which showspotential for use in the extraction and analysis of contaminants from water samples.

Numerical solution of one-dimensional transient, two-phase flows with temporal fully implicit high order schemes: Subcooled boiling in pipes

Energy Technology Data Exchange (ETDEWEB)

López, R., E-mail: ralope1@ing.uc3m.es; Lecuona, A., E-mail: lecuona@ing.uc3m.es; Nogueira, J., E-mail: goriba@ing.uc3m.es; Vereda, C., E-mail: cvereda@ing.uc3m.es

2017-03-15

Highlights: • A two-phase flows numerical algorithm with high order temporal schemes is proposed. • Transient solutions route depends on the temporal high order scheme employed. • ESDIRK scheme for two-phase flows events exhibits high computational performance. • Computational implementation of the ESDIRK scheme can be done in a very easy manner. - Abstract: An extension for 1-D transient two-phase flows of the SIMPLE-ESDIRK method, initially developed for incompressible viscous flows by Ijaz is presented. This extension is motivated by the high temporal order of accuracy demanded to cope with fast phase change events. This methodology is suitable for boiling heat exchangers, solar thermal receivers, etc. The methodology of the solution consist in a finite volume staggered grid discretization of the governing equations in which the transient terms are treated with the explicit first stage singly diagonally implicit Runge-Kutta (ESDIRK) method. It is suitable for stiff differential equations, present in instant boiling or condensation processes. It is combined with the semi-implicit pressure linked equations algorithm (SIMPLE) for the calculation of the pressure field. The case of study consists of the numerical reproduction of the Bartolomei upward boiling pipe flow experiment. The steady-state validation of the numerical algorithm is made against these experimental results and well known numerical results for that experiment. In addition, a detailed study reveals the benefits over the first order Euler Backward method when applying 3rd and 4th order schemes, making emphasis in the behaviour when the system is subjected to periodic square wave wall heat function disturbances, concluding that the use of the ESDIRK method in two-phase calculations presents remarkable accuracy and computational advantages.

The phase diagram of KNO3-KClO3

International Nuclear Information System (INIS)

Zhang Xuejun; Tian Jun; Xu Kangcheng; Gao Yici

2004-01-01

The binary phase diagram of KNO 3 -KClO 3 is studied by means of differential scanning calorimetry (DSC) and high-temperature X-ray diffraction. The limited solid solutions, K(NO 3 ) 1-x (ClO 3 ) x (0 3 ) 1-x (ClO 3 ) x (0.90 3 -based solid solutions and KClO 3 -based solid solutions phase, respectively. For KNO 3 -based solid solutions, KNO 3 ferroelectric phase can be stable from 423 to 223 K as a result of substituting of NO 3 by ClO 3 -radicals. The temperatures for solidus and liquidus have been determined based on limited solid solutions. Two models, Henrian solution and regular solution theory for KNO 3 -based (α) phase and KClO 3 -based (β) phase, respectively, are employed to reproduce solidus and liquidus of the phase diagram. The results are in good agreement with the DSC data. The thermodynamic properties for α and β solid solutions have been derived from an optimization procedure using the experimental data. The calculated phase diagram and optimized thermodynamic parameters are thermodynamically self-consistent

Formation of Microcracks During Micro-Arc Oxidation in a Phytic Acid-Containing Solution on Two-Phase AZ91HP

Science.gov (United States)

Zhang, R. F.; Chang, W. H.; Jiang, L. F.; Qu, B.; Zhang, S. F.; Qiao, L. P.; Xiang, J. H.

2016-04-01

Micro-arc oxidation (MAO) is an effective method to produce ceramic coatings on magnesium alloys and can considerably improve their corrosion resistance. The coating properties are closely related with microcracks, which are always inevitably developed on the coating surface. In order to find out the formation and development regularity of microcracks, anodic coatings developed on two-phase AZ91HP after different anodizing times were fabricated in a solution containing environmentally friendly organic electrolyte phytic acid. The results show that anodic film is initially developed on the α phase. At 50 s, anodic coatings begin to develop on the β phase, evidencing the formation of a rough area. Due to the coating successive development, the microcracks initially appear at the boundary between the initially formed coating on the α phase and the subsequently developed coating on the β phase. With the prolonging treatment time, the microcracks near the β phase become evident. After treating for 3 min, the originally rough area on the β phase disappears and the coatings become almost uniform with microcracks randomly distributed on the sample surface. Inorganic phosphates are found in MAO coatings, suggesting that phytate salts are decomposed due to the high instantaneous temperature on the sample surface resulted from spark discharge.

Effects of gamma radiation on phase behaviour and critical micelle concentration of Triton X-100 aqueous solutions

International Nuclear Information System (INIS)

Valdes Diaz, G.; Rodriguez-Calvo, S.; Perez-Gramatges, A.; Rapado-Paneque, M.; Fernandez-Lima, F. A.; Ponciano, C. R.; Silveira, E. F. . E-mail. apgram@instec.cu

2007-01-01

Ionising radiation used for sterilisation can have an effect on the physico-chemical properties of pharmaceutically relevant excipient systems, affecting therefore the stability of the formulation. The effect of gamma irradiation on the phase behaviour (cloud point - CP) and critical micelle concentration (CMC) of aqueous solutions of Triton X-100, used as a model nonionic surfactant, is investigated in this paper. Micellar solutions irradiated with ?-rays in a dose range between 0 and 70 kGy, including the sterilisation range of pharmaceutical preparations, were analysed using mass spectrometry. Results show a slight shift in molecular mass distribution of ethoxylated surfactant, which indicates degradation of polyethoxylated chains by water radical attacks. This fact, combined with the formation of cross-linked species, is considered to be responsible for the decrease observed in CP and CMC values of micellar solutions at all absorbed doses. There is no spectroscopic evidence of radiation damage to aromatic ring or hydrocarbon tail of surfactant. Models based on Flory-Huggins theory were employed to estimate CP from changes in mass distribution and to obtain cross-linking fractions. (Author)

The eigenvalue problem in phase space.

Science.gov (United States)

Cohen, Leon

2018-06-30

We formulate the standard quantum mechanical eigenvalue problem in quantum phase space. The equation obtained involves the c-function that corresponds to the quantum operator. We use the Wigner distribution for the phase space function. We argue that the phase space eigenvalue equation obtained has, in addition to the proper solutions, improper solutions. That is, solutions for which no wave function exists which could generate the distribution. We discuss the conditions for ascertaining whether a position momentum function is a proper phase space distribution. We call these conditions psi-representability conditions, and show that if these conditions are imposed, one extracts the correct phase space eigenfunctions. We also derive the phase space eigenvalue equation for arbitrary phase space distributions functions. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Soil conditions under a Fagus sylvatica CONECOFOR stand in Central Italy: an integrated assessment through combined solid phase and solution studies

Directory of Open Access Journals (Sweden)

Guido SANESI

2002-09-01

Full Text Available As soil solution represents the major phase of soil chemical reactions, its study is a powerful tool for ecological investigations. Soil solution chemical composition gives a realistic idea about the soil chemical components immediately available in the environment, mainly in relation to the soil ecosystem reaction to the disturbance due to acidifying loads. Within the CONECOFOR Program, the monitoring of forest soil conditions was performed in a level II plot (ABR I, under a Fagus sylvatica (European beech stand, through the study of throughfall and soil solutions collected from depths ranging between the base of the litter layers and 90 cm. To be able to investigate solution contents of nutrients, acidifying agents and DOC throughout the profile, both zero tension and tension lysimeters were used. The first ones were inserted below the organic horizons, while tension lysimeters were placed within the mineral horizons at 15, 25, 55 and 90 cm depth. Sampled solutions were analyzed for Na, K, Ca, Mg, NH4, Cl, F, NO3, SO4, and DOC. The results evidence a clear seasonal pattern, mainly for macronutrients and inorganic N components. Acidic pulses were mostly evident below the organic horizons, in relation to strong nitric N releases from litter; these last were not always immediately neutralized by basic cations. Acid solutions leaving the organic horizons were invariably neutralized in the surface mineral horizons, within 15 cm depth. Temporal patterns of sulphate retention and release suggest that the soil has low retention capability for this anion. Such behaviour can be explained by the composition of the solid phase, where potential anion adsorbants appear strongly linked with organic matter in long residence time complexes. Sulphate and nitrate loading of this soil appear, anyway, to be mostly non-anthropogenic, but rather linked to natural mineralization pulses and, for sulphate, to aeolian solid transport from the south.

Molecular thermodynamics using fluctuation solution theory

DEFF Research Database (Denmark)

Ellegaard, Martin Dela

. The framework relates thermodynamic variables to molecular pair correlation functions of liquid mixtures. In this thesis, application of the framework is illustrated using two approaches: 1. Solubilities of solid solutes in mixed solvent systems are determined from fluctuation solution theory application......Properties of chemicals and their mutual phase equilibria are critical variables in process design. Reliable estimates of relevant equilibrium properties, from thermodynamic models, can form the basis of good decision making in the development phase of a process design, especially when access...... to relevant experimental data is limited. This thesis addresses the issue of generating and using simple thermodynamic models within a rigorous statistical mechanical framework, the so-called fluctuation solution theory, from which relations connecting properties and phase equilibria can be obtained...

Optics Challenges and Solutions for the LHC Insertion Upgrade Phase I

CERN Document Server

Fartoukh, S

2010-01-01

The goal of the LHC Insertion (IR) Upgrade Phase-I is to enable a reliable operation of the machine with a performance at least doubled with respect to its design luminosity. One key ingredient is ideally a reduction of Beta* down to 25 cm, using a new inner triplet (IT) with longer Nb-Ti quadrupoles operating at a lower gradient (~ 120 T/m) and therefore offering a larger aperture (120 mm). Reducing Beta*, but also operating at a lower IT gradient (which, at a given Beta*, further increases the size of the Beta-functions all over the long straight section), has however a certain number of drawbacks which cannot be solved by only increasing the aperture of the new low-beta quadrupoles. Without modifying the current layout of the matching section (MS) and assuming that the arc sextupoles cannot safely operate above nominal current (550A), optics solutions with a Beta* of 30 cm are already at the edge of feasibility, both in terms of mechanical aperture in the MS and new IT (assuming 120 mm aperture), in terms ...

Selected topics in solution-phase biomolecular NMR spectroscopy

Science.gov (United States)

Kay, Lewis E.; Frydman, Lucio

2017-05-01

Solution bio-NMR spectroscopy continues to enjoy a preeminent role as an important tool in elucidating the structure and dynamics of a range of important biomolecules and in relating these to function. Equally impressive is how NMR continues to 'reinvent' itself through the efforts of many brilliant practitioners who ask increasingly demanding and increasingly biologically relevant questions. The ability to manipulate spin Hamiltonians - almost at will - to dissect the information of interest contributes to the success of the endeavor and ensures that the NMR technology will be well poised to contribute to as yet unknown frontiers in the future. As a tribute to the versatility of solution NMR in biomolecular studies and to the continued rapid advances in the field we present a Virtual Special Issue (VSI) that includes over 40 articles on various aspects of solution-state biomolecular NMR that have been published in the Journal of Magnetic Resonance in the past 7 years. These, in total, help celebrate the achievements of this vibrant field.

Calcium ferrite formation from the thermolysis of calcium tris (maleato)

Indian Academy of Sciences (India)

For preparing calcium ferrite, calcium tris (maleato) ferrate(III) precursor was prepared by mixing aqueous solutions of iron(III) maleate, calcium maleate and maleic acid. Various physico-chemical techniques i.e. TG, DTG, DTA, Mössbauer, XRD, IR etc have been used to study the decomposition behaviour from ambient to ...

CERPHASE: Computer-generated phase diagrams

International Nuclear Information System (INIS)

Ruys, A.J.; Sorrell, C.C.; Scott, F.H.

1990-01-01

CERPHASE is a collection of computer programs written in the programming language basic and developed for the purpose of teaching the principles of phase diagram generation from the ideal solution model of thermodynamics. Two approaches are used in the generation of the phase diagrams: freezing point depression and minimization of the free energy of mixing. Binary and ternary phase diagrams can be generated as can diagrams containing the ideal solution parameters used to generate the actual phase diagrams. Since the diagrams generated utilize the ideal solution model, data input required from the operator is minimal: only the heat of fusion and melting point of each component. CERPHASE is menu-driven and user-friendly, containing simple instructions in the form of screen prompts as well as a HELP file to guide the operator. A second purpose of CERPHASE is in the prediction of phase diagrams in systems for which no experimentally determined phase diagrams are available, enabling the estimation of suitable firing or sintering temperatures for otherwise unknown systems. Since CERPHASE utilizes ideal solution theory, there are certain limitations imposed on the types of systems that can be predicted reliably. 6 refs., 13 refs

Phase separation and formation of omega phase in the beta matrix of a Ti-V-Cu alloy

Energy Technology Data Exchange (ETDEWEB)

Ng, H.P. [ARC Centre of Excellence for Design in Light Metals, Department of Materials Engineering, Monash University, Victoria 3800 (Australia); Devaraj, A.; Nag, S. [Center for Advanced Research and Technology, Department of Materials Science and Engineering, University of North Texas, Denton, TX (United States); Bettles, C.J. [ARC Centre of Excellence for Design in Light Metals, Department of Materials Engineering, Monash University, Victoria 3800 (Australia); Gibson, M. [CSIRO Process Science and Engineering, Locked Bag 10, Clayton South, Victoria 3169 (Australia); Fraser, H.L. [Center for the Accelerated Maturation of Materials, Department of Materials Science and Engineering, The Ohio State University, Columbus, OH (United States); Muddle, B.C. [ARC Centre of Excellence for Design in Light Metals, Department of Materials Engineering, Monash University, Victoria 3800 (Australia); Banerjee, R., E-mail: rajarshi.banerjee@unt.edu [Center for Advanced Research and Technology, Department of Materials Science and Engineering, University of North Texas, Denton, TX (United States)

2011-05-15

The formation of the {omega} phase in the presence of simultaneous development of compositional modulations (or phase separation) within the body-centered cubic {beta} matrix phase of a Ti-10V-6Cu (wt.%) alloy during continuous cooling has been investigated using a combination of transmission electron microscopy and atom probe tomography. While a water quench from the high-temperature {beta} phase field allows apparently athermal formation of {omega} domains without any significant partitioning of solute or modulation in matrix composition, subsequent annealing at 500 {sup o}C for just 60 s leads to unusually rapid growth of the {omega} domains concurrent with, but apparently independent of, a slower development of finer-scale modulations in solute composition occurring apparently uniformly across both {omega} and {beta} phases. In contrast, on slower air cooling from the solution treatment temperature, there are pronounced compositional fluctuations within the {beta} phase, presumably as a product of spinodal decomposition, that are detectable prior to the formation of {omega} phase. The {omega} phase subsequently forms preferentially in solute-depleted regions of the matrix {beta}, with a composition reflecting the local matrix composition and a solute content significantly lower than the average matrix composition. As a result, it has a cuboidal morphology, distinguishably different from the elliposoidal form that is observed in samples water-quenched and annealed at 500 deg. C.

Behavior of neutral solutes in pressurized flow driven electrochromatography using a mixed stationary phase of ODS and anion-exchange.

Science.gov (United States)

Kitagawa, Shinya; Tsuda, Takao

2003-05-02

The behavior of neutral sample solutes in pressurized flow driven electrochromatography using a mixed stationary phase, which consisted of ODS and anion-exchange (ODS-SAX), was studied. Applications of both positive and negative voltage on a column induced increases in retention factors of sample solutes. The direction of an electroosmotic flow under applications of positive and negative voltage were the same, therefore, the sign of the surface charge density under positive and negative voltage was opposite. We proposed a new equation for the relationship between applied voltage and surface charge density, and the practical electroosmotic flow conformed to this equation. Studying the electroosmotic flow using our proposed equation revealed that the applied negative voltage accelerates the protonation of the quaternary ammonium group and dissociation of the silanol group on packing materials. The retention behavior of a neutral solute was affected by the existence of the charged functional groups. We propose that this phenomenon is applicable to the control of the retention behavior of a sample solute using an electric field.

Surface modeling and chemical solution deposition of SrO(SrTiO3)n Ruddlesden-Popper phases

International Nuclear Information System (INIS)

Zschornak, M.; Gemming, S.; Gutmann, E.; Weissbach, T.; Stoecker, H.; Leisegang, T.; Riedl, T.; Traenkner, M.; Gemming, T.; Meyer, D.C.

2010-01-01

Strontium titanate (STO) is a preferred substrate material for functional oxide growth, whose surface properties can be adjusted through the presence of Ruddlesden-Popper (RP) phases. Here, density functional theory (DFT) is used to model the (1 0 0) and (0 0 1) surfaces of SrO(SrTiO 3 ) n RP phases. Relaxed surface structures, electronic properties and stability relations have been determined. In contrast to pure STO, the near-surface SrO-OSr stacking fault can be employed to control surface roughness by adjusting SrO and TiO 2 surface rumpling, to stabilize SrO termination in an SrO-rich surrounding or to increase the band gap in the case of TiO 2 termination. RP thin films have been epitaxially grown on (0 0 1) STO substrates by chemical solution deposition. In agreement with DFT results, the fraction of particular RP phases n = 1-3 changes with varying heating rate and molar ratio Sr:Ti. This is discussed in terms of bulk formation energy.

Fabrication of platinum nanoparticles in aqueous solution and solid phase using amphiphilic PB-b-PEO copolymer nanoreactors

International Nuclear Information System (INIS)

Hoda, Numan; Budama, Leyla; Çakır, Burçin Acar; Topel, Önder; Ozisik, Rahmi

2013-01-01

Graphical abstract: TEM image of Pt nanoparticles produced by reducing by NaBH 4 within PB-b-PEO micelles in aqueous media (scale bar 1 nm). - Highlights: • Pt nanoparticles were synthesized within amphiphilic diblock copolymer micelles. • The effects of reducing agents and precursor dose on Pt np size were investigated. • The effect on fabrication of Pt np by reducing in aqueous and solid phases was compared. • The size of nanoparticles was about 1.4 nm for all doses and reducing agents types. - Abstract: Fabrication of Pt nanoparticles using an amphiphilic copolymer template in aqueous solution was achieved via polybutadiene-block-polyethyleneoxide copolymer micelles, which acted as nanoreactors. In addition, Pt nanoparticles were synthesized using hydrogen gas as the reducing agent in solid state for the first time to compare against solution synthesis. The influences of loaded precursor salt amount to micelles and the type of reducing agent on the size of nanoparticles were investigated through transmission electron microscopy. It was found that increasing the ratio of precursor salt to copolymer and using different type of reducing agent, even in solid phase reduction, did not affect the nanoparticle size. The average size of Pt nanoparticles was estimated to be 1.4 ± 0.1 nm. The reason for getting same sized nanoparticles was discussed in the light of nucleation, growth process, stabilization and diffusion of nanoparticles within micelles

Phase-field model and its numerical solution for coring and microstructure evolution studies in alloys

Science.gov (United States)

Turchi, Patrice E. A.; Fattebert, Jean-Luc; Dorr, Milo R.; Wickett, Michael E.; Belak, James F.

2011-03-01

We describe an algorithm for the numerical solution of a phase-field model (PFM) of microstructure evolution in alloys using physical parameters from thermodynamic (CALPHAD) and kinetic databases. The coupled system of PFM equations includes a local order parameter, a quaternion representation of local crystal orientation and a species composition parameter. Time evolution of microstructures and alloy composition is obtained using an implicit time integration of the system. Physical parameters in databases can be obtained either through experiment or first-principles calculations. Application to coring studies and microstructure evolution of Au-Ni will be presented. Prepared by LLNL under Contract DE-AC52-07NA27344

Unexpectedly normal phase behavior of single homopolymer chains

International Nuclear Information System (INIS)

Paul, W.; Strauch, T.; Rampf, F.; Binder, K.

2007-01-01

Employing Monte Carlo simulations, we show that the topology of the phase diagram of a single flexible homopolymer chain changes in dependence on the range of an attractive square well interaction between the monomers. For a range of attraction larger than a critical value, the equilibrium phase diagram of the single polymer chain and the corresponding polymer solution phase diagram exhibit vapor (swollen coil, dilute solution), liquid (collapsed globule, dense solution), and solid phases. Otherwise, the liquid-vapor transition vanishes from the equilibrium phase diagram for both the single chain and the polymer solution. This change in topology of the phase diagram resembles the behavior known for colloidal dispersions. The interplay of enthalpy and conformational entropy in the polymer case thus can lead to the same topology of phase diagrams as the interplay of enthalpy and translational entropy in simple liquids

A Designer Fluid for Aluminum Phase Change Devices, Vol. 1 of 3: General Inorganic Aqueous Solution (IAS) Chemistry

Science.gov (United States)

2016-11-17

out in wicked phase change heat transfer devices. Wen [18] used nanoparticle suspensions to successfully increase the boiling heat transfer...Aqueous Solution of an Anionic Surfactant,” Journal of Heat Transfer 122, No. 4: 708. [18] Wen , D. and Ding, Y., 2005, “Experimental Investigation...Li, Y., 1974, “Diffusion of Ions in Sea Water and in Deep -Sea Sediments,” Geochimica et Cosmochimica Acta, Vol. 88, pp. 703-714. [36] Negishi, K

Toward enhanced hydrogen generation from water using oxygen permeating LCF membranes

KAUST Repository

Wu, Xiao-Yu; Chang, Le; Uddi, Mruthunjaya; Kirchen, Patrick; Ghoniem, Ahmed F.

2015-01-01

and flow rates on the feed and sweep sides on the water thermolysis rate and oxygen flux. A single step reaction mechanism is proposed for surface reactions, and three-resistance permeation models are derived. Results show that water thermolysis

Precipitation in Al–Mg solid solution prepared by solidification under high pressure

International Nuclear Information System (INIS)

Jie, J.C.; Wang, H.W.; Zou, C.M.; Wei, Z.J.; Li, T.J.

2014-01-01

The precipitation in Al–Mg solid solution containing 21.6 at.% Mg prepared by solidification under 2 GPa was investigated. The results show that the γ-Al 12 Mg 17 phase is formed and the β′ phase cannot be observed in the solid solution during ageing process. The precipitation of γ and β phases takes place in a non-uniform manner during heating process, i.e. the γ and β phases are first formed in the interdendritic region, which is caused by the inhomogeneous distribution of Mg atoms in the solid solution solidified under high pressure. Peak splitting of X-ray diffraction patterns of Al(Mg) solid solution appears, and then disappears when the samples are aged at 423 K for different times, due to the non-uniform precipitation in Al–Mg solid solution. The direct transformation from the γ to β phase is observed after ageing at 423 K for 24 h. It is considered that the β phase is formed through a peritectoid reaction of α + γ → β which needs the diffusion of Mg atoms across the interface of α/γ phases. - Highlights: • The γ phase is formed and the β′ phase is be observed in Al(Mg) solid solution. • Peak splitting of XRD pattern of Al(Mg) solid solution appears during aged at 150 °C. • The β phase is formed through a peritectoid reaction of α + γ → β

Two-liquid-phase boundaries and critical phenomena at 275 to 4000C for high-temperature aqueous potassium phosphate and sodium phosphate solutions. Potential applications for steam generators

International Nuclear Information System (INIS)

Marshall, W.L.

