Chemical thermodynamic representations of and

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

Besmann, T.M.; Lindemer, T.B.

1984-01-01

All available oxygen potential-temperature-composition data for the calcium fluorite-structure phase were retrieved from the literature and utilized in the development of a binary solid solution representation of the phase. The data and phase relations are found to be best described by a solution of (Pu/sub 4/3/O/sub 2/) and (PuO/sub 2/) with a temperature dependent interaction energy. The fluorite-structure is assumed to be represented by a combination of the binaries and , and thus treated as a solution of (Pu/sub 4/3/O/sub 2/), (PuO/sub 2/), (UO/sub 2/), and either (U/sub 2/O/sub 4/./sub 5/) or (U/sub 3/O/sub 7/). The resulting equations wellmore » reproduce the large amount of oxygen potential-temperature-composition data for the mixed oxide system, all of which were also retrieved from the literature. These models are the first that appear to display the appropriate oxygen potential-temperature-composition and phase relation behavior over the entire range of existence for the phases. 39 refs., 10 figs., 3 tabs.« less

Effect of solution treatment on microstructure and properties of duplex stainless steel

NASA Astrophysics Data System (ADS)

Wang, X. Y.; Luo, J. M.; Huang, L. Q.; Wang, H. B.; Ma, C. W.

2017-09-01

The influence of solution treatment on microstructure and properties of 2205 duplex stainless steel (DSS) was studied. The microstructure, precipitates and corrosion resisting property were observed and analyzed by means of optical microscopy (OM), scanning electron microscopy (SEM) and electrochemical methods. The results showed that a large number of brittle σ-phase precipitates, which deteriorate the plasticity and corrosion resistance of the material, were easy to produce in the duplex stainless steel under the low temperature. The precipitation of σ-phase can be decreased and the plasticity and corrosion resistance can be improved by increasing solution temperature. In addition, the ferrite content increases with the increase of solution temperature, while less affected by cooling rate.

Study of Ti 4+ substitution in ZrW 2O 8 negative thermal expansion materials

NASA Astrophysics Data System (ADS)

De Buysser, Klaartje; Van Driessche, Isabel; Putte, Bart Vande; Schaubroeck, Joseph; Hoste, Serge

2007-08-01

Powder XRD-analysis and thermo-mechanical analysis on sintered TiO 2-WO 3-ZrO 2 mixtures revealed the formation of Zr 1-xTi xW 2O 8 solid solutions. A noticeable decrease in unit cell parameter ' a' and in the order-disorder transition temperature could be seen in the case of Zr 1-xTi xW 2O 8 solid solutions. Studies performed on other ZrW 2O 8 solid solutions have attributed an increase in phase transition temperature to a decrease in free lattice volume, whereas a decrease in phase transition temperature was suggested to be due to the presence of a more disordered state. Our studies indicate that the phase transition temperature in our materials is strongly influenced by the bond dissociation energy of the substituting ion-oxygen bond. A decrease in bond strength may compensate for the effect of a decrease in lattice free volume, lowering the phase transition temperature as the degree of substitution by Ti 4+ increases. This hypothesis is proved by differential scanning calorimetry.

Prediction of ice content in biological model solutions when frozen under high pressure.

PubMed

Guignon, B; Aparicio, C; Otero, L; Sanz, P D

2009-01-01

High pressure is, at least, as effective as cryoprotective agents (CPAs) and are used for decreasing both homogenous nucleation and freezing temperatures. This fact gives rise to a great variety of possible cryopreservation processes under high pressure. They have not been optimized yet, since they are relatively recent and are mainly based on the pressure-temperature phase diagram of pure water. Very few phase diagrams of biological material are available under pressure. This is owing to the lack of suitable equipment and to the difficulties encountered in carrying out the measurements. Different aqueous solutions of salt and CPAs as biological models are studied in the range of 0 degrees C down to -35 degrees C, 0.1 up to 250 MPa, and 0-20% w/w total solute concentration. The phase transition curves of glycerol and of sodium chloride with either glycerol or sucrose in aqueous solutions are determined in a high hydrostatic pressure vessel. The experimental phase diagrams of binary solutions were well described by a third-degree polynomial equation. It was also shown that Robinson and Stokes' equation at high pressure succeeds in predicting the phase diagrams of both binary and ternary solutions. The solute cryoconcentration and the ice content were calculated as a function of temperature and pressure conditions during the freezing of a binary solution. This information should provide a basis upon which high-pressure cryopreservation processes may be performed and the damages derived from ice formation evaluated. (c) 2009 American Institute of Chemical Engineers Biotechnol.

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

PubMed

Kanno, H; Kajiwara, K; Miyata, K

2010-05-21

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 T(H) (homogeneous ice nucleation temperature) and T(m) (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 T(H) 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 P(c2)= approximately 200 MPa and at T(c2)<-100 degrees C (P(c2): pressure of SCP, T(c2): temperature of SCP). The presence of two T(H) peaks for DMSO solutions (R=15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R

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

NASA Astrophysics Data System (ADS)

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 Tc2<-100 °C (Pc2: pressure 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 (<-90 °C). The 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.

Accelerated formation of cubic phases in phosphatidylethanolamine dispersions.

PubMed Central

Tenchov, B; Koynova, R; Rapp, G

1998-01-01

By means of x-ray diffraction we show that several sodium salts and the disaccharides sucrose and trehalose strongly accelerate the formation of cubic phases in phosphatidylethanolamine (PE) dispersions upon temperature cycling through the lamellar liquid crystalline-inverted hexagonal (Lalpha-HII) phase transition. Ethylene glycol does not have such an effect. The degree of acceleration increases with the solute concentration. Such an acceleration has been observed for dielaidoyl PE (DEPE), dihexadecyl PE, and dipalmitoyl PE. It was investigated in detail for DEPE dispersions. For DEPE (10 wt% of lipid) aqueous dispersions at 1 M solute concentration, 10-50 temperature cycles typically result in complete conversion of the Lalpha phase into cubic phase. Most efficient is temperature cycling executed by laser flash T-jumps. In that case the conversion completes within 10-15 cycles. However, the cubic phases produced by laser T-jumps are less ordered in comparison to the rather regular cubic structures produced by linear, uniform temperature cycling at 10 degrees C/min. Temperature cycles at scan rates of 1-3 degrees C/min also induce the rapid formation of cubic phases. All solutes used induce the formation of Im3m (Q229) cubic phase in 10 wt% DEPE dispersions. The initial Im3m phases appearing during the first temperature cycles have larger lattice parameters that relax to smaller values with continuation of the cycling after the disappearance of the Lalpha phase. A cooperative Im3m --> Pn3m transition takes place at approximately 85 degrees C and transforms the Im3m phase into a mixture of coexisting Pn3m (Q224) and Im3m phases. The Im3m/Pn3m lattice parameter ratio is 1. 28, as could be expected from a representation of the Im3m and Pn3m phases with the primitive and diamond infinite periodic minimal surfaces, respectively. At higher DEPE contents ( approximately 30 wt%), cubic phase formation is hindered after 20-30 temperature cycles. The conversion does not go through, but reaches a stage with coexisting Ia3d (Q230) and Lalpha phases. Upon heating, the Ia3d phase cooperatively transforms into a mixture of, presumably, Im3m and Pn3m phases at about the temperature of the Lalpha-HII transition. This transformation is readily reversible with the temperature. The lattice parameters of the DEPE cubic phases are temperature-insensitive in the Lalpha temperature range and decrease with the temperature in the range of the HII phase. PMID:9675186

A study of room-temperature LixMn1.5Ni0.5O4 solid solutions

PubMed Central

Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert; Chen, Guoying

2015-01-01

Understanding the kinetic implication of solid-solution vs. biphasic reaction pathways is critical for the development of advanced intercalation electrode materials. Yet this has been a long-standing challenge in materials science due to the elusive metastable nature of solid solution phases. The present study reports the synthesis, isolation, and characterization of room-temperature LixMn1.5Ni0.5O4 solid solutions. In situ XRD studies performed on pristine and chemically-delithiated, micron-sized single crystals reveal the thermal behavior of LixMn1.5Ni0.5O4 (0 ≤ x ≤ 1) cathode material consisting of three cubic phases: LiMn1.5Ni0.5O4 (Phase I), Li0.5Mn1.5Ni0.5O4 (Phase II) and Mn1.5Ni0.5O4 (Phase III). A phase diagram capturing the structural changes as functions of both temperature and Li content was established. The work not only demonstrates the possibility of synthesizing alternative electrode materials that are metastable in nature, but also enables in-depth evaluation on the physical, electrochemical and kinetic properties of transient intermediate phases and their role in battery electrode performance. PMID:25619504

A study of room-temperature Li xMn 1.5Ni 0.5O 4 solid solutions

DOE PAGES

Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert; ...

2015-01-26

Understanding the kinetic implication of solid-solution vs. biphasic reaction pathways is critical for the development of advanced intercalation electrode materials. Yet this has been a long-standing challenge in materials science due to the elusive metastable nature of solid solution phases. The present study reports the synthesis, isolation, and characterization of room-temperature Li xMn 1.5Ni 0.5O 4 solid solutions. In situ XRD studies performed on pristine and chemically-delithiated, micron-sized single crystals reveal the thermal behavior of Li xMn 1.5Ni 0.5O 4 (0 ≤ x ≤ 1) cathode material consisting of three cubic phases: LiMn 1.5Ni 0.5O 4 (Phase I), Li 0.5Mnmore » 1.5Ni 0.5O 4 (Phase II) and Mn 1.5Ni 0.5O 4 (Phase III). A phase diagram capturing the structural changes as functions of both temperature and Li content was established. In conclusion, the work not only demonstrates the possibility of synthesizing alternative electrode materials that are metastable in nature, but also enables in-depth evaluation on the physical, electrochemical and kinetic properties of transient intermediate phases and their role in battery electrode performance.« less

Temperature control in a 30 stage, 5-cm Centrifugal Contactor Pilot Plant

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

Jack D. Law; Troy G. Garn; David H. Meikrantz

2009-09-01

Temperature profile testing was performed using a 30 stage 5-cm centrifugal contactor pilot plant. These tests were performed to evaluate the ability to control process temperature by adjusting feed solution temperatures. This would eliminate the need for complex jacketed heat exchanger installation on the centrifugal contactors. Thermocouples were installed on the inlet and outlets of each stage, as well as directly in the mixing zone of several of the contactor stages. Lamp oil, a commercially available alkane mixture of C14 to C18 chains, and tap water adjusted to pH 2 with nitric acid were the solution feeds for the temperaturemore » profile testing. Temperature data profiles for an array of total throughputs and contactor rpm values for both single-phase and two-phase systems were collected with selected profiles. The total throughput ranged from 0.5-1.4 L/min with rotor speeds from 3500-4000 rpm. Inlet solution temperatures ranging from ambient up to 50 °C were tested. Results of the two-phase temperature profile testing are detailed« less

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

NASA Astrophysics Data System (ADS)

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

2011-09-01

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

Glass transition of aqueous solutions involving annealing-induced ice recrystallization resolves liquid-liquid transition puzzle of water

PubMed Central

Zhao, Li-Shan; Cao, Ze-Xian; Wang, Qiang

2015-01-01

Liquid-liquid transition of water is an important concept in condensed-matter physics. Recently, it was claimed to have been confirmed in aqueous solutions based on annealing-induced upshift of glass-liquid transition temperature, . Here we report a universal water-content, , dependence of for aqueous solutions. Solutions with vitrify/devitrify at a constant temperature, , referring to freeze-concentrated phase with left behind ice crystallization. Those solutions with totally vitrify at under conventional cooling/heating process though, of the samples annealed at temperatures   to effectively evoke ice recrystallization is stabilized at . Experiments on aqueous glycerol and 1,2,4-butanetriol solutions in literature were repeated, and the same samples subject to other annealing treatments equally reproduce the result. The upshift of by annealing is attributable to freeze-concentrated phase of solutions instead of ‘liquid II phase of water’. Our work also provides a reliable method to determine hydration formula and to scrutinize solute-solvent interaction in solution. PMID:26503911

Method for separating water soluble organics from a process stream by aqueous biphasic extraction

DOEpatents

Chaiko, David J.; Mego, William A.

1999-01-01

A method for separating water-miscible organic species from a process stream by aqueous biphasic extraction is provided. An aqueous biphase system is generated by contacting a process stream comprised of water, salt, and organic species with an aqueous polymer solution. The organic species transfer from the salt-rich phase to the polymer-rich phase, and the phases are separated. Next, the polymer is recovered from the loaded polymer phase by selectively extracting the polymer into an organic phase at an elevated temperature, while the organic species remain in a substantially salt-free aqueous solution. Alternatively, the polymer is recovered from the loaded polymer by a temperature induced phase separation (cloud point extraction), whereby the polymer and the organic species separate into two distinct solutions. The method for separating water-miscible organic species is applicable to the treatment of industrial wastewater streams, including the extraction and recovery of complexed metal ions from salt solutions, organic contaminants from mineral processing streams, and colorants from spent dye baths.

The solubility of hydrogen in plutonium in the temperature range 475 to 825 degrees centigrade

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

Allen, T.H.

1991-01-01

The solubility of hydrogen (H) in plutonium metal (Pu) was measured in the temperature range of 475 to 825{degree}C for unalloyed Pu (UA) and in the temperature range of 475 to 625{degree}C for Pu containing two-weight-percent gallium (TWP). For TWP metal, in the temperature range 475 to 600{degree}C, the saturated solution has a maximum hydrogen to plutonium ration (H/Pu) of 0.00998 and the standard enthalpy of formation ({Delta}H{degree}{sub f(s)}) is (-0.128 {plus minus} 0.0123) kcal/mol. The phase boundary of the solid solution in equilibrium with plutonium dihydride (PuH{sub 2}) is temperature independent. In the temperature range 475 to 625{degree}C, UAmore » metal has a maximum solubility at H/Pu = 0.011. The phase boundary between the solid solution region and the metal+PuH{sub 2} two-phase region is temperature dependent. The solubility of hydrogen in UA metal was also measured in the temperature range 650 to 825{degree}C with {Delta}H{degree}{sub f(s)} = (-0.104 {plus minus} 0.0143) kcal/mol and {Delta}S{degree}{sub f(s)} = 0. The phase boundary is temperature dependent and the maximum hydrogen solubility has H/Pu = 0.0674 at 825{degree}C. 52 refs., 28 figs., 9 tabs.« less

Solvent Properties of Water in Aqueous Solutions of Elastin-Like Polypeptide

PubMed Central

Ferreira, Luisa A.; Cole, James T.; Reichardt, Christian; Holland, Nolan B.; Uversky, Vladimir N.; Zaslavsky, Boris Y.

2015-01-01

The phase-transition temperatures of an elastin-like polypeptide (ELP) with the (GVGVP)40 sequence and solvent dipolarity/polarizability, hydrogen-bond donor acidity, and hydrogen-bond acceptor basicity in its aqueous solutions were quantified in the absence and presence of different salts (Na2SO4, NaCl, NaClO4, and NaSCN) and various osmolytes (sucrose, sorbitol, trehalose, and trimethylamine N-oxide (TMAO)). All osmolytes decreased the ELP phase-transition temperature, whereas NaCl and Na2SO4 decreased, and NaSCN and NaClO4 increased it. The determined phase-transition temperatures may be described as a linear combination of the solvent’s dipolarity/polarizability and hydrogen-bond donor acidity. The linear relationship established for the phase-transition temperature in the presence of salts differs quantitatively from that in the presence of osmolytes, in agreement with different (direct and indirect) mechanisms of the influence of salts and osmolytes on the ELP phase-transition temperature. PMID:26075870

Effects of a type I antifreeze protein (AFP) on the melting of frozen AFP and AFP+solute aqueous solutions studied by NMR microimaging experiment.

PubMed

Ba, Yong; Mao, Yougang; Galdino, Luiz; Günsen, Zorigoo

2013-01-01

The effects of a type I AFP on the bulk melting of frozen AFP solutions and frozen AFP+solute solutions were studied through an NMR microimaging experiment. The solutes studied include sodium chloride and glucose and the amino acids alanine, threonine, arginine, and aspartic acid. We found that the AFP is able to induce the bulk melting of the frozen AFP solutions at temperatures lower than 0 °C and can also keep the ice melted at higher temperatures in the AFP+solute solutions than those in the corresponding solute solutions. The latter shows that the ice phases were in super-heated states in the frozen AFP+solute solutions. We have tried to understand the first experimental phenomenon via the recent theoretical prediction that type I AFP can induce the local melting of ice upon adsorption to ice surfaces. The latter experimental phenomenon was explained with the hypothesis that the adsorption of AFP to ice surfaces introduces a less hydrophilic water-AFP-ice interfacial region, which repels the ionic/hydrophilic solutes. Thus, this interfacial region formed an intermediate chemical potential layer between the water phase and the ice phase, which prevented the transfer of water from the ice phase to the water phase. We have also attempted to understand the significance of the observed melting phenomena to the survival of organisms that express AFPs over cold winters.

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

PubMed

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.

Evaluation of ODS-AQ stationary phase for use in capillary electrochromatography.

PubMed

Djordjevic, N M; Fitzpatrick, F; Houdiere, F

2001-04-01

The aim of this study was to evaluate the applicability of ODS-AQ packing material as a stationary phase in capillary electrochromatography (CEC). The electroosmotic flow created on an ODS-AQ stationary phase was measured at different mobile phase compositions and at different column temperatures. It was observed that the electroosmotic flow generated in the column increased by 50% when the temperature of the system was raised from 20 degrees C to 60 degrees C, while all other conditions were kept constant. The electroosmotic flow produced by the ODS-AQ stationary phase was found to be comparable to the flow generated in a column packed with Nucleosil bare-silica material. In addition, a set of polar compounds (D-lysergic acid diethylamide derivatives) was utilized to determine the influence of temperature and mobile phase composition on their chromatographic behavior on an ODS-AQ stationary phase in a CEC mode. A linear relationship between the solute retention factor and column temperatures was seen over the temperature range studied (20 degrees C to 60 degrees C). A quadratic function was used to describe the changes in the solute retention factors with variation of acetonitrile concentration in the mobile phase.

Synthesis and Characterization of Functional Mesostructures Using Colloidal Crystal Templating

DTIC Science & Technology

2004-01-01

fluorescent probes in aqueous polymer solutions . Khoury and co-workers measured the diffusion coefficient of several fluorescein-labeled proteins in...diffraction naq refractive index of the aqueous solution phase xvii ni refractive index of component i ngel refractive index of the hydrogel...phase Tg glass transition temperature α angle of diffraction φaq volume fraction of the aqueous solution phase φi volume fraction of

Determination of gas-liquid partition coefficients of several organic solutes in trihexyl(tetradecyl)phosphonium bromide using capillary gas chromatography columns.

PubMed

Ronco, Nicolás R; Menestrina, Fiorella; Romero, Lílian M; Castells, Cecilia B

2017-06-09

In this paper, we report gas-liquid partition constants for thirty-five volatile organic solutes in the room temperature ionic liquid trihexyl(tetradecyl)phosphonium bromide measured by gas-liquid chromatography using capillary columns. The relative contribution of gas-liquid partition and interfacial adsorption to retention was evaluated through the use of columns with different the phase ratio. Four capillary columns with exactly known phase ratios were constructed and employed to measure the solute retention factors at four temperatures between 313.15 and 343.15K. The partition coefficients were calculated from the slopes of the linear regression between solute retention factors and the reciprocal of phase ratio at a given temperature according to the gas-liquid chromatographic theory. Gas-liquid interfacial adsorption was detected for a few solutes and it has been considered for the calculations of partition coefficient. Reliable solute's infinite dilution activity coefficients can be obtained when retention data are determined by a unique partitioning mechanism. The partial molar excess enthalpies at infinite dilution have been estimated from the dependence of experimental values of solute activity coefficients with the column temperature. A thorough discussion of the uncertainties of the experimental measurements and the main advantages of the use of capillary columns to acquire the aforementioned relevant thermodynamic information was performed. Copyright © 2017 Elsevier B.V. All rights reserved.

Physical properties of V 1-xTi xO₂ (0 < x < 0.187) single crystals

DOE PAGES

Kong, Tai; Masters, Morgan W.; Bud’ko, Sergey L.; ...

2015-02-13

Free standing, low strain, single crystals of pure and titanium doped VO₂ were grown out of an excess of V ₂O₅ using high temperature solution growth techniques. At T MI ~ 340 K, pure VO₂ exhibits a clear first-order phase transition from a high-temperature paramagnetic tetragonal phase (R) to a low-temperature non-magnetic monoclinic phase (M1). With Ti doping, another monoclinic phase (M2) emerges between the R and M1 phases. The phase transition temperature between R and M2 increases with increasing Ti doping while the transition temperature between M2 and M1 decreases.

Stability and Solid Solutions of Hydrous Alumino-Silicates in the Earth's Mantle

NASA Astrophysics Data System (ADS)

Panero, W. R.; Caracas, R.

2017-12-01

The degree to which the Earth's mantle stores and cycles water in excess of the storage capacity of nominally anhydrous minerals is dependent upon the stability of hydrous phases under mantle-relevant pressures, temperatures, and compositions. Two hydrous phases, phase D and phase H are stable to the pressures and temperatures of the Earth's lower mantle, suggesting that the Earth's lower mantle may participate in the cycling of water. Each phase has a wide solid solution series between MgSi2O6H2-Al2SiO6H2 and MgSiO4H2-2δAlOOH-SiO2, respectively, yet most work addresses end-member compositions for analysis of stability and elastic properties. We present the results of density functional theory calculations on the stability, structure, bonding, partitioning, and elasticity of hydrous phases D and H in the Al2O3-SiO2-MgO-H2O system, addressing the solid solution series through a statistical sampling of site occupancy and calculation of the partition function from the grand canonical ensemble. We find that the addition of Al to the endmember compositions stabilizes each phase to higher temperatures through additional configurational entropy. We further find that solid solutions tend not to undergo hydrogen-bond symmetrization as is found in the end member compositions as a result of non-symmetric bonding environments.

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

PubMed

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 (< or = -40 degrees C). Moreover, in these applications, chemicals are often added to improve their outcome, which can result in significant variation in the phase change behavior and thermal properties from those of the original biomaterials. These chemical additives include cryoprotective agents (CPAs), antifreeze protein (AFP), or cryosurgical adjuvants like sodium chloride (NaCl). In the present study, phase change behavior and thermal properties of saline 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 study are discussed in the context of the implications for cryobiology applications.

Phase-Field Simulation of Concentration and Temperature Distribution During Dendritic Growth in a Forced Liquid Metal Flow

NASA Astrophysics Data System (ADS)

Du, Lifei; Zhang, Rong

2014-12-01

A phase-field model with convection is employed to investigate the effect of liquid flow on the dendritic structure formation of a Ni-Cu alloy during rapid solidification. Temperature and solute diffusion are significantly changed with induced liquid metal flow, and distribution changes of concentration and temperature are also analyzed and discussed. The solute segregation is affected due to the concentration diffusion layer thickness change caused by the liquid flow. The flow reduces the solute segregation in the upstream and leads to a fast dendrite growing, while solidifying in the downstream gets constrained with the large solute diffusion layer. Increasing flow velocity increases the asymmetry of dendrite morphology with much more suppressed growth in the downstream. The temperature distribution is also asymmetrical due to the non-uniform latent heat released during solidification coupling with heat diffusion changed by the liquid flow. Therefore, the forced liquid flow significantly affects the dendrite morphology, concentration, and temperature distributions in the solidifying microstructure.