1982-01-01

Two-liquid-phase boundaries at temperatures between 275 and 400 0 C were determined for potassium phosphate and sodium phosphate aqueous solutions for compositions from 0 to 60 wt % dissolved salt. The stoichiometric mole ratios, K/PO 4 or Na/PO 4 , were varied from 1.00 to 2.12 and from 1.00 to 2.16 for the potassium and sodium systems, respectively. Liquid-vapor critical temperatures were also determined for most of the dilute liquid phases that formed. The minimum temperatures (below which a single solution existed) of two-liquid-phase formation were 360 0 C for the potassium system and 279 0 C for the sodium system at mole ratios of 2.00 and 2.16, respectively. For the sodium system at mole ratios greater than 2.16, solids crystallized at lower temperatures as expected from earlier studies. In contrast, potassium solutions that were explored at mole ratios from 2.12 to 3.16 and at temperatures below 360 0 C did not produce solid phases or liquid-liquid immisibilities. Aside from the generally unusual observations of two immiscible liquids in an aqueous inorganic salt system, the results could possibly be applied to the use of phosphate additives in steam power generators

Solid phase extraction of uranium and thorium on octadecyl bonded silica modified with Cyanex 302 from aqueous solutions

International Nuclear Information System (INIS)

Nilchi, A.; Shariati Dehaghan, T.; Rasouli Garmarodi, S.

2013-01-01

A simple and reliable method for rapid extraction and determination of uranium and thorium using octadecyl-bonded silica modified with Cyanex 302 is presented. Extraction efficiency and the influence of various parameters such as aqueous phase pH, flow rate of sample solution and amount of extractant has been investigated. The study showed that the extraction of uranium and thorium increase with increasing pH value and was found to be quantitative at pH 6; and the retention of ions was not affected significantly by the flow rate of sample solution. The extraction percent were found to be 89.55 and 86.27 % for uranium and thorium, respectively. The maximal capacity of the cartridges modified by 30 mg of Cyanex 302 was found to be 20 mg of uranium and thorium. The method was successfully applied to the extraction and determination of uranium and thorium in aqueous solutions. The percentage recovery of uranium and thorium in a number of natural as well as seawater samples of Iran were also investigated and found to be in the range of 85-95%. (author)

Intermolecular interactions in the condensed phase

DEFF Research Database (Denmark)

Christensen, Anders S.; Kromann, Jimmy Charnley; Jensen, Jan Halborg

2017-01-01

To facilitate further development of approximate quantum mechanical methods for condensed phase applications, we present a new benchmark dataset of intermolecular interaction energies in the solution phase for a set of 15 dimers, each containing one charged monomer. The reference interaction energy...... and solution phases. As most approximate QM methods are parametrized and evaluated using data measured or calculated in the gas phase, the dataset represents an important first step toward calibrating QM based methods for application in the condensed phase where polarization and exchange repulsion need...

Chemical stability of oseltamivir in oral solutions.

Science.gov (United States)

Albert, K; Bockshorn, J

2007-09-01

The stability of oseltamivir in oral aqueous solutions containing the preservative sodium benzoate was studied by a stability indicating HPLC-method. The separation was achieved on a RP-18 ec column using a gradient of mobile phase A (aqueous solution of 50 mM ammonium acetate) and mobile phase B (60% (v/v) acetonitrile/40% (v/v) mobile phase A). The assay was subsequently validated according to the ICH guideline Q2(R1). The extemporaneously prepared "Oseltamivir Oral Solution 15 mg/ml for Adults or for Children" (NRF 31.2.) according to the German National Formulary ("Neues Rezeptur-Formularium") was stable for 84 days if stored under refrigeration. After storage at 25 degrees C the content of oseltamivir decreased to 98.4%. Considering the toxicological limit of 0.5% of the 5-acetylamino derivative (the so-called isomer I) the solution is stable for 46 days. Oseltamivir was less stable in a solution prepared with potable water instead of purified water. Due to an increasing pH the stability of this solution decreased to 14 days. Furthermore a white precipitate of mainly calcium phosphate was observed. The addition of 0.1% anhydrous citric acid avoided these problems and improved the stability of the solution prepared with potable water to 63 days. Sodium benzoate was stable in all oral solutions tested.

Application of solution-mineral equilibrium chemistry to solution mining of uranium ores

International Nuclear Information System (INIS)

Riese, A.C.; Popp, C.J.

1979-01-01

The tests described were undertaken to determine the extent to leach solution-rock interactions with uranium-bearing ore obtained from the Mariano Lake mine. Leach solutions of an acidic (H/sub 2/O/sub 4/-sulfuric acid) and basic (NaHCO/sub 3/-sodium bicarbonate) nature were tested, in addition to a leach solution containing potassium chloride and sulfuric acid (KCl/H/sub 2/SO/sub 4/). The latter solution was chosen in an attempt to equilibrate the aqueous phase with the rock-forming silicate minerals and minimize adverse effects such as clay formation, porosity loss, and lixiviant loss. 29 refs

Effect of isotopic substitution upon the gas phase and solution electron affinities of nitrobenzene

International Nuclear Information System (INIS)

Stevenson, G.R.; Reiter, R.C.; Espe, M.E.; Bartmess, J.E.

1987-01-01

Ion cyclotron resonance and electron spin resonance have been utilized to determine the equilibrium constant for the electron transfer from the nitrobenzene anion radical to 15 N labeled nitrobenzene (Ph 14 NO 2 - + Ph 15 NO 2 ↔ Ph 14 NO 2 + Ph 15 NO 2 9 . It was found that the equilibrium constant is within experimental error of unity at 305 K. Molecular orbital calculations indicate that this might be accounted for by the shortening of the C-N bond and a counterbalancing lengthening of the N-O bonds upon electron attachment to nitrobenzene. An equilibrium constant that is much larger than unity can be observed in liquid ammonia at 208 K when K + serves as the gegenion (K/sub eq/ = 2.1). However, when Na + serves as the gegenion, the solution electron affinity of Ph 14 NO 2 is greater than that of Ph 15 NO 2 (K/sub eq/ = 0.4). These results are explained in terms of ion association. When the hydrogen atoms are replaced with deuteriums, the gas phase electron affinity is decreased. A similar decrease is observed in liquid ammonia. In the gas phase this is attributed to the slight lengthening of all the C-H bonds upon electron attachment

Solubility and hydrolysis of Np(V) in dilute to concentrated alkaline NaCl solutions. Formation of Na-Np(V)-OH solid phases at 22 C

Energy Technology Data Exchange (ETDEWEB)

Petrov, Vladimir G. [Lomonosov Moscow State Univ. (Russian Federation). Dept. of Chemistry; Fellhauer, David; Gaona, Xavier; Dardenne, Kathy; Rothe, Joerg; Altmaier, Marcus [Karlsruhe Institute of Technology (Germany). Inst. for Nuclear Waste Disposal; Kalmykov, Stepan N. [Lomonosov Moscow State Univ. (Russian Federation). Dept. of Chemistry; NRC Kurchatov Institute, Moscow (Russian Federation)

2017-03-01

The solubility of Np(V) was investigated at T=22±2 C in alkaline NaCl solutions of different ionic strength (0.1-5.0 M). The solid phases controlling the solubility at different -log{sub 10} m{sub H{sup +}}(pH{sub m}) and NaCl concentration were characterized by XRD, quantitative chemical analysis, SEM-EDS and XAFS (both XANES and EXAFS). Aqueous phases in equilibrium with Np(V) solids were investigated for selected samples within 8.9≤pH{sub m}≤10.3 by UV-vis/NIR absorption spectroscopy. In 0.1 M NaCl, the experimental solubility of the initial greenish NpO{sub 2}OH(am) solid phase is in good agreement with previous results obtained in NaClO{sub 4} solutions, and is consistent with model calculations for fresh NpO{sub 2}OH(am) using the thermodynamic data selection in NEA-TDB. Below pH{sub m}∝11.5 and for all NaCl concentrations studied, Np concentration in equilibrium with the solid phase remained constant during the timeframe of this study (∝2 years). This observation is in contrast to the aging of the initial NpO{sub 2}OH(am) into a more crystalline modification with the same stoichiometry, NpO{sub 2}OH(am, aged), as reported in previous studies for concentrated NaClO{sub 4} and NaCl. Instead, the greenish NpO{sub 2}OH(am) transforms into a white solid phase in those systems with [NaCl]≥1.0 M and pH{sub m}≥11.5, and into two different pinkish phases above pH{sub m}∝13.2. The solid phase transformation is accompanied by a drop in Np solubility of 0.5-2 log{sub 10}-units (depending upon NaCl concentration). XANES analyses of green, white and pink phases confirm the predominance of Np(V) in all cases. Quantitative chemical analysis shows the incorporation of Na{sup +} in the original NpO{sub 2}OH(am) material, with Na:Np ≤ 0.3 for the greenish solids and 0.8 ≤ Na:Np ≤ 1.6 for the white and pinkish phases. XRD data confirms the amorphous character of the greenish phase, whereas white and pink solids show well-defined but discrepant XRD patterns

Development of Hydrogen Storage Tank Systems Based on Complex Metal Hydrides

Directory of Open Access Journals (Sweden)

Morten B. Ley

2015-09-01

Full Text Available This review describes recent research in the development of tank systems based on complex metal hydrides for thermolysis and hydrolysis. Commercial applications using complex metal hydrides are limited, especially for thermolysis-based systems where so far only demonstration projects have been performed. Hydrolysis-based systems find their way in space, naval, military and defense applications due to their compatibility with proton exchange membrane (PEM fuel cells. Tank design, modeling, and development for thermolysis and hydrolysis systems as well as commercial applications of hydrolysis systems are described in more detail in this review. For thermolysis, mostly sodium aluminum hydride containing tanks were developed, and only a few examples with nitrides, ammonia borane and alane. For hydrolysis, sodium borohydride was the preferred material whereas ammonia borane found less popularity. Recycling of the sodium borohydride spent fuel remains an important part for their commercial viability.

Development of Hydrogen Storage Tank Systems Based on Complex Metal Hydrides

Science.gov (United States)

Ley, Morten B.; Meggouh, Mariem; Moury, Romain; Peinecke, Kateryna; Felderhoff, Michael

2015-01-01

This review describes recent research in the development of tank systems based on complex metal hydrides for thermolysis and hydrolysis. Commercial applications using complex metal hydrides are limited, especially for thermolysis-based systems where so far only demonstration projects have been performed. Hydrolysis-based systems find their way in space, naval, military and defense applications due to their compatibility with proton exchange membrane (PEM) fuel cells. Tank design, modeling, and development for thermolysis and hydrolysis systems as well as commercial applications of hydrolysis systems are described in more detail in this review. For thermolysis, mostly sodium aluminum hydride containing tanks were developed, and only a few examples with nitrides, ammonia borane and alane. For hydrolysis, sodium borohydride was the preferred material whereas ammonia borane found less popularity. Recycling of the sodium borohydride spent fuel remains an important part for their commercial viability. PMID:28793541

Investigation into isomolar series of Al(NO/sub 3/)/sub 3/, Na/sub 3/VO/sub 4/ solution mixture and composition of solid phases

Energy Technology Data Exchange (ETDEWEB)

Chernysh, L F; Nakhodnova, A P; Makarova, R A [Donetskij Gosudarstvennyj Univ. (Ukrainian SSR)

1979-11-01

Conducted is investigation of properties of isomolar series of aluminium nitrate and sodium vanadate solutions at pH of the latter 12.5; 10.0; 7.0 and the temperature of 25 deg C using the methods of pH-metry, conductometry, ''seeming'' volume of precipitations, residual concentration of aluminium and vanadium. It is shown, that the composition property diagram of the system investigated does not reflect the true composition of solid-phase products of the reaction, which depends on the component ratio in solution. Bottom phases of isomolar series are mainly heterogeneous. At the excess of sodium vanadate solution and its high pH values conditions for the basic salt formation are created. At pH of the Na/sub 3/VO/sub 4/ solution of 12.5 and 10.0 and Al(NO/sub 3/)/sub 3/: Na/sub 3/VO/sub 4/ ratios 4:6 and 3:7 respectively obtained are the basic aluminium vanadates of the (AlOH)/sub 3/(VO/sub 4/)/sub 2/x 7.5H/sub 2/O and (AlOH)/sub 2/V/sub 2/O/sub 7/x5H/sub 2/O composition, some of their physicochemical properties being investigated.

Three-dimensional electron diffraction as a complementary technique to powder X-ray diffraction for phase identification and structure solution of powders

Directory of Open Access Journals (Sweden)

Yifeng Yun

2015-03-01

Full Text Available Phase identification and structure determination are important and widely used techniques in chemistry, physics and materials science. Recently, two methods for automated three-dimensional electron diffraction (ED data collection, namely automated diffraction tomography (ADT and rotation electron diffraction (RED, have been developed. Compared with X-ray diffraction (XRD and two-dimensional zonal ED, three-dimensional ED methods have many advantages in identifying phases and determining unknown structures. Almost complete three-dimensional ED data can be collected using the ADT and RED methods. Since each ED pattern is usually measured off the zone axes by three-dimensional ED methods, dynamic effects are much reduced compared with zonal ED patterns. Data collection is easy and fast, and can start at any arbitrary orientation of the crystal, which facilitates automation. Three-dimensional ED is a powerful technique for structure identification and structure solution from individual nano- or micron-sized particles, while powder X-ray diffraction (PXRD provides information from all phases present in a sample. ED suffers from dynamic scattering, while PXRD data are kinematic. Three-dimensional ED methods and PXRD are complementary and their combinations are promising for studying multiphase samples and complicated crystal structures. Here, two three-dimensional ED methods, ADT and RED, are described. Examples are given of combinations of three-dimensional ED methods and PXRD for phase identification and structure determination over a large number of different materials, from Ni–Se–O–Cl crystals, zeolites, germanates, metal–organic frameworks and organic compounds to intermetallics with modulated structures. It is shown that three-dimensional ED is now as feasible as X-ray diffraction for phase identification and structure solution, but still needs further development in order to be as accurate as X-ray diffraction. It is expected that three

Three-dimensional electron diffraction as a complementary technique to powder X-ray diffraction for phase identification and structure solution of powders.

Science.gov (United States)

Yun, Yifeng; Zou, Xiaodong; Hovmöller, Sven; Wan, Wei

2015-03-01

Phase identification and structure determination are important and widely used techniques in chemistry, physics and materials science. Recently, two methods for automated three-dimensional electron diffraction (ED) data collection, namely automated diffraction tomography (ADT) and rotation electron diffraction (RED), have been developed. Compared with X-ray diffraction (XRD) and two-dimensional zonal ED, three-dimensional ED methods have many advantages in identifying phases and determining unknown structures. Almost complete three-dimensional ED data can be collected using the ADT and RED methods. Since each ED pattern is usually measured off the zone axes by three-dimensional ED methods, dynamic effects are much reduced compared with zonal ED patterns. Data collection is easy and fast, and can start at any arbitrary orientation of the crystal, which facilitates automation. Three-dimensional ED is a powerful technique for structure identification and structure solution from individual nano- or micron-sized particles, while powder X-ray diffraction (PXRD) provides information from all phases present in a sample. ED suffers from dynamic scattering, while PXRD data are kinematic. Three-dimensional ED methods and PXRD are complementary and their combinations are promising for studying multiphase samples and complicated crystal structures. Here, two three-dimensional ED methods, ADT and RED, are described. Examples are given of combinations of three-dimensional ED methods and PXRD for phase identification and structure determination over a large number of different materials, from Ni-Se-O-Cl crystals, zeolites, germanates, metal-organic frameworks and organic compounds to intermetallics with modulated structures. It is shown that three-dimensional ED is now as feasible as X-ray diffraction for phase identification and structure solution, but still needs further development in order to be as accurate as X-ray diffraction. It is expected that three-dimensional ED methods

Two-phase framework for optimal multi-target Lambert rendezvous

OpenAIRE

Bang, Jun; Ahn, Jaemyung

2017-01-01

This paper proposes a two-phase framework to solve an optimal multi-target Lambert rendezvous problem. The first phase solves a series of single-target rendezvous problems for all departure-arrival object pairs to generate the elementary solutions, which provides candidate rendezvous trajectories (elementary solutions). The second phase formulates a variant of traveling salesman problem (TSP) using the elementary solutions prepared in the first phase and determines the best rendezvous sequenc...

Rheological characterization of chicory root (Cichorium intybus L. inulin solution

Directory of Open Access Journals (Sweden)

J. T. C. L. Toneli

2008-09-01

Full Text Available Inulin is a polysaccharide frequently used as a sugar or fat replacer in the food industry, which offers the advantage of a functional effect similar to those of dietary fibers. By cooling or freezing an inulin concentrated solution, a more concentrated solution precipitates as a paste-like substance, while the liquid phase forms a diluted solution. In this work, the effect of storage temperature of inulin concentrated solution as well as temperature on the rheological behavior of liquid and precipitated phases obtained from a process of phase separation were evaluated. The precipitated phase of inulin was evaluated under two conditions: pure and formulated with encapsulating agents. It was observed that a reduction in storage temperature resulted in a higher inulin precipitation, which produced higher apparent viscosity values for the precipitated phase. All the samples analyzed had a shear-thinning rheological behavior.

Secondary α-deuterium isotope effects as a probe to the relationship between structure and mechanism of pyrolysis of secondary azoalkanes

International Nuclear Information System (INIS)

Grizzle, P.L.

1975-01-01

This study was carried out to investigate the mechanism of azoalkane thermolysis and the effect of molecular structure on the potential-energy hypersurface for pyrolysis utilizing secondary α-deuterium isotope effects. Since the magnitude of the α-effect for 1,1'-diphenylazoethane is of singular importance in the interpretation of those for related compounds, it has been redetermined. To investigate the effect of molecular structure on the potential-energy hypersurface for thermolysis, α-effects have been determined for 2,2,2',2'-tetramethyl-1,1'-diphenylazoethane and (2,2-dimethyl-1-phenylpropyl)azomethane; the inability to prepare these compounds by conventional methods necessitated the development of a new method for synthesis of secondary azoalkanes. A convenient synthesis of secondary azo compounds is reported. Secondary α-deuterium isotope effects were obtained for the thermal decomposition of 1,1'-diphenylazoethane (III) and 1,1'-diphenylazoethane-1,1'-d 2 (III-d 2 ). The isotope effect is entirely consistent with a simultaneous one-step thermolysis mechanism. Secondary α-deuterium isotope effects and activation parameters were obtained in the thermolysis of 2,2,2',2'-tetramethyl-1,1'-diphenylazopropane (VIII) and (2,2-dimethyl-1-phenylpropyl)azomethane (IX). The data for VIII is considered in terms of both a one- and two-step thermolysis mechanism. The α-effect and activation energy for VIII are not obviously reconcilable with a one-step mechanism. The α-effects, activation energies, and rates of thermolysis for VIII, IX, and (1-phenylethyl)azomethane are most easily rationalized by a two-step mechanism

Phase separation and shape deformation of two-phase membranes

International Nuclear Information System (INIS)

Jiang, Y.; Lookman, T.; Saxena, A.

2000-01-01

Within a coupled-field Ginzburg-Landau model we study analytically phase separation and accompanying shape deformation on a two-phase elastic membrane in simple geometries such as cylinders, spheres, and tori. Using an exact periodic domain wall solution we solve for the shape and phase separating field, and estimate the degree of deformation of the membrane. The results are pertinent to preferential phase separation in regions of differing curvature on a variety of vesicles. (c) 2000 The American Physical Society

Bonding and orientation of 1,4-benzenedimethanethiol on Au(111) prepared from solution and from gas phase

International Nuclear Information System (INIS)

Pasquali, L; Terzi, F; Zanardi, C; Seeber, R; Paolicelli, G; Mahne, N; Nannarone, S

2007-01-01

The orientation and bonding of 1,4-benzenedimethanethiol molecules on Au(111) is studied by means of x-ray and ultraviolet (UV) photoemission, x-ray absorption and metastable deexcitation spectroscopy. The organic films are prepared both from solution and by exposing the clean substrate to the vapours of the substance in an evacuated environment. This leads to two different growth modes: when self-assembled monolayers (SAMs) are prepared from solution, the molecules tend to form a bilayer film with the molecules standing upright and with the molecular axis forming an angle of about 30 0 with respect to the substrate normal; when growth is carried out from the gas phase, the molecules tend to assume at the earliest stages of exposure a flat-lying configuration, with both sulfur end-groups bonding to Au; at increasing exposure the surface coverage presents a saturation and the chemisorbed molecules tend to assume an upright arrangement

Phase equilibrium condition of marine carbon dioxide hydrate

International Nuclear Information System (INIS)

Sun, Shi-Cai; Liu, Chang-Ling; Ye, Yu-Guang

2013-01-01

Highlights: ► CO 2 hydrate phase equilibrium was studied in simulated marine sediments. ► CO 2 hydrate equilibrium temperature in NaCl and submarine pore water was depressed. ► Coarse-grained silica sand does not affect CO 2 hydrate phase equilibrium. ► The relationship between equilibrium temperature and freezing point was discussed. - Abstract: The phase equilibrium of ocean carbon dioxide hydrate should be understood for ocean storage of carbon dioxide. In this paper, the isochoric multi-step heating dissociation method was employed to investigate the phase equilibrium of carbon dioxide hydrate in a variety of systems (NaCl solution, submarine pore water, silica sand + NaCl solution mixture). The experimental results show that the depression in the phase equilibrium temperature of carbon dioxide hydrate in NaCl solution is caused mainly by Cl − ion. The relationship between the equilibrium temperature and freezing point in NaCl solution was discussed. The phase equilibrium temperature of carbon dioxide hydrate in submarine pore water is shifted by −1.1 K to lower temperature region than that in pure water. However, the phase equilibrium temperature of carbon dioxide hydrate in mixture samples of coarsed-grained silica sand and NaCl solution is in agreement with that in NaCl solution with corresponding concentrations. The relationship between the equilibrium temperature and freezing point in mixture samples was also discussed.

stripping of uranium from DEHPA/TOPO solvent by ammonium carbonate solutions

International Nuclear Information System (INIS)

Khorfan, S.; Shino, O.; Wahood, A.; Dahdouh, A.

2002-01-01

Uranium is recovered from phosphoric acid by the DEHPA/TOPO process. In this process uranium is stripped from the loaded DEHPA/TOPO solvent in the second cycle by an ammonium carbonate solution. This paper studied stripping of uranium from 0.3 Mol DEHPA/0.075 Mol TOPO in kerosene by different ammonium carbonate solutions. The ammonium carbonate solutions tested were either made locally from ammonia and carbon dioxide gases or commercial and laboratory grades available on the market. A comparison was made between these carbonate solutions in terms of purity, stripping efficiency and phase separation. Both stripping and phase separation were carried out under different conditions of phase ratio and concentrations. The results obtained showed that ammonium carbonate prepared from direct synthesis of ammonia and carbon dioxide gases had a high purity and gave the same stripping yield as the laboratory grade. The phase separation was also slightly improved using a pure synthesized ammonium carbonate solution. the phase separation was found to be best at concentration of 0.5 Mol/L ammonium carbonate solution and at a phase A/O of 1/1 and a temperature of 50 degree centigrade. It was possible to obtain >99% yield by operating 2 stripping stages counter currently under these conditions. (authors)

Switchable transport strategy to deposit active Fe/Fe3C cores into hollow microporous carbons for efficient chromium removal.

Science.gov (United States)

Liu, Dong-Hai; Guo, Yue; Zhang, Lu-Hua; Li, Wen-Cui; Sun, Tao; Lu, An-Hui

2013-11-25

Magnetic hollow structures with microporous shell and highly dispersed active cores (Fe/Fe3 C nanoparticles) are rationally designed and fabricated by solution-phase switchable transport of active iron species combined with a solid-state thermolysis technique, thus allowing selective encapsulation of functional Fe/Fe3 C nanoparticles in the interior cavity. These engineered functional materials show high loading (≈54 wt%) of Fe, excellent chromium removal capability (100 mg g(-1)), fast adsorption rate (8766 mL mg(-1) h(-1)), and easy magnetic separation property (63.25 emu g(-1)). During the adsorption process, the internal highly dispersed Fe/Fe3 C nanoparticles supply a driving force for facilitating Cr(VI) diffusion inward, thus improving the adsorption rate and the adsorption capacity. At the same time, the external microporous carbon shell can also efficiently trap guest Cr(VI) ions and protect Fe/Fe3 C nanoparticles from corrosion and subsequent leaching problems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Zn(NH3)4][PtCl6] and [Cd(NH3)4][PtCl6] as precursors for intermetallic compounds PtZn and PtCd

International Nuclear Information System (INIS)

Zadesenets, A.V.; Venediktov, A.B.; Shubin, Yu.V.; Korenev, S.V.