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

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

Kashiwar, A., E-mail: akashiwar@gmail.com; Vennela, N. Phani, E-mail: phanivennela@gmail.com; Kamath, S.L., E-mail: kamath@iitb.ac.in

2012-12-15

In the present study, effect of solution annealing temperature (1050 Degree-Sign C and 1100 Degree-Sign C) and isothermal ageing (700 Degree-Sign C: 15 min to 6 h) on the microstructural changes in 2205 duplex stainless steel has been investigated systematically. Scanning electron microscopy and X-ray diffraction were adopted to follow the microstructural evolution, while an energy dispersive spectrometer attached to scanning electron microscope was used to obtain localised chemical information of various phases. The ferritic matrix of the two phase 2205 duplex stainless steel ({approx} 45% ferrite and {approx} 55% austenite) undergoes a series of metallurgical transformations during ageing-formation ofmore » secondary austenite ({gamma}{sub 2}) and precipitation of Cr and Mo rich intermetallic (chi-{chi} and sigma-{sigma}) phases. For solution annealing at 1050 Degree-Sign C, significant amount of carbides were observed in the ferrite grains after 1 h of ageing at 700 Degree-Sign C. {chi} Phase precipitated after the precipitation of carbides-preferentially at the ferrite-ferrite and also at the ferrite-austenite boundaries. {sigma} Phase was not observed in significant quantity even after 6 h of ageing. The sequence of precipitation in samples solution annealed at 1050 Degree-Sign C was found to be carbides {yields} {chi} {yields} {sigma}. On the contrary, for samples solution annealed at 1100 Degree-Sign C, the precipitation of {chi} phase was negligible. {chi} Phase precipitated before {sigma} phase, preferentially along the ferrite-ferrite grain boundaries and was later consumed in the {sigma} phase precipitation. The {sigma} phase precipitated via the eutectoid transformation of ferrite to yield secondary austenite {gamma}{sub 2} and {sigma} phase in the ferrite and along the ferrite-austenite grain boundaries. An increase in the volume fraction of {gamma}{sub 2} and {sigma} phase with simultaneous decrease in the ferrite was evidenced with ageing. - Highlights: Black-Right-Pointing-Pointer Effect of solution annealing temperature on microstructural evolution is studied. Black-Right-Pointing-Pointer {chi} Phase precipitated preferentially in the samples solution annealed at 1050 Degree-Sign C. Black-Right-Pointing-Pointer {sigma} Phase precipitated preferentially in the samples solution annealed at 1100 Degree-Sign C. Black-Right-Pointing-Pointer For SA at 1050 Degree-Sign C, the sequence of precipitation was carbides {yields} {chi} phase {yields} {sigma} phase. Black-Right-Pointing-Pointer For SA at 1100 Degree-Sign C, {sigma} phase precipitated via the eutectoid reaction: ferrite (F) {yields} {sigma} + {gamma}{sub 2}.« less

Liquid-Liquid Phase Separation in a Dual Variable Domain Immunoglobulin Protein Solution: Effect of Formulation Factors and Protein-Protein Interactions.

PubMed

Raut, Ashlesha S; Kalonia, Devendra S

2015-09-08

Dual variable domain immunoglobulin proteins (DVD-Ig proteins) are large molecules (MW ∼ 200 kDa) with increased asymmetry because of their extended Y-like shape, which results in increased formulation challenges. Liquid-liquid phase separation (LLPS) of protein solutions into protein-rich and protein-poor phases reduces solution stability at intermediate concentrations and lower temperatures, and is a serious concern in formulation development as therapeutic proteins are generally stored at refrigerated conditions. In the current work, LLPS was studied for a DVD-Ig protein molecule as a function of solution conditions by measuring solution opalescence. LLPS of the protein was confirmed by equilibrium studies and by visually observing under microscope. The protein does not undergo any structural change after phase separation. Protein-protein interactions were measured by light scattering (kD) and Tcloud (temperature that marks the onset of phase separation). There is a good agreement between kD measured in dilute solution with Tcloud measured in the critical concentration range. Results indicate that the increased complexity of the molecule (with respect to size, shape, and charge distribution on the molecule) increases contribution of specific and nonspecific interactions in solution, which are affected by formulation factors, resulting in LLPS for DVD-Ig protein.

Dielectric Interactions and the Prediction of Retention Times of Pesticides in Supercritical Fluid Chromatography with CO2

NASA Astrophysics Data System (ADS)

Alvarez, Guillermo A.; Baumanna, Wolfram

2005-02-01

A thermodynamic model for the partition of a solute (pesticide) between two immiscible phases, such as the stationary and mobile phases of supercritical fluid chromatography with CO2, is developed from first principles. A key ingredient of the model is the result of the calculation made by Liptay of the energy of interaction of a polar molecule with a dielectric continuum, which represents the solvent. The strength of the interaction between the solute and the solvent, which may be considered a measure of the solvent power, is characterized by a function g = (ɛ - 1)/(2ɛ +1), where ɛ is the dielectric constant of the medium, which is a function of the temperature T and the pressure P. Since the interactions between the nonpolar supercritical CO2 solvent and the slightly polar pesticide molecules are considered to be extremely weak, a regular solution model is appropriate from the thermodynamic point of view. At constant temperature, the model predicts a linear dependence of the logarithm of the capacity factor (lnk) of the chromatographic experiment on the function g = g(P), as the pressure is varied, with a slope which depends on the dipole moment of the solute, dispersion interactions and the size of the solute cavity in the solvent. At constant pressure, once the term containing the g (solvent interaction) factor is subtracted from lnk, a plot of the resulting term against the inverse of temperature yields the enthalpy change of transfer of the solute from the mobile (supercritical CO2) phase to the stationary (adsorbent) phase. The increase in temperature with the consequent large volume expansion of the supercritical fluid lowers its solvent strength and hence the capacity factor of the column (or solute retention time) increases. These pressure and temperature effects, predicted by the model, agree excellently with the experimental retention times of seven pesticides. Beyond a temperature of about 393 K, where the liquid solvent densities approach those of a gas (and hence the solvent strength becomes negligible), a dramatic loss of the retention times of all pesticides is observed in the experiments; this is attributed to desorption of the solute from the stationary phase, as predicted by Le Châtelier's principle for the (exothermic) adsorption process.

The Effect of Solution Thermal History on Chicken Egg White Lysozyme Nucleation

NASA Technical Reports Server (NTRS)

Burke, Michael W.; Judge, Russell A.; Pusey, Marc L.

2001-01-01

Proteins are highly flexible molecules and often exhibit defined conformational changes in response to changes in the ambient temperature. Chicken egg white lysozyme has been previously shown to undergo an apparent structural change when warmed above the tetragonal/orthorhombic phase transition temperature. This is reflected by a change in the habit of the tetragonal and orthorhombic crystals so formed. In this study, we show that possible conformational changes induced by heating are stable and apparently non-reversible by simple cooling. Exposure of protein solutions to temperatures above the phase change transition temperature, before combining with precipitant solution to begin crystallization, reduces final crystal numbers. Protein that is briefly warmed to 37 C, then cooled shows no sign of reversal to the unheated nucleation behavior even after storage for four weeks at 4 C. The change in nucleation behavior of tetragonal lysozyme crystals, attributed to a structural shift, occurs faster the greater the exposure to temperature above the equi-solubility point for the two phases. Heating for 2 hours at 48 C reduces crystal numbers by 20 fold in comparison to the same solution heated for the same time at 30 C. Thermal treatment of solutions is therefore a possible tool to reduce crystal numbers and increase crystal size. The effects of a protein's previous thermal history are now shown to be a potentially critical factor in subsequent macromolecule crystal nucleation and growth studies.

The Effect of Solution Thermal History on Chicken Egg White Lysozyme Nucleation

NASA Technical Reports Server (NTRS)

Burke, Michael W.; Judge, Russell A.; Pusey, Marc L.; Rose, M. Franklin (Technical Monitor)

2000-01-01

Proteins are highly flexible molecules and often exhibit defined conformational changes in response to changes in the ambient temperature. Chicken egg white lysozyme has been previously shown to undergo an apparent structural change when warmed above the tetragonal/orthorhombic phase transition temperature. This is reflected by a change in the habit of the tetragonal and orthorhombic crystals so formed. In this study we show that possible conformational changes induced by heating are stable and apparently non- reversible by simple cooling. Exposure of protein solutions to temperatures above the phase change transition temperature, before combining with precipitant solution to begin crystallization, reduces final crystal numbers. Protein that is briefly warmed to 37 C, then cooled shows no sign of reversal to the unheated nucleation behavior even after storage for 4 weeks at 4 C. The change in nucleation behavior of tetragonal lysozyme crystals, attributed to a structural shift, occurs faster the greater the exposure to temperature above the equi-solubility point for the two phases. Heating for 2 h at 48 C reduces crystal numbers by 20 fold in comparison to the same solution heated for the same time at 30 C. Thermal treatment of solutions is therefore a possible tool to reduce crystal numbers and increase crystal size. The effects of a protein's previous thermal history are now shown to be a potentially critical factor in subsequent macromolecule crystal nucleation and growth studies.

Translational Diffusion Coefficient and Partition Coefficient of a Spin-Labeled Solute in Lecithin Bilayer Membranes

PubMed Central

Dix, James A.; Diamond, Jared M.; Kivelson, Daniel

1974-01-01

The translational diffusion coefficient and the partition coefficient of a spin-labeled solute, di-t-butyl nitroxide, in an aqueous suspension of dipalmitoyl lecithin vesicles have been studied by electron spin resonance spectroscopy. When the lecithin is cooled through its phase transition temperature near 41°C, some solute is “frozen out” of the bilayer, and the standard partial molar enthalpy and entropy of partition go more positive by a factor of 8 and 6, respectively. However, the apparent diffusion constant in the lecithin phase is only slightly smaller than that in water, both above and below the transition temperature. The fraction of bilayer volume within which solute is distributed may increase with temperature, contributing to the positive enthalpy of partition. Comparison of time constants suggests that there is a permeability barrier to this solute in the periphery of the bilayer. PMID:4360944

Characterization of alloy 718 subjected to different thermomechanical treatments

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

Silva, Chinthaka; Song, Miao; Leonard, Keith

2017-03-11

Chemical phase and microstructural investigations of alloy 718 solution-annealed and age-hardened were performed in this study. We focused on the effects of solution annealing temperature, aging temperature and holding time, and the amount of intermediate cold work on the alloy. We also studied the formation of secondary phases such as γ’-phase, γ”-phase, and δ-phase, grain sizes, and any deformations of the microstructure with respect to the processed conditions. Statistics such as size and number densities of these precipitates with respect to the processing conditions were evaluated and a discussion on optimum conditions in obtaining finer and higher density of γ’-more » and γ”-phase precipitates is also presented.« less

Comparison of vapor formation of water at the solid/water interface to colloidal solutions using optically excited gold nanostructures.

PubMed

Baral, Susil; Green, Andrew J; Livshits, Maksim Y; Govorov, Alexander O; Richardson, Hugh H

2014-02-25

The phase transformation properties of liquid water to vapor is characterized by optical excitation of the lithographically fabricated single gold nanowrenches and contrasted to the phase transformation properties of gold nanoparticles located and optically excited in a bulk solution system [two and three dimensions]. The 532 nm continuous wave excitation of a single gold nanowrench results in superheating of the water to the spinodal decomposition temperature of 580 ± 20 K with bubble formation below the spinodal decomposition temperature being a rare event. Between the spinodal decomposition temperature and the boiling point liquid water is trapped into a metastable state because a barrier to vapor nucleation exists that must be overcome before the thermodynamically stable state is realized. The phase transformation for an optically heated single gold nanowrench is different from the phase transformation of optically excited colloidal gold nanoparticles solution where collective heating effects dominates and leads to the boiling of the solution exactly at the boiling point. In the solution case, the optically excited ensemble of nanoparticles collectively raises the ambient temperature of water to the boiling point where liquid is converted into vapor. The striking difference in the boiling properties of the single gold nanowrench and the nanoparticle solution system can be explained in terms of the vapor-nucleation mechanism, the volume of the overheated liquid, and the collective heating effect. The interpretation of the observed regimes of heating and vaporization is consistent with our theoretical modeling. In particular, we explain with our theory why the boiling with the collective heating in a solution requires 3 orders of magnitude less intensity compared to the case of optically driven single nanowrench.

Nonlinear dynamics of mushy layers induced by external stochastic fluctuations.

PubMed

Alexandrov, Dmitri V; Bashkirtseva, Irina A; Ryashko, Lev B

2018-02-28

The time-dependent process of directional crystallization in the presence of a mushy layer is considered with allowance for arbitrary fluctuations in the atmospheric temperature and friction velocity. A nonlinear set of mushy layer equations and boundary conditions is solved analytically when the heat and mass fluxes at the boundary between the mushy layer and liquid phase are induced by turbulent motion in the liquid and, as a result, have the corresponding convective form. Namely, the 'solid phase-mushy layer' and 'mushy layer-liquid phase' phase transition boundaries as well as the solid fraction, temperature and concentration (salinity) distributions are found. If the atmospheric temperature and friction velocity are constant, the analytical solution takes a parametric form. In the more common case when they represent arbitrary functions of time, the analytical solution is given by means of the standard Cauchy problem. The deterministic and stochastic behaviour of the phase transition process is analysed on the basis of the obtained analytical solutions. In the case of stochastic fluctuations in the atmospheric temperature and friction velocity, the phase transition interfaces (mushy layer boundaries) move faster than in the deterministic case. A cumulative effect of these noise contributions is revealed as well. In other words, when the atmospheric temperature and friction velocity fluctuate simultaneously due to the influence of different external processes and phenomena, the phase transition boundaries move even faster. This article is part of the theme issue 'From atomistic interfaces to dendritic patterns'.This article is part of the theme issue 'From atomistic interfaces to dendritic patterns'. © 2018 The Author(s).

Diffusion anisotropy of poor metal solute atoms in hcp-Ti

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

Scotti, Lucia, E-mail: lxs234@bham.ac.uk; Mottura, Alessandro, E-mail: a.mottura@bham.ac.uk

2015-05-28

Atom migration mechanisms influence a wide range of phenomena: solidification kinetics, phase equilibria, oxidation kinetics, precipitation of phases, and high-temperature deformation. In particular, solute diffusion mechanisms in α-Ti alloys can help explain their excellent high-temperature behaviour. The purpose of this work is to study self- and solute diffusion in hexagonal close-packed (hcp)-Ti, and its anisotropy, from first-principles using the 8-frequency model. The calculated diffusion coefficients show that diffusion energy barriers depend more on bonding characteristics of the solute rather than the size misfit with the host, while the extreme diffusion anisotropy of some solute elements in hcp-Ti is a resultmore » of the bond angle distortion.« less

Seasonal multiphase equilibria in the atmospheres of Titan and Pluto

NASA Astrophysics Data System (ADS)

Tan, S. P.; Kargel, J. S.

2017-12-01

At the extremely low temperatures in Titan's upper troposphere and on Pluto's surface, the atmospheres as a whole are subject to freeze into solid solutions, not pure ices. The presence of the solid phases introduces conditions with rich phase equilibria upon seasonal changes, even if the temperature undergoes only small changes. For the first time, the profile of atmospheric methane in Titan's troposphere will be reproduced complete with the solid solutions. This means that the freezing point, i.e. the altitude where the first solid phase appears, is determined. The seasonal change will also be evaluated both at the equator and the northern polar region. For Pluto, also for the first time, the seasonal solid-vapor equilibria will be evaluated. The fate of the two solid phases, the methane-rich and carbon-monoxide-rich solid solutions, will be analyzed upon temperature and pressure changes. Such investigations are enabled by the development of a molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, which includes solid solutions in its phase-equilibria calculations. The atmospheres of Titan and Pluto are modeled as ternary gas mixtures: nitrogen-methane-ethane and nitrogen-methane-carbon monoxide, respectively. Calculations using CRYOCHEM can provide us with compositions not only in two-phase equilibria, but also that in three-phase equilibria. Densities of all phases involved will also be calculated. For Titan, density inversion between liquid and solid phases will be identified and presented. In the inversion, the density of solid phase is less than that in the liquid phase. The method and results of this work will be useful for further investigations and modeling on the atmospheres of Titan, Pluto, and other bodies with similar conditions in the Solar System and beyond.

Effects of Heat Treatment on Corrosion and Wear Behaviors of Mg-6Gd-2Zn-0.4Zr Alloy in Simulated Body Fluid

NASA Astrophysics Data System (ADS)

Zhao, Li; Chen, Wei; Dai, Jianwei; Wang, Zhangzhong; Zhang, Xiaobo

2017-11-01

Mg-6Gd-2Zn-0.4Zr (wt.%, GZ62K) alloy was processed by solution treatment under different temperatures. The microstructure, hardness, corrosion and wear behaviors in simulated body fluid (SBF) have been studied. The results indicate that the (Mg, Zn)3Gd phase decreases, the precipitated phases gradually increase, and the long-period stacking ordered structure disappears with the increase of solution temperature. The alloy has better corrosion resistance after solution treatment, and that solution treated at 490 °C for 12 h shows the best corrosion resistance. The friction coefficient of the alloy under dry sliding condition decreases slightly, but the mass loss increases with increasing the solution temperature. The alloy solution treated at 460 °C for 12 h exhibits the lowest friction coefficient and mass loss in SBF, and it also has the best wear resistance under dry sliding condition.

Production of chitosan-based non-woven membranes using the electrospinning process

NASA Astrophysics Data System (ADS)

Pakravan Lonbani, Mehdi

Chitosan is a modified natural polymer mainly produced from chitin, one of the most abundant organic materials in the world. Highly porous chitosan mats present the specific physicochemical properties of the base material and also benefit from the physical characteristics of nanoporous membranes. Electrospinning is a novel technique developed long time ago and revisited recently that can generate polymeric fibers with nanometric size. The ultimate purpose of this work is to fabricate microporous non-woven chitosan membranes for wound healing dressings and heavy metal ion removal from drinking water. In this dissertation, two approaches have been utilized to prepare chitosan-based nanofibers; blending and co-axial electrospinning of chitosan solution with a readily electrospinnable solution, i.e. an aqueous solution of polyethylene oxide (PEO). Consequently, understanding the phase behavior and miscibility of aqueous acidic solutions of chitosan and PEO and their blends is of crucial importance, as any phase separation occurring during the electrospinning process greatly changes the morphology and physico-mechanical properties of the final products. First we employed the rheological approach on a well-known aqueous PEO solution to develop the experimental protocol. By comparing these critical points with that obtained from other experimental techniques, we showed that rheological measurements can sensitively detect early stages of phase separation. Subsequently the method was applied to 50 wt% aqueous acetic acid solutions of PEO, chitosan and their blends at different ratios. These solutions showed a lower critical solution temperature (LCST) phase diagram that is attributed to the existence of hydrogen bonds between active groups on chitosan and PEO backbone and the solvent. Critical decomposition temperatures for binodal and spinodal points were estimated from isochronal temperature sweep experiments. The obtained binodal temperatures confirmed that chitosan/PEO solutions are miscible and stable at moderate temperatures and phase separate at higher temperatures of 60-75 °C. Then, we intended to obtain a thorough understanding of chitosan/PEO solution properties that lead to a successful electrospinning process, i.e. continuous and stable, and which produces defect free uniform beadless nanofibers. The effect of blend composition and acetic acid concentration on properties such as surface tension and conductivity and, ultimately, on electrospinnability were investigated. A highly deacetylated chitosan (DDA=97.5 %) in 50% acetic acid was used, which is the maximum deacetylated chitosan grade that has been reported for the preparation of electrospun chitosan-based nanofibers. The rheological characteristics of the chitosan/PEO solutions as a controlling parameter in the electrospinning process were examined and their relationships to electrospinnability presented. As we showed that chitosan/PEO solutions are miscible and stable at moderate temperatures, a modified electrospinning set up to electrospin at temperatures of 25-70 °C was designed to achieve content as high as 90 wt% of chitosan in beadless chitosan/PEO nanofibers of 60-80 nm in diameter. It was also found that increasing chitosan/PEO ratio from 50/50 to 90/10 led to a remarkable diameter reduction from 123 to 63 nm at room temperature. Additionally, we found that moderate process temperatures help to stabilize the electrospinning process of these solutions and produce beadless nanofibers. However, at higher temperatures, the electrospun jet became unstable and beaded fiber morphology was obtained. This phenomena occurs closely at the temperature range of phase separation, previously determined by rheology studies. Therefore, temperature-induced phase separation of these solutions is considered as the reason for that observation. On the other hand, an FTIR study at room temperature on cast films and nanofibers of chitosan/PEO blends at room temperature showed the presence of hydrogen bonding interactions between chitosan and PEO that could be an another indication of miscibility between these two polymers in solution at moderate temperatures. Finally, in order to remove the blending step, reducing the amount of chitosan used and also to put chitosan right on the outer surface of the nanofibers for further related applications, a co-axial electrospinning technique was employed. By using a one-step co-axial electrospinning process, for the first time core-shell structured PEO-chitosan nanofibers from aqueous solutions were produced in which chitosan is located at the shell (outer layer) and PEO at the core (inner layer). Uniform sized defect-free nanofibers of 100-190 nm diameter were produced. The core-shell nanostructure and existence of chitosan on the shell layer were confirmed by TEM images obtained before and after washing the PEO content with water. The presence of chitosan on the surface of the composite nanofibers was further supported by XPS studies. Bulk and local compositional analysis is performed by thermal gravimetry (TGA) and Fourier transform infrared spectroscopy (FTIR) techniques, respectively, to examine the homogeneity of the nanofibers. Additionally, it was shown that hollow chitosan nanofibers could be obtained by PEO washing of the co-axial PEO/chitosan nanofibers, which could also be of great interest in applications such as blood purification in hemodialysis.

Anomalistic Self-Assembled Phase Behavior of Block Copolymer Blended with Organic Derivative Depending on Temperature

DOE PAGES

Kim, Tae-Hwan; Kim, Eunhye; Do, Changwoo; ...

2016-08-16

Amphiphilic Pluronic block copolymers have attracted great attention in a broad spectrum of potential applications due to the excellent phase behaviors in an aqueous solution, and many efforts have been made to investigate their phase behaviors under various external conditions. With a variety of external conditions, however, the closed looplike phase behaviors of a Pluronic block copolymer in an aqueous solution have not been reported yet. Herein, we report the closed looplike (CLL) phase behavior of a Pluronic P65 triblock copolymer blended with an organic derivative, 5-methylsalicylic acid (5mS), in aqueous solution, which is very unique for block copolymers. Asmore » the 5mS concentration increases, the isotropic to ordered phase or back to isotropic phase transition temperature is decreased while the number of closed loops is increased to two. To the best of our knowledge, this is the first demonstration of a CLL phase transition of a Pluronic block copolymer in an aqueous solution, which is readily applicable to optical devices such as optical sensors or optoelectronics, and nanotemplates for a highly ordered superlattice. Additionally, this provides new insight into the understanding on the phase behavior of a Pluronic block copolymer blended with additives.« less

Anomalistic Self-Assembled Phase Behavior of Block Copolymer Blended with Organic Derivative Depending on Temperature

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

Kim, Tae-Hwan; Kim, Eunhye; Do, Changwoo

Amphiphilic Pluronic block copolymers have attracted great attention in a broad spectrum of potential applications due to the excellent phase behaviors in an aqueous solution, and many efforts have been made to investigate their phase behaviors under various external conditions. With a variety of external conditions, however, the closed looplike phase behaviors of a Pluronic block copolymer in an aqueous solution have not been reported yet. Herein, we report the closed looplike (CLL) phase behavior of a Pluronic P65 triblock copolymer blended with an organic derivative, 5-methylsalicylic acid (5mS), in aqueous solution, which is very unique for block copolymers. Asmore » the 5mS concentration increases, the isotropic to ordered phase or back to isotropic phase transition temperature is decreased while the number of closed loops is increased to two. To the best of our knowledge, this is the first demonstration of a CLL phase transition of a Pluronic block copolymer in an aqueous solution, which is readily applicable to optical devices such as optical sensors or optoelectronics, and nanotemplates for a highly ordered superlattice. Additionally, this provides new insight into the understanding on the phase behavior of a Pluronic block copolymer blended with additives.« less

Phase transformations of α-alumina made from waste aluminum via a precipitation technique.

PubMed

Matori, Khamirul Amin; Wah, Loy Chee; Hashim, Mansor; Ismail, Ismayadi; Zaid, Mohd Hafiz Mohd

2012-12-07

We report on a recycling project in which α-Al(2)O(3) was produced from aluminum cans because no such work has been reported in literature. Heated aluminum cans were mixed with 8.0 M of H(2)SO(4) solution to form an Al(2)(SO(4))(3) solution. The Al(2)(SO(4))(3) salt was contained in a white semi-liquid solution with excess H(2)SO(4); some unreacted aluminum pieces were also present. The solution was filtered and mixed with ethanol in a ratio of 2:3, to form a white solid of Al(2)(SO(4))(3)·18H(2)O. The Al(2)(SO(4))(3)·18H(2)O was calcined in an electrical furnace for 3 h at temperatures of 400-1400 °C. The heating and cooling rates were 10 °C /min. XRD was used to investigate the phase changes at different temperatures and XRF was used to determine the elemental composition in the alumina produced. A series of different alumina compositions, made by repeated dehydration and desulfonation of the Al(2)(SO(4))(3)·18H(2)O, is reported. All transitional alumina phases produced at low temperatures were converted to α-Al(2)O(3) at high temperatures. The X-ray diffraction results indicated that the α-Al(2)O(3) phase was realized when the calcination temperature was at 1200 °C or higher.

Phase Transformations of α-Alumina Made from Waste Aluminum via a Precipitation Technique

PubMed Central

Matori, Khamirul Amin; Wah, Loy Chee; Hashim, Mansor; Ismail, Ismayadi; Zaid, Mohd Hafiz Mohd

2012-01-01

We report on a recycling project in which α-Al2O3 was produced from aluminum cans because no such work has been reported in literature. Heated aluminum cans were mixed with 8.0 M of H2SO4 solution to form an Al2(SO4)3 solution. The Al2(SO4)3 salt was contained in a white semi-liquid solution with excess H2SO4; some unreacted aluminum pieces were also present. The solution was filtered and mixed with ethanol in a ratio of 2:3, to form a white solid of Al2(SO4)3·18H2O. The Al2(SO4)3·18H2O was calcined in an electrical furnace for 3 h at temperatures of 400–1400 °C. The heating and cooling rates were 10 °C/min. XRD was used to investigate the phase changes at different temperatures and XRF was used to determine the elemental composition in the alumina produced. A series of different alumina compositions, made by repeated dehydration and desulfonation of the Al2(SO4)3·18H2O, is reported. All transitional alumina phases produced at low temperatures were converted to α-Al2O3 at high temperatures. The X-ray diffraction results indicated that the α-Al2O3 phase was realized when the calcination temperature was at 1200 °C or higher. PMID:23222685

The application of rational approximation in the calculation of a temperature field with a non-linear surface heat-transfer coefficient during quenching for 42CrMo steel cylinder

NASA Astrophysics Data System (ADS)

Cheng, Heming; Huang, Xieqing; Fan, Jiang; Wang, Honggang

1999-10-01

The calculation of a temperature field has a great influence upon the analysis of thermal stresses and stains during quenching. In this paper, a 42CrMo steel cylinder was used an example for investigation. From the TTT diagram of the 42CrMo steel, the CCT diagram was simulated by mathematical transformation, and the volume fraction of phase constituents was calculated. The thermal physical properties were treated as functions of temperature and the volume fraction of phase constituents. The rational approximation was applied to the finite element method. The temperature field with phase transformation and non-linear surface heat-transfer coefficients was calculated using this technique, which can effectively avoid oscillationin the numerical solution for a small time step. The experimental results of the temperature field calculation coincide with the numerical solutions.

Influence of Solution Treatment Duration on Microstructural Features of an Industrial Forged UNS S32750/1.4410/F53 Super Duplex Stainless Steel (SDSS) Alloy

NASA Astrophysics Data System (ADS)

Cojocaru, Vasile Dănuţ; Răducanu, Doina; Angelescu, Mariana Lucia; Vintilă, Adrian Nicolae; Şerban, Nicolae; Dan, Ioan; Cojocaru, Elisabeta Mirela; Cinca, Ion

2017-08-01

The microstructural changes induced by solution treatment of an industrial forged F53 Super Duplex Stainless Steel alloy were studied, in order to emphasize how component phases are influenced by heat treatment temperature and duration. The solution treatment was done at a temperature of 1100°C, with variable holding times: 0.6 ks (10 min), 3.6 ks (60 min) and 10.8 ks (180 min). Scanning electron microscopy-electron backscattered diffraction was used as main characterization technique, to obtain and analyse data referring to microstructural features, such as: nature and morphology of constituent phases, average grain-size and grain misorientation. It was shown that in all studied cases the microstructure consisted of a mixture of about 45% δ-Fe (ferrite) and 55% γ-Fe (austenite). Besides δ-Fe and γ-Fe phases, other phases were also identified, such as τ-phase (chromium-iron carbide), σ-phase (chromium-iron) and δ-(Cr-Fe) (ferrite).

Study of phase relationships in the Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} system. Phase diagram and thermal characteristics of phases

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

Matraszek, Aleksandra, E-mail: aleksandra.matraszek@ue.wroc.pl

2013-07-15

A diagram representing phase relationships in the Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} phosphate system has been developed on the basis of results obtained by thermal analysis (DTA/DSC/TGA) and X-ray diffraction (XRD) methods. One intermediate compound with the formula Sr{sub 3}Ce(PO{sub 4}){sub 3} occurs in the Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} system at temperatures exceeding 1045 °C. The compound has a eulytite structure with the following structural parameters: a=b=c=10.1655(8) Å, α=β=γ=90.00°, V=1050.46(6) Å{sup 3}. It's melting point exceeds 1950 °C. A limited solid solution exists in the system, which possesses the structure of a low-temperature form of Sr{sub 3}(PO{sub 4}){sub 2}.more » At 1000 °C the maximal concentration of CePO{sub 4} in the solid solution is below 20 mol%. The solid solution phase field narrows with increased temperature. There is a eutectic point in the (Sr{sub 3}(PO{sub 4}){sub 2}+Sr{sub 3}Ce(PO{sub 4}){sub 3}) phase field at 1765 °C and 15 mol% of CePO{sub 4}. The melting temperature of Sr{sub 3}(PO{sub 4}){sub 2} is 1882±15 °C. - Graphical abstract: The phase diagram of Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} system showing the stability ranges of limited solid solution and Sr{sub 3}Ce(PO{sub 4}){sub 3} phases. - Highlights: • Sr{sub 3}(PO{sub 4}){sub 2} melts at 1882 °C. • Phase diagram of Sr{sub 3}(PO{sub 4}){sub 2}–CePO{sub 4} system has been proposed. • Limited solid solution of CePO{sub 4} in Sr{sub 3}(PO{sub 4}){sub 2} forms in the system. • The Sr{sub 3}Ce(PO{sub 4}){sub 2} phosphate is stable at temperatures above 1045 °C.« less

Thermal effects of carbonated hydroxyapatite modified by glycine and albumin

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Changes in apple liquid phase concentration throughout equilibrium in osmotic dehydration.

PubMed

Barat, J M; Barrera, C; Frías, J M; Fito, P

2007-03-01

Previous results on apple tissue equilibration during osmotic dehydration showed that, at very long processing times, the solute concentrations of the fruit liquid phase and the osmotic solution were the same. In the present study, changes in apple liquid phase composition throughout equilibrium in osmotic dehydration were analyzed and modeled. Results showed that, by the time osmosed samples reached the maximum weight and volume loss, solute concentration of the fruit liquid phase was higher than that of the osmotic solution. The reported overconcentration could be explained in terms of the apple structure shrinkage that occurred during the osmotic dehydration with highly concentrated osmotic solutions due to the elastic response of the food structure to the loss of water and intake of solutes. The fruit liquid phase overconcentration rate was observed to depend on the concentration of the osmotic solution, the processing temperature, the sample size, and shape of the cellular tissue.

Effect of Sequence Blockiness on the Morphologies of Surface-grafted Elastin-like Polypeptides

NASA Astrophysics Data System (ADS)

Albert, Julie; Sintavanon, Kornkanok; Mays, Robin; MacEwan, Sarah; Chilkoti, Ashutosh; Genzer, Jan

2014-03-01

The inter- and intra- molecular interactions among monomeric units of copolymers and polypeptides depend strongly on monomer sequence distribution and dictate the phase behavior of these species both in solution and on surfaces. To study the relationship between sequence and phase behavior, we have designed a series of elastin-like polypeptides (ELPs) with controlled monomer sequences that mimic copolymers with various co-monomer sequence distributions and attached them covalently to silicon substrates from buffer solutions at temperatures below and above the bulk ELPs' lower critical solution temperatures (LCSTs). The dependence of ELP grafting density on solution temperature was examined by ellipsometry and the resultant surface morphologies were examined in air and under water with atomic force microscopy. Depositions performed above the LCST resulted in higher grafting densities and greater surface roughness of ELPs relative to depositions carried out below the LCST. In addition, we are using gradient substrates to examine the effect of ELP grafting density on temperature responsiveness.

Dual-phase Cr-Ta alloys for structural applications

DOEpatents

Liu, Chain T.; Brady, Michael P.; Zhu, Jiahong; Tortorelli, Peter F.

2001-01-01

Dual phase alloys of chromium containing 2 to 11 atomic percent tantalum with minor amounts of Mo, Cr, Ti, Y, La, Cr, Si and Ge are disclosed. These alloys contain two phases including Laves phase and Cr-rich solid solution in either eutectic structures or dispersed Laves phase particles in the Cr-rich solid solution matrix. The alloys have superior mechanical properties at high temperature and good oxidation resistance when heated to above 1000.degree. C. in air.

Nitric acid uptake by sulfuric acid solutions under stratospheric conditions - Determination of Henry's Law solubility

NASA Technical Reports Server (NTRS)

Reihs, Christa M.; Golden, David M.; Tolbert, Margaret A.

1990-01-01

The uptake of nitric acid by sulfuric acid solutions representative of stratospheric particulate at low temperatures was measured to determine the solubility of nitric acid in sulfuric acid solutions as a function of H2SO4 concentration and solution temperature. Solubilities are reported for sulfuric acid solutions ranging from 58 to 87 wt pct H2SO4 over a temperature range from 188 to 240 K, showing that, in general, the solubility of nitric acid increases with decreasing sulfuric acid concentration and with decreasing temperature. The measured solubilities indicate that nitric acid in the global stratosphere will be found predominantly in the gas phase.

Single-phase and well-dispersed Cu1.75S nanocrystals by ambient pressure diethylene glycol solution synthesis

NASA Astrophysics Data System (ADS)

Zheng, Xuerong; Jin, Zhengguo; Liu, Hui; Wang, Yueqiu; Wang, Xin; Du, Haiyan

2013-02-01

Single-phase, well-dispersed Cu1.75S nanocrystals were synthesized by an ambient pressure, hydrazine hydrate and ethylenediamine co-assisted diethylene glycol based solution chemical process using copper chloride and thioacetamide as precursors at the temperature range from 180 to 210 °C. Influence of hydrazine hydrate and ethylenediamine adding amounts, synthetic temperature on crystal growth, size distribution and optical properties of the synthesized Cu1.75S nanocrystals were investigated by XRD, TEM, HRTEM, EDX and UV-vis measurements. The synthetic reaction at above 200 °C grew flaky-shaped nanocrystals with relatively narrow size distribution. The formation of single-phase Cu1.75S nanocrystals in the diethylene glycol based solution process might be involved in the presence of intermediate [Cu(en)n]1+ and [Cu(NH3)4]2+ complexes in reaction solution, providing a stable Cu(I) and Cu(II) valent-mixed precursor.

Effects of temperature and solvent condition on phase separation induced molecular fractionation of gum arabic/hyaluronan aqueous mixtures.

PubMed

Hu, Bing; Han, Lingyu; Gao, Zhiming; Zhang, Ke; Al-Assaf, Saphwan; Nishinari, Katsuyoshi; Phillips, Glyn O; Yang, Jixin; Fang, Yapeng

2018-05-14

Effects of temperature and solvent condition on phase separation-induced molecular fractionation of gum arabic/hyaluronan (GA/HA) mixed solutions were investigated. Two gum arabic samples (EM10 and STD) with different molecular weights and polydispersity indices were used. Phase diagrams, including cloud and binodal curves, were established by visual observation and GPC-RI methods. The molecular parameters of control and fractionated GA, from upper and bottom phases, were measured by GPC-MALLS. Fractionation of GA increased the content of arabinogalactan-protein complex (AGP) from ca. 11% to 18% in STD/HA system and 28% to 55% in EM10/HA system. The phase separation-induced molecular fractionation was further studied as a function of temperature and solvent condition (varying ionic strength and ethanol content). Increasing salt concentration (from 0.5 to 5 mol/L) greatly reduced the extent of phase separation-induced fractionation. This effect may be ascribed to changes in the degree of ionization and shielding of the acid groups. Increasing temperature (from 4 °C to 80 °C) also exerted a significant influence on phase separation-induced fractionation. The best temperature for GA/HA mixture system was 40 °C while higher temperature negatively affected the fractionation due to denaturation and possibly degradation in mixed solutions. Increasing the ethanol content up to 30% showed almost no effect on the phase separation induced fractionation. Copyright © 2018 Elsevier B.V. All rights reserved.

Temperature Profile Measurements in a Newly Constructed 30-Stage 5 cm Centrifugal Contactor pilot Plant

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

Troy G. Garn; Dave H. Meikrantz; Mitchell R. Greenhalgh

2008-09-01

An annular centrifugal contactor pilot plant incorporating 30 stages of commercial 5 cm CINC V-02 units has been built and operated at INL during the past year. The pilot plant includes an automated process control and data acquisitioning system. The primary purpose of the pilot plant is to evaluate the performance of a large number of inter-connected centrifugal contactors and obtain temperature profile measurements within a 30-stage cascade. Additional solvent extraction flowsheet testing using stable surrogates is also being considered. Preliminary hydraulic testing was conducted with all 30 contactors interconnected for continuous counter-current flow. Hydraulic performance and system operational testsmore » were conducted successfully but with higher single-stage rotor speeds found necessary to maintain steady interstage flow at flowrates of 1 L/min and higher. Initial temperature profile measurements were also completed in this configuration studying the performance during single aqueous and two-phase counter-current flow at ambient and elevated inlet solution temperatures. Temperature profile testing of two discreet sections of the cascade required additional feed and discharge connections. Lamp oil, a commercially available alkane mixture of C14 to C18 chains, and tap water adjusted to pH 2 were the solution feeds for all the testing described in this report. Numerous temperature profiles were completed using a newly constructed 30-stage centrifugal contactor pilot plant. The automated process control and data acquisition system worked very well throughout testing. Temperature data profiles for an array of total flowrates (FT) and contactor rpm values for both single-phase and two-phase systems have been collected with selected profiles and comparisons reported. Total flowrates (FT) ranged from 0.5-1.4 L/min with rotor speeds from 3500-4000 rpm. Solution inlet temperatures ranging from ambient up to 50° C were tested. Ambient temperature testing shows that a small amount of heat is added to the processed solution by the mechanical energy of the contactors. The temperature profiles match the ambient temperature of the laboratory but are nearly 10° C higher toward the middle of the cascade. Heated input solution testing provides temperature profiles with smaller temperature gradients and are more influenced by the temperature of the inlet solutions than the ambient laboratory temperature. The temperature effects of solution mixing, even at 4000 rpm, were insignificant in any of the studies conducted on lamp oil and water.« less

Preconcentration of aqueous dyes through phase-transfer liquid-phase microextraction with a room-temperature ionic liquid.

PubMed

Chen, Hsiu-Liang; Chang, Shuo-Kai; Lee, Chia-Ying; Chuang, Li-Lin; Wei, Guor-Tzo

2012-09-12

In this study, we employed the room-temperature ionic liquid [bmim][PF(6)] as both ion-pair agent and an extractant in the phase-transfer liquid-phase microextraction (PTLPME) of aqueous dyes. In the PTLPME method, a dye solution was added to the extraction solution, comprising a small amount of [bmim][PF(6)] in a relatively large amount of CH(2)Cl(2), which serves as the disperser solvent to an extraction solution. Following extraction, CH(2)Cl(2) was evaporated from the extractant, resulting in the extracted dyes being concentrated in a small volume of the ionic liquid phase to increase the enrichment factor. The enrichment factors of for the dye Methylene Blue, Neutral Red, and Methyl Red were approximately 500, 550 and 400, respectively; their detection limits were 0.014, 0.43, and 0.02 μg L(-1), respectively, with relative standard deviations of 4.72%, 4.20%, and 6.10%, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Phase Separation in Solutions of Monoclonal Antibodies

NASA Astrophysics Data System (ADS)

Benedek, George; Wang, Ying; Lomakin, Aleksey; Latypov, Ramil

2012-02-01

We report the observation of liquid-liquid phase separation (LLPS) in a solution of humanized monoclonal antibodies, IgG2, and the effects of human serum albumin, a major blood protein, on this phase separation. We find a significant reduction of phase separation temperature in the presence of albumin, and a preferential partitioning of the albumin into the antibody-rich phase. We provide a general thermodynamic analysis of the antibody-albumin mixture phase diagram and relate its features to the magnitude of the effective inter-protein interactions. Our analysis suggests that additives (HSA in this report), which have moderate attraction with antibody molecules, may be used to forestall undesirable protein condensation in antibody solutions. Our findings are relevant to understanding the stability of pharmaceutical solutions of antibodies and the mechanisms of cryoglobulinemia.

Crystallization from high temperature solutions of Si in copper

DOEpatents

Ciszek, Theodore F.

1994-01-01

A liquid phase epitaxy method for forming thin crystalline layers of device quality silicon having less than 5X10.sup.16 Cu atoms/cc impurity, comprising: preparing a saturated liquid solution melt of Si in Cu at about 16% to about 90% wt. Si at a temperature range of about 800.degree. C. to about 1400.degree. C. in an inert gas; immersing a substrate in the saturated solution melt; supersaturating the solution by lowering the temperature of the saturated solution melt and holding the substrate immersed in the solution melt for a period of time sufficient to cause growing Si to precipitate out of the solution to form a crystalline layer of Si on the substrate; and withdrawing the substrate from the solution.

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

NASA Astrophysics Data System (ADS)

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.

Diffuse phase ferroelectric vs. Polomska transition in (1-x) BiFeO3-(x) Ba Zr0.025Ti0.975O3 (0.1 ≤ x ≤ 0.3) solid solutions

NASA Astrophysics Data System (ADS)

Jha, Pardeep K.; Jha, Priyanka A.; Singh, Vikash; Kumar, Pawan; Asokan, K.; Dwivedi, R. K.

2015-01-01

Investigations on the solid solutions (1-x) BiFeO3 - (x) Ba Zr0.025Ti0.975O3 (0.1 ≤ x ≤ 0.3) in the temperature range 300-750 K show colossal permittivity behavior and the occurrence of diffuse phase ferroelectric transition along with frequency dependent anomaly which disappears at temperature ˜450 K. For x = 0.3, these anomalies have been verified through differential scanning calorimetry and dielectric/impedance/conductivity measurements. The occurrence of peak in pyrocurrent (dPs/dT) vs. T plots also supports phase transition. With the increasing x, transition temperature decreases and diffusivity increases. This anomaly is absent at high frequencies (>100 kHz) in conductivity plots, indicating Polomska like surface phase transition, which is supported by modulus study.

Can xenon in water inhibit ice growth? Molecular dynamics of phase transitions in water-Xe system.

PubMed

Artyukhov, Vasilii I; Pulver, Alexander Yu; Peregudov, Alex; Artyuhov, Igor

2014-07-21

Motivated by recent experiments showing the promise of noble gases as cryoprotectants, we perform molecular dynamics modeling of phase transitions in water with xenon under cooling. We follow the structure and dynamics of xenon water solution as a function of temperature. Homogeneous nucleation of clathrate hydrate phase is observed and characterized. As the temperature is further reduced we observe hints of dissociation of clathrate due to stronger hydrophobic hydration, pointing towards a possible instability of clathrate at cryogenic temperatures and conversion to an amorphous phase comprised of "xenon + hydration shell" Xe·(H2O)21.5 clusters. Simulations of ice-xenon solution interface in equilibrium and during ice growth reveal the effects of xenon on the ice-liquid interface, where adsorbed xenon causes roughening of ice surface but does not preferentially form clathrate. These results provide evidence against the ice-blocker mechanism of xenon cryoprotection.

Analytical solutions for benchmarking cold regions subsurface water flow and energy transport models: one-dimensional soil thaw with conduction and advection

USGS Publications Warehouse

Kurylyk, Barret L.; McKenzie, Jeffrey M; MacQuarrie, Kerry T. B.; Voss, Clifford I.

2014-01-01

Numerous cold regions water flow and energy transport models have emerged in recent years. Dissimilarities often exist in their mathematical formulations and/or numerical solution techniques, but few analytical solutions exist for benchmarking flow and energy transport models that include pore water phase change. This paper presents a detailed derivation of the Lunardini solution, an approximate analytical solution for predicting soil thawing subject to conduction, advection, and phase change. Fifteen thawing scenarios are examined by considering differences in porosity, surface temperature, Darcy velocity, and initial temperature. The accuracy of the Lunardini solution is shown to be proportional to the Stefan number. The analytical solution results obtained for soil thawing scenarios with water flow and advection are compared to those obtained from the finite element model SUTRA. Three problems, two involving the Lunardini solution and one involving the classic Neumann solution, are recommended as standard benchmarks for future model development and testing.

Liquid-vapor phase equilibria and the thermodynamic properties of 2-methylpropanol- n-alkyl propanoate solutions

NASA Astrophysics Data System (ADS)

Suntsov, Yu. K.; Goryunov, V. A.; Chuikov, A. M.; Meshcheryakov, A. V.

2016-08-01

The boiling points of solutions of five binary systems are measured via ebulliometry in the pressure range of 2.05-103.3 kPa. Equilibrium vapor phase compositions, the values of the excess Gibbs energies, enthalpies, and entropies of solution of these systems are calculated. Patterns in the changes of phase equilibria and thermodynamic properties of solutions are established, depending on the compositions and temperatures of the systems. Liquid-vapor equilibria in the systems are described using the equations of Wilson and the NRTL (Non-Random Two-Liquid Model).

A numerical study on dual-phase-lag model of bio-heat transfer during hyperthermia treatment.

PubMed

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

2015-01-01

The success of hyperthermia in the treatment of cancer depends on the precise prediction and control of temperature. It was absolutely a necessity for hyperthermia treatment planning to understand the temperature distribution within living biological tissues. In this paper, dual-phase-lag model of bio-heat transfer has been studied using Gaussian distribution source term under most generalized boundary condition during hyperthermia treatment. An approximate analytical solution of the present problem has been done by Finite element wavelet Galerkin method which uses Legendre wavelet as a basis function. Multi-resolution analysis of Legendre wavelet in the present case localizes small scale variations of solution and fast switching of functional bases. The whole analysis is presented in dimensionless form. The dual-phase-lag model of bio-heat transfer has compared with Pennes and Thermal wave model of bio-heat transfer and it has been found that large differences in the temperature at the hyperthermia position and time to achieve the hyperthermia temperature exist, when we increase the value of τT. Particular cases when surface subjected to boundary condition of 1st, 2nd and 3rd kind are discussed in detail. The use of dual-phase-lag model of bio-heat transfer and finite element wavelet Galerkin method as a solution method helps in precise prediction of temperature. Gaussian distribution source term helps in control of temperature during hyperthermia treatment. So, it makes this study more useful for clinical applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

Observation of glassy state relaxation during annealing of frozen sugar solutions by X-ray computed tomography.