2007-01-01

Double complex salts (tetraamminezinc and tetraamminecadmium hexachloroplatinates) have been synthesized. Their thermal properties have been studied, as well as the products of their degradation in hydrogen and helium atmospheres. Optimal thermolysis schedules have been determined. Thermolysis under hydrogen yields intermetallic compounds PtZn and PtCd [ru

Existence and regularity of solutions of a phase field model for solidification with convection of pure materials in two dimensions

Directory of Open Access Journals (Sweden)

Jose Luiz Boldrini

2003-11-01

Full Text Available We study the existence and regularity of weak solutions of a phase field type model for pure material solidification in presence of natural convection. We assume that the non-stationary solidification process occurs in a two dimensional bounded domain. The governing equations of the model are the phase field equation coupled with a nonlinear heat equation and a modified Navier-Stokes equation. These equations include buoyancy forces modelled by Boussinesq approximation and a Carman-Koseny term to model the flow in mushy regions. Since these modified Navier-Stokes equations only hold in the non-solid regions, which are not known a priori, we have a free boundary-value problem.

Distribution of uranium and radium radionuclides in the 'solid phase-interstitial soil solution' system and their migratory properties in ecosystems

International Nuclear Information System (INIS)

Sokolik, G.A.; Ovsyannikova, S.V.; Vojnikova, E.V.; Popenya, M.V.

2008-01-01

The background content of the main alpha-emitting radionuclides of uranium and radium in the soils of the south-east territory of the Republic of Belarus has been established. The reserve of migratory active species of uranium and radium in the soils has been determined using the data on the content of the radionuclides in the interstitial soil solutions, which are the most important chain of geochemical and biological migration of the chemical elements in ecosystems. The values of radionuclides distribution coefficients in the 'solid phase - interstitial solution of soil' system were estimated. It was shown that the migratory ability of uranium in the investigated soils is higher than that of radium. A direct correlation between the contents of organic components and uranium in the soil solution has been revealed. The used approach to the investigation of the uranium and radium behavior allows comparing their abilities to the migration in dependence of the soil medium peculiarities. (authors)

Numerical-solution package for transient two-phase-flow equations

International Nuclear Information System (INIS)

Mahaffy, J.H.; Liles, D.

1982-01-01

The methods presented have proven to be extremely reliable tools for reactor safety analysis. They can handle a wide range of fluid conditions and time scales with minimal failures, while maintaining time step sizes well above those possible with most other techniques. This robustness is due not only to the finite-difference equations themselves, but also to the choice of solution technique, because poorly chosen iterative solution procedures often require a limit on the time-step size for proper convergence of the iteration

Negative Saturation Approach for Non-Isothermal Compositional Two-Phase Flow Simulations

NARCIS (Netherlands)

Salimi, H.; Wolf, K.H.; Bruining, J.

2011-01-01

This article deals with developing a solution approach, called the non-isothermal negative saturation (NegSat) solution approach. The NegSat solution approach solves efficiently any non-isothermal compositional flow problem that involves phase disappearance, phase appearance, and phase transition.

The immiscible aqueous solutions of alkyl phosphates. Study for the purpose of uranium extraction from phosphoric acid solutions

International Nuclear Information System (INIS)

Mauborgne, Bernard

1979-01-01

Systems of immiscible aqueous solutions composed by a phase rich in mineral salt and by another phase almost totally containing an organic salt, have been studied for years, with quaternary ammonium salts with an organic cation. The objective of this research is to study systems symmetric to the previous ones, i.e. with organic anions such as alkyl phosphates, and then to try to understand mechanisms of extraction of metals in these environments. Based on properties of immiscible aqueous solutions, an original three-phase process of liquid-liquid extraction has been developed, and is used to separate uranium in phosphoric acids with better performance than the existing industrial processes [fr

The Substitution Effect on Reaction Enthalpies of Antioxidant Mechanisms of Juglone and Its Derivatives in Gas and Solution Phase: DFT Study

Directory of Open Access Journals (Sweden)

Aymard Didier Tamafo Fouegue

2018-01-01

Full Text Available We examined the structure-reaction enthalpies-antioxidant activity relationship of the molecule library built around juglone and its derivatives at B3LYP/6-31+G(d,p level. Three major antioxidant mechanisms (hydrogen atom transfer (HAT, single electron transfer-proton transfer (SET-PT, and sequential proton loss electron transfer (SPLET have been investigated in five solvents and in the gas phase. The delocalization of the unpaired electrons in the radicals or cation radicals has been explored by the natural bond orbital analysis and the interpretation of spin density maps. The results obtained have proven that the HAT mechanism is the thermodynamically preferred mechanism in the gas phase. But, in the solution phase, the SPLET mechanism has been shown to be more predominant than HAT. The reactivity order of compounds towards selected reactive oxygen species has also been studied.

Energy condensed packaged systems. Composition, production, properties

Directory of Open Access Journals (Sweden)

Igor L. Kovalenko

2015-03-01

Full Text Available In this paper it is presented the substantiation of choice of fuel phase composition and optimal technology of emulsion production on the basis of binary solution of ammonium and calcium nitrates, which provide the obtaining of energy condensed packaged systems with specified properties. The thermal decomposition of energy condensed systems on the basis of ammonium nitrate is investigated. It is shown that the fuel phase of emulsion systems should be based on esters of polyunsaturated acids or on combinations thereof with petroleum products. And ceresin or petroleum wax can be used as the structuring additive. The influence of the technology of energy condensed systems production on the physicochemical and detonation parameters of emulsion explosives is considered. It is shown the possibility of obtaining of emulsion systems with dispersion of 1.3...1.8 microns and viscosity higher than 103 Pa∙s in the apparatus of original design. The sensitizing effect of chlorinated paraffin CP-470 on the thermolysis of energy condensed emulsion system is shown. The composition and production technology of energy condensed packaged emulsion systems of mark Ukrainit-P for underground mining in mines not dangerous on gas and dust are developed.

Solution-phase parallel synthesis of aryloxyimino amides via a novel multicomponent reaction among aromatic (Z)-chlorooximes, isocyanides, and electron-deficient phenols.

Science.gov (United States)

Mercalli, Valentina; Giustiniano, Mariateresa; Del Grosso, Erika; Varese, Monica; Cassese, Hilde; Massarotti, Alberto; Novellino, Ettore; Tron, Gian Cesare

2014-11-10

A library of 41 aryloxyimino amides was prepared via solution phase parallel synthesis by extending the multicomponent reaction of (Z)-chlorooximes and isocyanides to the use of electron-deficient phenols. The resulting aryloxyiminoamide derivatives can be used as intermediates for the synthesis of benzo[d]isoxazole-3-carboxamides, dramatically reducing the number of synthetic steps required by other methods reported in literature.

Exhaustive Classification of the Invariant Solutions for a Specific Nonlinear Model Describing Near Planar and Marginally Long-Wave Unstable Interfaces for Phase Transition

Science.gov (United States)

Ahangari, Fatemeh

2018-05-01

Problems of thermodynamic phase transition originate inherently in solidification, combustion and various other significant fields. If the transition region among two locally stable phases is adequately narrow, the dynamics can be modeled by an interface motion. This paper is devoted to exhaustive analysis of the invariant solutions for a modified Kuramoto-Sivashinsky equation in two spatial and one temporal dimensions is presented. This nonlinear partial differential equation asymptotically characterizes near planar interfaces, which are marginally long-wave unstable. For this purpose, by applying the classical symmetry method for this model the classical symmetry operators are attained. Moreover, the structure of the Lie algebra of symmetries is discussed and the optimal system of subalgebras, which yields the preliminary classification of group invariant solutions is constructed. Mainly, the Lie invariants corresponding to the infinitesimal symmetry generators as well as associated similarity reduced equations are also pointed out. Furthermore, the nonclassical symmetries of this nonlinear PDE are also comprehensively investigated.

Study of the crystallographic phase change on copper (I) selenide thin films prepared through chemical bath deposition by varying the pH of the solution

Energy Technology Data Exchange (ETDEWEB)

Sandoval-Paz, M.G., E-mail: myrnasandoval@udec.cl [Departament of Physics, Faculty of Physical Sciences and Mathematics, University of Concepcion, Box 160-C, Concepción (Chile); Rodríguez, C.A. [Department of Materials Engineering, Faculty of Engineering, University of Concepción, Edmundo Larenas 270, Concepción 4070409 (Chile); Porcile-Saavedra, P.F. [Departament of Physics, Faculty of Physical Sciences and Mathematics, University of Concepcion, Box 160-C, Concepción (Chile); Trejo-Cruz, C. [Department of Physics, Faculty of Science, University of Biobío, Avenue Collao 1202, Box 5C, Concepción 4051381 (Chile)

2016-07-15

Copper (I) selenide thin films with orthorhombic and cubic structure were deposited on glass substrates by using the chemical bath deposition technique. The effects of the solution pH on the films growth and subsequently the structural, optical and electrical properties of the films were studied. Films with orthorhombic structure were obtained from baths wherein both metal complex and hydroxide coexist; while films with cubic structure were obtained from baths where the metal hydroxide there is no present. The structural modifications are accompanied by changes in bandgap energy, morphology and electrical resistivity of the films. - Graphical abstract: “Study of the crystallographic phase change on copper (I) selenide thin films prepared through chemical bath deposition by varying the pH of the solution” by M. G. Sandoval-Paz, C. A. Rodríguez, P. F. Porcile-Saavedra, C. Trejo-Cruz. Display Omitted - Highlights: • Copper (I) selenide thin films were obtained by chemical bath deposition. • Orthorhombic to cubic phase change was induced by varying the reaction solution pH. • Orthorhombic phase is obtained mainly from a hydroxides cluster mechanism. • Cubic phase is obtained mainly from an ion by ion mechanism. • Structural, optical and electrical properties are presented as a function of pH.

Contribution to the study of the evaporation of aqueous uranyl nitrate solutions; Contribution a l'etude de l'evaporation des solutions aqueuses de nitrate d'uranyle

Energy Technology Data Exchange (ETDEWEB)

Billy, J [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1967-05-15

This work was carried out with a view to define the conditions under which is affected the concentration of aqueous uranyl nitrate solutions one of the steps in uranium extraction metallurgy. The first port is devoted to the experimental determination of the physical characteristics of aqueous uranyl nitrate solutions, from dilute to concentrated solutions. The second part of this work is devoted to the isothermal evaporation of solution a west ted-wall column; this chemical engineering study has been more particularly devoted to the definition of the influence of the dynamics of the liquid phase on the exchange of matter between the two phases in contact. (author) [French] La concentration par evaporation des solutions aqueuses de nitrate d'uranyle constitue une etape de la metallurgie de l'uranium dont ce travail a voulu preciser la connaissance. Dans ce but, une premiere partie a ete consacree a la determination experimentale de caracteristiques physiques des solutions aqueuses de nitrate d'uranyle, des solutions diluees aux solutions saturees. Dans une deuxieme partie, ce travail a porte sur l'evaporation isotherme des solutions dans une colonne a paroi mouillee; cette etude de genie chimique a ete plus particulierement orientee de facon a preciser l'influence de la dynamique de la phase liquide sur l'echange de matiere entre les deux phases en contact. (auteur)

Regularity of solutions of a phase field model

KAUST Repository

Amler, Thomas; Botkin, Nikolai D.; Hoffmann, Karl Heinz; Ruf, K. A.

2013-01-01

are proved in the case of nonsmooth initial data. Continuity of solutions with respect to time is established. In particular, it is shown that the governing initial boundary value problem can be considered as a dynamical system. © 2013 International Press.

Elucidating the weak protein-protein interaction mechanisms behind the liquid-liquid phase separation of a mAb solution by different types of additives.

Science.gov (United States)

Wu, Guoliang; Wang, Shujing; Tian, Zhou; Zhang, Ning; Sheng, Han; Dai, Weiguo; Qian, Feng

2017-11-01

Liquid-liquid phase separation (LLPS) has long been observed during the physical stability investigation of therapeutic protein formulations. The buffer conditions and the presence of various excipients are thought to play important roles in the formulation development of monoclonal antibodies (mAbs). In this study, the effects of several small-molecule excipients (histidine, alanine, glycine, sodium phosphate, sodium chloride, sorbitol and sucrose) with diverse physical-chemical properties on LLPS of a model IgG1 (JM2) solutions were investigated by multiple techniques, including UV-vis spectroscopy, circular dichroism, differential scanning calorimetry/fluorimetry, size exclusion chromatography and dynamic light scattering. The LLPS of JM2 was confirmed to be a thermodynamic equilibrium process with no structural changes or irreversible aggregation of proteins. Phase diagrams of various JM2 formulations were constructed, suggesting that the phase behavior of JM2 was dependent on the solution pH, ionic strength and the presence of other excipients such as glycine, alanine, sorbitol and sucrose. Furthermore, we demonstrated that for this mAb, the interaction parameter (k D ) determined at low protein concentration appeared to be a good predictor for the occurrence of LLPS at high concentration. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of solution annealing temperature on precipitation in 2205 duplex stainless steel

International Nuclear Information System (INIS)

Kashiwar, A.; Vennela, N. Phani; Kamath, S.L.; Khatirkar, R.K.

2012-01-01

In the present study, effect of solution annealing temperature (1050 °C and 1100 °C) and isothermal ageing (700 °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 (∼ 45% ferrite and ∼ 55% austenite) undergoes a series of metallurgical transformations during ageing—formation of secondary austenite (γ 2 ) and precipitation of Cr and Mo rich intermetallic (chi-χ and sigma-σ) phases. For solution annealing at 1050 °C, significant amount of carbides were observed in the ferrite grains after 1 h of ageing at 700 °C. χ Phase precipitated after the precipitation of carbides—preferentially at the ferrite–ferrite and also at the ferrite–austenite boundaries. σ Phase was not observed in significant quantity even after 6 h of ageing. The sequence of precipitation in samples solution annealed at 1050 °C was found to be carbides → χ → σ. On the contrary, for samples solution annealed at 1100 °C, the precipitation of χ phase was negligible. χ Phase precipitated before σ phase, preferentially along the ferrite–ferrite grain boundaries and was later consumed in the σ phase precipitation. The σ phase precipitated via the eutectoid transformation of ferrite to yield secondary austenite γ 2 and σ phase in the ferrite and along the ferrite–austenite grain boundaries. An increase in the volume fraction of γ 2 and σ phase with simultaneous decrease in the ferrite was evidenced with ageing. - Highlights: ► Effect of solution annealing temperature on microstructural evolution is studied. ► χ Phase precipitated preferentially in the samples solution annealed at

Effect of solution annealing temperature on precipitation in 2205 duplex stainless steel

Energy Technology Data Exchange (ETDEWEB)

Kashiwar, A., E-mail: akashiwar@gmail.com [Department of Metallurgical and Materials Engineering, Visvesvaraya National Institute of Technology (VNIT), South Ambazari Road, Nagpur-440010, Maharashtra (India); Vennela, N. Phani, E-mail: phanivennela@gmail.com [Department of Metallurgical and Materials Engineering, Visvesvaraya National Institute of Technology (VNIT), South Ambazari Road, Nagpur-440010, Maharashtra (India); Kamath, S.L., E-mail: kamath@iitb.ac.in [Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay (IITB), Powai, Mumbai-400076, Maharashtra (India); Khatirkar, R.K., E-mail: rajesh.khatirkar@gmail.com [Department of Metallurgical and Materials Engineering, Visvesvaraya National Institute of Technology (VNIT), South Ambazari Road, Nagpur-440010, Maharashtra (India)

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 of 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

Purification of biomaterials by phase partitioning

Science.gov (United States)

Harris, J. M.

1984-01-01

A technique which is particularly suited to microgravity environments and which is potentially more powerful than electrophoresis is phase partitioning. Phase partitioning is purification by partitioning between the two immiscible aqueous layers formed by solution of the polymers poly(ethylene glycol) and dextran in water. This technique proved to be very useful for separations in one-g but is limited for cells because the cells are more dense than the phase solutions thus tend to sediment to the bottom of the container before reaching equilibrium with the preferred phase. There are three phases to work in this area: synthesis of new polymers for affinity phase partitioning; development of automated apparatus for ground-based separations; and design of apparatus for performing simple phase partitioning space experiments, including examination of mechanisms for separating phases in the absence of gravity.

A positivity preserving and conservative variational scheme for phase-field modeling of two-phase flows

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Joshi, Vaibhav; Jaiman, Rajeev K.

2018-05-01

We present a positivity preserving variational scheme for the phase-field modeling of incompressible two-phase flows with high density ratio. The variational finite element technique relies on the Allen-Cahn phase-field equation for capturing the phase interface on a fixed Eulerian mesh with mass conservative and energy-stable discretization. The mass conservation is achieved by enforcing a Lagrange multiplier which has both temporal and spatial dependence on the underlying solution of the phase-field equation. To make the scheme energy-stable in a variational sense, we discretize the spatial part of the Lagrange multiplier in the phase-field equation by the mid-point approximation. The proposed variational technique is designed to reduce the spurious and unphysical oscillations in the solution while maintaining the second-order accuracy of both spatial and temporal discretizations. We integrate the Allen-Cahn phase-field equation with the incompressible Navier-Stokes equations for modeling a broad range of two-phase flow and fluid-fluid interface problems. The coupling of the implicit discretizations corresponding to the phase-field and the incompressible flow equations is achieved via nonlinear partitioned iterative procedure. Comparison of results between the standard linear stabilized finite element method and the present variational formulation shows a remarkable reduction of oscillations in the solution while retaining the boundedness of the phase-indicator field. We perform a standalone test to verify the accuracy and stability of the Allen-Cahn two-phase solver. We examine the convergence and accuracy properties of the coupled phase-field solver through the standard benchmarks of the Laplace-Young law and a sloshing tank problem. Two- and three-dimensional dam break problems are simulated to assess the capability of the phase-field solver for complex air-water interfaces involving topological changes on unstructured meshes. Finally, we demonstrate the phase

Methods of Uranium Determination in solutions of Tributyl Phosphate and Kerosene

International Nuclear Information System (INIS)

Petrement Eguiluz, J.; Palomares Delgado, F.

1962-01-01

A new analytical method for the determination of uranium in organic solutions of tributyl phosphate and kerosene is proposed. In this method the uranium is reextracted from the aqueous phase by reduction with cadmium in acid solution. The uranium can be determined in this solution by the usual methods. In case of very diluted solutions, a direct spectrophtometrical determination of uranium in the organic phase with dibenzoylmethane is proposed. (Author) 21 refs

Exact solution for a two-phase Stefan problem with variable latent heat and a convective boundary condition at the fixed face

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Bollati, Julieta; Tarzia, Domingo A.

2018-04-01

Recently, in Tarzia (Thermal Sci 21A:1-11, 2017) for the classical two-phase Lamé-Clapeyron-Stefan problem an equivalence between the temperature and convective boundary conditions at the fixed face under a certain restriction was obtained. Motivated by this article we study the two-phase Stefan problem for a semi-infinite material with a latent heat defined as a power function of the position and a convective boundary condition at the fixed face. An exact solution is constructed using Kummer functions in case that an inequality for the convective transfer coefficient is satisfied generalizing recent works for the corresponding one-phase free boundary problem. We also consider the limit to our problem when that coefficient goes to infinity obtaining a new free boundary problem, which has been recently studied in Zhou et al. (J Eng Math 2017. https://doi.org/10.1007/s10665-017-9921-y).

Photo-induced isomerization of ethylene-bridged azobenzene explored by ab initio based non-adiabatic dynamics simulation: A comparative investigation of the isomerization in the gas and solution phases

Energy Technology Data Exchange (ETDEWEB)

Cao Jun; Liu Lihong; Fang Weihai [Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875 (China); Xie Zhizhong [Department of Chemistry, School of Science, Wuhan University of Technology, Wuhan 430070 (China); Zhang Yong [Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, New Jersey 07030 (United States)

2013-04-07

Azobenzene is one of the most widely used photoactive units and recently an ethylene-bridged azobenzene (BAB) was reported to have greatly enhanced conversion efficiency, quantum yield, and other favorable properties. As the first step towards exploring its photo-switchable character in real systems, we report here a systematic study on the photoisomerization dynamics between trans (E) and cis (Z) isomers in the gas phase and the CH{sub 3}OH solution, using ab initio based surface hopping and molecular dynamics, which is the first report of dynamics simulation to reveal the environmental effects on BAB photoreactions. Results show that while the relatively faster S{sub 1} relaxation of the photo-induced E{yields}Z process is only mildly affected by the solvent effect, the relatively slower S{sub 1} relaxation of the reverse reaction becomes even slower in the solution compared to the gas phase. The subsequent S{sub 0} dynamics from the conical intersection between S{sub 1} and S{sub 0} (CI{sub E}) to Z is accelerated in solution compared to the gas phase because of avoided re-crossing to the S{sub 1} state, while the S{sub 0} dynamics from the conical intersection between S{sub 1} and S{sub 0} (CI{sub Z}) to E are basically the same in both phases. Overall, the solvent effect was found to enhance the back-and-forth photo-switch efficiency between the Z and E isomers compared to the gas phase, while the quantum yields are reduced. But the solution yields of both the forward and backward photoreactions are still around 0.4. Therefore, BAB may have good photo-responsive properties if used as a photoactive unit in real systems. These results will facilitate future experimental and theoretical studies in this area to help design new azobenzene derivatives as photoactive units in biological processes, nanoscale devices, and photo-responsive materials.

Crystal phase transition in LixNa1-xGdF4 solid solution nanocrystals - Tuning of optical properties

KAUST Repository

Bański, Mateusz

2014-01-01

The influence of precursor composition on the crystallization of LixNa1-xGdF4 is investigated and discussed. Nanocrystals are prepared from the thermal decomposition of trifluoroacetates in the presence of trioctylphosphine oxide to provide control over particle size. A crystal phase transition from hexagonal to cubic and to tetragonal is observed by increasing lithium trifluoroacetate (Li-TFA) in the solution. Controlling the composition of LixNa1-xGdF4 nanocrystals results in modified crystal field symmetry and emission properties from doped europium (Eu3+) ions. We report that for lithium (Li+) substitution <15%, the hexagonal crystal field is preferred, while the Eu3+ emission is already tuned, whereas at higher Li+ substitution, a phase change takes place and the number of crystalline matrix defects increases which is reflected in the optical properties of Eu3+. From Eu3+ emission properties, the optimum Li+ content is determined to be ∼6.2% in the prepared LixNa1-xGdF4 nanocrystals.

Numerical solution of non-linear dual-phase-lag bioheat transfer equation within skin tissues.