PubMed

Nakagawa, Kyuya; Tamiya, Shinri; Do, Gabsoo; Kono, Shinji; Ochiai, Takaaki

2018-06-01

Glassy phase formation in a frozen product determines various properties of the freeze-dried products. When an aqueous solution is subjected to freezing, a glassy phase forms as a consequence of freeze-concentration. During post-freezing annealing, the relaxation of the glassy phase and the ripening of ice crystals (i.e. Ostwald ripening) spontaneously occur, where the kinetics are controlled by the annealing and glass transition temperatures. This study was motivated to observe the progress of glassy state relaxation separate from ice coarsening during annealing. X-ray computed tomography (CT) was used to observe a frozen and post-freezing annealed solutions by using monochromatized X-ray from the synchrotron radiation. CT images were successfully obtained, and the frozen matrix were analyzed based on the gray level values that were equivalent to the linear X-ray attenuation coefficients of the observed matters. The CT images obtained from rapidly frozen sucrose and dextrin solutions with different concentrations gave clear linear relationships between the linear X-ray attenuation coefficients values and the solute concentrations. It was confirmed that the glassy state relaxation progressed as increasing annealing time, and this trend was larger in the order of the glass transition temperature of the maximally freeze-concentrated phase. The sucrose-water system required nearly 20 h of annealing time at -5 °C for the completion of the glassy phase relaxation, whereas dextrin-water systems required much longer periods because of their higher glass transition temperatures. The trends of ice coarsening, however, did not perfectly correspond to the trends of the relaxation, suggesting that the glassy phase relaxation and Ostwald ripening would jointly control the ice crystal growth/ripening kinetics, and the dominant mechanism differed by the annealing stage. Copyright © 2018 Elsevier B.V. All rights reserved.

Solid state phase change materials for thermal energy storage in passive solar heated buildings

NASA Astrophysics Data System (ADS)

Benson, D. K.; Christensen, C.

1983-11-01

A set of solid state phase change materials was evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol, pentaglycerine and neopentyl glycol. Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature within the range from less than 25 deg to 188 deg. Thermophysical properties such as thermal conductivity, density and volumetric expansion were measured. Computer simulations were used to predict the performance of various Trombe wall designs incorporating solid state phase change materials. Optimum performance was found to be sensitive to the choice of phase change temperatures and to the thermal conductivity of the phase change material. A molecular mechanism of the solid state phase transition is proposed and supported by infrared spectroscopic evidence.

Materials research for passive solar systems: Solid-state phase-change materials

NASA Astrophysics Data System (ADS)

Benson, D. K.; Webb, J. D.; Burrows, R. W.; McFadden, J. D. O.; Christensen, C.

1985-03-01

A set of solid-state phase-change materials is being evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol (C5H12O4), pentaglycerinve (C5H12O3), and neopentyl glycol (C5H12O2). Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature between 25 C and 188 C, and have latent heats of transformation etween 20 and 70 cal/g. Transformation temperatures, specific heats, and latent heats of transformation have been measured for a number of these materials. Limited cyclic experiments suggest that the solid solutions are stable. These phase-change materials exhibit large amounts of undercooling; however, the addition of certain nucleating agents as particulate dispersions in the solid phase-change material greatly reduces this effect. Computer simulations suggest that the use of an optimized solid-state phase-change material in a Trombe wall could provide better performance than a concrete Trombe wall four times thicker and nine times heavier.

Use of frit-disc crucibles for routine and exploratory solution growth of single crystalline samples

DOE PAGES

Canfield, Paul C.; Kong, Tai; Kaluarachchi, Udhara S.; ...

2016-01-05

Solution growth of single crystals from high temperature solutions often involves the separation of residual solution from the grown crystals. For many growths of intermetallic compounds, this separation has historically been achieved with the use of plugs of silica wool. Whereas this is generally efficient in a mechanical sense, it leads to a significant contamination of the decanted liquid with silica fibres. In this paper, we present a simple design for frit-disc alumina crucible sets that has made their use in the growth single crystals from high temperature solutions both simple and affordable. An alumina frit-disc allows for the cleanmore » separation of the residual liquid from the solid phase. This allows for the reuse of the decanted liquid, either for further growth of the same phase, or for subsequent growth of other, related phases. In this article, we provide examples of the growth of isotopically substituted TbCd 6 and icosahedral i-RCd quasicrystals, as well as the separation of (i) the closely related Bi 2Rh 3S 2 and Bi 2Rh 3.5S 2 phases and (ii) and PrZn 11 and PrZn 17.« less

Impact of heat treatment on the physical properties of noncrystalline multisolute systems concentrated in frozen aqueous solutions.

PubMed

Izutsu, Ken-ichi; Yomota, Chikako; Kawanishi, Toru

2011-12-01

The purpose of this study was to elucidate the effect of heat treatment on the miscibility of multiple concentrated solutes that mimic biopharmaceutical formulations in frozen solutions. The first heating thermal analysis of frozen solutions containing either a low-molecular-weight saccharide (e.g., sucrose, trehalose, and glucose) or a polymer (e.g., polyvinylpyrrolidone and dextran) and their mixtures from -70°C showed a single transition at glass transition temperature of maximally freeze-concentrated solution (T(g) ') that indicated mixing of the freeze-concentrated multiple solutes. The heat treatment of single-solute and various polymer-rich mixture frozen solutions at temperatures far above their T(g) ' induced additional ice crystallization that shifted the transitions upward in the following scan. Contrarily, the heat treatment of frozen disaccharide-rich solutions induced two-step heat flow changes (T(g) ' splitting) that suggested separation of the solutes into multiple concentrated noncrystalline phases, different in the solute compositions. The extent of the T(g) ' splitting depended on the heat treatment temperature and time. Two-step glass transition was observed in some sucrose and dextran mixture solids, lyophilized after the heat treatment. Increasing mobility of solute molecules during the heat treatment should allow spatial reordering of some concentrated solute mixtures into thermodynamically favorable multiple phases. Copyright © 2011 Wiley-Liss, Inc.

[Anomalous Properties of Water and Aqueous Solutions at Low Temperatures].

PubMed

Matsumoto, Masakazu

2015-01-01

Water has many anomalous properties below the room temperature. The temperature range overlaps with that of the Earth's atmosphere and also with that natural life forms favor. We review the origin of the anomalous properties of water and aqueous solutions in association with the hypothetical second critical point and liquid-liquid phase separation of water hidden in the supercooled state of liquid water.

Nonequilibrium Phase Chemistry in High Temperature Structure Alloys

NASA Technical Reports Server (NTRS)

Wang, R.

1991-01-01

Titanium and nickel aluminides of nonequilibrium microstructures and in thin gauge thickness were identified, characterized and produced for potential high temperature applications. A high rate sputter deposition technique for rapid surveillance of the microstructures and nonequilibrium phase is demonstrated. Alloys with specific compositions were synthesized with extended solid solutions, stable dispersoids, and specific phase boundaries associated with different heat treatments. Phase stability and mechanical behavior of these nonequilibrium alloys were investigated and compared.

Microstructural Evolution and Phase Formation in 2nd-Generation Refractory-Based High Entropy Alloys

PubMed Central

Eshed, Eyal; Larianovsky, Natalya; Kovalevsky, Alexey; Popov, Vladimir; Gorbachev, Igor; Popov, Vladimir; Katz-Demyanetz, Alexander

2018-01-01

Refractory-based high entropy alloys (HEAs) of the 2nd-generation type are new intensively-studied materials with a high potential for structural high-temperature applications. This paper presents investigation results on microstructural evolution and phase formation in as-cast and subsequently heat-treated HEAs at various temperature-time regimes. Microstructural examination was performed by means of scanning electron microscopy (SEM) combined with the energy dispersive spectroscopy (EDS) mode of electron probe microanalysis (EPMA) and qualitative X-ray diffraction (XRD). The primary evolutionary trend observed was the tendency of Zr to gradually segregate as the temperature rises, while all the other elements eventually dissolve in the BCC solid solution phase once the onset of Laves phase complex decomposition is reached. The performed thermodynamic modelling was based on the Calculation of Phase Diagrams method (CALPHAD). The BCC A2 solid solution phase is predicted by the model to contain increasing amounts of Cr as the temperature rises, which is in perfect agreement with the actual results obtained by SEM. However, the model was not able to predict the existence of the Zr-rich phase or the tendency of Zr to segregate and form its own solid solution—most likely as a result of the Zr segregation trend not being an equilibrium phenomenon. PMID:29360763

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

Tan, Y.B.; Yang, L.H.; Duan, J.L.

The kinetics of the β → α phase transformation in the 47Zr–45Ti–5Al–3V (wt.%) alloy with different initial β grain sizes under isothermal conditions was investigated by X-ray diffraction. The results showed that the volume fraction of α phase first increased with increasing aging time, and then reached an equilibrium value. The equilibrium value of α phase decreased with increased aging temperature. At the same aging temperature and time, the volume fraction of α phase in the 47Zr–45Ti–5Al–3V alloy solution-treated at 850 °C was higher than at 1050 °C, and the size of α phase in the 47Zr–45Ti–5Al–3V alloy solution-treated atmore » 850 °C was larger than that at 1050 °C. The kinetics of the β → α phase transformation was modeled under isothermal conditions in the theoretical frame of the Johnson–Mehl–Avrami–Kolmogorov (JMAK) theory. The Avrami index (n) increased with increasing aging temperature, while the reaction rate constant (k) decreased. - Highlights: • The kinetics of the β → α phase transformation in the ZrTiAlV alloy was investigated. • The volume fraction of α phase first increased and then reached an equilibrium value. • The kinetics of the β → α phase transformation was modeled by the JMAK theory. • The n increased with increasing aging temperature, while the k decreased.« less

Development of SiAlON materials

NASA Technical Reports Server (NTRS)

Layden, G. K.

1977-01-01

Cold pressing and sintering techniques were used to produce ceramic bodies in which the major phase was beta prime Si3-Al-O-N4 solid solution. A variety of foreign oxides were used to promote liquid phase sintering, and this resulted in the incorporation of additional solid phases in the ceramic bodies which controlled elevated temperature properties. None of the bodies studied to date exhibited both adequate high temperature mechanical properties and oxidation resistance. Criteria are suggested to guide the formulation of bodies with improved high temperature properties.

Phase separation in solutions of monoclonal antibodies and the effect of human serum albumin

PubMed Central

Wang, Ying; Lomakin, Aleksey; Latypov, Ramil F.; Benedek, George B.

2011-01-01

We report the observation of liquid-liquid phase separation in a solution of human monoclonal antibody, IgG2, and the effects of human serum albumin, a major blood protein, on this phase separation. We find a significant reduction of phase separation temperature in the presence of albumin, and a preferential partitioning of the albumin into the antibody-rich phase. We provide a general thermodynamic analysis of the antibody-albumin mixture phase diagram and relate its features to the magnitude of the effective interprotein interactions. Our analysis suggests that additives (HSA in this report), which have moderate attraction with antibody molecules, may be used to forestall undesirable proetin condensation in antibody solutions. Our findings are relevant to understanding the stability of pharmaceutical solutions of antibodies and the mechanisms of cryoglobulinemia. PMID:21921237

Raman Spectroscopic Observations of the Ion Association between Mg(2+) and SO4(2-) in MgSO4-Saturated Droplets at Temperatures of ≤380 °C.

PubMed

Wan, Ye; Wang, Xiaolin; Hu, Wenxuan; Chou, I-Ming

2015-08-27

Liquid–liquid phase separation was observed in aqueous MgSO4 solutions with excess H2SO4 at elevated temperatures; the aqueous MgSO4/H2SO4 solutions separated into MgSO4-rich droplets (fluid F1) and a MgSO4-poor phase (fluid F2) during heating. The phase separation temperature increases with SO4(2–)/Mg2+ ratio at a constant MgSO4 concentration. At a MgSO4/H2SO4 ratio of 5, the liquid–liquid phase separation temperature decreases with an increase in MgSO4 concentration up to ∼1.0 mol/kg and then increases at higher concentrations, showing a typical macroscale property of polymer solutions with a lower critical solution temperature (LCST) of ∼271.4 °C. In situ Raman spectroscopic analyses show that the MgSO4 concentration in fluid F1 increases with an increase in temperature, whereas that in fluid F2 decreases with an increase in temperature. In addition, HSO4(–), which does not readily form complexes with Mg(2+), tends to accumulate in fluid F2. Analyses of the v1(SO4(2–)) bands confirmed the presence of four-sulfate species of unassociated SO4(2–) (∼980 cm(–1)), contact ion pairs (CIPs; ∼995 cm(–1)), and triple ion pairs (TIPs; ∼1005 cm(–1)) in aqueous solution, and more complex ion pair chain structure (∼1020 cm(–1)) in fluid F1. Comparison of the sulfate species in fluids F1 and F2 at 280 °C suggests that SO4(2–) in fluid F2 is less associated with Mg(2+). On the basis of in situ visual and Raman spectroscopic observations, we suggest that the formation of the complex Mg(2+)–SO4(2–) ion association might be responsible for the liquid–liquid phase separation. In addition, Raman spectroscopic analyses of the OH stretching bands indicate that the hydrogen bonding in fluid F1 is stronger than that in fluid F2, which might be ascribed to the increasing probability of collision of H2O with Mg(2+) and SO4(2–) in fluid F1.

Impact of heat treatment on miscibility of proteins and disaccharides in frozen solutions.

PubMed

Izutsu, Ken-ichi; Yomota, Chikako; Okuda, Haruhiro; Kawanishi, Toru; Randolph, Theodore W; Carpenter, John F

2013-10-01

The purpose of this study was to elucidate the effect of heat treatment (annealing) on the miscibility of concentrated protein and disaccharide mixtures in the freezing segment of lyophilization. Frozen solutions containing a protein (e.g., recombinant human albumin, chicken egg lysozyme, bovine plasma immunoglobulin G, or a humanized IgG1k monoclonal antibody) and a non-reducing disaccharide (e.g., sucrose or trehalose) showed single thermal transitions of the solute mixtures (glass transition temperature of maximally freeze-concentrated solutes: T(g)(')) in their first heating scans. Heat treatment (e.g., -5 °C, 30 min) of some disaccharide-rich mixture frozen solutions at temperatures far above their T(g)(') induced two-step T(g)(') transitions in the subsequent scans, suggesting the separation of the solutes into concentrated protein-disaccharide mixture phase and disaccharide phase. Other frozen solutions showed a single transition of the concentrated solute mixture both before and after heat treatment. The apparent effects of the heat treatment temperature and time on the changes in thermal properties suggest molecular reordering of the concentrated solutes from a kinetically fixed mixture state to a more thermodynamically favorable state as a result of increased mobility. The implications of these phenomena on the quality of protein formulations are discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

Crystallization from high temperature solutions of Si in Cu/Al solvent

DOEpatents

Ciszek, Theodore F.; Wang, Tihu

1996-01-01

A liquid phase epitaxy method for forming thin crystalline layers of device quality silicon having less than 3.times.10.sup.16 Cu atoms/cc impurity, comprising: preparing a saturated liquid solution of Si in a Cu/Al solvent at about 20 to about 40 at. % Si at a temperature range of about 850.degree. to about 1100.degree. C. in an inert gas; immersing or partially immersing a substrate in the saturated liquid solution; super saturating the solution by lowering the temperature of the saturated solution; holding the substrate in the saturated solution for a period of time sufficient to cause Si to precipitate out of solution and form a crystalline layer of Si on the substrate; and withdrawing the substrate from the solution.

Crystallization from high temperature solutions of Si in Cu/Al solvent

DOEpatents

Ciszek, T.F.; Wang, T.

1996-08-13

A liquid phase epitaxy method is disclosed for forming thin crystalline layers of device quality silicon having less than 3{times}10{sup 16} Cu atoms/cc impurity, comprising: preparing a saturated liquid solution of Si in a Cu/Al solvent at about 20 to about 40 at. % Si at a temperature range of about 850 to about 1100 C in an inert gas; immersing or partially immersing a substrate in the saturated liquid solution; super saturating the solution by lowering the temperature of the saturated solution; holding the substrate in the saturated solution for a period of time sufficient to cause Si to precipitate out of solution and form a crystalline layer of Si on the substrate; and withdrawing the substrate from the solution. 3 figs.

Elevated temperature and temperature programming in conventional liquid chromatography--fundamentals and applications.

PubMed

Vanhoenacker, Gerd; Sandra, Pat

2006-08-01

Temperature, as a powerful variable in conventional LC is discussed from a fundamental point of view and illustrated with applications from the author's laboratory. Emphasis is given to the influence of temperature on speed, selectivity, efficiency, detectability, and mobile phase composition (green chromatography). The problems accompanying the use of elevated temperature and temperature programming in LC are reviewed and solutions are described. The available stationary phases for high temperature operation are summarized and a brief overview of recent applications reported in the literature is given.

Crystallization of pure anhydrous polymorphs of carbamazepine by solution enhanced dispersion with supercritical fluids (SEDS).

PubMed

Edwards, A D; Shekunov, B Y; Kordikowski, A; Forbes, R T; York, P

2001-08-01

Pure anhydrous polymorphs of carbamazepine were prepared by solution-enhanced dispersion with supercritical fluids (SEDS). Crystallization of the polymorphs was studied. Mechanisms are proposed that consider the thermodynamics of carbamazepine, supersaturation in the SEDS process, and the binary phase equilibria of organic solvents and the carbon dioxide antisolvent. alpha-Carbamazepine was crystallized at high supersaturations and low temperatures, beta-carbamazepine crystallized from a methanol-carbon dioxide phase split, and gamma-carbamazepine crystallized via nucleation at high temperatures and low supersaturation. Copyright 2001 Wiley-Liss, Inc.

Chemical Corrosion of Liquid-Phase Sintered SiC in Acidic/Alkaline Solutions Part 1. Corrosion in HNO3 Solution

NASA Astrophysics Data System (ADS)

Zhang, Lei; Zhang, Ming; He, Xinnong; Tang, Wenming

2016-03-01

The corrosion behavior of the liquid-phase sintered SiC (LPS-SiC) was studied by dipping in 3.53 mol/L HNO3 aqueous solution at room temperature and 70 °C, respectively. The weight loss, strength reduction and morphology evolution of the SiC specimens during corroding were revealed and also the chemical corrosion process and mechanism of the SiC specimens in the acidic solution were clarified. The results show that the corrosion of the LPS-SiC specimens in the HNO3 solution is selective. The SiC particles are almost free from corrosion, but the secondary phases of BaAl2Si2O8 (BAS) and Y2Si2O7 are corroded via an acid-alkali neutralization reaction. BAS has a higher corrosion rate than Y2Si2O7, resulting in the formation of the bamboo-leaf-like corrosion pits. As the SiC specimens etched in the HNO3 solution at room temperature for 75 days, about 80 μm thickness corrosion layer forms. The weight loss and bending strength reduction of the etched SiC specimens are 2.6 mg/cm2 and 52%, respectively. The corrosion of the SiC specimens is accelerated in the 70 °C HNO3 solution with a rate about five times bigger than that in the same corrosion medium at room temperature.

Effect of mixing, concentration and temperature on the formation of mesostructured solutions and their role in the nucleation of DL-valine crystals.

PubMed

Jawor-Baczynska, Anna; Moore, Barry D; Sefcik, Jan

2015-01-01

We report investigations on the formation of mesostructured solutions in DL-valine-water-2-propanol mixtures, and the crystallization of DL-valine from these solutions. Mesostructured liquid phases, similar to those previously observed in aqueous solutions of glycine and DL-alanine, were observed using Dynamic Light Scattering and Brownian microscopy, in both undersaturated and supersaturated solutions below a certain transition temperature. Careful experimentation was used to demonstrate that the optically clear mesostructured liquid phase, comprising colloidal mesoscale clusters dispersed within bulk solution, is thermodynamically stable and present in equilibrium with the solid phase at saturation conditions. Solutions prepared by slow cooling contained mesoscale clusters with a narrow size distribution and a mean hydrodynamic diameter of around 200 nm. Solutions of identical composition prepared by rapid isothermal mixing of valine aqueous solutions with 2-propanol contained mesoscale clusters which were significantly larger than those observed in slowly cooled solutions. The presence of larger mesoscale clusters was found to correspond to faster nucleation. Observed induction times were strongly dependent on the rapid initial mixing step, although solutions were left undisturbed afterwards and the induction times observed were up to two orders of magnitude longer than the initial mixing period. We propose that mesoscale clusters above a certain critical size are likely to be the location of productive nucleation events.

Hyperscaling violating black hole solutions and magneto-thermoelectric DC conductivities in holography

NASA Astrophysics Data System (ADS)

Ge, Xian-Hui; Tian, Yu; Wu, Shang-Yu; Wu, Shao-Feng

2017-08-01

We derive new black hole solutions in Einstein-Maxwell-axion-dilaton theory with a hyperscaling violation exponent. We then examine the corresponding anomalous transport exhibited by cuprate strange metals in the normal phase of high-temperature superconductors via gauge-gravity duality. Linear-temperature-dependence resistivity and quadratic-temperature-dependence inverse Hall angle can be achieved. In the high-temperature regime, the heat conductivity and Hall Lorenz ratio are proportional to the temperature. The Nernst signal first increases as temperature goes up, but it then decreases with increasing temperature in the high-temperature regime.

Supercritical fluid reverse micelle separation

DOEpatents

Fulton, John L.; Smith, Richard D.

1993-01-01

A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W.sub.o that determines the maximum size of the reverse micelles. The maximum ratio W.sub.o of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions.

Supercritical fluid reverse micelle separation

DOEpatents

Fulton, J.L.; Smith, R.D.

1993-11-30

A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W[sub o] that determines the maximum size of the reverse micelles. The maximum ratio W[sub o] of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions. 27 figures.

A Novel Method of Measuring the Phase Behavior and Rheology of Polyethylene Solutions Using a Multi-Pass Rheometer

NASA Astrophysics Data System (ADS)

Lee, Karen; Lacombe, Y.; Cheluget, E.

2008-07-01

The Advanced SCLAIRTECH™ Technology process is used to manufacture Linear Low Density Polyethylene using solution polymerization. In this process ethylene is polymerized in an inert solvent, which is subsequently evaporated and recycled. The reactor effluent in the process is a polymer solution containing the polyethylene product, which is separated from the solvent and unconverted ethylene/co-monomer before being extruded and pelletized. The design of unit operations in this process requires a detailed understanding of the thermophysical properties, phase behaviour and rheology of polymer containing streams at high temperature and pressure, and over a wide range of composition. This paper describes a device used to thermo-rheologically characterize polymer solutions under conditions prevailing in polymerization reactors, downstream heat exchangers and attendant phase separation vessels. The downstream processing of the Advanced SCLAIRTECH™ Technology reactor effluent occurs at temperatures and pressures near the critical point of the solvent and co-monomer mixture. In addition, the process trajectory encompasses regions of liquid-liquid and liquid-liquid-vapour co-existence, which are demarcated by a `cloud point' curve. Knowing the location of this phase boundary is essential for the design of downstream devolatilization processes and for optimizing operating conditions in existing plants. In addition, accurate solution rheology data are required for reliable equipment sizing and design. At NOVA Chemicals, a robust high-temperature and high-pressure-capable version of the Multi-Pass Rheometer (MPR) is used to provide data on solution rheology and phase boundary location. This sophisticated piece of equipment is used to quantify the effects of solvent types, comonomer, and free ethylene concentration on the properties of the reactor effluent. An example of the experimental methodology to characterize a polyethylene solution with hexane solvent, and the ethylene dosing technique developed for the MPR will be described. ™Advanced SCLAIRTECH is a trademark of NOVA Chemicals.

Mathematical analysis of the multiband BCS gap equations in superconductivity

NASA Astrophysics Data System (ADS)

Yang, Yisong

2005-01-01

In this paper, we present a mathematical analysis for the phonon-dominated multiband isotropic and anisotropic BCS gap equations at any finite temperature T. We establish the existence of a critical temperature T so that, when TT, the only nonnegative gap solution is the zero solution, representing the normal phase. Furthermore, when T=T, we prove that the only gap solution is the zero solution and that the positive gap solution depend on the temperature T

Effect of polyethylene glycol on the liquid–liquid phase transition in aqueous protein solutions

PubMed Central

Annunziata, Onofrio; Asherie, Neer; Lomakin, Aleksey; Pande, Jayanti; Ogun, Olutayo; Benedek, George B.

2002-01-01

We have studied the effect of polyethylene glycol (PEG) on the liquid–liquid phase separation (LLPS) of aqueous solutions of bovine γD-crystallin (γD), a protein in the eye lens. We observe that the phase separation temperature increases with both PEG concentration and PEG molecular weight. PEG partitioning, which is the difference between the PEG concentration in the two coexisting phases, has been measured experimentally and observed to increase with PEG molecular weight. The measurements of both LLPS temperature and PEG partitioning in the ternary γD-PEG-water systems are used to successfully predict the location of the liquid–liquid phase boundary of the binary γD-water system. We show that our LLPS measurements can be also used to estimate the protein solubility as a function of the concentration of crystallizing agents. Moreover, the slope of the tie-lines and the dependence of LLPS temperature on polymer concentration provide a powerful and sensitive check of the validity of excluded volume models. Finally, we show that the increase of the LLPS temperature with PEG concentration is due to attractive protein–protein interactions. PMID:12391331

Energetics of a uranothorite (Th 1–xU xSiO 4) solid solution

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

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

Energetics of a uranothorite (Th 1–xU xSiO 4) solid solution

DOE PAGES

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel; ...

2016-10-11

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

Thermoresponsive Polymers with Lower Critical Solution Temperature- or Upper Critical Solution Temperature-Type Phase Behaviour Do Not Induce Toxicity to Human Endothelial Cells.

PubMed

Ji, Yuejia; Zhu, Mengxiang; Gong, Yu; Tang, Haoyu; Li, Juan; Cao, Yi

2017-01-01

Thermoresponsive polymers have gained extensive attention as biomedical materials especially for targeted drug delivery systems. We have recently developed water-soluble polypeptide-based thermoresponsive polymers that exhibit lower critical solution temperature (LCST)- or upper critical solution temperature (UCST)-type phase behaviours. In this study, the toxicity of these polymers to human umbilical vein endothelial cells (HUVECs) was investigated to assess the safety and biocompatibility. Up to 100 μg/ml, thermoresponsive polymers did not induce cytotoxicity to HUVECs, showing as unaltered mitochondrial viability assessed as cell counting kit-8 (CCK-8) assay and membrane integrity assessed as lactate dehydrogenase (LDH) assay. Inflammatory response, assessed as the release of chemokine-soluble monocyte chemotactic protein 1 (sMCP-1) and interleukin-8 (IL-8) as well as cytokine IL-6, was not significantly affected by the polymers. In addition, 1 μM thapsigargin (TG), an endoplasmic reticulum (ER) stress inducer, significantly decreased mitochondrial viability, but did not affect membrane integrity or inflammatory response. The presence of thermoresponsive polymers with LCST-type phase behaviour did not further affect the effects of TG. In conclusion, the thermoresponsive polymers used in this study are not toxic to endothelial cells and therefore could be further considered as safe materials for biomedical applications. © 2016 Nordic Association for the Publication of BCPT (former Nordic Pharmacological Society).

Why the Heyd-Scuseria-Ernzerhof hybrid functional description of VO2 phases is not correct

NASA Astrophysics Data System (ADS)

Grau-Crespo, Ricardo; Wang, Hao; Schwingenschlögl, Udo

2012-08-01

In contrast with recent claims that the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid functional can provide a good description of the electronic and magnetic structures of VO2 phases [Eyert, Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.107.016401 107, 016401 (2011)], we show here that the HSE lowest-energy solutions for both the low-temperature monoclinic (M1) phase and the high-temperature rutile (R) phase, which are obtained upon inclusion of spin polarization, are at odds with experimental observations. For the M1 phase the ground state is (but should not be) magnetic, while the ground state of the R phase, which is also spin polarized, is not (but should be) metallic. The energy difference between the low-temperature and high-temperature phases has strong discrepancies with the experimental latent heat.

Tube radial distribution phenomenon with a two-phase separation solution of a fluorocarbon and hydrocarbon organic solvent mixture in a capillary tube and metal compounds separation.

PubMed

Kitaguchi, Koichi; Hanamura, Naoya; Murata, Masaharu; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

2014-01-01

A fluorocarbon and hydrocarbon organic solvent mixture is known as a temperature-induced phase-separation solution. When a mixed solution of tetradecafluorohexane as a fluorocarbon organic solvent and hexane as a hydrocarbon organic solvent (e.g., 71:29 volume ratio) was delivered in a capillary tube that was controlled at 10°C, the tube radial distribution phenomenon (TRDP) of the solvents was clearly observed through fluorescence images of the dye, perylene, dissolved in the mixed solution. The homogeneous mixed solution (single phase) changed to a heterogeneous solution (two phases) with inner tetradecafluorohexane and outer hexane phases in the tube under laminar flow conditions, generating the dynamic liquid-liquid interface. We also tried to apply TRDP to a separation technique for metal compounds. A model analyte mixture, copper(II) and hematin, was separated through the capillary tube, and detected with a chemiluminescence detector in this order within 4 min.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Isothermal lipid phase transitions.

PubMed

Cevc, G

1991-03-01

In liotropic lipid systems phase transitions can be induced isothermally by changing the solvent concentration or composition; alternatively, lipid composition can be modified by (bio)chemical means. The probability for isothermal phase transitions increases with the decreasing transition entropy; it is proportional to the magnitude of the transition temperature shift caused by transformation-inducing system variation. Manipulations causing large thermodynamic effects, such as lipid (de)hydration, binding of protons or divalent ions and macromolecular adsorption, but also close bilayer approach are, therefore, likely to cause structural lipid change(s) at a constant temperature. Net lipid charges enhance the membrane susceptibility to salt-induced isothermal phase transitions; a large proportion of this effect is due to the bilayer dehydration, however, rather than being a consequence of the decreased Coulombic electrostatic interactions. Membrane propensity for isothermal phase transitions, consequently, always increases with the hydrophilicity of the lipid heads, as well as with the desaturation and shortening of the lipid chains. Upon a phase change at a constant temperature, some of the interfacially bound solutes (e.g. protons or calcium) are released in the solution. Membrane permeability and fusogenicity simultaneously increase. In mixed systems, isothermal phase transitions, moreover, may result in lateral phase separation. All this opens up ways for the involvement of isothermal phase transitions in the regulation of biological processes.

Effect of Process Parameter on Barium Titanate Stannate (BTS) Materials Sintered at Low Sintering

NASA Astrophysics Data System (ADS)

Shukla, Alok; Bajpai, P. K.

2011-11-01

Ba(Ti1-xSnx)O3 solid solutions with (x = 0.15, 0.20, 0.30 and 0.40) are synthesized using conventional solid state reaction method. Formation of solid solutions in the range 0 ≤ x ≤0.40 is confirmed using X-ray diffraction technique. Single phase solid solutions with homogeneous grain distribution are observed at relatively low sintering by controlling process parameters viz. sintering time. Composition at optimized temperature (1150 °C) sintered by varying the sintering time, stabilize in cubic perovskite phase. The % experimental density increase with increasing the time of sintering instead of increasing sintering temperature. The lattice parameter increases by increasing the tin composition in the material. This demonstrates that process parameter optimization can lead to single phase at relatively lower sintering-a major advantage for the materials used as capacitor element in MLCC.

Pressureless sintered beta prime-Si3N4 solid solution: Fabrication, microstructure, and strength

NASA Technical Reports Server (NTRS)

Dutta, S.

1977-01-01

Si3N4, AlN, and Al2O3 were used as basic constituents in a study of the pressureless sintering of beta prime-Si3N4 solid solution as a function of temperature. Y2O3-SiO2 additions were used to promote liquid-phase sintering. The sintered specimens were characterized with respect to density, microstructure, strength, oxidation, and thermal shock resistance. Density greater than 98 percent of theoretical was achieved by pressureless sintering at 1750 C. The microstructure consisted essentially of fine-grained beta prime-Si3N4 solid solution as the major phase. Modulus of rupture strengths up to 483 MPa were achieved at moderate temperature (1000 C), but decreased to 228 MPa at 1380 C. This substantial strength loss was attributed to a glassy grain boundary phase formed during cooling from the sintering temperature. The best oxidation resistance was exhibited by a composition containing 3 mol % Y2O3-SiO2 additives. Water quench thermal shock resistance was equivalent to that of reaction sintered silicon nitride but lower than hot-pressed silicon nitride.

Stabilizing Superionic-Conducting Structures via Mixed-Anion Solid Solutions of Monocarba- closo -borate Salts

DOE PAGES

Tang, Wan Si; Yoshida, Koji; Soloninin, Alexei V.; ...

2016-09-01

Solid lithium and sodium closo-polyborate-based salts are capable of superionic conductivities surpassing even liquid electrolytes, but often only at above-ambient temperatures where their entropically driven disordered phases become stabilized. Here we show by X-ray diffraction, quasielastic neutron scattering, differential scanning calorimetry, NMR, and AC impedance measurements that by introducing 'geometric frustration' via the mixing of two different closo-polyborate anions, namely, 1-CB 9H 10- and CB 11H 12-, to form solid-solution anion-alloy salts of lithium or sodium, we can successfully suppress the formation of possible ordered phases in favor of disordered, fast-ion-conducting alloy phases over a broad temperature range from subambientmore » to high temperatures. Finally, this result exemplifies an important advancement for further improving on the remarkable conductive properties generally displayed by this class of materials and represents a practical strategy for creating tailored, ambient-temperature, solid, superionic conductors for a variety of upcoming all-solid-state energy devices of the future.« less

Quantitative evaluation of colloidal stability of antibody solutions using PEG-induced liquid-liquid phase separation.

PubMed

Wang, Ying; Latypov, Ramil F; Lomakin, Aleksey; Meyer, Julie A; Kerwin, Bruce A; Vunnum, Suresh; Benedek, George B

2014-05-05

Colloidal stability of antibody solutions, i.e., the propensity of the folded protein to precipitate, is an important consideration in formulation development of therapeutic monoclonal antibodies. In a protein solution, different pathways including crystallization, colloidal aggregation, and liquid-liquid phase separation (LLPS) can lead to the formation of precipitates. The kinetics of crystallization and aggregation are often slow and vary from protein to protein. Due to the diverse mechanisms of these protein condensation processes, it is a challenge to develop a standardized test for an early evaluation of the colloidal stability of antibody solutions. LLPS would normally occur in antibody solutions at sufficiently low temperature, provided that it is not preempted by freezing of the solution. Poly(ethylene glycol) (PEG) can be used to induce LLPS at temperatures above the freezing point. Here, we propose a colloidal stability test based on inducing LLPS in antibody solutions and measuring the antibody concentration of the dilute phase. We demonstrate experimentally that such a PEG-induced LLPS test can be used to compare colloidal stability of different antibodies in different solution conditions and can be readily applied to high-throughput screening. We have derived an equation for the effects of PEG concentration and molecular weight on the results of the LLPS test. Finally, this equation defines a binding energy in the condensed phase, which can be determined in the PEG-induced LLPS test. This binding energy is a measure of attractive interactions between antibody molecules and can be used for quantitative characterization of the colloidal stability of antibody solutions.

High-temperature solution growth and characterization of (1-x)PbTiO3-xBi(Zn2/3Nb1/3)O3 piezo-/ferroelectric single crystals

NASA Astrophysics Data System (ADS)

Paterson, Alisa R.; Zhao, Jinyan; Liu, Zenghui; Wu, Xiaoqing; Ren, Wei; Ye, Zuo-Guang

2018-03-01

Complex perovskite PbTiO3-Bi(Me‧Me″)O3 solid solutions represent new materials systems that possess a higher Curie temperature (TC) than the relaxor-PbTiO3 solid solutions, and are useful for potential applications. To this end, novel ferroelectric single crystals of the (1-x)PbTiO3-xBi(Zn2/3Nb1/3)O3 (PT-BZN) solid solution were successfully grown by the high-temperature solution growth (HTSG) method. Powder X-ray diffraction shows that the symmetry of the grown crystals is tetragonal. The dielectric permittivity and optical domain structures were characterized by dielectric measurements and polarized light microscopy, respectively, as a function of temperature, revealing a first-order ferroelectric-paraelectric phase transition at a TC of 436 ± 2 °C. Based on the TC, the average composition of the crystal platelet was estimated to be 0.58PT-0.42BZN. Piezoresponse force microscopy measurements of the phase and amplitude as a function of voltage reveal the complex polar domain structure and demonstrate the ferroelectric switching behaviour of these materials. These results suggest that the PT-BZN single crystals indeed form a new family of high TC piezo-/ferroelectric materials which are potentially useful for the fabrication of electromechanical transducers for high-temperature applications.

Acoustical experiment of yogurt fermentation process.

PubMed

Ogasawara, H; Mizutani, K; Ohbuchi, T; Nakamura, T

2006-12-22

One of the important factors through food manufacturing is hygienic management. Thus, food manufactures prove their hygienic activities by taking certifications like a Hazard Analysis and Critical Control Point (HACCP). This concept also applies to food monitoring. Acoustical measurements have advantage for other measurement in food monitoring because they make it possible to measure with noncontact and nondestructive. We tried to monitor lactic fermentation of yogurt by a probing sensor using a pair of acoustic transducers. Temperature of the solution changes by the reaction heat of fermentation. Consequently the sound velocity propagated through the solution also changes depending on the temperature. At the same time, the solution change its phase from liquid to gel. The transducers usage in the solution indicates the change of the temperature as the change of the phase difference between two transducers. The acoustic method has advantages of nondestructive measurement that reduces contamination of food product by measuring instrument. The sensor was inserted into milk with lactic acid bacterial stain of 19 degrees C and monitored phase retardation of propagated acoustic wave and its temperature with thermocouples in the mild. The monitoring result of fermentation from milk to Caspian Sea yogurt by the acoustic transducers with the frequency of 3.7 MHz started to show gradient change in temperature caused by reaction heat of fermentation but stop the gradient change at the end although the temperature still change. The gradient change stopped its change because of phase change from liquid to gel. The present method will be able to measure indirectly by setting transducers outside of the measuring object. This noncontact sensing method will have great advantage of reduces risk of food contamination from measuring instrument because the measurement probes are set out of fermentation reactor or food containers. Our proposed method will contribute to the hygienization for the food manufacture industry.

Structural and ferroelectric phase evolution in [KNbO3]1-x[BaNi1/2Nb1/2O3 -δ] x (x =0 ,0.1 )

NASA Astrophysics Data System (ADS)

Hawley, Christopher J.; Wu, Liyan; Xiao, Geoffrey; Grinberg, Ilya; Rappe, Andrew M.; Davies, Peter K.; Spanier, Jonathan E.

2017-08-01

The phase transition evolution for [KNbO3]1-x[BaNi1/2Nb1/2O3 -δ] x(x =0 ,0.1 ) is determined via complementary dielectric permittivity and Raman-scattering measurements. Raman scattering by optical phonons over the range of 100-1000 cm-1 for 83 K

Raman effect in multiferroic Bi5Fe1+xTi3-xO15 solid solutions: A temperature study

NASA Astrophysics Data System (ADS)

Rodríguez Aranda, Ma. Del Carmen; Rodríguez-Vázquez, Ángel G.; Salazar-Kuri, Ulises; Mendoza, María Eugenia; Navarro-Contreras, Hugo R.

2018-02-01

In this work, a Raman study of powder samples of multiferroic Bi5Fe1+xTi3-xO15 solid solutions and Bi6Fe2Ti3O18 as a function of temperature from 27 °C (room temperature) to 850 °C is presented. The values of x (i.e., the Fe composition) for the solid solutions were 1.0, 1.1, 1.3, and 1.4. The temperature coefficients of eight phonon frequencies were determined for all the samples. The large observed phonon broadenings with increasing temperature precluded the observation of several of the phonon bands above defined temperatures in the range of 200-700 °C depending on the sample. These phonon broadenings were explained on the basis of the Klemens model, which considers that the broadenings are due to the thermal expansion of the lattice with a major contribution in terms of magnitude from anharmonic phonon-phonon interactions. However, some evidence for the presence of several of the phonons persisted up to 800-850 °C. These solid solutions are expected to exhibit a ferroelectric-paraelectric phase transition at 742 to 750 °C and a ferromagnetic-antiferromagnetic transition at 426 °C. We also observed changes in the slopes of the temperature dependence of the phonon frequencies for the lines at 228 cm-1 for Bi5FeTi3O15 and 330 cm-1 for Bi6Fe2Ti3O18 at temperatures of 247 °C and 347 °C, respectively. No similar temperature-frequency slope changes indicative of possible phase transitions were observed for any of the phonon lines of the other three Bi5Fe1+xTi3-xO15 solid solutions examined.

Aluminum Target Dissolution in Support of the Pu-238 Program

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

McFarlane, Joanna; Benker, Dennis; DePaoli, David W

2014-09-01

Selection of an aluminum alloy for target cladding affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the caustic dissolution step, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. We present a study to maximize dissolution of aluminum metal alloy, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as a function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. These datamore » have been compared with published calculations of aluminum phase diagrams. Temperature logging during the transients has been investigated as a means to generate kinetic and mass transport data on the dissolution process. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.« less

Thermoresponsive Poly(Ionic Liquid)s in Aqueous Salt Solutions: Salting-Out Effect on Their Phase Behavior and Water Absorption/Desorption Properties.

PubMed

Okafuji, Akiyoshi; Kohno, Yuki; Ohno, Hiroyuki

2016-07-01

Here, a thermoresponsive phase behavior of polymerized ionic liquids (PILs) composed of poly([tri-n-alkyl(vinylbenzyl)phosphonium]chloride) (poly([Pnnn VB ]Cl) is reported, where n (the number of carbon atoms of an alkyl chain) = 4, 5, or 6 after mixing with aqueous sodium chloride solutions. Both monomeric [P555VB ]Cl and the resulting poly([P555VB ]Cl) linear homopolymer show a lower critical solution temperature (LCST)-type phase behavior in aq. NaCl solutions. The phase transition temperature of the PIL shifts to lower value by increasing concentration of NaCl. Also the swelling degree of cross-linked poly([P555VB ]Cl) gel decreases by increasing NaCl concentration, clearly suggesting the "salting-out" effect of NaCl results in a significant dehydration of the poly([P555VB ]Cl) gel. The absorbed water in the PIL gel is desorbed by moderate heating via the LCST behavior, and the absolute absorption/desorption amount is improved by copolymerization of [P555VB ]Cl with more hydrophilic [P444VB ]Cl monomer. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quench-age method for the fabrication of niobium-aluminum superconductors

DOEpatents

Pickus, Milton R.; Ciardella, Robert L.

1978-01-01

A flexible Nb.sub.3 Al superconducting wire is fabricated from a niobium-aluminum composite wire by heating to form a solid solution which is retained at room temperature as a metastable solid solution by quenching. The metastable solid solution is then transformed to the stable superconducting A-15 phase by low temperature aging. The transformation induced by aging can be controlled to yield either a multifilamentary or a solid A-15 core surrounded by ductile niobium.

High temperature decomposition of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Parrish, Clyde F. (Inventor)

2005-01-01

Nitric oxide (NO) is oxidized into nitrogen dioxide (NO2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydroperoxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

Dynamics of the Exchange of Carbon Dioxide in Arctic and Subarctic Regions,

DTIC Science & Technology

1973-01-01

snow, at temperatures too low for significant biological activity. The phenomena of gas evasion under conditions of 3 freezing soil solution , confirmed...1972) have observed a de- pression rather than an acceleration in soil respiration, as the soil solution undergoes a phase change near 0C. On the other...temperatures are too low for significant biological activity. CO2 from biological sources expressed by freezing the soil solution , evidently leaks to the

High Temperature Decomposition of Hydrogen Peroxide

NASA Technical Reports Server (NTRS)

Parrish, Clyde F. (Inventor)

2004-01-01

Nitric oxide (NO) is oxidized into nitrogen dioxide (NO2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydropemxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

Temperature-dependent phase-specific deformation mechanisms in a directionally solidified NiAl-Cr(Mo) lamellar composite

DOE PAGES

Yu, Dunji; An, Ke; Chen, Xu; ...

2015-10-09

Phase-specific thermal expansion and mechanical deformation behaviors of a directionally solidified NiAl–Cr(Mo) lamellar in situ composite were investigated by using real-time in situ neutron diffraction during compression at elevated temperatures up to 800 °C. Tensile and compressive thermal residual stresses were found to exist in the NiAl phase and Crss (solid solution) phase, respectively. Then, based on the evolution of lattice spacings and phase stresses, the phase-specific deformation behavior was analyzed qualitatively and quantitatively. Moreover, estimates of phase stresses were derived by Hooke's law on the basis of a simple method for the determination of stress-free lattice spacing in inmore » situ composites. During compressive loading, the NiAl phase yields earlier than the Crss phase. The Crss phase carries much higher stress than the NiAl phase, and displays consistent strain hardening at all temperatures. The NiAl phase exhibits strain hardening at relatively low temperatures and softening at high temperatures. During unloading, the NiAl phase yields in tension whereas the Crss phase unloads elastically. Additionally, post-test microstructural observations show phase-through cracks at room temperature, micro cracks along phase interfaces at 600 °C and intact lamellae kinks at 800 °C, which is due to the increasing deformability of both phases as temperature rises.« less

Solid solubility, phase transitions, thermal expansion, and compressibility in Sc{sub 1−x}Al{sub x}F{sub 3}

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

Morelock, Cody R.; Gallington, Leighanne C.; Wilkinson, Angus P., E-mail: angus.wilkinson@chemistry.gatech.edu

2015-02-15

With the goal of thermal expansion control, the synthesis and properties of Sc{sub 1−x}Al{sub x}F{sub 3} were investigated. The solubility limit of AlF{sub 3} in ScF{sub 3} at ∼1340 K is ∼50%. Solid solutions (x≤0.50) were characterized by synchrotron powder diffraction at ambient pressure between 100 and 900 K and at pressures <0.414 GPa while heating from 298 to 523 K. A phase transition from cubic to rhombohedral is observed. The transition temperature increases smoothly with Al{sup 3+} content, approaching 500 K at the solid solubility limit, and also upon compression at fixed Al{sup 3+} content. The slope of themore » pressure–temperature phase boundary is ∼0.5 K MPa{sup −1}, which is steep relative to that for most symmetry-lowering phase transitions in perovskites. The volume coefficient of thermal expansion (CTE) for the rhombohedral phase is strongly positive, but the cubic-phase CTE varies from negative (x<0.15) to near-zero (x=0.15) to positive (x>0.20) between ∼600 and 800 K. The cubic solid solutions elastically stiffen on heating, while Al{sup 3+} substitution causes softening at a given temperature. - Graphical abstract: The cubic-phase coefficient of thermal expansion for Sc{sub 1−x}Al{sub x}F{sub 3}(solubility limit ∼50% at ∼1340 K) becomes more positive with increased Al{sup 3+} substitution, but the average isothermal bulk modulus decreases (elastic softening). - Highlights: • The solubility limit of AlF{sub 3} in ScF{sub 3} at ∼1340 K is ∼50%. • The phase transition temperature of Sc{sub 1−x}Al{sub x}F{sub 3} increases smoothly with x. • The cubic-phase volume CTE varies from negative to positive with increasing x. • The cubic solid solutions elastically stiffen on heating. • Al{sup 3+} substitution causes softening at a given temperature.« less

A renaissance of soaps? - How to make clear and stable solutions at neutral pH and room temperature.