Science.gov (United States)

Kumar, Dinesh; Kumar, P; Rai, K N

2017-11-01

This paper deals with numerical modeling and simulation of heat transfer in skin tissues using non-linear dual-phase-lag (DPL) bioheat transfer model under periodic heat flux boundary condition. The blood perfusion is assumed temperature-dependent which results in non-linear DPL bioheat transfer model in order to predict more accurate results. A numerical method of line which is based on finite difference and Runge-Kutta (4,5) schemes, is used to solve the present non-linear problem. Under specific case, the exact solution has been obtained and compared with the present numerical scheme, and we found that those are in good agreement. A comparison based on model selection criterion (AIC) has been made among non-linear DPL models when the variation of blood perfusion rate with temperature is of constant, linear and exponential type with the experimental data and it has been found that non-linear DPL model with exponential variation of blood perfusion rate is closest to the experimental data. In addition, it is found that due to absence of phase-lag phenomena in Pennes bioheat transfer model, it achieves steady state more quickly and always predict higher temperature than thermal and DPL non-linear models. The effect of coefficient of blood perfusion rate, dimensionless heating frequency and Kirchoff number on dimensionless temperature distribution has also been analyzed. The whole analysis is presented in dimensionless form. Copyright © 2017 Elsevier Inc. All rights reserved.

Solution phase and membrane immobilized iron-based free radical reactions: Fundamentals and applications for water treatment

Science.gov (United States)

Lewis, Scott Romak

Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. Reactive membranes synthesized through functionalization of the membrane pores offer enhanced reactivity due to increased surface area at the polymer-solution interface and low diffusion limitations. Oxidative techniques utilizing free radicals have proven effective for both the destruction of toxic organics and non-environmental applications. Most previous work focuses on reactions in the homogeneous phase; however, the immobilization of reactants in membrane pores offers several advantages. The use of polyanions immobilized in a membrane or chelates in solution prevents ferric hydroxide precipitation at near-neutral pH, a common limitation of iron(Fe(II/III))-catalyzed hydrogen peroxide (H 2O2) decomposition. The objectives of this research are to develop a membrane-based platform for the generation of free radicals, degrade toxic organic compounds using this and similar solution-based reactions, degrade toxic organic compounds in droplet form, quantify hydroxyl radical production in these reactions, and develop kinetic models for both processes. In this study, a functionalized membrane containing poly(acrylic acid) (PAA) was used to immobilize iron ions and conduct free radical reactions by permeating H2O2 through the membrane. The membrane's responsive behavior to pH and divalent cations was investigated and modeled. The conversion of Fe(II) to Fe(III) in the membrane and its effect on the decomposition of hydrogen peroxide were monitored and used to develop kinetic models for predicting H2O2 decomposition in these systems. The rate of hydroxyl radical production, and hence contaminant degradation can be varied by changing the residence time, H2O2 concentration, and/or iron loading. Using these membrane-immobilized systems, successful removal of toxic organic compounds, such as pentachlorophenol (PCP), from water

Transport of organic solutes through amorphous teflon AF films.

Science.gov (United States)

Zhao, Hong; Zhang, Jie; Wu, Nianqiang; Zhang, Xu; Crowley, Katie; Weber, Stephen G

2005-11-02

Fluorous media have great potential for selective extraction (e.g., as applied to organic synthesis). Fluorous polymer films would have significant advantages in fluorous separations. Stable films of Teflon AF 2400 were cast from solution. Films appear defect-free (SEM; AFM). Rigid aromatic solutes are transported (from chloroform solution to chloroform receiving phase) in a size-dependent manner (log permeability is proportional to -0.0067 times critical volume). Benzene's permeability is about 2 orders of magnitude higher than in comparable gas-phase experiments. The films show selectivity for fluorinated solutes in comparison to the hydrogen-containing control. Transport rates are dependent on the solvent making up the source and receiving phases. The effect of solvent is, interestingly, not due to changes in partition ratio, but rather it is due to changes in the solute diffusion coefficient in the film. Solvents plasticize the films. A less volatile compound, -COOH-terminated poly(hexafluoropropylene oxide) (4), plasticizes the films (T(g) = -40 degrees C). Permeabilities are decreased in comparison to 4-free films apparently because of decreased diffusivity of solutes. The slope of dependence of log permeability on critical volume is not changed, however.

Towards the description of the phase behavior of electrolyte solutions in slit-like pores. Density functional approach for the restricted primitive model

Directory of Open Access Journals (Sweden)

O.Pizio

2004-01-01

Full Text Available We develop a density functional approach for the phase behavior of the restricted primitive model for electrolyte solutions confined to slit-like pores. The theory permits to evaluate the effects of confinement on the ionic vapor - ionic liquid coexistence envelope. We have shown that due to confinement in pores with uncharged walls the critical temperature of the model decreases compared to the bulk. Also the coexistence envelope of the transition is narrower in comparison to the bulk model. The transition between dense and dilute phase represents capillary evaporation. We have analyzed changes of the density profiles of ions during transition. Possible extensions of this study are discussed.

Thermodynamically Consistent Algorithms for the Solution of Phase-Field Models

KAUST Repository

Vignal, Philippe

2016-01-01

of thermodynamically consistent algorithms for time integration of phase-field models. The first part of this thesis focuses on an energy-stable numerical strategy developed for the phase-field crystal equation. This model was put forward to model microstructure

Berry phase in Heisenberg representation

Science.gov (United States)

Andreev, V. A.; Klimov, Andrei B.; Lerner, Peter B.

1994-01-01

We define the Berry phase for the Heisenberg operators. This definition is motivated by the calculation of the phase shifts by different techniques. These techniques are: the solution of the Heisenberg equations of motion, the solution of the Schrodinger equation in coherent-state representation, and the direct computation of the evolution operator. Our definition of the Berry phase in the Heisenberg representation is consistent with the underlying supersymmetry of the model in the following sense. The structural blocks of the Hamiltonians of supersymmetrical quantum mechanics ('superpairs') are connected by transformations which conserve the similarity in structure of the energy levels of superpairs. These transformations include transformation of phase of the creation-annihilation operators, which are generated by adiabatic cyclic evolution of the parameters of the system.

Stress corrosion cracking of duplex stainless steels in caustic solutions

Science.gov (United States)

Bhattacharya, Ananya

Duplex stainless steels (DSS) with roughly equal amount of austenite and ferrite phases are being used in industries such as petrochemical, nuclear, pulp and paper mills, de-salination plants, marine environments, and others. However, many DSS grades have been reported to undergo corrosion and stress corrosion cracking in some aggressive environments such as chlorides and sulfide-containing caustic solutions. Although stress corrosion cracking of duplex stainless steels in chloride solution has been investigated and well documented in the literature but the SCC mechanisms for DSS in caustic solutions were not known. Microstructural changes during fabrication processes affect the overall SCC susceptibility of these steels in caustic solutions. Other environmental factors, like pH of the solution, temperature, and resulting electrochemical potential also influence the SCC susceptibility of duplex stainless steels. In this study, the role of material and environmental parameters on corrosion and stress corrosion cracking of duplex stainless steels in caustic solutions were investigated. Changes in the DSS microstructure by different annealing and aging treatments were characterized in terms of changes in the ratio of austenite and ferrite phases, phase morphology and intermetallic precipitation using optical micrography, SEM, EDS, XRD, nano-indentation and microhardness methods. These samples were then tested for general and localized corrosion susceptibility and SCC to understand the underlying mechanisms of crack initiation and propagation in DSS in the above-mentioned environments. Results showed that the austenite phase in the DSS is more susceptible to crack initiation and propagation in caustic solutions, which is different from that in the low pH chloride environment where the ferrite phase is the more susceptible phase. This study also showed that microstructural changes in duplex stainless steels due to different heat treatments could affect their SCC

Stability of phase locking in a ring of unidirectionally coupled oscillators

International Nuclear Information System (INIS)

Rogge, J A; Aeyels, D

2004-01-01

We discuss the dynamic behaviour of a finite group of phase oscillators unidirectionally coupled in a ring. The dynamics are based on the Kuramoto model. In the case of identical oscillators, all phase locking solutions and their stability properties are obtained. For nonidentical oscillators it is proven that there exist phase locking solutions for sufficiently strong coupling. An algorithm to obtain all phase locking solutions is proposed. These solutions can be classified into classes, each with its own stability properties. The stability properties are obtained by means of a novel extension of Gershgorin's theorem. One class of stable solutions has the property that all phase differences between neighbouring cells are contained in (-π/2, π/2). Contrary to intuition, a second class of stable solutions is established with exactly one of the phase differences contained in (π/2, 3π/2). The stability results are extended from sinusoidal interconnections to a class of odd functions. To conclude, a connection with the field of active antenna arrays is made, generalizing some results earlier obtained in this field

Stability of a family of travelling wave solutions in a feedforward chain of phase oscillators

International Nuclear Information System (INIS)

Lanford, O E III; Mintchev, S M

2015-01-01

Travelling waves are an important class of signal propagation phenomena in extended systems with a preferred direction of information flow. We study the generation of travelling waves in unidirectional chains of coupled oscillators communicating via a phase-dependent pulse-response interaction borrowed from mathematical neuroscience. Within the context of such systems, we develop a widely applicable, jointly numerical and analytical methodology for deducing existence and stability of periodic travelling waves. We provide careful numerical studies that support the existence of a periodic travelling wave solution as well as the asymptotic relaxation of a single oscillator to the wave when it is forced with the wave profile. Using this evidence as an assumption, we analytically prove global stability of waves in the infinite chain, with respect to initial perturbations of downstream sites. This rigorous stability result suggests that asymptotic relaxation to the travelling wave occurs even when the forcing is perturbed from the wave profile, a property of the motivating system that is supported by previous work as well as the convergence of the more sophisticated numerical algorithm that we propose in order to compute a high-precision approximation to the solution. We provide additional numerical studies that show that the wave is part of a one-parameter family, and we illustrate the structural robustness of this family with respect to changes in the coupling strength. (paper)

Exact phase boundaries and topological phase transitions of the X Y Z spin chain

Science.gov (United States)

Jafari, S. A.

2017-07-01

Within the block spin renormalization group, we give a very simple derivation of the exact phase boundaries of the X Y Z spin chain. First, we identify the Ising order along x ̂ or y ̂ as attractive renormalization group fixed points of the Kitaev chain. Then, in a global phase space composed of the anisotropy λ of the X Y interaction and the coupling Δ of the Δ σzσz interaction, we find that the above fixed points remain attractive in the two-dimesional parameter space. We therefore classify the gapped phases of the X Y Z spin chain as: (1) either attracted to the Ising limit of the Kitaev-chain, which in turn is characterized by winding number ±1 , depending on whether the Ising order parameter is along x ̂ or y ̂ directions; or (2) attracted to the charge density wave (CDW) phases of the underlying Jordan-Wigner fermions, which is characterized by zero winding number. We therefore establish that the exact phase boundaries of the X Y Z model in Baxter's solution indeed correspond to topological phase transitions. The topological nature of the phase transitions of the X Y Z model justifies why our analytical solution of the three-site problem that is at the core of the present renormalization group treatment is able to produce the exact phase boundaries of Baxter's solution. We argue that the distribution of the winding numbers between the three Ising phases is a matter of choice of the coordinate system, and therefore the CDW-Ising phase is entitled to host appropriate form of zero modes. We further observe that in the Kitaev-chain the renormalization group flow can be cast into a geometric progression of a properly identified parameter. We show that this new parameter is actually the size of the (Majorana) zero modes.

Physical nature of structural and phase transformations in Cu-Al α solid solutions upon low-temperature irradiation and subsequent annealing

Science.gov (United States)

Petrenko, P. V.; Kulish, N. P.; Mel'nikova, N. A.; Grabovskii, Yu. E.

2013-12-01

Methods of X-ray diffraction analysis and measurements of residual resistivity have been used to study effects of electron irradiation in the temperature range of 250-330 K on the structural and phase state of the Cu-15 at % Al solid solution. The results obtained are explained by the presence in the Cu-Al alloys of an inhomogeneous short-range order of two types, i.e., low-temperature, α2 type; and high-temperature, γ2 type.

Production method of carbamazepine/saccharin cocrystal particles by using two solution mixing based on the ternary phase diagram

Science.gov (United States)

Kudo, Shoji; Takiyama, Hiroshi

2014-04-01

In the pharmaceutical field, improvement of drug solubility is required, and an interest in cocrystals is growing. Crystallization methods for industrial production of cocrystals have not been developed enough whereas many cocrystals have been prepared in order to find a new crystal form by screening in the laboratory. The objective of this study was the development of the crystallization method which is useful for the industrial production of cocrystal particles based on the phase diagram. A cocrystal of carbamazepine and saccharin was selected as a model substance. The ternary phase diagram of carbamazepine and saccharin in methanol at 303 K was measured. A cocrystallization method of mixing two kinds of different eutectic solutions was designed based on the ternary phase diagram. In order to adjust the cocrystallization conditions, the determination method of the driving force for cocrystal deposition such as supersaturation based on mass balance was proposed. The cocrystal particles were obtained under all the conditions of the five mixing ratios. From these experimental results, the relationship between the supersaturation and the induction time for nucleation was confirmed as well as conventional crystallization. In conclusion, the crystallization method for industrial production of cocrystal particles including the determination of the supersaturation was suggested.

Study of interaction of bismuth, strontium, calcium copper, lead nitrates solutions with sodium oxalate solution with the aim of HTSC synthesis

International Nuclear Information System (INIS)

Danilov, V.P.; Krasnobaeva, O.N.; Nosova, T.A.

1993-01-01

With the aim of developing a new technique for HTSC oxides synthesis on the base of combined sedimentation of hydroxy salts and their heat treatment is studied interaction of bismuth, strontium, calcium, copper and lead nitrates with alkali solution of sodium oxalate. Conditions for total sedimentation of all five metals from the solution are found. The phase composition of interaction products is determined. It is established that they are high-dispersed homogeneous mixture of three phases of variable composition: twin hydroxalate of copper-bismuth, lead hydroxalate and twin oxalate of strontium-calcium. After heat treatment of the phases are obtained the HTSC oxides

Enhanced Open-Circuit Voltage in Colloidal Quantum Dot Photovoltaics via Reactivity-Controlled Solution-Phase Ligand Exchange

KAUST Repository

Jo, Jea Woong; Kim, Younghoon; Choi, Jongmin; de Arquer, F. Pelayo Garcí a; Walters, Grant; Sun, Bin; Ouellette, Olivier; Kim, Junghwan; Proppe, Andrew H.; Quintero-Bermudez, Rafael; Fan, James; Xu, Jixian; Tan, Chih Shan; Voznyy, Oleksandr; Sargent, Edward H.

2017-01-01

The energy disorder that arises from colloidal quantum dot (CQD) polydispersity limits the open-circuit voltage (VOC) and efficiency of CQD photovoltaics. This energy broadening is significantly deteriorated today during CQD ligand exchange and film assembly. Here, a new solution-phase ligand exchange that, via judicious incorporation of reactivity-engineered additives, provides improved monodispersity in final CQD films is reported. It has been found that increasing the concentration of the less reactive species prevents CQD fusion and etching. As a result, CQD solar cells with a VOC of 0.7 V (vs 0.61 V for the control) for CQD films with exciton peak at 1.28 eV and a power conversion efficiency of 10.9% (vs 10.1% for the control) is achieved.

Pile composting of two-phase centrifuged olive husk residues: technical solutions and quality of cured compost.

Science.gov (United States)

Alfano, G; Belli, C; Lustrato, G; Ranalli, G

2008-07-01

The present work proposed an economically sustainable solution for composting olive humid husks (OHH) and leaves (OL) at a small/medium sized olive oil mill. We planned and set up a composting plant, the prototype taking the form of a simplified low-cost turning machine, and evaluated the use of an inoculum of one year-old composted humid husks (CHH) and sheep manure (SM) to facilitate the starting phase of the process. Trials were carried out using four piles under different experimental conditions (turnover, static, and type of inoculum). The best results were achieved with turnover and an inoculum that induced fast start-up and a correct evolution of the composting process. The final product was a hygienically clean, cured compost.

Enhanced Open-Circuit Voltage in Colloidal Quantum Dot Photovoltaics via Reactivity-Controlled Solution-Phase Ligand Exchange

KAUST Repository

Jo, Jea Woong

2017-10-09

The energy disorder that arises from colloidal quantum dot (CQD) polydispersity limits the open-circuit voltage (VOC) and efficiency of CQD photovoltaics. This energy broadening is significantly deteriorated today during CQD ligand exchange and film assembly. Here, a new solution-phase ligand exchange that, via judicious incorporation of reactivity-engineered additives, provides improved monodispersity in final CQD films is reported. It has been found that increasing the concentration of the less reactive species prevents CQD fusion and etching. As a result, CQD solar cells with a VOC of 0.7 V (vs 0.61 V for the control) for CQD films with exciton peak at 1.28 eV and a power conversion efficiency of 10.9% (vs 10.1% for the control) is achieved.

Investigation of uranyl-ion hydrolysis in uranyl pertechnetate and uranyl perchlorates solutions by two-phases potentiometric titration method

International Nuclear Information System (INIS)

Volk, V.I.; Belikov, A.D.

1977-01-01

The applicability of the method of two-phase potentiometric titration for studying hydrolysis of multi-charge ions has been shown. Hydrolysis of uranyl-ion has been investigated and hydrolysis constants in the solutions of uranyl pertechnetate and perchlorate have been calculated equal to (6.2+-0.15)x10 -5 and (9.25+-0.5)10 -5 , respectively. Infrared spectra of the initial crystallohydrates of uranyl pertechnetate and perchlorate has been analyzed. The data on hydrolysis of an uranyl-ion and IR spectra of crystallohydrates of the investigated salts have revealed the ability of pertechnetate ion to complexing with an uranyl group

Phase Change Materials as a solution to improve energy efficiency in Portuguese residential buildings

Science.gov (United States)

Araújo, C.; Pinheiro, A.; Castro, M. F.; Bragança, L.

2017-10-01

The buildings sector contributes to 30% of annual greenhouse gas emissions and consumes about 40% of energy. However, this consumption can be reduced by between 30% and 80% through commercially available technologies. The consumption of energy in the dwellings is mostly associated with the heating and cooling of the interior environment. One solution to reduce these consumptions is the implementation of technologies and Phase Change Materials (PCMs) for Thermal Energy Storage (TES). So, the aim of this work is to analyse the advantages, in terms of decreasing energy consumption, associated with the application of PCMs in Portuguese residential buildings. For this, eight PCMs with different melting ranges were analysed. These materials were analysed through a dynamic simulation performed with EnergyPlus software. The results achieved, showed that the materials studied allow to reduce up to 13% of the heating needs and up to 92% of the cooling needs of a building located in the North of Portugal, at an altitude higher than 100m.

On multiphase negative flash for ideal solutions

DEFF Research Database (Denmark)

Yan, Wei; Stenby, Erling Halfdan

2012-01-01

simpler than the corresponding normal flash algorithm. Unlike normal flash, multiphase negative flash for ideal solutions can diverge if the feasible domain for phase amounts is not closed. This can be judged readily during the iteration process. The algorithm can also be extended to the partial negative......There is a recent interest to solve multiphase negative flash problems where the phase amounts can be negative for normal positive feed composition. Solving such a negative flash problem using successive substitution needs an inner loop for phase distribution calculation at constant fugacity...... coefficients. It is shown that this inner loop, named here as multiphase negative flash for ideal solutions, can be solved either by Michelsen's algorithm for multiphase normal flash, or by its variation which uses F−1 phase amounts as independent variables. In either case, the resulting algorithm is actually...

Numerical simulation of heterogeneous phase transformations

International Nuclear Information System (INIS)

Combeau, H.; Lacaze, J.

1993-01-01

A numerical model is presented for the simulation of diffusion controlled phase transformations in multicomponent alloys. A closed system is considered, with simple geometric shape, either planar, cylindrical or spherical. The temperature inside this microscopic volume is homogeneous, but can vary according to any specified monoteneous law. Particular care has been given to the description of the solute profiles where the concentration gradients are the steepest, i.e. near the interface between the parent and the resultant phases. Solute redistribution at the interface is described by means of an original method which ensures that the overall solute balance is satisfied. A non linear system is obtained which includes the diffusion equations in both phases and the boundary conditions. The solution of this system makes use of a special algorithm which has been devised for a quick convergence. An example is presented which deals with microsegregation build-up during solidification of a multi-component nickel base alloy. (orig.)

Toward enhanced hydrogen generation from water using oxygen permeating LCF membranes

KAUST Repository

Wu, Xiao-Yu

2015-01-01

© the Owner Societies. Hydrogen production from water thermolysis can be enhanced by the use of perovskite-type mixed ionic and electronic conducting (MIEC) membranes, through which oxygen permeation is driven by a chemical potential gradient. In this work, water thermolysis experiments were performed using 0.9 mm thick La0.9Ca0.1FeO3-δ (LCF-91) perovskite membranes at 990 °C in a lab-scale button-cell reactor. We examined the effects of the operating conditions such as the gas species concentrations and flow rates on the feed and sweep sides on the water thermolysis rate and oxygen flux. A single step reaction mechanism is proposed for surface reactions, and three-resistance permeation models are derived. Results show that water thermolysis is facilitated by the LCF-91 membrane especially when a fuel is added to the sweep gas. Increasing the gas flow rate and water concentration on the feed side or the hydrogen concentration on the sweep side enhances the hydrogen production rate. In this work, hydrogen is used as the fuel by construction, so that a single-step surface reaction mechanism can be developed and water thermolysis rate parameters can be derived. Both surface reaction rate parameters for oxygen incorporation/dissociation and hydrogen-oxygen reactions are fitted at 990 °C. We compare the oxygen fluxes in water thermolysis and air separation experiments, and identify different limiting steps in the processes involving various oxygen sources and sweep gases for this 0.9 mm thick LCF-91 membrane. In the air feed-inert sweep case, the bulk diffusion and sweep side surface reaction are the two limiting steps. In the water feed-inert sweep case, surface reaction on the feed side dominates the oxygen permeation process. Yet in the water feed-fuel sweep case, surface reactions on both the feed and sweep sides are rate determining when hydrogen concentration in the sweep side is in the range of 1-5 vol%. Furthermore, long term studies show that the surface

Phase instability of alloys caused by transmutation effects during neutron irradiation

International Nuclear Information System (INIS)

Platov, Yu.M.; Pletnev, M.N.

1994-01-01

A theory of the phase changes in a two-phase binary A-B alloy in the coarsening condition caused by burnout of solute B due to nuclear reactions is presented. It is shown that this burnout process introduces diffusion redistribution of solute between second phase precipitates and solid solution. The burnout induced solute flux away from second phase precipitates to solid solution maintaining the concentration of element B in the vicinity to its solubility limit and stimulates, thus, the second phase particle dissolution. This occurs in addition to a process decreasing their sizes as a result of direct burnout of atoms B in the precipitates. In the framework of the theory developed here, analytical expressions describing time evolution of the precipitate size distributions, changes of mean radius and number density of the precipitates, and second phase dissolution times are obtained. On the basis of these results and numerical calculations for aluminium-scandium alloy, it is shown that the burnout processes can induce essential phase changes, and thus cause significant changes of the properties of irradiated materials at high neutron fluences. ((orig.))

Behaviour of Fe4O5-Mg2Fe2O5 solid solutions and their relation to coexisting Mg-Fe silicates and oxide phases

Science.gov (United States)

Uenver-Thiele, Laura; Woodland, Alan B.; Miyajima, Nobuyoshi; Ballaran, Tiziana Boffa; Frost, Daniel J.