PubMed

Wolfrum, Stefan; Marcus, Julien; Touraud, Didier; Kunz, Werner

2016-10-01

Soaps are the oldest and perhaps most natural surfactants. However, they lost much of their importance since "technical surfactants", usually based on sulfates or sulfonates, have been developed over the last fifty years. Indeed, soaps are pH- and salt-sensitive and they are irritant, especially to the eyes. In food emulsions, although authorized, they have a bad taste, and long-chain saturated soaps have a high Krafft temperature. We believe that most or perhaps all of these problems can be solved with modern formulation approaches. We start this paper with a short overview of our present knowledge of soaps and soap formulations. Then we focus on the problem of the lacking soap solubility at neutral pH values. For example, it is well known that with the food emulsifier sodium oleate (NaOl), clear and stable aqueous solutions can only be obtained at pH values higher than 10. A decrease in the pH value leads to turbid and unstable solutions. This effect is not compatible with the formulation of aqueous stable and drinkable formulations with neutral or even acidic pH values. However, the pH value/phase behavior of aqueous soap solutions can be altered by the addition of other surfactants. Such a surfactant can be Rebaudioside A (RebA), a steviol glycoside from the plant Stevia rebaudiana which is used as a natural food sweetener. In a recent paper, we showed the influence of RebA on the apKa value of sodium oleate in a beverage microemulsion and on its clearing temperature. In the present paper, we report on the effect of the edible bio-surfactant RebA, on the macroscopic and microscopic phase behavior of simple aqueous sodium oleate solutions at varying pH values. The macroscopic phase behavior is investigated by visual observation and turbidity measurements. The microscopic phase behavior is analyzed by acid-base titration curves, phase-contrast and electron microscopy. It turned out that even at neutral pH, aqueous NaOl/RebA solutions can be completely clear and stable for more than 50days at room temperature. This is for the first time that a long chain soap could be really solubilized in water at neutral pH at room temperature. At last, these findings were applied to prepare stable, highly translucent and drinkable aqueous solutions of omega-3-fatty acids at a pH value of 7.5. Copyright © 2016 Elsevier B.V. All rights reserved.

Analysis of thermomechanical states in single-pass GMAW surfaced steel element

NASA Astrophysics Data System (ADS)

Winczek, Jerzy; Gawronska, Elzbieta; Murcinkova, Zuzana; Hatala, Michal; Pavlenko, Slavko; Makles, Krzysztof

2017-03-01

In the paper the model of temperature field, phase changes and stress states calculation during single-pass arc weld surfacing have been presented. In temperature field solution the temperature changes caused by the heat of weld and by electric arc have been taken into consideration. Kinetics of phase changes during heating is limited by temperature values at the beginning and at the end of austenitic transformation, while progress of phase transformations during cooling has been determined on the basis of time-temperature-transformation (TTT) - welding diagram. The analysis of stress state has been presented for S235 steel flat assuming planar section hypothesis and using integral equations of stress equilibrium. It has enabled a clear interpretation of influence of temperature field and phase transformation on stresses caused by surfacing using Gas Metal Arc Welding (GMAW) method.

Effect of temperature gradient on liquid-liquid phase separation in a polyolefin blend.

PubMed

Jiang, Hua; Dou, Nannan; Fan, Guoqiang; Yang, Zhaohui; Zhang, Xiaohua

2013-09-28

We have investigated experimentally the structure formation processes during phase separation via spinodal decomposition above and below the spinodal line in a binary polymer blend system exposed to in-plane stationary thermal gradients using phase contrast optical microscopy and temperature gradient hot stage. Below the spinodal line there is a coupling of concentration fluctuations and thermal gradient imposed by the temperature gradient hot stage. Also under the thermal gradient annealing phase-separated domains grow faster compared with the system under homogeneous temperature annealing on a zero-gradient or a conventional hot stage. We suggest that the in-plane thermal gradient accelerates phase separation through the enhancement in concentration fluctuations in the early and intermediate stages of spinodal decomposition. In a thermal gradient field, the strength of concentration fluctuation close to the critical point (above the spinodal line) is strong enough to induce phase separation even in one-phase regime of the phase diagram. In the presence of a temperature gradient the equilibrium phase diagrams are no longer valid, and the systems with an upper critical solution temperature can be quenched into phase separation by applying the stationary temperature gradient. The in-plane temperature gradient drives enhanced concentration fluctuations in a binary polymer blend system above and below the spinodal line.

Formation of anisotropic hollow-fiber membranes via thermally induced phase separation

NASA Astrophysics Data System (ADS)

Batarseh, Melanie Turkett

The goal of this research project was to study the formation of anisotropic hollow fiber membranes via thermally induced phase separation (TIPS). This objective included developing a fundamental knowledge of the factors that contribute to anisotropy and studying how anisotropy can be controlled via operational parameters in hollow fiber spinning. The objective was met by creating a model to simulate the mass and heat transfer in the fiber wall during spinning and by experimentally varying spinning parameters and observing the affect on the membrane microstructure. The TIPS membrane formation process consists of forming a homogeneous solution of polymer and diluent and extruding the solution through a spinneret to form a hollow fiber. The fiber is cooled in an air gap followed by a quench bath, which results in phase separation of the solution into a diluent-rich phase dispersed in a continuous polymer-rich liquid phase. The diluent-rich domains grow in size until the polymer-rich phase crystallizes. Then the diluent is removed, and the spaces left behind become the pores of the microporous membrane. Therefore, the size of the diluent-rich domains when the polymer solidifies is related to the size of the pores in the finished membrane. Increasing the polymer concentration of the homogeneous solution or increasing the cooling rate of the phase separated solution decreases the domain size, and thus decreases pore size. An anisotropic membrane, which has a gradation of pore size from small pores at the feed-side to large pores at the permeate-side, can be formed by creating a concentration gradient or a cooling rate gradient across the membrane. In hollow fiber spinning, a concentration gradient can be created by allowing diluent to evaporate from the outside wall of the fiber in the air gap, and a cooling rate gradient can be created by quenching the fiber in a liquid bath. The spinning model calculates concentration and temperature profiles across the hollow fiber wall over time. The model results indicate that spinning temperature, air velocity, and air gap length have a significant effect on the concentration profile in the wall, and spinning temperature and quench temperature have a significant effect on the cooling rate profile. Experimental results indicate that increasing the air gap length from 5 to 50 cm. or increasing the quench temperature from 298 to 323 K has a significant effect on the anisotropic structure of the hollow fiber.

PHASE DIAGRAM FOR THE SYSTEM TITANIUM-TIN (in Russian)

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

Kornilov, I.I.; Nartova, T.T.

1960-03-01

Differential thermal analysis, microstructural analyses, and determinations of hardness values and electric resistance were used to construct a diagram of state for the binary system Ti-Sn up to the composition of the compound Ti/sub 3/Sn (from 0 to 25 at.% Sn). Analyses of the thermograms showed that all conversions proceeding with the absorption of heat could be detected on the heating curves. Tin lowers the temperature of conversion of titunium with 5.0 at.% tin first to a minimum at 860 tained C which then increases to 890 tained C at higher tin contents. A peritectoid reaction ( alpha / submore » 2/ were ob ore resistant t + ) takes place with a conversion temperature at 890 tained C. A HF-HNO/sub 3/-glycerin etch showed a single-phase homogeneous structure of an alpha -solid solution with alloys containing up to 9 at.% Q. The amount of a second -phase increases with increasing tin content until a single-phase structure of a -solid solution of the compound Ti/sub 3/Sn is noted with alloys containing 23 to 25 at.% Sn. Alloys containing 8 to 22.5 at.% Sn undergo a peritectoid reaction, at a temperature of 890 tained C as shown by thermal analyses and by microstructural analyses of samples quenched frorn above and below the conversion temperature. A study of the microstructure of quenched alloys showed that the solubility of tin in ore resistant t -titanium increases from 8 at.% Sn at 890 tained C to 10.5 at.% Sn at 1100 tained C. X-ray analyses of annealed samples of alloy showed only the lines of an alpha solid solution for 5, 8, 9 at.% Sn, a -solid solution for 23 at.% Sn (close to the composition Ti/sub 3/Sn), and an alpha and mixed phase for a 15 at.% Sn. Vickers hardness numbers were determined with a diamond pyramid at a loading of 10 kg. The hardness increases smoothly with increasing tin content to a maximum at the saturation solubility of the tin in the alpha - or ore resistant t -solid solution. The hardness decreases smoothly with the appearance of the -phase until it attains a minimum at the composition of the compound Ti/sub 3/Sn. The specific electric resistance increases with an increase of tin in the solid solution of alpha -titanium. The rate of increase of the specific electric resistance decreases markedly with the appearance of the -phase. The electric resistance of an alloy with 14.3 at.% Sn was studied as a function of temperature from room temperature to 1100 tained C in special vacuum equipment. A sharp drop in electric resistance a; 890 tained C confirmed the existence of a peritectoid reaction in the system Ti-Sn. (TTT)« less

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals

PubMed Central

Li, Dehui; Wang, Gongming; Cheng, Hung-Chieh; Chen, Chih-Yen; Wu, Hao; Liu, Yuan; Huang, Yu; Duan, Xiangfeng

2016-01-01

Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase transition in perovskite can significantly alter its optical, electrical properties and impact the corresponding applications. Here, we report a systematic investigation of the size-dependent orthorhombic-to-tetragonal phase transition using a combined temperature-dependent optical, electrical transport and transmission electron microscopy study. Our studies of individual perovskite microplates with variable thicknesses demonstrate that the phase transition temperature decreases with reducing microplate thickness. The sudden decrease of mobility around phase transition temperature and the presence of hysteresis loops in the temperature-dependent mobility confirm that the orthorhombic-to-tetragonal phase transition is a first-order phase transition. Our findings offer significant fundamental insight on the temperature- and size-dependent structural, optical and charge transport properties of perovskite materials, and can greatly impact future exploration of novel electronic and optoelectronic devices from these materials. PMID:27098114

Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals

DOE PAGES

Li, Dehui; Wang, Gongming; Cheng, Hung -Chieh; ...

2016-04-21

Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase transition in perovskite can significantly alter its optical, electrical properties and impact the corresponding applications. Here, we report a systematic investigation of the size-dependent orthorhombic-to-tetragonal phase transition using a combined temperature-dependent optical, electrical transport and transmission electron microscopy study. Our studies of individual perovskite microplates with variable thicknesses demonstrate that the phase transition temperature decreases with reducing microplate thickness. The sudden decrease of mobility around phase transition temperature and the presence of hysteresis loops in the temperature-dependent mobility confirmmore » that the orthorhombic-to-tetragonal phase transition is a first-order phase transition. Lastly, our findings offer significant fundamental insight on the temperature-and size-dependent structural, optical and charge transport properties of perovskite materials, and can greatly impact future exploration of novel electronic and optoelectronic devices from these materials.« less

Heat pipe dynamic behavior

NASA Technical Reports Server (NTRS)

Issacci, F.; Roche, G. L.; Klein, D. B.; Catton, I.

1988-01-01

The vapor flow in a heat pipe was mathematically modeled and the equations governing the transient behavior of the core were solved numerically. The modeled vapor flow is transient, axisymmetric (or two-dimensional) compressible viscous flow in a closed chamber. The two methods of solution are described. The more promising method failed (a mixed Galerkin finite difference method) whereas a more common finite difference method was successful. Preliminary results are presented showing that multi-dimensional flows need to be treated. A model of the liquid phase of a high temperature heat pipe was developed. The model is intended to be coupled to a vapor phase model for the complete solution of the heat pipe problem. The mathematical equations are formulated consistent with physical processes while allowing a computationally efficient solution. The model simulates time dependent characteristics of concern to the liquid phase including input phase change, output heat fluxes, liquid temperatures, container temperatures, liquid velocities, and liquid pressure. Preliminary results were obtained for two heat pipe startup cases. The heat pipe studied used lithium as the working fluid and an annular wick configuration. Recommendations for implementation based on the results obtained are presented. Experimental studies were initiated using a rectangular heat pipe. Both twin beam laser holography and laser Doppler anemometry were investigated. Preliminary experiments were completed and results are reported.

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

NASA Astrophysics Data System (ADS)

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

2015-11-01

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

Study of liquid?liquid demixing from drug solution

NASA Astrophysics Data System (ADS)

Lafferrère, Laurent; Hoff, Christian; Veesler, Stéphane

2004-09-01

In pharmaceutical industry, a deep understanding of the phase diagram is required in design of crystallization processes. We have investigated the phase diagram of a pharmaceutical compound (C 35H 41Cl 2N 3O 2) in a mixture of ethanol/water. This phase diagram exhibits a solid-solid (polymorphism) and a liquid-liquid-phase separation (LLPS) as a function of temperature and drug substance concentration. This study focuses on the LLPS which is metastable with respect to the crystallization of the two polymorphs FI and FII of C 35H 41Cl 2N 3O 2 in an ethanol/water mixture. The LLPS is metastable towards the solubility curve on the whole solvent-solute concentrations and temperature range studied. The LLPS occurred within the metastable zone for crystallization. In our experiments the liquid-liquid-phase transition prevented the drug from crystallizing, while it changed the medium and the conditions of crystallization, which consequently affected the process. The coexistence curves for the liquid phases, also named TL-L boundary, and the spinodal line were measured for a ternary mixture of water-drug-ethanol at atmospheric pressure over a temperature range of 10-50°C. This temperature range corresponds to that used in the crystallization process. Static Light Scattering, HPLC measurements and Karl-Fischer titration were applied to investigate the drug-phase diagram. The isoplethe section of the phase diagram exhibits four regions: one homogeneous (one liquid) and three two-phases (two regions with one liquid+one solid and one region with two liquids), the two solids phases being two polymorphs.

Pressure-induced fcc to hcp phase transition in Ni-based high entropy solid solution alloys

DOE PAGES

Zhang, Fuxiang; Zhao, Shijun; Jin, Ke; ...

2017-01-04

In this research, pressure-induced phase transition from the fcc to a hexagonal close-packed (hcp) structure wasfound in NiCoCrFe solid solution alloy starting at 13.5 GPa. The phase transition is very sluggish and the transition did not complete at ~ 40 GPa. The hcp structure is quenchable to ambient pressure. Only a very small amount (<5%) of hcp phase was found in the isostructural NiCoCr ternary alloy up to the pressure of 45 GPa and no obvious hcp phase was found in NiCoCrFePd system till to 74 GPa. Ab initio Gibbs free energy calculations indicated the energy differences between the fccmore » and the hcp phases for the three alloys are very small, but they are sensitive to temperature. Finally, the critical transition pressure in NiCoCrFe varies from 1 GPa at room temperature to 6 GPa at 500 K.« less

Pressure-induced fcc to hcp phase transition in Ni-based high entropy solid solution alloys

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

Zhang, F. X.; Zhao, Shijun; Jin, Ke

2017-01-04

A pressure-induced phase transition from the fcc to a hexagonal close-packed (hcp) structure was found in NiCoCrFe solid solution alloy starting at 13.5 GPa. The phase transition is very sluggish and the transition did not complete at ~40 GPa. The hcp structure is quenchable to ambient pressure. Only a very small amount (<5%) of hcp phase was found in the isostructural NiCoCr ternary alloy up to the pressure of 45 GPa and no obvious hcp phase was found in NiCoCrFePd system till to 74 GPa. Ab initio Gibbs free energy calculations indicated the energy differences between the fcc and themore » hcp phases for the three alloys are very small, but they are sensitive to temperature. The critical transition pressure in NiCoCrFe varies from ~1 GPa at room temperature to ~6 GPa at 500 K.« less

Effects of Gas-Phase Radiation and Detailed Kinetics on the Burning and Extinction of a Solid Fuel

NASA Technical Reports Server (NTRS)

Rhatigan, Jennifer L.

2001-01-01

This is the first attempt to analyze both radiation and detailed kinetics on the burning and extinction of a solid fuel in a stagnation-point diffusion flame. We present a detailed and comparatively accurate computational model of a solid fuel flame along with a quantitative study of the kinetics mechanism, radiation interactions, and the extinction limits of the flame. A detailed kinetics model for the burning of solid trioxane (a trimer of formaldehyde) is coupled with a narrowband radiation model, with carbon dioxide, carbon monoxide, and water vapor as the gas-phase participating media. The solution of the solid trioxane diffusion flame over the flammable regime is presented in some detail, as this is the first solution of a heterogeneous trioxane flame. We identify high-temperature and low-temperature reaction paths for the heterogeneous trioxane flame. We then compare the adiabatic solution to solutions that include Surface radiation only and gas-phase and surface radiation using a black surface model. The analysis includes discussion of detailed flame chemistry over the flammable regime and, in particular, at the low stretch extinction limit. We emphasize the low stretch regime of the radiatively participating flame, since this is the region representative of microgravity flames. When only surface radiation is included, two extinction limits exist (the blow-off limit, and the low stretch radiative limit), and the burning rate and maximum flame temperatures are lower, as expected. With the inclusion of surface and gas-phase radiation, results show that, while flame temperatures are lower, the burning rate of the trioxane diffusion flame may actually increase at low stretch rate due to radiative feedback from the flame to the surface.

Self-assembled pentacenequinone derivative for trace detection of picric acid.

PubMed

Bhalla, Vandana; Gupta, Ankush; Kumar, Manoj; Rao, D S Shankar; Prasad, S Krishna

2013-02-01

Pentacenequinone derivative 3 forms luminescent supramolecular aggregates both in bulk as well as in solution phase. In bulk phase at high temperature, long-range stacking of columns leads to formation of stable and ordered columnar mesophase. Further, derivative 3 works as sensitive chemosensor for picric acid (PA) and gel-coated paper strips detect PA at nanomolar level and provide a simple, portable, and low-cost method for detection of PA in aqueous solution, vapor phase, and in contact mode.

Solution-processed phase-change VO(2) metamaterials from colloidal vanadium oxide (VO(x)) nanocrystals.

PubMed

Paik, Taejong; Hong, Sung-Hoon; Gaulding, E Ashley; Caglayan, Humeyra; Gordon, Thomas R; Engheta, Nader; Kagan, Cherie R; Murray, Christopher B

2014-01-28

We demonstrate thermally switchable VO2 metamaterials fabricated using solution-processable colloidal nanocrystals (NCs). Vanadium oxide (VOx) NCs are synthesized through a nonhydrolytic reaction and deposited from stable colloidal dispersions to form NC thin films. Rapid thermal annealing transforms the VOx NC thin films into monoclinic, nanocrystalline VO2 thin films that show a sharp, reversible metal-insulator phase transition. Introduction of precise concentrations of tungsten dopings into the colloidal VOx NCs enables the still sharp phase transition of the VO2 thin films to be tuned to lower temperatures as the doping level increases. We fabricate "smart", differentially doped, multilayered VO2 films to program the phase and therefore the metal-insulator behavior of constituent vertically structured layers with temperature. With increasing temperature, we tailored the optical response of multilayered films in the near-IR and IR regions from that of a strong light absorber, in a metal-insulator structure, to that of a Drude-like reflector, characteristic of a pure metallic structure. We demonstrate that nanocrystal-based nanoimprinting can be employed to pattern multilayered subwavelength nanostructures, such as three-dimensional VO2 nanopillar arrays, that exhibit plasmonic dipolar responses tunable with a temperature change.

High temperature decomposition of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Parrish, Clyde F. (Inventor)

2004-01-01

Nitric oxide (NO) is oxidized into nitrogen dioxide (NO.sub.2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydroperoxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

High temperature decomposition of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Parrish, Clyde F. (Inventor)

2011-01-01

Nitric oxide (NO) is oxidized into nitrogen dioxide (NO.sub.2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydroperoxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

Lattice crossover and phase transitions in NdAlO{sub 3}-GdAlO{sub 3} system

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

Vasylechko, L., E-mail: crystal-lov@polynet.lviv.ua; Shmanko, H.; Ohon, N.

2013-02-15

Phase and structural behaviour in the (1-x)NdAlO{sub 3}-xGdAlO{sub 3} system in a whole concentration range has been studied by means of in situ high-resolution X-ray synchrotron powder diffraction technique and differential thermal analysis. Two kinds of solid solutions Nd{sub 1-x}Gd{sub x}AlO{sub 3} have been found at room temperature: one with rhombohedral (x<0.15) and one with orthorhombic (x{>=}0.20) symmetry. A morphotropic phase transition occurs at x Almost-Equal-To 0.15, where the co-existence of both phases was observed. Peculiarity of the orthorhombic solid solution is the lattice parameter crossover at the compositions with x=0.33, 0.49 and 0.62. First-order structural transition Pbnm{r_reversible}R3{sup Macron }cmore » has been detected both from in situ powder diffraction and thermal analysis data. Continuous phase transformation R3{sup Macron }c{r_reversible}Pm3{sup Macron }m above 2140 K has been predicted for Nd-rich sample Nd{sub 0.85}Gd{sub 0.15}AlO{sub 3} from the extrapolation of high-temperature behaviour of the lattice parameter ratio of the rhombohedral phase. Based on the experimental data, the phase diagram of the pseudo-binary system NdAlO{sub 3}-GdAlO{sub 3} has been constructed. - Graphical abstract: Concentration dependencies of normalized lattice parameters of Nd{sub 1-x}Gd{sub x}AlO{sub 3} perovskite solid solutions. Highlights: Black-Right-Pointing-Pointer Two kinds of solid solutions Nd{sub 1-x}Gd{sub x}AlO{sub 3} were found in the NdAlO{sub 3}-GdAlO{sub 3} system. Black-Right-Pointing-Pointer Morphotropic transition between both perovskite phases occurs at x Almost-Equal-To 0.15. Black-Right-Pointing-Pointer Lattice parameter crossover was found in orthorhombic solid solution. Black-Right-Pointing-Pointer Temperature driven first-order phase transition Pbnm{r_reversible}R3{sup Macron }c was found in Nd{sub 1-x}Gd{sub x}AlO{sub 3}. Black-Right-Pointing-Pointer Phase diagram of the pseudo-binary system NdAlO{sub 3}-GdAlO{sub 3} has been constructed.« less

Multiphase Simulated Annealing Based on Boltzmann and Bose-Einstein Distribution Applied to Protein Folding Problem.

PubMed

Frausto-Solis, Juan; Liñán-García, Ernesto; Sánchez-Hernández, Juan Paulo; González-Barbosa, J Javier; González-Flores, Carlos; Castilla-Valdez, Guadalupe

2016-01-01

A new hybrid Multiphase Simulated Annealing Algorithm using Boltzmann and Bose-Einstein distributions (MPSABBE) is proposed. MPSABBE was designed for solving the Protein Folding Problem (PFP) instances. This new approach has four phases: (i) Multiquenching Phase (MQP), (ii) Boltzmann Annealing Phase (BAP), (iii) Bose-Einstein Annealing Phase (BEAP), and (iv) Dynamical Equilibrium Phase (DEP). BAP and BEAP are simulated annealing searching procedures based on Boltzmann and Bose-Einstein distributions, respectively. DEP is also a simulated annealing search procedure, which is applied at the final temperature of the fourth phase, which can be seen as a second Bose-Einstein phase. MQP is a search process that ranges from extremely high to high temperatures, applying a very fast cooling process, and is not very restrictive to accept new solutions. However, BAP and BEAP range from high to low and from low to very low temperatures, respectively. They are more restrictive for accepting new solutions. DEP uses a particular heuristic to detect the stochastic equilibrium by applying a least squares method during its execution. MPSABBE parameters are tuned with an analytical method, which considers the maximal and minimal deterioration of problem instances. MPSABBE was tested with several instances of PFP, showing that the use of both distributions is better than using only the Boltzmann distribution on the classical SA.

Do We Really Need Sinusoidal Surface Temperatures to Apply Heat Tracing Techniques to Estimate Streambed Fluid Fluxes?

NASA Astrophysics Data System (ADS)

Luce, C. H.; Tonina, D.; Applebee, R.; DeWeese, T.