2018-03-01

Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe4O5-Mg2Fe2O5 solid solutions and (2) to explore the phase relations involving (Mg,Fe)2Fe2O5 (denoted as O5-phase) and Mg-Fe silicates. Multi-anvil experiments were performed at 11-20 GPa and 1100-1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O5-phase coexists with Fe2O3, hp-(Mg,Fe)Fe2O4, (Mg,Fe)3Fe4O9 or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O5-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe3+-bearing phase B. However, (Mg,Fe)2Fe2O5 does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe2+ and Fe3+ (at least 1.0 cations Fe per formula unit). Fe-L2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe3+/Fetot = 0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si4+ + [6]Mg2+ = 2Fe3+. The ability to accommodate Fe2+ and Fe3+ makes this potential "water-storing" mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg2Fe2O5 have been refined, yielding H°1bar,298 = - 1981.5 kJ mol- 1. Solid solution is complete across the Fe4O5-Mg2Fe2O5 binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe2+ with silicates indicates that (Mg,Fe)2Fe2O5 has a strong preference for Fe2+. Modelling of partitioning with olivine is consistent with the O5-phase exhibiting ideal mixing behaviour. Mg-Fe2+ partitioning between (Mg,Fe)2Fe2O5 and ringwoodite or wadsleyite is influenced by the presence of Fe3+ and OH incorporation in the silicate phases.

Extraction of lanthanide(III) nitrates from water-salt solutions with n.-octanol

International Nuclear Information System (INIS)

Keskinov, V.A.; Kudrova, A.V.; Valueva, O.V.; Pyartman, A.K.

2004-01-01

Extraction of lanthanide(III) nitrates (Ln=La-Nd, Sm-Gd) from aqueous-salt solutions at 298.15 K was studied using solution of n.-octanol, its concentration 6.31 mol/l. It was ascertained that at Ln(NO 3 ) 3 concentration in aqueous phase below 0.6 mol/l, there is actually no extraction. At higher concentrations of nitrates in aqueous phase the content of lanthanides(III) in organic phase increases in the series La-Gd. Isotherms of extraction were ascertained, its phase equilibria being described mathematically. It is shown that extraction of lanthanide(III) nitrates with n.-octanol should be realized from concentrated aqueous solutions [ru

Solution and precipitation hardening of two-phase gamma titanium alloy; Mischkristall- und Ausscheidungshaertung zweiphasiger Gamma-Titanaluminidlegierungen

Energy Technology Data Exchange (ETDEWEB)

Christoph, U. [GKSS-Forschungszentrum Geesthacht GmbH (Germany). Inst. fuer Werkstofforschung

1997-12-31

The present study on solution and precipitation hardening of two-phase gamma titanium aluminides was directed towards improved creep resistance. Alloys were systematically doped with carbon up to 0.37 atomic percent. Solid solutions and precipitates of carbon were formed by different thermal treatments. The hardening obtained as a result of the different precipitate conditions was measured by deformation experiments between 293 and 973 K. An increase of yield stress of up to 300 MPa was observed for finely distributed perovskite precipitates. This increase of yield stress was maintained up to 973 K and was shown to be dominantly athermal in character from activation parameter measurements. Electron microscopic investigations confirmed the athermal nature of the perovskite precipitates to dislocation motion. The precipitates thus act as barriers to dislocation glide over a wide temperature range and can therefore increase the creep resistance at the anticipated operation temperature of 973 K. In addition to studying the mechanism of precipitation hardening, the pinning of dislocations by the formation of impurity atmospheres has also been investigated. This phenomenon is effective at intermediate temperatures of around 550 K and is thought to be caused by very mobile elements such as iron and boron. These elements are present in all alloys of technical relevance. (orig.) 158 refs.

Spontaneous imbibition in fractal tortuous micro-nano pores considering dynamic contact angle and slip effect: phase portrait analysis and analytical solutions.

Science.gov (United States)

Li, Caoxiong; Shen, Yinghao; Ge, Hongkui; Zhang, Yanjun; Liu, Tao

2018-03-02

Shales have abundant micro-nano pores. Meanwhile, a considerable amount of fracturing liquid is imbibed spontaneously in the hydraulic fracturing process. The spontaneous imbibition in tortuous micro-nano pores is special to shale, and dynamic contact angle and slippage are two important characteristics. In this work, we mainly investigate spontaneous imbibition considering dynamic contact angle and slip effect in fractal tortuous capillaries. We introduce phase portrait analysis to analyse the dynamic state and stability of imbibition. Moreover, analytical solutions to the imbibition equation are derived under special situations, and the solutions are verified by published data. Finally, we discuss the influences of slip length, dynamic contact angle and gravity on spontaneous imbibition. The analysis shows that phase portrait is an ideal tool for analysing spontaneous imbibition because it can evaluate the process without solving the complex governing ordinary differential equations. Moreover, dynamic contact angle and slip effect play an important role in fluid imbibition in fractal tortuous capillaries. Neglecting slip effect in micro-nano pores apparently underestimates imbibition capability, and ignoring variations in contact angle causes inaccuracy in predicting imbibition speed at the initial stage of the process. Finally, gravity is one of the factors that control the stabilisation of the imbibition process.

NMR study of temperature-induced phase separation and polymer-solvent interactions in poly(vinyl methyl ether)/D.sub.2./sub.O/ethanol solutions

Czech Academy of Sciences Publication Activity Database

Hanyková, L.; Labuta, J.; Spěváček, Jiří

2006-01-01

Roč. 47, č. 17 (2006), s. 6107-6116 ISSN 0032-3861 Grant - others:GA UK 294/2004/B Institutional research plan: CEZ:AV0Z40500505 Keywords : poly(vinyl methyl ether)/D2O/ ethanol solutions * temperature-induced phase separation * 1H and 13C NMR spectroscopy Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.773, year: 2006

Liquid crystalline states of surfactant solutions of isotropic micelles

International Nuclear Information System (INIS)

Bagdassarian, C.; Gelbart, W.M.; Ben-Shaul, A.

1988-01-01

We consider micellar solutions whose surfactant molecules prefer strongly to form small, globular aggregates in the absence of intermicellar interactions. At sufficiently high volume fraction of surfactant, the isotropic phase of essentially spherical micelles is shown to be unstable with respect to an orientationally ordered (nematic) state of rodlike aggregates. This behavior is relevant to the phase diagrams reported for important classes of aqueous amphiphilic solutions

Crichton's phase-shift ambiguity

NARCIS (Netherlands)

Atkinson, D.; Johnson, P.W.; Mehta, N.; Roo, M. de

1973-01-01

A re-examination of the SPD phase-shift ambiguity is made with a view to understanding certain singular features of the elastic unitarity constraint. An explicit solution of Crichton's equations is presented, and certain features of this solution are displayed graphically. In particular, it is shown

Phase transformation of the L12 phase to kappa-carbide after spinodal decomposition and ordering in an Fe–C–Mn–Al austenitic steel

International Nuclear Information System (INIS)

Cheng, Wei-Chun; Cheng, Chih-Yao; Hsu, Chia-Wei; Laughlin, David E.

2015-01-01

Fe–C–Mn–Al steels have the potential to substitute for commercial Ni–Cr stainless steels. For the development of Fe–C–Mn–Al stainless steels, phase transformations play an important role. Our methods of studying the phase transformations of the steel include heating, cooling, and/or annealing. The results of our study show that spinodal decomposition, an atomic ordering reaction and the transformation of the L1 2 phase to kappa-carbide occur in the Fe–C–Mn–Al steel. After cooling, the austenite decomposes by the spinodal mechanism into solute-lean and solute-rich austenite phases. The solute-rich austenite phase also transforms into the L1 2 phase via the ordering reaction upon cooling to lower temperatures. After quenching and prolonged annealing, the L1 2 phase grows in the austenite and finally transforms into kappa-carbide. This L1 2 phase to kappa-carbide transformation has not been observed previously

Pointwise asymptotic convergence of solutions for a phase separation model

Czech Academy of Sciences Publication Activity Database

Krejčí, Pavel; Zheng, S.

2006-01-01

Roč. 16, č. 1 (2006), s. 1-18 ISSN 1078-0947 Institutional research plan: CEZ:AV0Z10190503 Keywords : phase-field system * asymptotic phase separation * energy Subject RIV: BA - General Mathematics Impact factor: 1.087, year: 2006 http://aimsciences.org/journals/pdfs.jsp?paperID=1875&mode=full

Simulation of solution phase electron transfer in a compact donor-acceptor dyad.

Science.gov (United States)

Kowalczyk, Tim; Wang, Lee-Ping; Van Voorhis, Troy

2011-10-27

Charge separation (CS) and charge recombination (CR) rates in photosynthetic architectures are difficult to control, yet their ratio can make or break photon-to-current conversion efficiencies. A rational design approach to the enhancement of CS over CR requires a mechanistic understanding of the underlying electron-transfer (ET) process, including the role of the environment. Toward this goal, we introduce a QM/MM protocol for ET simulations and use it to characterize CR in the formanilide-anthraquinone dyad (FAAQ). Our simulations predict fast recombination of the charge-transfer excited state, in agreement with recent experiments. The computed electronic couplings show an electronic state dependence and are weaker in solution than in the gas phase. We explore the role of cis-trans isomerization on the CR kinetics, and we find strong correlation between the vertical energy gaps of the full simulations and a collective solvent polarization coordinate. Our approach relies on constrained density functional theory to obtain accurate diabatic electronic states on the fly for molecular dynamics simulations, while orientational and electronic polarization of the solvent is captured by a polarizable force field based on a Drude oscillator model. The method offers a unified approach to the characterization of driving forces, reorganization energies, electronic couplings, and nonlinear solvent effects in light-harvesting systems.

The chemistry of high temperature phosphate solutions in relation to steam generation

International Nuclear Information System (INIS)

Broadbent, D.; Lewis, G.G.; Wetton, E.A.M.

1978-01-01

The problems associated with the use of phosphate for chemical treatment of the P.W.R. secondary circuit have prompted renewed interest in the physical chemistry of these solutions. Solubility and phase studies have been carried out at 250, 300 and 350 0 C with solutions having sodium to phosphate ratios from 1.0 to above 3.0. A solid phase of ratio about 2.8 exists in equilibrium with a wide range of saturated solution compositions at each temperature. Invariant points at which three phases are in equilibrium have been identified and at the two higher temperatures a region of liquid-liquid immiscibility occurs. Phase diagrams have been constructed for each temperature from which it is possible to predict the compositional changes occurring during the isothermal evaporation process. The corrosivity of these phosphate solutions to a range of steel alloys is being studied, the results reported in the present work, however, are confined to mild steel in the temperature and phosphate composition ranges of the phase studies. The corrosion of mild steel is generally considerably less than in sodium hydroxide solutions of equivalent concentration. The dependence of corrosion rate on sodium and phosphate concentrations in not readily explicable in terms of the solubility and phase studies and it is thought that the solubility of iron in the phosphate solutions is an important rate-determining factor since several complex compounds containing sodium, phosphorus and ferrous iron are present in the corrosion films. (author)

Ternary and quaternary solid solutions in rare earth alloy phases with the CaCu5-type structure

International Nuclear Information System (INIS)

Malani, G.K.; Raman, A.; Mohanty, R.C.

1992-01-01

Crystal structural data were analyzed in seleced CaCu 5 -type ternary and quaternary solid solutions to assess the crystal chemical characteristics and stability features of the CaCu 5 -type structure in rare earth containing alloy phases. LaNi 5 was found to dissolve 100 mol% LaCu 5 , 100 mol% ErNi 5 , about 50 mol% LaIr 5 , 40 mol% 'LaMn 5 ', 20 mol% 'LaFe 5 ', and 25 mol% ErRh 5 . In contrast, LaCo 5 did not dissolve any Mn or any of the other elements other than Al - it dissolved about 20 mol% 'LaAl 5 '. LaCu 5 behaves similar to LaNi 5 in solid solutions. From the lack of solubility of any other element in LaFe 5 , LaCo 5 , LaRh 5 , and LaIr 5 and their great instability, these are inferred to be borderline cases in the realm of the CaCu 5 -type structure. In the CaCu 5 and related crystal structures, Ir is compatible with Ni, but not with Co or Rh, and Rh is not compatible with either Ni or Ir. (orig.) [de

A closed-form solution for moving source localization using LBI changing rate of phase difference only

Directory of Open Access Journals (Sweden)

Zhang Min

2014-04-01

Full Text Available Due to the deficiencies in the conventional multiple-receiver localization systems based on direction of arrival (DOA such as system complexity of interferometer or array and amplitude/phase unbalance between multiple receiving channels and constraint on antenna configuration, a new radiated source localization method using the changing rate of phase difference (CRPD measured by a long baseline interferometer (LBI only is studied. To solve the strictly nonlinear problem, a two-stage closed-form solution is proposed. In the first stage, the DOA and its changing rate are estimated from the CRPD of each observer by the pseudolinear least square (PLS method, and then in the second stage, the source position and velocity are found by another PLS minimization. The bias of the algorithm caused by the correlation between the measurement matrix and the noise in the second stage is analyzed. To reduce this bias, an instrumental variable (IV method is derived. A weighted IV estimator is given in order to reduce the estimation variance. The proposed method does not need any initial guess and the computation is small. The Cramer–Rao lower bound (CRLB and mean square error (MSE are also analyzed. Simulation results show that the proposed method can be close to the CRLB with moderate Gaussian measurement noise.

Effect of β-phase decomposition on the superconducting properties of Ti-27 at percent Nb solid solution

International Nuclear Information System (INIS)

Hariharan, Y.; Valsakumar, M.C.; Radhakrishnan, T.S.

1980-01-01

The effect of β-phase decomposition on the superconducting transition temperature (Tsub(c)) of a Ti-27 at % Nb solid solution has been studied by the resistive technique. The samples were β-quenched from 900deg C and cold rolled to 30%. Annealing at 400deg C for various times upto 15 hours causes Ti-rich phases to precipitate out of the matrix. This decomposition of the β-phase is seen to lead to a progressive enhancement in Tsub(c) from 7.7 K in the β-quenched state to 8.8 K in the sample annealed for 15 hours; further, the width Δ Tsub(c) of the superconducting transition (=90 mK in the β-quenched state) reaches a maximum value (360 mK) for a 10-hour anneal. The conjecture that the enhancement in Tsub(c) occurs as a result of precipitation and the consequent enrichment of the Nb content of the matrix is examined. It is estimated that to account for the large observed enhancement of Tsub(c), the Nb enrichment would have to be of the order of 5-6%; whereas a TEM study has revealed the enrichment to be of the order of 0.2% only. Analysis of the X-ray diffractograms is also not in favour of this hypothesis. Hence alternative mechanisms to account for the Tsub(c) enhancement are currently under investigation. Also discussed is the calculation of Tsub(c) using McMillan's formula for strongly coupled superconductors. (author)

Interactions of acidic solutions with sediments: a case study

International Nuclear Information System (INIS)

Peterson, S.R.; Serne, R.J.; Felmy, A.R.; Erikson, R.L.; Krupka, K.M.; Gee, G.W.

1984-01-01

A methodology is presented for investigating the chemical interactions of acidic solutions with sediments. The MINTEQ geochemical computer code was used to predict solid-phase reactions that might occur when acidic solutions contact neutral sediments which, in turn, may control the concentrations of certain dissolved components. Results of X-ray diffraction analysis of laboratory samples of sediments that have been contacted with acidic uranium mill tailings solutions suggest gypsum and jarosite precipitated. These same mineralogical changes were identified in sediment samples collected from a drained uranium mill evaporation pond (Lucky Mc mine in Wyoming) with a 10-year history of acid attack. Geochemical modeling predicted that these same phases and several amorphous solids not identifiable by X-ray diffraction should have precipitated in the contacted sediments. An equilibrium conceptual model consisting of an assemblage of minerals and amorphous solid phases was then developed to represent a sediment column through which uranium mill tailings solutions were percolated. The MINTEQ code was used to predict effluent solution concentrations resulting from the reactions of the tailings solution with the assemblage of solid phases in the conceptual model. The conceptual model successfully predicted the concentrations of several of the macro-constituents (e.g., Ca, SO 4 , Al, Fe, and Mn), but was not successful in modeling the concentrations of trace elements. The lack of success in predicting the observed trace metal concentrations suggests that other mechanisms, such as adsorption, must be included in future models. The geochemical modeling methodology coupled with the laboratory and field studies should be applicable to a variety of waste disposal problems

Effect of Cu2+ ion incorporation on the phase development of ZrO2-type solid solutions during the thermal treatments

International Nuclear Information System (INIS)

Stefanic, Goran; Music, Svetozar; Ivanda, Mile

2010-01-01

The amorphous precursors of the ZrO 2 -CuO system at the ZrO 2 -rich side of the concentration range were prepared by co-precipitation from aqueous solutions of the corresponding salts. Thermal behavior of the amorphous precursors was monitored using X-ray powder diffraction, Raman spectroscopy, field emission scanning electron microscopy, energy dispersive X-ray spectrometry, differential scanning calorimetry and thermogravimetric analysis. The crystallization temperature of the amorphous precursors rose with an increase in the CuO content for ∼180 o C. Maximum solubility of Cu 2+ ions in the ZrO 2 lattice (∼23 mol%) occurs in the metastable products obtained upon crystallization of the amorphous precursors. The results of Raman spectroscopy indicate that the incorporation of Cu 2+ ions stabilize the tetragonal ZrO 2 polymorph. A precise determination of lattice parameters, using both Rietveld and Le Bail refinements of the powder diffraction patterns, showed that the axial ratio c/a in the ZrO 2 -type solid solutions with a Cu 2+ content ≥20 mol% approach 1 (formation of t''-form of tetragonal phase). The terminal solid solubility limit of Cu 2+ ions in the ZrO 2 lattice rapidly drops with an increase in treatment temperature (up to 1000 o C) that is followed by the formation of and increase in phases structurally closely related to tenorite and monoclinic ZrO 2 . Low thermal stability of the t-ZrO 2 -type phase was attributed to the reduction of the sintering temperature in the presence of CuO and a significant difference in size and shape of zirconia and tenorite particles, which prevent surface interactions.

Glucose and insulin dynamics associated with continuous rate infusion of dextrose solution or dextrose solution and insulin in healthy and endotoxin-exposed horses.

Science.gov (United States)

Han, Janet H; McKenzie, Harold C; McCutcheon, L Jill; Geor, Raymond J

2011-04-01

To investigate the effects of a continuous rate infusion (CRI) of dextrose solution or dextrose solution and insulin on glucose and insulin concentrations in healthy and endotoxin-exposed horses. 9 adult mares. During phase 1, treatments consisted of saline (0.9% NaCl) solution (control group; n = 4) or 20% dextrose solution (group 1; 4) administered IV as a 360-minute CRI. During phase 2, treatments consisted of 360-minute CRIs of 20% dextrose solution and insulin administered simultaneously at 367.6 mg/kg/h (30 kcal/kg/d) and 0.07 U/kg/h, respectively, in healthy horses (group 2; n = 4) or horses administered 35 ng of lipopolysaccharide/kg, IV, 24 hours before starting the dextrose solution and insulin CRIs (group 3; 4). A balanced crossover study design was used in both phases. Blood samples were collected for measurement of plasma glucose and insulin concentrations. Infusion of dextrose solution alone resulted in hyperglycemia for most of the 360-minute CRI. Insulin concentration increased significantly in group 1, compared with that in the control group. Mean insulin concentration of group 2 was significantly higher throughout most of the infusion period, compared with concentrations of the control group and group 1. Mean glucose concentration did not differ significantly between groups 2 and 3. Insulin infusion at a rate of 0.07 U/kg/h was found to be effective for the prevention of hyperglycemia when administered concurrently with dextrose solution. This rate was considered to be safe because horses did not become hypoglycemic during infusions of dextrose solution.

Determination of the quaternary phase diagram of the water-ethylene glycol-sucrose-NaCl system and a comparison between two theoretical methods for synthetic phase diagrams.

Science.gov (United States)

Han, Xu; Liu, Yang; Critser, John K

2010-08-01

Characterization of the thermodynamic properties of multi-solute aqueous solutions is of critical importance for biological and biochemical research. For example, the phase diagrams of aqueous systems, containing salts, saccharides, and plasma membrane permeating solutes, are indispensible in the field of cryobiology and pharmacology. However, only a few ternary phase diagrams are currently available for these systems. In this study, an auto-sampler differential scanning calorimeter (DSC) was used to determine the quaternary phase diagram of the water-ethylene glycol-sucrose-NaCl system. To improve the accuracy of melting point measurement, a "mass-redemption" method was also applied for the DSC technique. Base on the analyses of these experimental data, a comparison was made between the two practical approaches to generate phase diagrams of multi-solute solutions from those of single-solute solutions: the summation of cubic polynomial melting point equations versus the use of osmotic virial equations with cross coefficients. The calculated values of the model standard deviations suggested that both methods are satisfactory for characterizing this quaternary system. (c) 2010 Elsevier Inc. All rights reserved.

Acidities of Water and Methanol in Aqueous Solution and DMSO

Science.gov (United States)

Gao, Daqing

2009-01-01

The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

Migration of 137Cs, 90Sr, 239,240Pu and 241Am in the chain soil-soil solution-plant. The soil-soil solution link

International Nuclear Information System (INIS)

Sokolik, G.A.; Ovsyannikova, S.V.; Kil'chitskaya, S.L.; Ehjsmont, E.A.; Zhukovich, N.V.; Kimlenko, I.M.; Duksina, V.V.; Rubinchik, S.Ya.

1999-01-01

The mobility of 137 Cs, 90 Sr, 239,240 Pu and 241 Am in the link soil-soil solution is analysed for different soil types on the basis of radionuclide distribution coefficients between solid and liquid soil phases. The distribution coefficients allow to differentiate soils in correlation with radionuclide migration rate from the solid phase to the soil solution. The reasons of different radionuclide mobility are considered

Controlling solution-phase polymer aggregation with molecular weight and solvent additives to optimize polymer-fullerene bulk heterojunction solar cells

KAUST Repository

Bartelt, Jonathan A.

2014-03-20

The bulk heterojunction (BHJ) solar cell performance of many polymers depends on the polymer molecular weight (M n) and the solvent additive(s) used for solution processing. However, the mechanism that causes these dependencies is not well understood. This work determines how M n and solvent additives affect the performance of BHJ solar cells made with the polymer poly(di(2-ethylhexyloxy)benzo[1,2-b:4,5-b\\']dithiophene-co- octylthieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD). Low M n PBDTTPD devices have exceedingly large fullerene-rich domains, which cause extensive charge-carrier recombination. Increasing the M n of PBDTTPD decreases the size of these domains and significantly improves device performance. PBDTTPD aggregation in solution affects the size of the fullerene-rich domains and this effect is linked to the dependency of PBDTTPD solubility on M n. Due to its poor solubility high M n PBDTTPD quickly forms a fibrillar polymer network during spin-casting and this network acts as a template that prevents large-scale phase separation. Furthermore, processing low M n PBDTTPD devices with a solvent additive improves device performance by inducing polymer aggregation in solution and preventing large fullerene-rich domains from forming. These findings highlight that polymer aggregation in solution plays a significant role in determining the morphology and performance of BHJ solar cells. The performance of poly(di(2-ethylhexyloxy) benzo[1,2-b:4,5-b\\']dithiophene-co-octylthieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) bulk heterojunction solar cells strongly depends on the polymer molecular weight, and processing these bulk heterojunctions with a solvent additive preferentially improves the performance of low molecular weight devices. It is demonstrated that polymer aggregation in solution significantly impacts the thin-film bulk heterojunction morphology and is vital for high device performance. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transient phases during fast crystallization of organic thin films from solution

Science.gov (United States)

Wan, Jing; Li, Yang; Ulbrandt, Jeffrey G.; Smilgies, Detlef-M.; Hollin, Jonathan; Whalley, Adam C.; Headrick, Randall L.

2016-01-01

We report an in situ microbeam grazing incidence X-ray scattering study of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) organic semiconductor thin film deposition by hollow pen writing. Multiple transient phases are observed during the crystallization for substrate temperatures up to ≈93 °C. The layered smectic liquid-crystalline phase of C8-BTBT initially forms and preceedes inter-layer ordering, followed by a transient crystalline phase for temperature >60 °C, and ultimately the stable phase. Based on these results, we demonstrate a method to produce extremely large grain size and high carrier mobility during high-speed processing. For high writing speed (25 mm/s), mobility up to 3.0 cm2/V-s has been observed.

Halogen bonding in solution: thermodynamics and applications.

Science.gov (United States)

Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

2013-02-21

Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

dispersion equation parameters of solute transport in agricultural

African Journals Online (AJOL)

Jane

2011-08-31

Aug 31, 2011 ... fields for predicting soil quality property. Key words: ... The classical approach of modeling solute transport in porous media uses the deterministic ... concentration of the solution in the liquid phase, u0 is the mean velocity and ...

Determination of uranium in organic phase by flow injection spectrophotometric analysis

International Nuclear Information System (INIS)

Yu Yiyun

1998-01-01

Based on the use of merging zone circuit and simulating a series of standard solution of uranium in organic phase, uranium in unknown organic phase sample was determined by flow injection spectrophotometry. A linear calibration graph was obtained with correlation coefficient of 0.999 for uranium concentration in organic phase over 10∼200 mg/L. Isopropyl alcohol was used as carrier solution. Mixing colour solution contains isopropyl alcohol, triethanolamine, masking reagent and Br-PADAP. The relative standard deviation of the method was better than +-5%. Determination of each sample can be completed in one minute. The method characteristic is: (1) using merging zone and simulating standard solution of uranium in organic phase, the method is sensitive and reliable; (2) even if the determined solution was in turbid condition, it can be quantitatively determined; (3) by means of solution replace technique, the tube of peristaltic pump can be used over a long period of time

Phase transformation of the L1{sub 2} phase to kappa-carbide after spinodal decomposition and ordering in an Fe–C–Mn–Al austenitic steel

Energy Technology Data Exchange (ETDEWEB)

Cheng, Wei-Chun, E-mail: weicheng@mail.ntust.edu.tw [Department of Mechanical Engineering, National Taiwan University of Science and Technology, 43 Keelung Road, Section 4, Taipei 106, Taiwan (China); Cheng, Chih-Yao; Hsu, Chia-Wei [Department of Mechanical Engineering, National Taiwan University of Science and Technology, 43 Keelung Road, Section 4, Taipei 106, Taiwan (China); Laughlin, David E. [Department of Materials Science and Engineering, Carnegie Mellon University, 5000 Forbes Avenue, Pittsburgh, PA (United States)

2015-08-26

Fe–C–Mn–Al steels have the potential to substitute for commercial Ni–Cr stainless steels. For the development of Fe–C–Mn–Al stainless steels, phase transformations play an important role. Our methods of studying the phase transformations of the steel include heating, cooling, and/or annealing. The results of our study show that spinodal decomposition, an atomic ordering reaction and the transformation of the L1{sub 2} phase to kappa-carbide occur in the Fe–C–Mn–Al steel. After cooling, the austenite decomposes by the spinodal mechanism into solute-lean and solute-rich austenite phases. The solute-rich austenite phase also transforms into the L1{sub 2} phase via the ordering reaction upon cooling to lower temperatures. After quenching and prolonged annealing, the L1{sub 2} phase grows in the austenite and finally transforms into kappa-carbide. This L1{sub 2} phase to kappa-carbide transformation has not been observed previously.

Electrochemical processing of nitrate waste solutions. Phase 2, Final report

Energy Technology Data Exchange (ETDEWEB)

Genders, D.; Weinberg, N.; Hartsough, D. [Electrosynthesis Co., Inc., Cheektowaga, NY (US)

1992-10-07

The second phase of research performed at The Electrosynthesis Co., Inc. has demonstrated the successful removal of nitrite and nitrate from a synthetic effluent stream via a direct electrochemical reduction at a cathode. It was shown that direct reduction occurs at good current efficiencies in 1,000 hour studies. The membrane separation process is not readily achievable for the removal of nitrites and nitrates due to poor current efficiencies and membrane stability problems. A direct reduction process was studied at various cathode materials in a flow cell using the complete synthetic mix. Lead was found to be the cathode material of choice, displaying good current efficiencies and stability in short and long term tests under conditions of high temperature and high current density. Several anode materials were studied in both undivided and divided cell configurations. A divided cell configuration was preferable because it would prevent re-oxidation of nitrite by the anode. The technical objective of eliminating electrode fouling and solids formation was achieved although anode materials which had demonstrated good stability in short term divided cell tests corroded in 1,000 hour experiments. The cause for corrosion is thought to be F{sup {minus}} ions from the synthetic mix migrating across the cation exchange membrane and forming HF in the acid anolyte. Other possibilities for anode materials were explored. A membrane separation process was investigated which employs an anion and cation exchange membrane to remove nitrite and nitrate, recovering caustic and nitric acid. Present research has shown poor current efficiencies for nitrite and nitrate transport across the anion exchange membrane due to co-migration of hydroxide anions. Precipitates form within the anion exchange membranes which would eventually result in the failure of the membranes. Electrochemical processing offers a highly promising and viable method for the treatment of nitrate waste solutions.

Supercharging Protein Complexes from Aqueous Solution Disrupts their Native Conformations

Science.gov (United States)

Sterling, Harry J.; Kintzer, Alexander F.; Feld, Geoffrey K.; Cassou, Catherine A.; Krantz, Bryan A.; Williams, Evan R.

2012-02-01

The effects of aqueous solution supercharging on the solution- and gas-phase structures of two protein complexes were investigated using traveling-wave ion mobility-mass spectrometry (TWIMS-MS). Low initial concentrations of m-nitrobenzyl alcohol ( m-NBA) in the electrospray ionization (ESI) solution can effectively increase the charge of concanavalin A dimers and tetramers, but at higher m-NBA concentrations, the increases in charge are accompanied by solution-phase dissociation of the dimers and up to a ~22% increase in the collision cross section (CCS) of the tetramers. With just 0.8% m-NBA added to the ESI solution of a ~630 kDa anthrax toxin octamer complex, the average charge is increased by only ~4% compared with the "native" complex, but it is sufficiently destabilized so that extensive gas-phase fragmentation occurs in the relatively high pressure regions of the TWIMS device. Anthrax toxin complexes exist in either a prechannel or a transmembrane channel state. With m-NBA, the prechannel state of the complex has the same CCS/charge ratio in the gas phase as the transmembrane channel state of the same complex formed without m-NBA, yet undergoes extensive dissociation, indicating that destabilization from supercharging occurs in the ESI droplet prior to ion formation and is not a result of Coulombic destabilization in the gas phase as a result of higher charging. These results demonstrate that the supercharging of large protein complexes is the result of conformational changes induced by the reagents in the ESI droplets, where enrichment of the supercharging reagent during droplet evaporation occurs.

Transient phases during fast crystallization of organic thin films from solution

Directory of Open Access Journals (Sweden)

Jing Wan

2016-01-01

Full Text Available We report an in situ microbeam grazing incidence X-ray scattering study of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT organic semiconductor thin film deposition by hollow pen writing. Multiple transient phases are observed during the crystallization for substrate temperatures up to ≈93 °C. The layered smectic liquid-crystalline phase of C8-BTBT initially forms and preceedes inter-layer ordering, followed by a transient crystalline phase for temperature >60 °C, and ultimately the stable phase. Based on these results, we demonstrate a method to produce extremely large grain size and high carrier mobility during high-speed processing. For high writing speed (25 mm/s, mobility up to 3.0 cm2/V-s has been observed.

Bifurcations and new exact travelling wave solutions for the ...

Indian Academy of Sciences (India)

By using the method of dynamical system, the bidirectional wave equations are considered. Based on this method, all kinds of phase portraits of the reduced travelling wave system in the parametric space are given. All possible bounded travelling wave solutions such as dark soliton solutions, bright soliton solutions and ...

Determination of chemical solute transport parameters effecting radiostrontium interbed sediments

International Nuclear Information System (INIS)

Hemming, C.; Bunde, R.L.; Rosentreter, J.J.

1993-01-01

The extent to which radionuclides migrate in an aquifer system is a function of various physical, chemical, and biological processes. A measure of this migration rate is of primary concern when locating suitable storage sites for such species. Parameters including water-rock interactions, infiltration rates, chemical phase modification, and biochemical reactions all affect solute transport. While these different types of chemical reactions can influence solute transport in subsurface waters, distribution coefficients (Kd) can be send to effectively summarize the net chemical factors which dictate transport efficiency. This coefficient describes the partitioning of the solute between the solution and solid phase. Methodology used in determining and interpreting the distribution coefficient for radiostrontium in well characterized sediments will be presented

Treatment of organic waste solutions containing tributyl phosphate

International Nuclear Information System (INIS)

Drobnik, S.

The two processes developed in the laboratory for treating waste solutions containing TBP, namely TBP separation with phosphoric acid and saponification were tested on a semi-industrial scale. A waste solution from the first phase of the Karlsruhe reprocessing plant was used

A family of four stages embedded explicit six-step methods with eliminated phase-lag and its derivatives for the numerical solution of the second order problems

Science.gov (United States)

Simos, T. E.

2017-11-01

A family of four stages high algebraic order embedded explicit six-step methods, for the numerical solution of second order initial or boundary-value problems with periodical and/or oscillating solutions, are studied in this paper. The free parameters of the new proposed methods are calculated solving the linear system of equations which is produced by requesting the vanishing of the phase-lag of the methods and the vanishing of the phase-lag's derivatives of the schemes. For the new obtained methods we investigate: • Its local truncation error (LTE) of the methods.• The asymptotic form of the LTE obtained using as model problem the radial Schrödinger equation.• The comparison of the asymptotic forms of LTEs for several methods of the same family. This comparison leads to conclusions on the efficiency of each method of the family.• The stability and the interval of periodicity of the obtained methods of the new family of embedded finite difference pairs.• The applications of the new obtained family of embedded finite difference pairs to the numerical solution of several second order problems like the radial Schrödinger equation, astronomical problems etc. The above applications lead to conclusion on the efficiency of the methods of the new family of embedded finite difference pairs.

Exact solutions for the static bending of Euler-Bernoulli beams using Eringen’s two-phase local/nonlocal model

International Nuclear Information System (INIS)

Wang, Y. B.; Zhu, X. W.; Dai, H. H.

2016-01-01

Though widely used in modelling nano- and micro- structures, Eringen’s differential model shows some inconsistencies and recent study has demonstrated its differences between the integral model, which then implies the necessity of using the latter model. In this paper, an analytical study is taken to analyze static bending of nonlocal Euler-Bernoulli beams using Eringen’s two-phase local/nonlocal model. Firstly, a reduction method is proved rigorously, with which the integral equation in consideration can be reduced to a differential equation with mixed boundary value conditions. Then, the static bending problem is formulated and four types of boundary conditions with various loadings are considered. By solving the corresponding differential equations, exact solutions are obtained explicitly in all of the cases, especially for the paradoxical cantilever beam problem. Finally, asymptotic analysis of the exact solutions reveals clearly that, unlike the differential model, the integral model adopted herein has a consistent softening effect. Comparisons are also made with existing analytical and numerical results, which further shows the advantages of the analytical results obtained. Additionally, it seems that the once controversial nonlocal bar problem in the literature is well resolved by the reduction method.

Exact solutions for the static bending of Euler-Bernoulli beams using Eringen’s two-phase local/nonlocal model

Energy Technology Data Exchange (ETDEWEB)

Wang, Y. B. [Department of Mathematics, ShaoXing University, No.900, ChengNan Avenue 312000, ShaoXing, Zhejiang (China); Zhu, X. W., E-mail: xiaowuzhu1026@znufe.edu.cn [School of Statistics and Mathematics, Zhongnan University of Economics and Law, Wuhan 430073 (China); Dai, H. H. [Department of Mathematics, City University of HongKong, 83 Tat Chee Avenue, Kowloon Tong, Hong Kong (China)

2016-08-15

Though widely used in modelling nano- and micro- structures, Eringen’s differential model shows some inconsistencies and recent study has demonstrated its differences between the integral model, which then implies the necessity of using the latter model. In this paper, an analytical study is taken to analyze static bending of nonlocal Euler-Bernoulli beams using Eringen’s two-phase local/nonlocal model. Firstly, a reduction method is proved rigorously, with which the integral equation in consideration can be reduced to a differential equation with mixed boundary value conditions. Then, the static bending problem is formulated and four types of boundary conditions with various loadings are considered. By solving the corresponding differential equations, exact solutions are obtained explicitly in all of the cases, especially for the paradoxical cantilever beam problem. Finally, asymptotic analysis of the exact solutions reveals clearly that, unlike the differential model, the integral model adopted herein has a consistent softening effect. Comparisons are also made with existing analytical and numerical results, which further shows the advantages of the analytical results obtained. Additionally, it seems that the once controversial nonlocal bar problem in the literature is well resolved by the reduction method.

Sythesis of metal sulfide nanomaerials via thermal decomposition of single-source percursors

Energy Technology Data Exchange (ETDEWEB)

Jen-La Plante, Ilan; Zeid, Tahani W.; Yang, Peidong; Mokari, Taleb

2010-06-03

In this report, we present a synthetic method for the formation of cuprous sulfide (Cu2S) and lead sulfide (PbS) nanomaterials directly on substrates from the thermolysis of single-source precursors. We find that the final morphology and arrangement of the nanomaterials may be controlled through the concentration of the dissolved precursors and choice of solvent. One-dimensional (1-D) morphologies may also be grown onto substrates with the addition of a metal catalyst layer through solution-liquid-solid (SLS) growth. These synthetic techniques may be expanded to other metal sulfide materials.

Continuous gas-phase hydroformylation of 1-butene using supported ionic liquid phase (SILP) catalysts

DEFF Research Database (Denmark)

Haumann, Marco; Dentler, Katharina; Joni, Joni

2007-01-01

The concept of supported ionic liquid phase (SILP) catalysis has been extended to 1-butene hydroformylation. A rhodium-sulfoxantphos complex was dissolved in [BMIM][n-C8H17OSO3] and this solution was highly dispersed on silica. Continuous gas-phase experiments in a fixed-bed reactor revealed...

An integrodifferential model for phase transitions: stationary solutions in higher dimensions

Science.gov (United States)

Cortazar, Carmen; Elgueta, Manuel; Rossi, Julio D.; Wolanski, Noemi

2008-01-01

We present a model for nonlocal diffusion with Neumann boundary conditions in a bounded smooth domain prescribing the flux through the boundary. We study the limit of this family of nonlocal diffusion operators when a rescaling parameter related to the kernel of the nonlocal operator goes to zero. We prove that the solutions of this family of problems converge to a solution of the heat equation with Neumann boundary conditions.

Black Hole Solution of Einstein-Born-Infeld-Yang-Mills Theory

Directory of Open Access Journals (Sweden)

Kun Meng

2017-01-01

Full Text Available A new four-dimensional black hole solution of Einstein-Born-Infeld-Yang-Mills theory is constructed; several degenerated forms of the black hole solution are presented. The related thermodynamical quantities are calculated, with which the first law of thermodynamics is checked to be satisfied. Identifying the cosmological constant as pressure of the system, the phase transition behaviors of the black hole in the extended phase space are studied.

Solution based synthesis of mixed-phase materials in the Li{sub 2}TiO{sub 3}–Li{sub 4}SiO{sub 4} system

Energy Technology Data Exchange (ETDEWEB)

Hanaor, Dorian A.H., E-mail: dorian.hanaor@sydney.edu.au [School of Civil Engineering, University of Sydney, NSW 2006 (Australia); Kolb, Matthias H.H. [Institute for Applied Materials, Karlsruhe Institute of Technology, 76021 (Germany); Gan, Yixiang [School of Civil Engineering, University of Sydney, NSW 2006 (Australia); Kamlah, Marc; Knitter, Regina [Institute for Applied Materials, Karlsruhe Institute of Technology, 76021 (Germany)

2015-01-15

Highlights: • Investigation of phase stability in the quasi-binary Li{sub 2}TiO{sub 3}–Li{sub 4}SiO{sub 4} system. • Sol-based syntheses of mixed phase materials from organometallic precursors. • LiCl based synthesis results in greater lithium deficiency than LiOH synthesis. • The Li{sub 2}TiO{sub 3}–Li{sub 4}SiO{sub 4} quasi binary system appears to exhibit monotectic behaviour. • Mixed phase materials show liquid formation from melting of silicate material at 1100 °C. - Abstract: As candidate tritium breeder materials for use in the ITER helium cooled pebble bed, ceramic multiphasic compounds lying in the region of the quasi-binary lithium metatitanate–lithium orthosilicate system may exhibit mechanical and physical advantages relative to single phase materials. Here we present an organometallic solution-based synthesis procedure for the low-temperature fabrication of compounds in the Li{sub 2}TiO{sub 3}–Li{sub 4}SiO{sub 4} region and investigate phase stability and transformations through temperature varied X-ray diffraction and scanning calorimetry. Results demonstrate that the metatitanate and metasilicate phases Li{sub 2}TiO{sub 3} and Li{sub 2}SiO{sub 3} readily crystallise in nanocrystalline form at temperatures below 180 °C. Lithium deficiency in the region of 5% results from Li sublimation from Li{sub 4}SiO{sub 4} and/or from excess Li incorporation in the metatitanate phase and brings about a stoichiometry shift, with product compounds exhibiting mixed lithium orthosilicate/metasilicate content towards the Si rich region and predominantly Li{sub 2}TiO{sub 3} content towards the Ti rich region. Above 1150 °C the transformation of monoclinic to cubic γ-Li{sub 2}TiO{sub 3} disordered solid-solution occurs while the melting of silicate phases indicates a likely monotectic type system with a solidus line in the region 1050–1100 °C. Synthesis procedures involving a lithium chloride precursor are not likely to be a viable option for

Drilling solutions developed on organo-silicon compounds

Energy Technology Data Exchange (ETDEWEB)

Belov, V P

1981-01-01

Confirms the positive effect of polymers on various clay solutions, including heavy barite, over a wide range of temperatures. Depending on the mineralogical composition of the solid phase of the solution and its level of mineralization, these substances may be used as reagent-stabilizers or viscosity reducers and, in certain instances, as combined-action reagents.

On the phase strucutre of baryonic matter

International Nuclear Information System (INIS)

Heide, E.; Ellis, P.J.

1991-01-01

We have studied the phase structure of baryonic matter in a model which includes nucleons and delta resonances interacting with σ- and ω-mesons. In the mean-field approximation, the existence of phase transitions to delta matter and to a baryon-antibaryon plasma was strongly dependent on the values chosen for the equilibrium effective mass and compression modulus. When vacuum fluctuations were included, the physically acceptable solutions only yielded a liquid-gas phase transition. Further, these solutions were restricted to rather large values of the effective mass and compression modulus which did not include the currently accepted values. (orig.)

Effects of Solution Annealing Temperature on the Galvanic Corrosion Behavior of the Super Duplex Stainless Steels

Science.gov (United States)

Lee, Jun-Seob; Jeon, Soon-Hyeok; Park, Yong-Soo

2013-02-01

This study investigated the active dissolution of super duplex stainless steel (SDSS) at various solution annealing temperatures. The active dissolutions of the α-phase and γ-phase were compared, and the effects of the surface area ratio on the active dissolutions of both phases were investigated. There were two peaks in the active-passive transition region in the potentiodynamic test in the modified green-death solution. The two peaks changed as the solution annealing temperature was increased from 1050 to 1150 °C. The solution annealing temperature difference affected the critical anodic current densities. This provides useful information for determining the appropriate solution annealing temperature in the modified green-death solution for SDSS.

Thermal decomposition of Cu(NO{sub 3}){sub 2}{center_dot}3H{sub 2}O at reduced pressures

Energy Technology Data Exchange (ETDEWEB)

Morozov, I.V.; Znamenkov, K.O.; Korenev, Yu.M.; Shlyakhtin, O.A

2003-07-28

Thermolysis of Cu(NO{sub 3}){sub 2}{center_dot}3H{sub 2}O is studied by means of XRD analysis in situ and mass spectral analysis of the gas phase at P=1/10 Pa at low heating rate. It is shown that stage I of the dehydration (40-80 deg. C) results in the consecutive appearance of crystalline Cu(NO{sub 3}){sub 2}{center_dot}2.5H{sub 2}O and Cu(NO{sub 3}){center_dot}H{sub 2}O. Anhydrous Cu(NO{sub 3}){sub 2} formed during further dehydration at 80-110 deg. C is moderately sublimed at 120-150 deg. C. Dehydration is accompanied by thermohydrolysis, leading to the appearance of Cu{sub 2}(OH){sub 3}NO{sub 3} and gaseous H{sub 2}O, HNO{sub 3}, NO{sub 2}, and H{sub 2}O. The higher pressure in the system, the larger amount of thermohydrolysis products is observed. The formation of the crystalline intermediate CuO{sub x}(NO{sub 3}){sub y} was observed by diffraction methods. Final product of thermolysis (CuO) is formed at 200-250 deg. C.

Using UCST ionic liquid as a draw solute in forward osmosis to treat high-salinity water

KAUST Repository

Zhong, Yujiang

2015-12-09

The concept of using a thermo-responsive ionic liquid (IL) with an upper critical solution temperature (UCST) as a draw solute in forward osmosis (FO) was successfully demonstrated here experimentally. A 3.2 M solution of protonated betaine bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) was obtained by heating and maintaining the temperature above 56°C. This solution successfully drew water from high-salinity water up to 3.0 M through FO. When the IL solution cooled to room temperature, it spontaneously separated into a water-rich phase and an IL-rich phase: the water-rich phase was the produced water that contained a low IL concentration, and the IL-rich phase could be used directly as the draw solution in the next cycle of the FO process. The thermal stability, thermal-responsive solubility and UV-vis absorption spectra of the IL were also studied in detail.

Studies on third phase formation in the extraction of Zr(NO3)4 by solutions of tri-iso-amyl phosphate and tri-n-butyl phosphate in n-dodecane

International Nuclear Information System (INIS)

Benadict Rakesh, K.; Suresh, A.; Vasudeva Rao, P.R.