2017-12-01

Two common refrains about using the one-dimensional advection diffusion equation to estimate fluid fluxes, thermal conductivity, or bed surface elevation from temperature time series in streambeds are that the solution assumes that 1) the surface boundary condition is a sine wave or nearly so, and 2) there is no gradient in mean temperature with depth. Concerns on these subjects are phrased in various ways, including non-stationarity in frequency, amplitude, or phase. Although the mathematical posing of the original solution to the problem might lead one to believe these constraints exist, the perception that they are a source of error is a fallacy. Here we re-derive the inverse solution of the 1-D advection-diffusion equation starting with an arbitrary surface boundary condition for temperature. In doing so, we demonstrate the frequency-independence of the solution, meaning any single frequency can be used in the frequency-domain solutions to estimate thermal diffusivity and 1-D fluid flux in streambeds, even if the forcing has multiple frequencies. This means that diurnal variations with asymmetric shapes, gradients in the mean temperature with depth, or `non-stationary' amplitude and frequency (or phase) do not actually represent violations of assumptions, and they should not cause errors in estimates when using one of the suite of existing solution methods derived based on a single frequency. Misattribution of errors to these issues constrains progress on solving real sources of error. Numerical and physical experiments are used to verify this conclusion and consider the utility of information at `non-standard' frequencies and multiple frequencies to augment the information derived from time series of temperature.

Phase structure of higher spin black hole

NASA Astrophysics Data System (ADS)

Chen, Bin; Long, Jiang; Wang, Yi-Nan

2013-03-01

In this paper, we investigate the phase structure of the black holes with one single higher spin hair, focusing specifically on the spin 3 and spin widetilde{4} black holes. Based on dimensional analysis and the requirement of thermodynamic consistency, we derive a universal formula relating the entropy with the conserved charges for arbitrary AdS 3 higher spin black holes. Then we use it to study the phase structure of the higher spin black holes. We find that there are six branches of solutions in the spin 3 gravity, eight branches of solutions in the spin widetilde{4} gravity and twelve branches of solutions in the G 2 gravity. In each case, all the branches are related by a simple angle shift in the entropy functions. In the spin 3 case, we reproduce all the results found before. In the spin widetilde{4} case, we find that at low temperature it lies in the BTZ branch while at high temperature it undergoes a phase transition to one of the two other branches, depending on the signature of the chemical potential, a reflection of charge conjugate asymmetry found before.

First-order wetting transition at a liquid-vapor interface

NASA Technical Reports Server (NTRS)

Schmidt, J. W.; Moldover, M. R.

1983-01-01

Evidence from reflectance and contact angle measurements is presented that three-phase mixtures of i-C3H7OH-C7F14 exhibit a first-order wetting phase transition at the liquid-vapor interface at 38 C. Equilibration phenomena support this interpretation. Ellipsometry was used to measure the apparent thickness of the intruding layer in the three-phase mixture. At temperatures slightly above the wetting temperature T(w), the intruding layer's thickness is several hundred angstroms and its variation with temperature is extremely weak. Below T(w), three-phase contact can occur between the vapor and both the upper and lower liquid phases; one of the angles which characterizes this contact has a very simple temperature dependence. The thickness of the intruding layer, monitored as the solutions approached equilibrium, is found to depend quite weakly on the height spanned by the upper liquid phase in the vicinity of a first-order wetting transition.

Cermets and method for making same

DOEpatents

Aaron, W. Scott; Kinser, Donald L.; Quinby, Thomas C.

1983-01-01

The present invention is directed to a method for making a wide variety of general-purpose cermets and for radioactive waste disposal from ceramic powders prepared from urea-dispersed solutions containing various metal values. The powders are formed into a compact and subjected to a rapid temperature increase in a reducing atmosphere. During this reduction, one or more of the more readily reducible oxides in the compact is reduced to a selected substoichiometric state at a temperature below the eutectic phase for that particular oxide or oxides and then raised to a temperature greater than the eutectic temperature to provide a liquid phase in the compact prior to the reduction of the liquid phase forming oxide to solid metal. This liquid phase forms at a temperature below the melting temperature of the metal and bonds together the remaining particulates in the cermet to form a solid polycrystalline cermet.

Relationship between intracellular ice formation in oocytes of the mouse and Xenopus and the physical state of the external medium--a revisit.

PubMed

Mazur, Peter; Kleinhans, F W

2008-02-01

We have previously reported that intracellular ice formation (IIF) in mouse oocytes suspended in glycerol/PBS solutions or ethylene glycol (EG)/PBS solutions and rapidly cooled to -50 degrees C or below occurs at temperatures where a critical fraction of the external water remains unfrozen [P. Mazur, S. Seki, I.L. Pinn, F.W. Kleinhans, K. Edashige, Extra- and intracellular ice formation in mouse oocytes, Cryobiology 51 (2005) 29-53; P. Mazur, I.L. Pinn, F.W. Kleinhans, The temperature of intracellular ice formation in mouse oocytes vs. the unfrozen fraction at that temperature, Cryobiology 54 (2007) 223-233]. For mouse oocytes in PBS or glycerol/PBS that fraction is 0.06; for oocytes in EG that fraction was calculated to be 0.13, more than double. The fractions unfrozen are computed from ternary phase diagrams. In the previous publication, we used the EG data of Woods et al. [E.J. Woods, M.A.J. Zieger, D.Y. Gao, J.K. Critser, Equations for obtaining melting points for the ternary system ethylene glycol/sodium chloride/Water and their application to cryopreservation., Cryobiology 38 (1999) 403-407]. Since then, we have determined that ternary phase diagrams for EG/NaCl/water synthesized by summing binary phase data for EG/water NaCl/water gives substantially different curves, which seem more realistic [F.W. Kleinhans, P. Mazur, Comparison of actual vs. synthesized ternary phase diagrams for solutes of cryobiological interest, Cryobiology 54 (2007) 212-222]. Unfrozen fractions at the temperatures of IIF computed from these synthesized phase diagrams are about half of those calculated from the Woods et al. data, and are in close agreement with the computations for glycerol; i.e., IIF occurs when about 92-94% of the external water is frozen. A parallel paper was published by Guenther et al. [J.F. Guenther, S. Seki, F.W. Kleinhans, K. Edashige, D.M. Roberts, P. Mazur, Extra-and intra-cellular ice formation in Stage I and II Xenopus laevis oocytes, Cryobiology 52 (2006) 401-416] on IIF in oocytes of the frog Xenopus. It too examined whether the temperatures of IIF were related to the unfrozen fractions at those temperatures. It also used the Woods et al. ternary phase data to calculate the unfrozen fractions for EG solutions. As reported here, once again the values of these unfrozen fractions are substantially different from those calculated using synthesized phase diagrams. With the latter, the unfrozen fractions at IIF become very similar for EG and glycerol.

RH-temperature phase diagrams of hydrate forming deliquescent crystalline ingredients.

PubMed

Allan, Matthew; Mauer, Lisa J

2017-12-01

Several common deliquescent crystalline food ingredients (including glucose and citric acid) are capable of forming crystal hydrate structures. The propensity of such crystals to hydrate/dehydrate or deliquesce is dependent on the environmental temperature and relative humidity (RH). As an anhydrous crystal converts to a crystal hydrate, water molecules internalize into the crystal structure resulting in different physical properties. Deliquescence is a solid-to-solution phase transformation. RH-temperature phase diagrams of the food ingredients alpha-d-glucose and citric acid, along with sodium sulfate, were produced using established and newly developed methods. Each phase diagram included hydrate and anhydrate deliquescence boundaries, the anhydrate-hydrate phase boundary, and the peritectic temperature (above which the hydrate was no longer stable). This is the first report of RH-temperature phase diagrams of glucose and citric acid, information which is beneficial for selecting storage and processing conditions to promote or avoid hydrate formation or loss and/or deliquescence. Copyright © 2017 Elsevier Ltd. All rights reserved.

Numerical Simulation of the Freeze-Thaw Behavior of Mortar Containing Deicing Salt Solution

PubMed Central

Esmaeeli, Hadi S.; Farnam, Yaghoob; Bentz, Dale P.; Zavattieri, Pablo D.; Weiss, Jason

2016-01-01

This paper presents a one-dimensional finite difference model that is developed to describe the freeze-thaw behavior of an air-entrained mortar containing deicing salt solution. A phenomenological model is used to predict the temperature and the heat flow for mortar specimens during cooling and heating. Phase transformations associated with the freezing/melting of water/ice or transition of the eutectic solution from liquid to solid are included in this phenomenological model. The lever rule is used to calculate the quantity of solution that undergoes the phase transformation, thereby simulating the energy released/absorbed during phase transformation. Undercooling and pore size effects are considered in the numerical model. To investigate the effect of pore size distribution, this distribution is considered using the Gibbs-Thomson equation in a saturated mortar specimen. For an air-entrained mortar, the impact of considering pore size (and curvature) on freezing was relatively insignificant; however the impact of pore size is much more significant during melting. The fluid inside pores smaller than 5 nm (i.e., gel pores) has a relatively small contribution in the macroscopic freeze-thaw behavior of mortar specimens within the temperature range used in this study (i.e., +24 °C to −35 °C), and can therefore be neglected for the macroscopic freeze-thaw simulations. A heat sink term is utilized to simulate the heat dissipation during phase transformations. Data from experiments performed using a low-temperature longitudinal guarded comparative calorimeter (LGCC) on mortar specimens fully saturated with various concentration NaCl solutions or partially saturated with water is compared to the numerical results and a promising agreement is generally obtained. PMID:28082830

Numerical Simulation of the Freeze-Thaw Behavior of Mortar Containing Deicing Salt Solution.

PubMed

Esmaeeli, Hadi S; Farnam, Yaghoob; Bentz, Dale P; Zavattieri, Pablo D; Weiss, Jason

2017-02-01

This paper presents a one-dimensional finite difference model that is developed to describe the freeze-thaw behavior of an air-entrained mortar containing deicing salt solution. A phenomenological model is used to predict the temperature and the heat flow for mortar specimens during cooling and heating. Phase transformations associated with the freezing/melting of water/ice or transition of the eutectic solution from liquid to solid are included in this phenomenological model. The lever rule is used to calculate the quantity of solution that undergoes the phase transformation, thereby simulating the energy released/absorbed during phase transformation. Undercooling and pore size effects are considered in the numerical model. To investigate the effect of pore size distribution, this distribution is considered using the Gibbs-Thomson equation in a saturated mortar specimen. For an air-entrained mortar, the impact of considering pore size (and curvature) on freezing was relatively insignificant; however the impact of pore size is much more significant during melting. The fluid inside pores smaller than 5 nm (i.e., gel pores) has a relatively small contribution in the macroscopic freeze-thaw behavior of mortar specimens within the temperature range used in this study (i.e., +24 °C to -35 °C), and can therefore be neglected for the macroscopic freeze-thaw simulations. A heat sink term is utilized to simulate the heat dissipation during phase transformations. Data from experiments performed using a low-temperature longitudinal guarded comparative calorimeter (LGCC) on mortar specimens fully saturated with various concentration NaCl solutions or partially saturated with water is compared to the numerical results and a promising agreement is generally obtained.

A physicochemical research of the Dy-Sn-O system

NASA Astrophysics Data System (ADS)

Malinovskaya, Tatyana; Lysak, Ilya; Zhek, Valentina; Kuznetsova, Svetlana

2017-11-01

A physicochemical research of the processes of phase composition formation in the materials of the Dy-Sn-O system was performed. Phase composition was taking place in the course of thermal treatment of dysprosium (III) and tin (IV) codeposition products. These were codeposited from nitrate solutions at pH 7, and 25% ammonia water was used as the precipitant. Using thermal and X-ray diffraction analysis, it was found that in the above system at 90 wt. % of Dy2O3 and 10 wt. % of SnO2, when the precursors were heated above 600°C there are no solid solutions. In the meanwhile, at temperatures below 1000°C there is only one phase, Dy2O3. At temperatures above 1000°C, the system becomes bi-phase and includes Dy2O3 and Dy2Sn2O7.

Olivine-modified spinel-spinel transitions in the system Mg2SiO4-Fe2SiO4: Calorimetric measurements, thermochemical calculation, and geophysical application

NASA Astrophysics Data System (ADS)

Akaogi, Masaki; Ito, Eiji; Navrotsky, Alexandra

1989-11-01

The olivine(α)-modified spinel(β)-spinel (γ) transitions in the system Mg2SiO4-Fe2SiO4 were studied by high-temperature solution calorimetry. Enthalpies of the β-γ and a α-γ transitions in Mg2SiO4 at 975 K and of the α-γ transition in Fe2SiO4 at 298 K were measured. The γ solid solution showed a positive enthalpy of mixing. Phase relations at high pressures and high temperatures were calculated from these thermochemical data including correction for the effect of nonideality of α, β, and γ solid solutions. The calculated phase diagrams agree well with those determined experimentally by Katsura and Ito very recently. The α - (Mg0.89, Fe0.11)2SiO4 transforms to β through a region of α+β without passing through the α+γ phase field at around 400 km depth in the mantle with an interval of about 18(±5) km. Temperatures at 390 and 650 km depths are estimated to be about 1673 and 1873 K, respectively, assuming an adiabatic geotherm.

SPECIAL ISSUE DEVOTED TO THE 80TH ANNIVERSARY OF ACADEMICIAN N G BASOV'S BIRTH: Structural rearrangements in the aqueous phase of cell suspensions and protein solutions induced by a light-oxygen effect

NASA Astrophysics Data System (ADS)

Zakharov, S. D.; Ivanov, Andrei V.; Wolf, E. B.; Danilov, V. P.; Murina, T. M.; Nguen, K. T.; Novikov, E. G.; Panasenko, N. A.; Perov, S. N.; Skopinov, S. A.; Timofeev, Yu P.

2003-02-01

Temperature-dependent transient processes initiated by a direct photogeneration of singlet oxygen in suspensions of human erythrocytes and solutions of serum albumin are studied. The processes appear as anomalous jumps in the temperature dependences of the deformability coefficient of erythrocytes and the refractive index of the extracellular medium and protein solution. In the temperature regions of anomalous jumps, cells and proteins transfer to a metastable state of a lower activity, but they can be isothermally photoreactivated. Simultaneously, a reversible rearrangement of the aqueous phase occurs near the cell and protein surfaces, accompanied by the formation of an extended corona (hydrogel). The transient processes are interpreted as phase transitions in the membrane of erythrocytes and conformation transitions in proteins. The interaction between erythrocytes and albumin via hydrogel is discovered (hydro-conformational interaction). A qualitative physical model of the early stages of the light-oxygen effect is proposed, in which collective magnetic interactions between the electron spins of oxygen molecules and the nuclear magnetic moments of protons in H2O molecules play a dominant role.

Hierarchical Sol-Gel Transition Induced by Thermosensitive Self-Assembly of an ABC Triblock Polymer in an Ionic Liquid

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

Kitazawa, Yuzo; Ueki, Takeshi; McIntosh, Lucas D.

2016-04-29

Here we investigate a hierarchical morphology change and accompanying sol–gel transition using a doubly thermosensitive ABC-triblock copolymer in an ionic liquid (IL). The triblock copolymer contains two different lower critical solution temperature (LCST) thermosensitive polymers, poly(benzyl methacrylate) (PBnMA) and poly(2-phenylethyl methacrylate) (PPhEtMA), as the end blocks and poly(methyl methacrylate) (PMMA) as the middle block (PBnMA-b-PMMA-b-PPhEtMA: BMP). BMP undergoes a hierarchical phase transition corresponding to the self-assembly of each of the thermosensitive blocks in the IL, and a sol–gel transition was observed in concentrated, above 10 wt %, polymer solutions. The gelation behavior was affected by polymer concentration, and at 20more » wt %, the BMP/IL composite showed a phase transition, with increasing temperature, from solution through a jammed micelle suspension to a physically cross-linked gel. For each phase was formed reversibly and rapidly over the corresponding temperature range. Finally, the jammed micelle and cross-linked gel states were characterized using viscoelastic measurements and small-angle X-ray scattering (SAXS).« less

Microstructural stability and mechanical behavior of FeNiMnCr high entropy alloy under ion irradiation

DOE PAGES

Leonard, Keith J.; Bei, Hongbin; Zinkle, Steven J.; ...

2016-05-13

In recent years, high entropy alloys (HEAs) have attracted significant attention due to their excellent mechanical properties and good corrosion resistance, making them potential candidates for high temperature fission and fusion structural applications. However there is very little known about their radiation resistance, particularly at elevated temperatures relevant for energy applications. In the present study, a single phase (face centered cubic) concentrated solid solution alloy of composition 27%Fe-28%Ni-27%Mn-18%Cr was irradiated with 3 or 5.8 MeV Ni ions at temperatures ranging from room temperature to 700 °C and midrange doses from 0.03 to 10 displacements per atom (dpa). Transmission electron microscopymore » (TEM), scanning transmission electron microscopy with energy dispersive x-ray spectrometry (STEM/EDS) and X-ray diffraction (XRD) were used to characterize the radiation defects and microstructural changes. Irradiation at higher temperatures showed evidence of relatively sluggish solute diffusion with limited solute depletion or enrichment at grain boundaries. The main microstructural feature at all temperatures was high-density small dislocation loops. Voids were not observed at any irradiation condition. Nano-indentation tests on specimens irradiated at room temperature showed a rapid increase in hardness ~35% and ~80% higher than the unirradiated value at 0.03 and 0.3 dpa midrange doses, respectively. The irradiation-induced hardening was less pronounced for 500 °C irradiations (<20% increase after 3 dpa). Overall, the examined HEA material exhibits superior radiation resistance compared to conventional single phase Fe-Cr-Ni austenitic alloys such as stainless steels. Furthermore, the present study provides insight on the fundamental irradiation behavior of a single phase HEA material over a broad range of irradiation temperatures.« less

Structural transformation in antiferroelectric PbZrO3-relaxor ferroelectric Pb(Ni1/3Nb2/3)O3 solid solution system

NASA Astrophysics Data System (ADS)

Wirunchit, S.; Vittayakorn, N.

2008-07-01

The solid solution between the antiferroelectric (AFE) PbZrO3 (PZ) and the relaxor ferroelectric (FE) Pb(Ni1/3Nb2/3)O3 (PNN) was synthesized by the columbite precursor method. The crystal structure, phase transformations, and dielectric and thermal properties of (1-x )PZ-xPNN where x =0.00-0.30 were investigated. With these data, the FE phase diagram between PZ and PNN has been established. The crystal structure data obtained from X-ray diffraction indicate that the solid solution PZ-PNN, where x =0.00-0.30, successively transforms from orthorhombic to rhombohedral symmetry with an increase in the PNN concentration. The AFE phase→FE phase transition occurs in compositions of 0.00⩽x⩽0.08. The AFE →FE phase transition shifts to lower temperatures with higher compositions of x. The FE phase temperature range width increases with increased PNN. Apparently the replacement of the Zr4+ ion by Ni2+/Nb5+ ions decreases the driving force for an antiparallel shift of Pb2+ ions because they interrupt the translational symmetry and facilitates the appearance of a rhombohedral FE phase when the amount of PNN is higher than 8mol%.

Drug Loading Capacity of Environmentally Sensitive Polymeric Microgels

NASA Astrophysics Data System (ADS)

McDonough, Ryan; Streletzky, Kiril; Bayachou, Mekki; Peiris, Pubudu

2009-10-01

Microgel nanoparticles consisting of cross-linked polymer hydroxypropyl cellulose chains have a temperature dependent volume phase transition, prompting the use of microgels for controlled drug transport. Drug particles aggregate in the slightly hydrophobic interior of microgels. Microgels are stored in equilibrium until the critical temperature (Tv) is reached and the volume phase transition limits available space, thus expelling the drugs. Our study was designed to test this property of microgels using amperometric electrochemical methods. A critical assumption was that small molecules inside microgels would not interact via diffusion with the electrode surface and thus total current would be decreased across the electrodes in a microgel sample. A room temperature (Troom) flow amperometric measurement comparing microgel/tylenol solution with control tylenol samples yielded about 20% tylenol concentration reduction of the microgel sample. Results from the steady state electrochemical experiment confirm the presence of about 20% tylenol concentration drop of the microgel sample compared to control sample at Troom. Using the steady-state experiment with a cyclic temperature ramp from Troom to beyond Tv showed that the tylenol concentration change between the temperature extremes was greater for the microgel solution than for the control solution.

Carbothermal shock synthesis of high-entropy-alloy nanoparticles

NASA Astrophysics Data System (ADS)

Yao, Yonggang; Huang, Zhennan; Xie, Pengfei; Lacey, Steven D.; Jacob, Rohit Jiji; Xie, Hua; Chen, Fengjuan; Nie, Anmin; Pu, Tiancheng; Rehwoldt, Miles; Yu, Daiwei; Zachariah, Michael R.; Wang, Chao; Shahbazian-Yassar, Reza; Li, Ju; Hu, Liangbing

2018-03-01

The controllable incorporation of multiple immiscible elements into a single nanoparticle merits untold scientific and technological potential, yet remains a challenge using conventional synthetic techniques. We present a general route for alloying up to eight dissimilar elements into single-phase solid-solution nanoparticles, referred to as high-entropy-alloy nanoparticles (HEA-NPs), by thermally shocking precursor metal salt mixtures loaded onto carbon supports [temperature ~2000 kelvin (K), 55-millisecond duration, rate of ~105 K per second]. We synthesized a wide range of multicomponent nanoparticles with a desired chemistry (composition), size, and phase (solid solution, phase-separated) by controlling the carbothermal shock (CTS) parameters (substrate, temperature, shock duration, and heating/cooling rate). To prove utility, we synthesized quinary HEA-NPs as ammonia oxidation catalysts with ~100% conversion and >99% nitrogen oxide selectivity over prolonged operations.

Solution-phase synthesis of nanomaterials at low temperature

NASA Astrophysics Data System (ADS)

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.

Cooling induces phase separation in membranes derived from isolated CNS myelin

PubMed Central

Pusterla, Julio M.; Schneck, Emanuel; Funari, Sérgio S.; Démé, Bruno; Tanaka, Motomu

2017-01-01

Purified myelin membranes (PMMs) are the starting material for biochemical analyses such as the isolation of detergent-insoluble glycosphingolipid-rich domains (DIGs), which are believed to be representatives of functional lipid rafts. The normal DIGs isolation protocol involves the extraction of lipids under moderate cooling. Here, we thus address the influence of cooling on the structure of PMMs and its sub-fractions. Thermodynamic and structural aspects of periodic, multilamellar PMMs are examined between 4°C and 45°C and in various biologically relevant aqueous solutions. The phase behavior is investigated by small-angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC). Complementary neutron diffraction (ND) experiments with solid-supported myelin multilayers confirm that the phase behavior is unaffected by planar confinement. SAXS and ND consistently show that multilamellar PMMs in pure water become heterogeneous when cooled by more than 10–15°C below physiological temperature, as during the DIGs isolation procedure. The heterogeneous state of PMMs is stabilized in physiological solution, where phase coexistence persists up to near the physiological temperature. This result supports the general view that membranes under physiological conditions are close to critical points for phase separation. In presence of elevated Ca2+ concentrations (> 10 mM), phase coexistence is found even far above physiological temperatures. The relative fractions of the two phases, and thus presumably also their compositions, are found to vary with temperature. Depending on the conditions, an “expanded” phase with larger lamellar period or a “compacted” phase with smaller lamellar period coexists with the native phase. Both expanded and compacted periods are also observed in DIGs under the respective conditions. The observed subtle temperature-dependence of the phase behavior of PMMs suggests that the composition of DIGs is sensitive to the details of the isolation protocol. PMID:28915267

Phase equilibria, crystal structure and oxygen content of intermediate phases in the Y-Ba-Co-O system

NASA Astrophysics Data System (ADS)

Urusova, A. S.; Cherepanov, V. A.; Aksenova, T. V.; Gavrilova, L. Ya.; Kiselev, E. A.