2015-01-01

The knowledge about Limiting Organic Concentration (LOC) and Critical aqueous concentration (CAC) as a function of equilibrium aqueous phase HNO 3 concentration and extractant concentration is essential to restrict the metal ion concentration in the feed and loading of metal ion in to the organic phase to avoid third phase formation. Due to the lesser third phase formation tendency of tri-iso-amyl phosphate (TiAP) compared to tri-n-butyl phosphate (TBP) in the extraction of tetravalent metal ions, TiAP can be used as an alternate extractant to TBP for Zr/Hf separation. In this regard, the LOC and CAC values in the extraction of Zr(IV) by 1.1 M solutions of TiAP and TBP in n-dodecane from Zr(NO 3 ) 4 solutions with various concentrations of HNO 3 have been measured as a function of (HNO 3 ) aq,eq at 303K. The LOC and the CAC values decrease with increase in (HNO 3 ) aq,eq in all the cases. An increase in TBP concentration from 1.1 M to 2.2 M in the organic phase increases the LOC and the CAC. It is also observed that loading of Zr(IV) in 2.2 M TiAP/n-dodecane is much higher than Zr(IV) loading in 2.2 M TBP/n-dodecane under identical conditions. For example, 0.521 mol/L Zr(IV) can be loaded in 2.2 M TiAP/n-dodecane without third phase formation at 303K (corresponding CAC is 0.736 mol/L at 7.12 M HNO 3 ). It can be concluded that the third phase formation tendency is higher for TBP/n-dodecane-Zr(NO 3 ) 4 /HNO 3 system as compared to TiAP/n-dodecane- Zr(NO 3 ) 4 /HNO 3 system under identical conditions. (author)

Radionuclide solubility control by solid solutions

Energy Technology Data Exchange (ETDEWEB)

Brandt, F.; Klinkenberg, M.; Rozov, K.; Bosbach, D. [Forschungszentrum Juelich GmbH (Germany). Inst. of Energy and Climate Research - Nuclear Waste Management and Reactor Safety (IEK-6); Vinograd, V. [Frankfurt Univ. (Germany). Inst. of Geosciences

2015-07-01

The migration of radionuclides in the geosphere is to a large extend controlled by sorption processes onto minerals and colloids. On a molecular level, sorption phenomena involve surface complexation, ion exchange as well as solid solution formation. The formation of solid solutions leads to the structural incorporation of radionuclides in a host structure. Such solid solutions are ubiquitous in natural systems - most minerals in nature are atomistic mixtures of elements rather than pure compounds because their formation leads to a thermodynamically more stable situation compared to the formation of pure compounds. However, due to a lack of reliable data for the expected scenario at close-to equilibrium conditions, solid solution systems have so far not been considered in long-term safety assessments for nuclear waste repositories. In recent years, various solid-solution aqueous solution systems have been studied. Here we present state-of-the art results regarding the formation of (Ra,Ba)SO{sub 4} solid solutions. In some scenarios describing a waste repository system for spent nuclear fuel in crystalline rocks {sup 226}Ra dominates the radiological impact to the environment associated with the potential release of radionuclides from the repository in the future. The solubility of Ra in equilibrium with (Ra,Ba)SO{sub 4} is much lower than the one calculated with RaSO{sub 4} as solubility limiting phase. Especially, the available literature data for the interaction parameter W{sub BaRa}, which describes the non-ideality of the solid solution, vary by about one order of magnitude (Zhu, 2004; Curti et al., 2010). The final {sup 226}Ra concentration in this system is extremely sensitive to the amount of barite, the difference in the solubility products of the end-member phases, and the degree of non-ideality of the solid solution phase. Here, we have enhanced the fundamental understanding regarding (1) the thermodynamics of (Ra,Ba)SO{sub 4} solid solutions and (2) the

Determination of partition coefficient and analysis of nitrophenols by three-phase liquid-phase microextraction coupled with capillary electrophoresis.

Science.gov (United States)

Sanagi, Mohd Marsin; Miskam, Mazidatulakmam; Wan Ibrahim, Wan Aini; Hermawan, Dadan; Aboul-Enein, Hassan Y

2010-07-01

A three-phase hollow fiber liquid-phase microextraction method coupled with CE was developed and used for the determination of partition coefficients and analysis of selected nitrophenols in water samples. The selected nitrophenols were extracted from 14 mL of aqueous solution (donor solution) with the pH adjusted to pH 3 into an organic phase (1-octanol) immobilized in the pores of the hollow fiber and finally backextracted into 40.0 microL of the acceptor phase (NaOH) at pH 12.0 located inside the lumen of the hollow fiber. The extractions were carried out under the following optimum conditions: donor solution, 0.05 M H(3)PO(4), pH 3.0; organic solvent, 1-octanol; acceptor solution, 40 microL of 0.1 M NaOH, pH 12.0; agitation rate, 1050 rpm; extraction time, 15 min. Under optimized conditions, the calibration curves for the analytes were linear in the range of 0.05-0.30 mg/L with r(2)>0.9900 and LODs were in the range of 0.01-0.04 mg/L with RSDs of 1.25-2.32%. Excellent enrichment factors of up to 398-folds were obtained. It was found that the partition coefficient (K(a/d)) values were high for 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol and 2,6-dinitrophenol and that the individual partition coefficients (K(org/d) and K(a/org)) promoted efficient simultaneous extraction from the donor through the organic phase and further into the acceptor phase. The developed method was successfully applied for the analysis of water samples.

Analysis of phases in the structure determination of an icosahedral virus

Energy Technology Data Exchange (ETDEWEB)

Plevka, Pavel; Kaufmann, Bärbel; Rossmann, Michael G. (Purdue)

2012-03-15

The constraints imposed on structure-factor phases by noncrystallographic symmetry (NCS) allow phase improvement, phase extension to higher resolution and hence ab initio phase determination. The more numerous the NCS redundancy and the greater the volume used for solvent flattening, the greater the power for phase determination. In a case analyzed here the icosahedral NCS phasing appeared to have broken down, although later successful phase extension was possible when the envelope around the NCS region was tightened. The phases from the failed phase-determination attempt fell into four classes, all of which satisfied the NCS constraints. These four classes corresponded to the correct solution, opposite enantiomorph, Babinet inversion and opposite enantiomorph with Babinet inversion. These incorrect solutions can be seeded from structure factors belonging to reciprocal-space volumes that lie close to icosahedral NCS axes where the structure amplitudes tend to be large and the phases tend to be 0 or {pi}. Furthermore, the false solutions can spread more easily if there are large errors in defining the envelope designating the region in which NCS averaging is performed.

Time-periodic solutions of the Benjamin-Ono equation

Energy Technology Data Exchange (ETDEWEB)

Ambrose , D.M.; Wilkening, Jon

2008-04-01

We present a spectrally accurate numerical method for finding non-trivial time-periodic solutions of non-linear partial differential equations. The method is based on minimizing a functional (of the initial condition and the period) that is positive unless the solution is periodic, in which case it is zero. We solve an adjoint PDE to compute the gradient of this functional with respect to the initial condition. We include additional terms in the functional to specify the free parameters, which, in the case of the Benjamin-Ono equation, are the mean, a spatial phase, a temporal phase and the real part of one of the Fourier modes at t = 0. We use our method to study global paths of non-trivial time-periodic solutions connecting stationary and traveling waves of the Benjamin-Ono equation. As a starting guess for each path, we compute periodic solutions of the linearized problem by solving an infinite dimensional eigenvalue problem in closed form. We then use our numerical method to continue these solutions beyond the realm of linear theory until another traveling wave is reached (or until the solution blows up). By experimentation with data fitting, we identify the analytical form of the solutions on the path connecting the one-hump stationary solution to the two-hump traveling wave. We then derive exact formulas for these solutions by explicitly solving the system of ODE's governing the evolution of solitons using the ansatz suggested by the numerical simulations.

Time-periodic solutions of the Benjamin-Ono equation

International Nuclear Information System (INIS)

Ambrose, D.M.; Wilkening, Jon

2008-01-01

We present a spectrally accurate numerical method for finding non-trivial time-periodic solutions of non-linear partial differential equations. The method is based on minimizing a functional (of the initial condition and the period) that is positive unless the solution is periodic, in which case it is zero. We solve an adjoint PDE to compute the gradient of this functional with respect to the initial condition. We include additional terms in the functional to specify the free parameters, which, in the case of the Benjamin-Ono equation, are the mean, a spatial phase, a temporal phase and the real part of one of the Fourier modes at t = 0. We use our method to study global paths of non-trivial time-periodic solutions connecting stationary and traveling waves of the Benjamin-Ono equation. As a starting guess for each path, we compute periodic solutions of the linearized problem by solving an infinite dimensional eigenvalue problem in closed form. We then use our numerical method to continue these solutions beyond the realm of linear theory until another traveling wave is reached (or until the solution blows up). By experimentation with data fitting, we identify the analytical form of the solutions on the path connecting the one-hump stationary solution to the two-hump traveling wave. We then derive exact formulas for these solutions by explicitly solving the system of ODE's governing the evolution of solitons using the ansatz suggested by the numerical simulations

A cost-effective process to prepare VO2 (M) powder and films with superior thermochromic properties

International Nuclear Information System (INIS)

Xiao, Xiudi; Zhang, Hua; Chai, Guanqi; Sun, Yaoming; Yang, Tao; Cheng, Haoliang; Chen, Lihua; Miao, Lei; Xu, Gang

2014-01-01

Graphical abstract: Combining codeposition and short time post annealing, VO 2 (M) with high quality and excellent phase transition performance is obtained. After mixing the VO 2 powder with acrylic resin, the composite films deposited on glass show superior visible transmission and solar modulation, which can be used as an excellent candidate of low cost smart window in energy saving field. - Highlights: • The VO 2 powder obtained by short time thermolysis method is high purity and crystallinity with superior phase transition performance. • The maximum decreasing efficiency of phase transition temperature is about −30 K/at% with w = 0.4 at%. • After mixing VO 2 powder with acrylic resin, the maximal visible transmission of the composite films is 48% and the transmission modulation at 2000 nm is 37.3% with phase transition temperature of 66.2 °C. • Though the phase transition performance is weakened by tungsten doping, the film prepared by 1.3 at% tungsten doped VO 2 still show superior transmission modulation about 26.4%, which means that it is a potential candidate as smart windows. - Abstract: VO 2 powder with superior phase transition performance was prepared by convenient thermolysis method. The results illustrated that VO 2 powder show high purity and crystallinity. VO 2 particles are transformed from cluster to quasi-sphere with the increase of annealing temperature. The DSC analysis proves that VO 2 show superior phase transition performance around 68 °C. The phase transition temperature can be reduced to 33.5 °C by 1.8 at% tungsten doping. The maximum decreasing efficiency of phase transition temperature is about −30 K/at% with w = 0.4 at%. After mixing VO 2 powder with acrylic resin, the maximal visible transmission of the composite thin films on glass is 48% and the transmission modulation at 2000 nm is 37.3% with phase transition temperature of 66.2 °C. Though the phase transition performance is weakened by tungsten doping, the film

Contributions to reversed-phase column selectivity: III. Column hydrogen-bond basicity.

Science.gov (United States)

Carr, P W; Dolan, J W; Dorsey, J G; Snyder, L R; Kirkland, J J

2015-05-22

Column selectivity in reversed-phase chromatography (RPC) can be described in terms of the hydrophobic-subtraction model, which recognizes five solute-column interactions that together determine solute retention and column selectivity: hydrophobic, steric, hydrogen bonding of an acceptor solute (i.e., a hydrogen-bond base) by a stationary-phase donor group (i.e., a silanol), hydrogen bonding of a donor solute (e.g., a carboxylic acid) by a stationary-phase acceptor group, and ionic. Of these five interactions, hydrogen bonding between donor solutes (acids) and stationary-phase acceptor groups is the least well understood; the present study aims at resolving this uncertainty, so far as possible. Previous work suggests that there are three distinct stationary-phase sites for hydrogen-bond interaction with carboxylic acids, which we will refer to as column basicity I, II, and III. All RPC columns exhibit a selective retention of carboxylic acids (column basicity I) in varying degree. This now appears to involve an interaction of the solute with a pair of vicinal silanols in the stationary phase. For some type-A columns, an additional basic site (column basicity II) is similar to that for column basicity I in primarily affecting the retention of carboxylic acids. The latter site appears to be associated with metal contamination of the silica. Finally, for embedded-polar-group (EPG) columns, the polar group can serve as a proton acceptor (column basicity III) for acids, phenols, and other donor solutes. Copyright © 2015 Elsevier B.V. All rights reserved.

Disorder trapping by rapidly moving phase interface in an undercooled liquid

Science.gov (United States)

Galenko, Peter; Danilov, Denis; Nizovtseva, Irina; Reuther, Klemens; Rettenmayr, Markus

2017-08-01

Non-equilibrium phenomena such as the disappearance of solute drag, the origin of solute trapping and evolution of disorder trapping occur during fast transformations with originating metastable phases [D.M. Herlach, P.K. Galenko, D. Holland-Moritz, Metastable solids from undrercooled melts (Elsevier, Amsterdam, 2007)]. In the present work, a theoretical investigation of disorder trapping by a rapidly moving phase interface is presented. Using a model of fast phase transformations, a system of governing equations for the diffusion of atoms, and the evolution of both long-range order parameter and phase field variable is formulated. First numerical solutions are carried out for a congruently melting binary alloy system.

Some aspects of the formation of the dispersed phase in aqueous solutions

International Nuclear Information System (INIS)

Ershov, B.G.; Sukhov, N.L.; Troitskii, D.I.

1992-01-01

The experimental results on the formation of silver colloids and some insoluble salts in aqueous solutions are discussed. Colloidal silver particles are formed as a result of radiation-chemical reduction of Ag + ions in deaerated solution containing alcohols or formic acid. Subcolloidal species containing 12-16 atoms are the precursors of the metal sol. The rate of nucleation increases with increasing concentration of indifferent electrolyte (NaClO 4 ) in solution as a result of the change in the ionic strength. Some anions such as sulphate, formate and others are chemisorbed on the subcolloidal silver surfaces, which dramatically decreases their stability. (author)

Phases, periphases, and interphases equilibrium by molecular modeling. I. Mass equilibrium by the semianalytical stochastic perturbations method and application to a solution between (120) gypsum faces

Science.gov (United States)

Pedesseau, Laurent; Jouanna, Paul

2004-12-01

The SASP (semianalytical stochastic perturbations) method is an original mixed macro-nano-approach dedicated to the mass equilibrium of multispecies phases, periphases, and interphases. This general method, applied here to the reflexive relation Ck⇔μk between the concentrations Ck and the chemical potentials μk of k species within a fluid in equilibrium, leads to the distribution of the particles at the atomic scale. The macroaspects of the method, based on analytical Taylor's developments of chemical potentials, are intimately mixed with the nanoaspects of molecular mechanics computations on stochastically perturbed states. This numerical approach, directly linked to definitions, is universal by comparison with current approaches, DLVO Derjaguin-Landau-Verwey-Overbeek, grand canonical Monte Carlo, etc., without any restriction on the number of species, concentrations, or boundary conditions. The determination of the relation Ck⇔μk implies in fact two problems: a direct problem Ck⇒μk and an inverse problem μk⇒Ck. Validation of the method is demonstrated in case studies A and B which treat, respectively, a direct problem and an inverse problem within a free saturated gypsum solution. The flexibility of the method is illustrated in case study C dealing with an inverse problem within a solution interphase, confined between two (120) gypsum faces, remaining in connection with a reference solution. This last inverse problem leads to the mass equilibrium of ions and water molecules within a 3 Å thick gypsum interface. The major unexpected observation is the repulsion of SO42- ions towards the reference solution and the attraction of Ca2+ ions from the reference solution, the concentration being 50 times higher within the interphase as compared to the free solution. The SASP method is today the unique approach able to tackle the simulation of the number and distribution of ions plus water molecules in such extreme confined conditions. This result is of prime

Orientational structure formation of silk fibroin with anisotropic properties in solutions

International Nuclear Information System (INIS)

Kholmuminov, A.A.

2008-06-01

Key words:silk fibroin, dissolution, solution's model systems, gelation, orientational crystallization, optical polarization, longitudinal stream, α - β transition, structure formation, phase transformations, relaxation, anisotropy of swelling and desorption, thermo- and biodegradation. Subjects of the inquiry: silk fibroin is the main subject of investigation. Fibroin's solutions were obtained on the base of water and organic solvents, containing salts. Comparative investigations were carried out by using biosolution - secretion of silkworm, solutions of silk sericin, cotton cellulose, methylcellulose, polystyrene and (co) polycrylonitrile. Aim of the inquiry: the elucidation of the regularities of silk fibroin anisotropic structures formation in the direct generation of orientational ordering in solutions taking into account of influences of its the molecular structures, configuration information, α - β conformational transformations, and development jointly using polarization-optical and hydrodynamic methods to control of structure formation. And also definition of possibility fields for use biopolymers anisotropic structure formation principles. Method of inquiry: birefringence, dispersion optical rotation, circular dichroism, polarization- ultramicroscope, ultracentrifuge, viscosimetry, potentiometry, differential thermal analysis, chromatography, x-ray analysis, spectroscopy. The results achieved and their novelty: the physical regularity amorphous-crystalline fibroin dissolutions in salt-containing solvents based on chains melting, distribution and redistribution were recognized; fibroin statistical parameters, molecular-mass and conformational characteristics were established; It was shown that fibroin molecules turned into fully uncoiled and oriented state with the breakdown decay of α-spiral chain sections by I type phase transition mechanism, but in oriented state with α-spiral conservation by II type transition; the presence of longitudinal field

New wine in old flasks: a new solution of the Clapeyron equation

Energy Technology Data Exchange (ETDEWEB)

Shilo, Doron [Department of Mechanical Engineering, Technion, Haifa 32000 (Israel); Ghez, Richard [Department of Materials Engineering, Technion, Haifa 32000 (Israel)

2008-01-15

The coexisting equilibrium states between single-component gas and condensed phases (liquid or solid) are often calculated by assuming that the condensed phase's molar volume is negligible in comparison with the gas's. Here, we present an analytic solution of Clapeyron's equation when this assumption is relaxed. It differs substantially from Clausius's solution because, mathematically, it is not always monotonic. Our solution depends essentially on the dimensionless ratio pv/L, where p is the gas pressure, v is the condensed phase's molar volume and L is the molar latent heat of the phase transition. Similar to Clausius's, our calculation is predicated on the assumption of weakly varying L and v, and of ideal gas behaviour. These assumptions are discussed in the end of this paper.

Single-phase high-entropy alloys. An overview

Energy Technology Data Exchange (ETDEWEB)

Kozak, Roksolana; Steurer, Walter [ETH Zurich (Switzerland). Lab. of Crystallography; Sologubenko, Alla [ETH Zurich (Switzerland). Lab. of Nanotechnology

2015-02-01

The term 'high-entropy alloys (HEAs)' first appeared about 10 years ago defining alloys composed of n=5-13 principal elements with concentrations of approximately 100/n at.% each. Since then many equiatomic (or near equiatomic) single- and multi-phase multicomponent alloys were developed, which are reported for a combination of tunable properties: high hardness, strength and ductility, oxidation and wear resistance, magnetism, etc. In our paper, we focus on probably single-phase HEAs (solid solutions) out of all HEAs studied so far, discuss ways of their prediction, mechanical properties. In contrast to classical multielement/multiphase alloys, only single-phase multielement alloys (solid solutions) represent the basic concept underlying HEAs as mixing-entropy stabilized homogenous materials. The literature overview is complemented by own studies demonstrating that the alloys CrFeCoNi, CrFeCoNiAl{sub 0.3} and PdFeCoNi homogenized at 1300 and 1100 C, respectively, for 1 week are not single-phase HEAs, but a coherent mixture of two solid solutions.

Synthesis, thermolysis and pyrolysis of group IV metal pinacolates: The impact of a vicinal diol as a supporting ligand for molecular precursors

Science.gov (United States)

Zechmann, Cecilia A.

In an effort to investigate the suitability of an alternative ligand class for molecular precursors, the following studies were carried out: (1) New zirconium species were obtained by reaction of zirconium isopropoxide alcoholate, Zr2(OiPr)8(HOiPr) 2, with pinacol (HOCMe2CMe2OH). Control of reaction stoichiometries followed by azeotropic distillation of evolved isopropanol led to the successful preparation of a range of homo- and heteroleptic trinuclear species, Zr3(OCMe2CMe2O)2(O iPr)8(HOiPr)2, Zr3(OCMe 2CMe2O)4(OCMe2CMe2OH) 2(OiPr)2, and Zr3(OCMe2CMe 2O)4(OCMe2CMe2OH)4. Dinuclear products could be obtained by carrying out the reactions at room temperature or by addition of excess pinacol (in which case Zr2(OCMe2 CMe2O)2(OCMe2CMe2OH) 4 was the product). (2) Similar reactions between Ti(Oi Pr)4 and pinacol gave dinuclear products under all conditions. Both homo- (Ti2(OiPr)2(OCMe2CMe 2O)2(OCMe2CMe2OH)2) and heterometallic complexes (Ti2(OCMe2CMe2O) 2(OCMe2CMe2OH)4) were characterized. (3) Controlled addition of water to either of the isolated titanium pinacolates gave Ti3(mu3-O)(OCMe2CMe2O) 4(OCMe2CMe2OH)2. (4) Reaction of zirconium pinacolates with water led to the isolation of Zr4(mu 2-O)(OCMe2CMe2O)4(OCMe2CMe 2OH)6 and Zr6(mu3-O)4(H 2O)2(OCMe2CMe2O)5(OCMe 2CMe2OH)5. 17O NMR studies aided in the investigation of active equilibria and reversibility of hydrolysis. (5) The thermolysis of Zr2(OCMe2CMe2O) 2(OCMe2CMe2OH)4 gave ZrO2 in a mixture of crystalline phases. GC-MS and NMR analysis of the volatiles revealed 4 C6 products as well as two ligand coupled products. Isotope-labeling studies were carried out to probe the mechanisms by which the organic products were formed. (6) Reaction of Zr2(OCMe 2CMe2O)2(OCMe2CMe2OH) 4 with Ti(OiPr)4 gives (OiPr) 2TiZr2(OCMe2CMe2O)4(OCMe 2CMe2OH)2 which reacts with a second equivalent of Ti(OiPr)4 to give (OiPr) 4Ti2Zr2(OCMe2CMe2O) 6. (7) Reaction of Li{N(SiMe3)2}·Et 2O or Na{N(SiMe3)2}·x THF with Zr2(OCMe2CMe2O)2(OCMe 2CMe2OH)4

An exact solution of two friendly interacting directed walks near a sticky wall

International Nuclear Information System (INIS)

Tabbara, R; Owczarek, A L; Rechnitzer, A

2014-01-01

We find the exact solution of two interacting friendly directed walks (modelling polymers) on the square lattice. These walks are confined to the quarter plane by a horizontal attractive surface, to capture the effects of DNA-denaturation and adsorption. We find the solution to the model’s corresponding generating function by means of the obstinate kernel method. Specifically, we apply this technique in two different instances to establish partial solutions for two simplified generating functions of the same underlying model that ignore either surface or shared contacts. We then subsequently combine our two partial solutions to find the solution for the full generating function in terms of the two simpler variants. This expression guides our analysis of the model, where we find the system exhibits four phases, and proceed to delineate the full phase diagram, showing that all observed phase transitions are second-order. (paper)

Study of Sigma Phase in Duplex SAF 2507

Science.gov (United States)

Fellicia, D. M.; Sutarsis; Kurniawan, B. A.; Wulanari, D.; Purniawan, A.; Wibisono, A. T.

2017-05-01

Super duplex stainless steel is one of the stainless steel which has a combination between high strength properties and excellent corrosion resistance. However, the resistance can decrease by precipitation of sigma phase which is formed at high temperature, for example after welding processes. A series of experiments has been performed to study the effect of solution annealing to existence of sigma phase on super duplex SAF 2507. Variations of solution-annealing temperatures were 1000 °C, 1065 °C and 1125 °C with holding time of 15 and 30 minutes for each temperature. Effect of solution annealing process was characterized by using XRD, SEM, and Optical Microscopy. The result showed precipitation of sigma phase completely dissolved at 1065 °C and 1125 °C because it reformed to austenite. After it was heated at 1065 °C, chromium carbide appeared in ferrite site and grain boundary. The amount of chromium carbide increased with the increasing of solution annealing temperature.

Perovskite phase thin films and method of making

Science.gov (United States)

Boyle, Timothy J.; Rodriguez, Mark A.

2000-01-01

The present invention comprises perovskite-phase thin films, of the general formula A.sub.x B.sub.y O.sub.3 on a substrate, wherein A is selected from beryllium, magnesium, calcium, strontium, and barium or a combination thereof; B is selected from niobium and tantalum or a combination thereof; and x and y are mole fractions between approximately 0.8 and 1.2. More particularly, A is strontium or barium or a combination thereof and B is niobium or tantalum or a combination thereof. Also provided is a method of making a perovskite-phase thin film, comprising combining at least one element-A-containing compound, wherein A is selected from beryllium, magnesium, calcium, strontium or barium, with at least one element-B-containing compound, wherein B niobium or tantalum, to form a solution; adding a solvent to said solution to form another solution; spin-coating the solution onto a substrate to form a thin film; and heating the film to form the perovskite-phase thin film.

The synthesis of aqueous-dispersible anatase TiO2 nanoplatelets

International Nuclear Information System (INIS)

Shan Guobin; Demopoulos, George P

2010-01-01

Aqueous well-dispersed and phase-pure anatase TiO 2 truncated octahedron nanoplatelets (NPLs) were prepared via controlled hydrolysis of titanium tetrachloride (TiCl 4 ) in ethylene glycol at 240 deg. C. Two shapes, square and hexagon, were observed by microscopy, exactly corresponding to the truncated octahedron NPLs. Ethylene glycol was found to produce water in situ that reacts with TiCl 4 to produce TiO 2 and HCl-the latter promoting TiO 2 colloid peptization. TiO 2 truncated octahedron NPLs are formed under the stabilizing action of ethylene glycol thermolysis derivatives, such as aldehydes. Crystal growth of the TiO 2 NPLs was affected by the reaction temperature that determines the water production rate and HCl-assisted peptization. TGA and FT-IR results showed ∼1.2% ethylene glycol thermolysis derivatives are attached to the surface of the TiO 2 NPLs, which prevents their agglomeration, hence making them easily dispersible in aqueous media. HR-TEM and SAED results showed that the TiO 2 NPLs are well crystallized and that the SAED patterns of the single TiO 2 NPL changes with its size and shape. XRD patterns showed that the TiO 2 NPLs are phase-pure anatase and the percentage of the {101} plane in the TiO 2 NPLs to be only 18%-a structural feature that renders the TiO 2 NPLs with enhanced UV absorption and reactivity properties.

Thermal processing of Khoot coal and characterization of obtained solid and liquid products

Directory of Open Access Journals (Sweden)

S Batbileg

2014-12-01

Full Text Available On 21st January 2015, the abstract of this paper was replaced with the correct abstract.The coal of Khoot deposit have been investigated and determined the technical characteristics, elemental and petrographical maceral compositions. On the basis of proximate, ultimate, petrographic and IR analysis results have been confirmed that the Khoot coal is a sub-bituminous coal. The hard residue after pyrolysis have been activated by heated water steam and determined the iodine and methylene blue adsorption of initial coal and activated carbon samples from pyrolysis hard residue. The porosity structure of initial coal, activated carbon of pyrolysis hard residue and hard residue after thermolysis (thermal dissolution have been determined by SEM analysis. The liquid tar product of thermolysis of Khoot coal was investigated by FTIR, 13C and 1H NMR spectrometric analysis. The results of thermolysis of Khoot coal in tetralin with constant mass ratio between coal and tetralin (1:1.8 at 450°C show that 60.8% of liquid product can be obtained after thermolysis of the coal organic mass.DOI: http://doi.dx.org/10.5564/mjc.v15i0.326 Mongolian Journal of Chemistry 15 (41, 2014, p66-72

Precipitation of Nd-Ca carbonate solid solution at 25 degrees C

International Nuclear Information System (INIS)

Carroll, S.A.

1993-01-01

The formation of a Nd-Ca carbonate solid solution was studied by monitoring the reactions of calcite with aqueous Nd, orthorhombic NdOHCO 3 (s) with aqueous Ca, and calcite with hexagonal Nd-carbonate solid phase as a function of time at 25 degrees C and controlled pCO 2 (g). All experiments reached steady state after 200 h of reaction. The dominant mechanism controlling the formation of the solid solution was precipitation of a Nd-Ca carbonate phase from the bulk solution as individual crystals or at the orthorhombic NdOHCO 3 (s)-solution interface. The lack of Nd adsorption or solid solution at the calcite-solution interface suggests that the solid solution was orthorhombic and may be modeled as a mixture of orthorhombic NdOHCO 3 (s) and aragonite. Orthorhombic NdOHCO 3 (s) was determined to be the stable Nd-carbonate phase in the Nd-CO 2 -H 2 O system at pCO 2 (g) 0.1 atmospheres at 25 degrees C. The equilibrium constant corrected to zero ionic strength for orthorhombic NdOHCO 3 (s) solubility is 10 10.41(±0.29) for the following: NdOHCO 3 (s) + 3H + = Nd 3+ + CO 2 (g) + H 2 O. Results are discussed in relation to radioactive waste disposal by burial, and specifically in relation to americium chemistry

Modeling solute segregation during the solidification of γ-phase U-Mo alloys

Energy Technology Data Exchange (ETDEWEB)

Steiner, M.A., E-mail: mas4cw@virginia.edu [University of Virginia, Material Science and Engineering, 395 McCormick Rd, Charlottesville, VA 22904 (United States); Garlea, E. [Y-12 National Security Complex, Oak Ridge, TN 37831 (United States); Agnew, S.R. [University of Virginia, Material Science and Engineering, 395 McCormick Rd, Charlottesville, VA 22904 (United States)

2016-06-15

Using first principles calculations, it is demonstrated that solute segregation during U-Mo solidification can be modeled using the classic Brody-Fleming limited diffusion framework. The necessary supporting equations specific to the U-Mo alloy, along with careful verification of the assumptions underpinning the Brody-Fleming model are developed, allowing for concentration profile predictions as a function of alloy composition and cooling rate. The resulting model is compared to experimental solute concentration profiles, showing excellent agreement. Combined with complementary modeling of dendritic feature sizes, the solute segregation model can be used to predict the complete microstructural state of individual U-Mo volume elements based upon cooling rates, informing ideal processing routes.

Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution.

Science.gov (United States)

Comitani, Federico; Rossi, Kevin; Ceriotti, Michele; Sanz, M Eugenia; Molteni, Carla

2017-04-14

The conformational free energy landscape of aspartic acid, a proteogenic amino acid involved in a wide variety of biological functions, was investigated as an example of the complexity that multiple rotatable bonds produce even in relatively simple molecules. To efficiently explore such a landscape, this molecule was studied in the neutral and zwitterionic forms, in the gas phase and in water solution, by means of molecular dynamics and the enhanced sampling method metadynamics with classical force-fields. Multi-dimensional free energy landscapes were reduced to bi-dimensional maps through the non-linear dimensionality reduction algorithm sketch-map to identify the energetically stable conformers and their interconnection paths. Quantum chemical calculations were then performed on the minimum free energy structures. Our procedure returned the low energy conformations observed experimentally in the gas phase with rotational spectroscopy [M. E. Sanz et al., Phys. Chem. Chem. Phys. 12, 3573 (2010)]. Moreover, it provided information on higher energy conformers not accessible to experiments and on the conformers in water. The comparison between different force-fields and quantum chemical data highlighted the importance of the underlying potential energy surface to accurately capture energy rankings. The combination of force-field based metadynamics, sketch-map analysis, and quantum chemical calculations was able to produce an exhaustive conformational exploration in a range of significant free energies that complements the experimental data. Similar protocols can be applied to larger peptides with complex conformational landscapes and would greatly benefit from the next generation of accurate force-fields.

Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution

Science.gov (United States)

Comitani, Federico; Rossi, Kevin; Ceriotti, Michele; Sanz, M. Eugenia; Molteni, Carla

2017-04-01

The conformational free energy landscape of aspartic acid, a proteogenic amino acid involved in a wide variety of biological functions, was investigated as an example of the complexity that multiple rotatable bonds produce even in relatively simple molecules. To efficiently explore such a landscape, this molecule was studied in the neutral and zwitterionic forms, in the gas phase and in water solution, by means of molecular dynamics and the enhanced sampling method metadynamics with classical force-fields. Multi-dimensional free energy landscapes were reduced to bi-dimensional maps through the non-linear dimensionality reduction algorithm sketch-map to identify the energetically stable conformers and their interconnection paths. Quantum chemical calculations were then performed on the minimum free energy structures. Our procedure returned the low energy conformations observed experimentally in the gas phase with rotational spectroscopy [M. E. Sanz et al., Phys. Chem. Chem. Phys. 12, 3573 (2010)]. Moreover, it provided information on higher energy conformers not accessible to experiments and on the conformers in water. The comparison between different force-fields and quantum chemical data highlighted the importance of the underlying potential energy surface to accurately capture energy rankings. The combination of force-field based metadynamics, sketch-map analysis, and quantum chemical calculations was able to produce an exhaustive conformational exploration in a range of significant free energies that complements the experimental data. Similar protocols can be applied to larger peptides with complex conformational landscapes and would greatly benefit from the next generation of accurate force-fields.

Phase equilibria in chemical reactive fluid mixtures

International Nuclear Information System (INIS)

Maurer, Gerd

2011-01-01

Downstream processing is a major part of nearly all processes in the chemical industries. Most separation processes in the chemical (and related) industries for fluid mixtures are based on phase equilibrium phenomena. The majority of separation processes can be modelled assuming that chemical reactions are of no (or very minor) importance, i.e., assuming that the overall speciation remains unchanged during a separation process. However, there are also a large number of industrially important processes where the thermodynamic properties are influenced by chemical reactions. The phase equilibrium of chemical reactive mixtures has been a major research area of the author's group over nearly 40 years. In this contribution, three examples from that research are discussed. The first example deals with the vapour phase dimerisation of carboxylic acids and its consequences on phase equilibrium phenomena and phase equilibrium predictions. The second example deals with the solubility of sour gases (e.g., carbon dioxide and sulfur dioxide) in aqueous solutions of ammonia. That topic has been of interest for many years, e.g., in relation with the gasification and liquefaction of coal and, more recently, with the removal of carbon dioxide from flue gas in the 'chilled ammonia process'. The third example deals with phase equilibrium phenomena in aqueous solutions of polyelectrolytes. It deals with the phenomenon of 'counter ion condensation' and methods to model the Gibbs free energy of such solutions.

Phase-locked patterns of the Kuramoto model on 3-regular graphs

Science.gov (United States)

DeVille, Lee; Ermentrout, Bard

2016-09-01

We consider the existence of non-synchronized fixed points to the Kuramoto model defined on sparse networks: specifically, networks where each vertex has degree exactly three. We show that "most" such networks support multiple attracting phase-locked solutions that are not synchronized and study the depth and width of the basins of attraction of these phase-locked solutions. We also show that it is common in "large enough" graphs to find phase-locked solutions where one or more of the links have angle difference greater than π/2.

Na-Si binary phase diagram and solution growth of silicon crystals

International Nuclear Information System (INIS)

Morito, H.; Yamada, T.; Ikeda, T.; Yamane, H.

2009-01-01

In the present study, a Na-Si binary phase diagram was first presented from the results of differential thermal analysis and X-ray diffraction. Based on the phase diagram, we performed low-temperature formation of single crystals, film and porous bulk of Si by vaporizing Na from a Na-Si melt at 800 or 900 deg. C.

Investigations on the oxidation of nitric acid plutonium solutions with ozone

International Nuclear Information System (INIS)

Boehm, M.

1983-01-01

The reaction of ozone with nitric acid Pu solutions was studied as a function of reaction time, acid concentration and Pu concentration. Strong nitric acid Pu solutions are important in nuclear fuel element production and reprocessing. The Pu must be converted into hexavalent Pu before precipitation from the homogeneous solution together with uranium-IV, ammonia and CO 2 in the form of ammonium uranyl/plutonyl carbonate (AUPuC). Formation of a solid phase during ozonation was observed for the first time. The proneness to solidification increases with incrasing plutonium concentrations and with decreasing acid concentrations. If the formation of a solid phase during ozonation of nitric acid Pu solutions cannot be prevented, the PU-IV oxidation process described is unsuitable for industrial purposes as Pu solutions in industrial processes have much higher concentrations than the solutions used in the present investigation. (orig./EF) [de

Effects of viscoelastic ophthalmic solutions on cell cultures

Directory of Open Access Journals (Sweden)

Madhavan Hajib

1998-01-01

Full Text Available The development of mild but significant inflammation probably attributable to viscoelastic ophthalmic solutions in cataract surgery was recently brought to the notice of the authors, and hence a study of the effects of these solutions available in India, on cell cultures was undertaken. We studied the effects of 6 viscoelastic ophthalmic solutions (2 sodium hyaluronate designated as A and B, and 4 hydroxypropylmethylcellulose designated as C, D, E and F on HeLa, Vero and BHK-21 cell lines in tissue culture microtitre plates using undiluted, 1:10 and 1:100 dilutions of the solutions, and in cover slip cultures using undiluted solutions. Phase contrast microscopic examination of the solutions was also done to determine the presence of floating particles. The products D and F produced cytotoxic changes in HeLa cell line and these products also showed the presence of floating particles under phase contrast microscopy. Other products did not have any adverse effects on the cell lines nor did they show floating particles. The viscoelastic ophthalmic pharmaceutical products designated D and F have cytotoxic effects on HeLa cell line which appears to be a useful cell line for testing these products for their toxicity. The presence of particulate materials in products D and F indicates that the methods used for purification of the solution are not effective.

Phases of Kaluza-Klein black holes

DEFF Research Database (Denmark)

Elvang, Henriette; Obers, Niels; Harmark, Troels

2004-01-01

We review the latest progress in understanding the phase structure of static and neutral Kaluza-Klein black holes, i.e. static and neutral solutions of pure gravity with an event horizon and with asymptotics Md × S1, Md being d-dimensional Minkowski space.......We review the latest progress in understanding the phase structure of static and neutral Kaluza-Klein black holes, i.e. static and neutral solutions of pure gravity with an event horizon and with asymptotics Md × S1, Md being d-dimensional Minkowski space....

Geometric analysis of the solutions of two-phase flows: two-fluid model

International Nuclear Information System (INIS)

Kestin, J.; Zeng, D.L.

1984-01-01

This report contains a lightly edited draft of a study of the two-fluid model in two-phase flow. The motivation for the study stems from the authors' conviction that the construction of a computer code for any model should be preceded by a geometrical analysis of the pattern of trajectories in the phase space appropriate for the model. Such a study greatly facilitates the understanding of the phenomenon of choking and anticipates the computational difficulties which arise from the existence of singularities. The report contains a derivation of the six conservation equations of the model which includes a consideration of the simplifications imposed on a one-dimensional treatment by the presence of boundary layers at the wall and between the phases. The model is restricted to one-dimensional adiabatic flows of a single substance present in two phases, but thermodynamic equilibrium between the phases is not assumed. The role of closure conditions is defined but no specific closure conditions, or explicit equations of state, are introduced

A novel numerical approach for the solution of the problem of two-phase, immiscible flow in porous media: Application to LNAPL and DNAPL

KAUST Repository

Salama, Amgad

2012-06-17

The flow of two immiscible fluids in porous media is ubiquitous particularly in petroleum exploration and extraction. The displacement of one fluid by another immiscible with it represents a very important aspect in what is called enhanced oil recovery. Another example is related to the long-term sequestration of carbon dioxide, CO2 , in deep geologic formations. In this technique, supercritical CO2 is introduced into deep saline aquifer where it displaces the hosting fluid. Furthermore, very important classes of contaminants that are very slightly soluble in water and represent a huge concern if they get introduced to groundwater could basically be assumed immiscible. These are called light non-aqueous phase liquids (LNAPL) and dense non-aqueous phase liquids (DNAPL). All these applications necessitate that efficient algorithms be developed for the numerical solution of these problems. In this work we introduce the use of shifting matrices to numerically solving the problem of two-phase immiscible flows in the subsurface. We implement the cell-center finite difference method which discretizes the governing set of partial differential equations in conservative manner. Unlike traditional solution methodologies, which are based on performing the discretization on a generic cell and solve for all the cells within a loop, in this technique, the cell center information for all the cells are obtained all at once without loops using matrix oriented operations. This technique is significantly faster than the traditional looping algorithms, particularly for larger systems when coding using languages that require repeating interpretation each time a loop is called like Mat Lab, Python and the like. We apply this technique to the transport of LNAPL and DNAPL into a rectangular domain.

α-Bromodiazoacetamides – a new class of diazo compounds for catalyst-free, ambient temperature intramolecular C–H insertion reactions

Directory of Open Access Journals (Sweden)

Åsmund Kaupang

2013-07-01

Full Text Available In this work, we introduce a new class of halodiazocarbonyl compounds, α-halodiazoacetamides, which through a metal-free, ambient-temperature thermolysis perform intramolecular C–H insertions to produce α-halo-β-lactams. When carried out with α-bromodiazoacetamides bearing cyclic side chains, the thermolysis reaction affords bicyclic α-halo-β-lactams, in some cases in excellent yields, depending on the ring size and substitution pattern of the cyclic amide side chains.

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

Science.gov (United States)

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.

Aqueous two-phase system patterning of detection antibody solutions for cross-reaction-free multiplex ELISA

Science.gov (United States)

Frampton, John P.; White, Joshua B.; Simon, Arlyne B.; Tsuei, Michael; Paczesny, Sophie; Takayama, Shuichi

2014-05-01

Accurate disease diagnosis, patient stratification and biomarker validation require the analysis of multiple biomarkers. This paper describes cross-reactivity-free multiplexing of enzyme-linked immunosorbent assays (ELISAs) using aqueous two-phase systems (ATPSs) to confine detection antibodies at specific locations in fully aqueous environments. Antibody cross-reactions are eliminated because the detection antibody solutions are co-localized only to corresponding surface-immobilized capture antibody spots. This multiplexing technique is validated using plasma samples from allogeneic bone marrow recipients. Patients with acute graft versus host disease (GVHD), a common and serious condition associated with allogeneic bone marrow transplantation, display higher mean concentrations for four multiplexed biomarkers (HGF, elafin, ST2 and TNFR1) relative to healthy donors and transplant patients without GVHD. The antibody co-localization capability of this technology is particularly useful when using inherently cross-reactive reagents such as polyclonal antibodies, although monoclonal antibody cross-reactivity can also be reduced. Because ATPS-ELISA adapts readily available antibody reagents, plate materials and detection instruments, it should be easily transferable into other research and clinical settings.

Phase-space formalism: Operational calculus and solution of evolution equations in phase-space

International Nuclear Information System (INIS)

Dattoli, G.; Torre, A.

1995-05-01

Phase-space formulation of physical problems offers conceptual and practical advantages. A class of evolution type equations, describing the time behaviour of a physical system, using an operational formalism useful to handle time ordering problems has been described. The methods proposed generalize the algebraic ordering techniques developed to deal with the ordinary Schroedinger equation, and how they are taylored suited to treat evolution problems both in classical and quantum dynamics has been studied

Achievement report for 1st phase (fiscal 1974-80) Sunshine Program research and development - Hydrogen energy. Research on fuel cell (Research on high-temperature solid electrolyte fuel cell); 1974-1980 nendo suiso energy seika hokokusho. Nenryo denchi no kenkyu (koon kotai denkaishitsu nenryo denchi no kenkyu)

Energy Technology Data Exchange (ETDEWEB)

NONE

1981-03-01

Relative to the research and development of technologies for fabricating, and assessing, materials for the constitution of high-temperature solid electrolyte fuel cells, stabilized zirconia solid electrolyte fuel cell manufacturing technologies are developed by use of thin film formation techniques such as high-frequency sputtering, plasma CVD (chemical vapor deposition), and the thermolysis of organic zirconia compound coating. As the result, it is found that high-frequency sputtering produces thin film which is satisfying in terms of cost efficiency. Furthermore, it is found that defects in solid electrolytic thin film formed by the high-frequency sputtering method, that is, pinholes and cracks, will be remedied when the coating thermolysis method is jointly applied. In the research on fuel cell power systems, column-type high-temperature solid electrolyte fuel cells are built, and a power generation test is conducted. The test is successfully completed when the output of a fuel cell of the 9-column module structure gradually increases until a maximum output of 110W is achieved. (NEDO)

Effect of solution heat treatment time on a rheocast Al-Zn-Mg-Cu alloy

CSIR Research Space (South Africa)

Mazibuko, NE

2011-06-01

Full Text Available During rheo-high pressure die casting (R-HPDC) of Al-Zn-Mg-Cu alloys a coarse eutectic phase is formed. This eutectic phase is difficult to take into solution because of its size and it would require longer solution heat treatment times...

Reinforced PEI/PVdF Multicore-Shell Structure Composite Membranes by Phase Prediction on a Ternary Solution

Directory of Open Access Journals (Sweden)

Jihye Chae

2018-04-01

Full Text Available To construct a polyetherimide (PEI-reinforced polyvinylidene fluoride (PVdF composite membrane with multicore-shell structure, a ternary solution was prepared and electrospun by single-nozzle electrospinning. A theoretical prediction was made for the feasibility of complete distinction of two phases. The diameters of the membrane fibers and the PEI multi-core fibrils varied with the PEI ratio and the spinning time, respectively. The tensile strength and modulus were improved to 48 MPa and 1.5 GPa, respectively. The shrinkage of the membrane was only 6.6% at 180 °C, at which temperature the commercial PE separator melted down. The reinforcement in mechanical and thermal properties is associated with multiple PEI nanofibrils oriented along the fiber axis. Indeed, the unique morphology of self-assembled multicore-shell fibers plays an important role in their properties. All in all, PEI/PVdF membranes are appropriate for a lithium-ion battery application due to their high mechanical strength, excellent thermal stability, and controllable textural properties.

On hierarchical solutions to the BBGKY hierarchy

Science.gov (United States)

Hamilton, A. J. S.

1988-01-01

It is thought that the gravitational clustering of galaxies in the universe may approach a scale-invariant, hierarchical form in the small separation, large-clustering regime. Past attempts to solve the Born-Bogoliubov-Green-Kirkwood-Yvon (BBGKY) hierarchy in this regime have assumed a certain separable hierarchical form for the higher order correlation functions of galaxies in phase space. It is shown here that such separable solutions to the BBGKY equations must satisfy the condition that the clustered component of the solution has cluster-cluster correlations equal to galaxy-galaxy correlations to all orders. The solutions also admit the presence of an arbitrary unclustered component, which plays no dyamical role in the large-clustering regime. These results are a particular property of the specific separable model assumed for the correlation functions in phase space, not an intrinsic property of spatially hierarchical solutions to the BBGKY hierarchy. The observed distribution of galaxies does not satisfy the required conditions. The disagreement between theory and observation may be traced, at least in part, to initial conditions which, if Gaussian, already have cluster correlations greater than galaxy correlations.

In Situ Observations of Thermoreversible Gelation and Phase Separation of Agarose and Methylcellulose Solutions under High Pressure.

Science.gov (United States)

Kometani, Noritsugu; Tanabe, Masahiro; Su, Lei; Yang, Kun; Nishinari, Katsuyoshi

2015-06-04

Thermoreversible sol-gel transitions of agarose and methylcellulose (MC) aqueous solutions on isobaric cooling or heating under high pressure up to 400 MPa have been investigated by in situ observations of optical transmittance and falling-ball experiments. For agarose, which undergoes the gelation on cooling, the application of pressure caused a gradual rise in the cloud-point temperature over the whole pressure range examined, which is almost consistent with the pressure dependence of gelling temperature estimated by falling-ball experiments, suggesting that agarose gel is stabilized by compression and that the gelation occurs nearly in parallel with phase separation under ambient and high-pressure conditions. For MC, which undergoes the gelation on heating, the cloud-point temperature showed a slight rise with an initial elevation of pressure up to ∼150 MPa, whereas it showed a marked depression above 200 MPa. In contrast, the gelling temperature of MC, which is nearly identical to the cloud-point temperature at ambient pressure, showed a monotonous rise with increasing pressure up to 350 MPa, which means that MC undergoes phase separation prior to gelation on heating under high pressure above 200 MPa. Similar results were obtained for the melting process of MC gel on cooling. The unique behavior of the sol-gel transition of MC under high pressure has been interpreted in terms of the destruction of hydrophobic hydration by compression.

Improvement of stress-rupture life of GTD-111 by second solution heat treatment

International Nuclear Information System (INIS)

Yang, Caixiong; Xu, Yulai; Zhang, Zixing; Nie, Heng; Xiao, Xueshan; Jia, Guoqing; Shen, Zhi