2013-06-01

The phase equilibria in the Y-Ba-Co-O system were systematically studied at 1373 K in air. The intermediate phases formed in the Y-Ba-Co-O system at 1373 K in air were: YBaCo2O5+δ, YBaCo4O7 and BaCo1-yYyO3-δ (0.09≤y≤0.42). It was shown that YBaCo2O5+δ possesses tetragonal structure with the 3ap×3ap×2ap superstructure (sp. gr. P4/mmm). High-temperature X-ray diffraction analysis of the YBaCo2O5+δ in the temperature range from 298 K up to 1073 K under Po2=0.21 аtm has not shown any phase transformations. The value of oxygen content for the YBaCo2O5+δ at room temperature was estimated as 5.40 and at 1323 K it was equal to 5.04. Thermal expansion of sample shows a linear characteristics and the average thermal expansion coefficient (TEC) is about 13.8×10-6, K-1 in the temperature range 298-1273 K. The homogeneity range and crystal structure of the BaCo1-yYyO3-δ (0.09≤y≤0.42) solid solutions were determined by X-ray diffraction of quenched samples. All BaCo1-yYyO3-δ solid solutions were found to have cubic structure (sp. gr. Pm3m). The unit cell parameters were refined using Rietveld full-profile analysis. Oxygen nonstoichiometry of BaCo1-yYyO3-δ solid solutions with 0.1≤y≤0.4 was measured by means of thermogravimetric technique within the temperature range 298-1373 K in air. Thermal expansion of BaCo1-yYyO3-δ (у=0.0; 0.1; 0.2; 0.3) samples was studied within the temperature range 298-1200 K in air. The projection of isothermal-isobaric phase diagram for the Y-Ba-Co-O system to the compositional triangle of metallic components was presented.

Thermosetting gels with modulated gelation temperature for ophthalmic use: the rheological and gamma scintigraphic studies.

PubMed

Wei, Gang; Xu, Hui; Ding, Ping Tian; Li, San Ming; Zheng, Jun Min

2002-09-18

For ophthalmic drug delivery, Pluronic F127 solutions have a phase transition temperature too low for them to be instilled into the eye at room temperature. Refrigerator storage is usually required to make administration easier, whereas the potential irritation of cold to the sensitive ocular tissues may result in poor topical bioavailability. The purpose of this study is to develop a thermosetting gel with a suitable phase transition temperature by combining Pluronic analogs and to examine the influence of incorporating mucoadhesive polysaccharide, sodium hyaluronate (HA-Na), on the ocular retention of the gel. Dynamic rheological method and single photon emission computing tomography (SPECT) technique were used to ex/in vivo evaluate the thermosetting gels, respectively. An optimized formulation containing 21% F127 and 10% F68 increased the phase transition temperature by 9 degrees C as evaluated by elasticity modulus compared to that of individual 21% F127 solution. Rheological behaviors of the Pluronic solutions showed that the combined Pluronic formulation was free flowing liquid below 25 degrees C and converted to a firm gel under the physiological condition. Furthermore, this formulation possessed the highest viscosity both before and after tear dilution at 35 degrees C. Gamma scintigraphic data demonstrated that the clearance of the thermosetting gel labeled with 99mTc-DTPA was significantly delayed with respect to the phosphate buffered solution, and at least a threefold increase of the corneal residence time was achieved. However, no further improvement in the ocular retention was observed when adding HA-Na into the thermosetting gel due to the substantially decreased gel strength. Copyright 2002 Elsevier Science B.V.

In situ observation of sol-gel transition of agarose aqueous solution by fluorescence measurement.

PubMed

Wang, Zheng; Yang, Kun; Li, Haining; Yuan, Chaosheng; Zhu, Xiang; Huang, Haijun; Wang, Yongqiang; Su, Lei; Fang, Yapeng

2018-06-01

Sol-gel transition behavior of agarose aqueous solution was investigated by using rheology and fluorescence measurement. On heating, the storage modulus G' decreased gradually, then deviated abruptly at the temperature of about 65°C, and finally decreased slowly again. For fluorescence measurement, the phase transition point kept almost at the temperature of 65°C, which was consistent with that in rheology measurement. Upon compression, it was indicated that the fluorescence lifetime for the probe in the agarose aqueous solution showed a dramatic change in the vicinity of the phase transition point. T vs. P phase diagram of agarose aqueous solution was constructed, which showed that the melting point was an increasing function of pressure. Based on the phase diagram, the agarose gels were prepared by cooling under atmospheric pressure and the pressure of 300MPa, respectively. From the result of the recovered samples studied by optical rheometry, it was found that agarose gel prepared under high pressure had a higher elasticity and lower viscosity index, compared with that under atmospheric pressure. It could be speculated that such kinds of properties might be attributed to the smaller pore size during gelation under high pressure. Copyright © 2018. Published by Elsevier B.V.

Blue phase liquid crystal: strategies for phase stabilization and device development

PubMed Central

Rahman, M D Asiqur; Mohd Said, Suhana; Balamurugan, S

2015-01-01

The blue phase liquid crystal (BPLC) is a highly ordered liquid crystal (LC) phase found very close to the LC–isotropic transition. The BPLC has demonstrated potential in next-generation display and photonic technology due to its exceptional properties such as sub-millisecond response time and wide viewing angle. However, BPLC is stable in a very small temperature range (0.5–1 °C) and its driving voltage is very high (∼100 V). To overcome these challenges recent research has focused on solutions which incorporate polymers or nanoparticles into the blue phase to widen the temperature range from around few °C to potentially more than 60 °C. In order to reduce the driving voltage, strategies have been attempted by modifying the device structure by introducing protrusion or corrugated electrodes and vertical field switching mechanism has been proposed. In this paper the effectiveness of the proposed solution will be discussed, in order to assess the potential of BPLC in display technology and beyond. PMID:27877782

Characterization of a New Phase and Its Effect on the Work Characteristics of a Near-Stoichiometric Ni30Pt20Ti50 High-Temperature Shape Memory Alloy (HTSMA)

NASA Technical Reports Server (NTRS)

Garg, A.; Gaydosh, D.; Noebe, R.D.; Padula II, Santo; Bigelow, G.S.; Kaufman, M.; Kovarik, L.; Mills, M.J.; Diercks, D.; McMurray, S.

2008-01-01

A new phase observed in a nominal Ni30Pt20Ti50 (at.%) high temperature shape memory alloy has been characterized using transmission electron microscopy and 3-D atom probe tomography. This phase forms homogeneously in the B2 austenite matrix by a nucleation and growth mechanism and results in a concomitant increase in the martensitic transformation temperature of the base alloy. Although the structure of this phase typically contains a high density of faults making characterization difficult, it appears to be trigonal (-3m point group) with a(sub o) approx. 1.28 nm and c(sub o) approx. 1.4 nm. Precipitation of this phase increases the microhardness of the alloy substantially over that of the solution treated and quenched single-phase material. The effect of precipitation strengthening on the work characteristics of the alloy has been explored through load-biased strain-temperature testing in the solution-treated condition and after aging at 500 C for times ranging from 1 to 256 hours. Work output was found to increase in the aged alloy as a result of an increase in transformation strain, but was not very sensitive to aging time. The amount of permanent deformation that occurred during thermal cycling under load was small but increased with increasing aging time and stress. Nevertheless, the dimensional stability of the alloy at short aging times (1-4 hours) was still very good making it a potentially useful material for high-temperature actuator applications.

Ternary Phase-Separation Investigation of Sol-Gel Derived Silica from Ethyl Silicate 40

PubMed Central

Wang, Shengnan; Wang, David K.; Smart, Simon; Diniz da Costa, João C.

2015-01-01

A ternary phase-separation investigation of the ethyl silicate 40 (ES40) sol-gel process was conducted using ethanol and water as the solvent and hydrolysing agent, respectively. This oligomeric silica precursor underwent various degrees of phase separation behaviour in solution during the sol-gel reactions as a function of temperature and H2O/Si ratios. The solution composition within the immiscible region of the ES40 phase-separated system shows that the hydrolysis and condensation reactions decreased with decreasing reaction temperature. A mesoporous structure was obtained at low temperature due to weak drying forces from slow solvent evaporation on one hand and formation of unreacted ES40 cages in the other, which reduced network shrinkage and produced larger pores. This was attributed to the concentration of the reactive sites around the phase-separated interface, which enhanced the condensation and crosslinking. Contrary to dense silica structures obtained from sol-gel reactions in the miscible region, higher microporosity was produced via a phase-separated sol-gel system by using high H2O/Si ratios. This tailoring process facilitated further condensation reactions and crosslinking of silica chains, which coupled with stiffening of the network, made it more resistant to compression and densification. PMID:26411484

High-temperature experimental and thermodynamic modelling research on the pyrometallurgical processing of copper

NASA Astrophysics Data System (ADS)

Hidayat, Taufiq; Shishin, Denis; Decterov, Sergei A.; Hayes, Peter C.; Jak, Evgueni

2017-01-01

Uncertainty in the metal price and competition between producers mean that the daily operation of a smelter needs to target high recovery of valuable elements at low operating cost. Options for the improvement of the plant operation can be examined and decision making can be informed based on accurate information from laboratory experimentation coupled with predictions using advanced thermodynamic models. Integrated high-temperature experimental and thermodynamic modelling research on phase equilibria and thermodynamics of copper-containing systems have been undertaken at the Pyrometallurgy Innovation Centre (PYROSEARCH). The experimental phase equilibria studies involve high-temperature equilibration, rapid quenching and direct measurement of phase compositions using electron probe X-ray microanalysis (EPMA). The thermodynamic modelling deals with the development of accurate thermodynamic database built through critical evaluation of experimental data, selection of solution models, and optimization of models parameters. The database covers the Al-Ca-Cu-Fe-Mg-O-S-Si chemical system. The gas, slag, matte, liquid and solid metal phases, spinel solid solution as well as numerous solid oxide and sulphide phases are included. The database works within the FactSage software environment. Examples of phase equilibria data and thermodynamic models of selected systems, as well as possible implementation of the research outcomes to selected copper making processes are presented.

Method for forming single phase, single crystalline 2122 BCSCO superconductor thin films by liquid phase epitaxy

NASA Technical Reports Server (NTRS)

Pandey, Raghvendra K. (Inventor); Raina, Kanwal (Inventor); Solayappan, Narayanan (Inventor)

1994-01-01

A substantially single phase, single crystalline, highly epitaxial film of Bi.sub.2 CaSr.sub.2 Cu.sub.2 O.sub.8 superconductor which has a T.sub.c (zero resistance) of 83 K is provided on a lattice-matched substrate with no intergrowth. This film is produced by a Liquid Phase Epitaxy method which includes the steps of forming a dilute supercooled molten solution of a single phase superconducting mixture of oxides of Bi, Ca, Sr, and Cu having an atomic ratio of about 2:1:2:2 in a nonreactive flux such as KCl, introducing the substrate, e.g., NdGaO.sub.3, into the molten solution at 850.degree. C., cooling the solution from 850.degree. C. to 830.degree. C. to grow the film and rapidly cooling the substrate to room temperature to maintain the desired single phase, single crystalline film structure.

Translational diffusion coefficients of volatile compounds in various aqueous solutions at low and subzero temperatures.

PubMed

Covarrubias-Cervantes, Marco; Champion, Dominique; Debeaufort, Frédéric; Voilley, Andrée

2005-08-24

Translational diffusion coefficients (D(12)) of volatile compounds were measured in model media with the profile concentration method. The influence of sample temperature (from 25 to -10 degrees C) was studied on translational diffusion in sucrose or maltodextrin solutions at various concentrations. Results show that diffusivity of volatile compounds in sucrose solutions is controlled by temperature, molecule size, and the viscosity of the liquid phase as expected with the Stokes-Einstein equation; moreover, physicochemical interactions between volatile compounds and the medium are determinant for diffusion estimation. At negative temperature, the winding path induced by an ice crystal content of >70% lowered volatile compound diffusion. On the contrary, no influence on translational diffusion coefficients was observed for lower ice content.

Solution based synthesis of mixed-phase materials in the Li2TiO3-Li4SiO4 system

NASA Astrophysics Data System (ADS)

Hanaor, Dorian A. H.; Kolb, Matthias H. H.; Gan, Yixiang; Kamlah, Marc; Knitter, Regina

2015-01-01

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 Li2TiO3-Li4SiO4 region and investigate phase stability and transformations through temperature varied X-ray diffraction and scanning calorimetry. Results demonstrate that the metatitanate and metasilicate phases Li2TiO3 and Li2SiO3 readily crystallise in nanocrystalline form at temperatures below 180 °C. Lithium deficiency in the region of 5% results from Li sublimation from Li4SiO4 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 Li2TiO3 content towards the Ti rich region. Above 1150 °C the transformation of monoclinic to cubic γ-Li2TiO3 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 breeder pebble synthesis as this route was found to yield materials with a more significant Li-deficiency exhibiting the crystallisation of the Li2TiSiO5 phase at intermediate compositions.

Application of the windowed-Fourier-transform-based fringe analysis technique for investigating temperature and concentration fields in fluids.

PubMed

Mohanan, Sharika; Srivastava, Atul

2014-04-10

The present work is concerned with the development and application of a novel fringe analysis technique based on the principles of the windowed-Fourier-transform (WFT) for the determination of temperature and concentration fields from interferometric images for a range of heat and mass transfer applications. Based on the extent of the noise level associated with the experimental data, the technique has been coupled with two different phase unwrapping methods: the Itoh algorithm and the quality guided phase unwrapping technique for phase extraction. In order to generate the experimental data, a range of experiments have been carried out which include cooling of a vertical flat plate in free convection conditions, combustion of mono-propellant flames, and growth of organic as well as inorganic crystals from their aqueous solutions. The flat plate and combustion experiments are modeled as heat transfer applications wherein the interest is to determine the whole-field temperature distribution. Aqueous-solution-based crystal growth experiments are performed to simulate the mass transfer phenomena and the interest is to determine the two-dimensional solute concentration field around the growing crystal. A Mach-Zehnder interferometer has been employed to record the path-integrated quantity of interest (temperature and/or concentration) in the form of interferometric images in the experiments. The potential of the WFT method has also been demonstrated on numerically simulated phase data for varying noise levels, and the accuracy in phase extraction have been quantified in terms of the root mean square errors. Three levels of noise, i.e., 0%, 10%, and 20% have been considered. Results of the present study show that the WFT technique allows an accurate extraction of phase values that can subsequently be converted into two-dimensional temperature and/or concentration distribution fields. Moreover, since WFT is a local processing technique, speckle patterns and the inherent noise in the interferometric data do not affect the resultant phase values. Brief comparisons of the accuracy of the WFT with other standard techniques such as conventional Fourier-filtering methods are also presented.

Water/ice phase transition: The role of zirconium acetate, a compound with ice-shaping properties

NASA Astrophysics Data System (ADS)

Marcellini, Moreno; Fernandes, Francisco M.; Dedovets, Dmytro; Deville, Sylvain

2017-04-01

Few compounds feature ice-shaping properties. Zirconium acetate is one of the very few inorganic compounds reported so far to have ice-shaping properties similar to that of ice-shaping proteins, encountered in many organisms living at low temperature. When a zirconium acetate solution is frozen, oriented and perfectly hexagonal ice crystals can be formed and their growth follows the temperature gradient. To shed light on the water/ice phase transition while freezing zirconium acetate solution, we carried out differential scanning calorimetry measurements. From our results, we estimate how many water molecules do not freeze because of their interaction with Zr cations. We estimate the colligative properties of the Zr acetate on the apparent critical temperature. We further show that the phase transition is unaffected by the nature of the base which is used to adjust the pH. Our results provide thus new hints on the ice-shaping mechanism of zirconium acetate.

Water/ice phase transition: The role of zirconium acetate, a compound with ice-shaping properties.

PubMed

Marcellini, Moreno; Fernandes, Francisco M; Dedovets, Dmytro; Deville, Sylvain

2017-04-14

Few compounds feature ice-shaping properties. Zirconium acetate is one of the very few inorganic compounds reported so far to have ice-shaping properties similar to that of ice-shaping proteins, encountered in many organisms living at low temperature. When a zirconium acetate solution is frozen, oriented and perfectly hexagonal ice crystals can be formed and their growth follows the temperature gradient. To shed light on the water/ice phase transition while freezing zirconium acetate solution, we carried out differential scanning calorimetry measurements. From our results, we estimate how many water molecules do not freeze because of their interaction with Zr cations. We estimate the colligative properties of the Zr acetate on the apparent critical temperature. We further show that the phase transition is unaffected by the nature of the base which is used to adjust the pH. Our results provide thus new hints on the ice-shaping mechanism of zirconium acetate.

Separation by solvent extraction

DOEpatents

Holt, Jr., Charles H.

1976-04-06

17. A process for separating fission product values from uranium and plutonium values contained in an aqueous solution, comprising adding an oxidizing agent to said solution to secure uranium and plutonium in their hexavalent state; contacting said aqueous solution with a substantially water-immiscible organic solvent while agitating and maintaining the temperature at from -1.degree. to -2.degree. C. until the major part of the water present is frozen; continuously separating a solid ice phase as it is formed; separating a remaining aqueous liquid phase containing fission product values and a solvent phase containing plutonium and uranium values from each other; melting at least the last obtained part of said ice phase and adding it to said separated liquid phase; and treating the resulting liquid with a new supply of solvent whereby it is practically depleted of uranium and plutonium.

Mg2+ ion effect on conformational equilibrium of poly A . 2 poly U and poly A poly U in aqueous solutions.

PubMed

Sorokin, Victor A; Valeev, Vladimir A; Gladchenko, Galina O; Degtiar, Marina V; Karachevtsev, Victor A; Blagoi, Yuri P

2003-01-15

Differential UV spectroscopy and thermal denaturation were used to study the Mg(2+) ion effect on the conformational equilibrium in poly A.2 poly U (A2U) and poly A . poly U (AU) solutions at low (0.01 M Na(+)) and high (0.1 M Na(+)) ionic strengths. Four complete phase diagrams were obtained for Mg(2+)-polynucleotide complexes in ranges of temperatures 20-96 degrees C and concentrations (10(-5)-10(-2)) M Mg(2+). Three of them have a 'critical' point at which the type of the conformational transition changes. The value of the 'critical' concentration ([Mg(t)(2+)](cr)=(4.5+/-1.0) x 10(-5) M) is nearly independent of the initial conformation of polynucleotides (AU, A2U) and of Na(+) contents in the solution. Such a value is observed for Ni(2+) ions too. The phase diagram of the (A2U+Mg(2+)) complex with 0.01 M Na(+) has no 'critical' point: temperatures of (3-->2) and (2-->1) transitions increase in the whole Mg(2+) range. In (AU+Mg(2+)) phase diagram at 0.01 M Na(+) the temperature interval in which triple helices are formed and destroyed is several times larger than at 0.1 M Na(+). Using the ligand theory, a qualitative thermodynamic analysis of the phase diagrams was performed.

The Influence of Calcium Chloride Deicing Salt on Phase Changes and Damage Development in Cementitious Materials.

PubMed

Farnam, Yaghoob; Dick, Sarah; Wiese, Andrew; Davis, Jeffrey; Bentz, Dale; Weiss, Jason

2015-11-01

The conventional CaCl 2 -H 2 O phase diagram is often used to describe how calcium chloride behaves when it is used on a concrete pavement undergoing freeze-thaw damage. However, the chemistry of the concrete can alter the appropriateness of using the CaCl 2 -H 2 O phase diagram. This study shows that the Ca(OH) 2 present in a hydrated portland cement can interact with CaCl 2 solution creating a behavior that is similar to that observed in isoplethal sections of a ternary phase diagram for a Ca(OH) 2 -CaCl 2 -H 2 O system. As such, it is suggested that such isoplethal sections provide a reasonable model that can be used to describe the behavior of concrete exposed to CaCl 2 solution as the temperature changes. Specifically, the Ca(OH) 2 can react with CaCl 2 and H 2 O resulting in the formation of calcium oxychloride. The formation of the calcium oxychloride is expansive and can produce damage in concrete at temperatures above freezing. Its formation can also cause a significant decrease in fluid ingress into concrete. For solutions with CaCl 2 concentrations greater than about 11.3 % (by mass), it is found that calcium oxychloride forms rapidly and is stable at room temperature (23 °C).

The Influence of Calcium Chloride Deicing Salt on Phase Changes and Damage Development in Cementitious Materials

PubMed Central

Farnam, Yaghoob; Dick, Sarah; Wiese, Andrew; Davis, Jeffrey; Bentz, Dale; Weiss, Jason

2015-01-01

The conventional CaCl2-H2O phase diagram is often used to describe how calcium chloride behaves when it is used on a concrete pavement undergoing freeze-thaw damage. However, the chemistry of the concrete can alter the appropriateness of using the CaCl2-H2O phase diagram. This study shows that the Ca(OH)2 present in a hydrated portland cement can interact with CaCl2 solution creating a behavior that is similar to that observed in isoplethal sections of a ternary phase diagram for a Ca(OH)2-CaCl2-H2O system. As such, it is suggested that such isoplethal sections provide a reasonable model that can be used to describe the behavior of concrete exposed to CaCl2 solution as the temperature changes. Specifically, the Ca(OH)2 can react with CaCl2 and H2O resulting in the formation of calcium oxychloride. The formation of the calcium oxychloride is expansive and can produce damage in concrete at temperatures above freezing. Its formation can also cause a significant decrease in fluid ingress into concrete. For solutions with CaCl2 concentrations greater than about 11.3 % (by mass), it is found that calcium oxychloride forms rapidly and is stable at room temperature (23 °C). PMID:26692655

Heat Stable Polymers: Polyphenylene and Other Aromatic Polymers

DTIC Science & Technology

1977-01-01

crystalline transition temperature . Model reactions on 4- and 6-phienyl-2-pyrones show that this monomer type is unsuitable for the syntheses of... temperature to a rod-like molecule with a high glass transition temperature . The polymerization reaction is acid catalyzed, but is carried out most...Polymerization Reactions...................24 Solution Properties......................27 Phase Transition Temperatures , Thermal Stability and Thermomechanical

Phase formation and UV luminescence of Gd3+ doped perovskite-type YScO3

NASA Astrophysics Data System (ADS)

Shimizu, Yuhei; Ueda, Kazushige

2016-10-01

Synthesis of pure and Gd3+doped perovskite-type YScO3 was attempted by a polymerized complex (PC) method and solid state reaction (SSR) method. Crystalline phases and UV luminescence of samples were examined with varying heating temperatures. The perovskite-type single phase was not simply formed in the SSR method, as reported in some literatures, and two cubic C-type phases of starting oxide materials remained forming slightly mixed solid solutions. UV luminescence of Gd3+ doped samples increased with an increase in heating temperatures and volume of the perovskite-type phase. In contrast, a non-crystalline precursor was crystallized to a single C-type phase at 800 °C in the PC method forming a completely mixed solid solution. Then, the phase of perovskite-type YScO3 formed at 1200 °C and its single phase was obtained at 1400 °C. It was revealed that high homogeneousness of cations was essential to generate the single perovskite-phase of YScO3. Because Gd3+ ions were also dissolved into the single C-type phase in Gd3+ doped samples, intense UV luminescence was observed above 800 °C in both C-type phase and perovskite-type phase.

Effects of Mo Content on Microstructure and Mechanical Property of PH13-8Mo Martensitic Precipitation-Hardened Stainless Steel

NASA Astrophysics Data System (ADS)

Yubing, Pei; Tianjian, Wang; Zhenhuan, Gao; Hua, Fan; Gongxian, Yang

This paper introduces the effects of Mo content on microstructure and mechanical property of PH13-8Mo martensitic precipitation-hardened stainless steel which is used for LP last stage blade in steam turbine. Thermodynamic software Thermo-Calc has been used to calculate precipitation temperature and the mass fraction of precipitated phases in PH13-8Mo steel with different Mo content. The result shows that when the mass of Mo is below 0.6wt.%, chi-phase mu-phase and sigma-phase could disappear. The microstructure and mechanical property of high Mo PH13-8Mo (Mo=0.57wt.%) and low Mo PH13-8Mo (Mo=2.15wt.%)have been investigated in different heat treatments. The investigations reveal that austenitizing temperature decrease with the reduce of Mo content, so the optimum solution temperature for low Mo PH13-8Mo is lower than that for high Mo PH13-8Mo.The influence of solution temperature on grain size is weakened with the increase of Mo content, Mo rich carbides could retard coarsening of grain. An enormous amount of nano-size uniformly distributed β-NiAl particles are found in both kinds of steels using transmission electron microscopy, they are the most important strengthening phase in PH13-8Mo.

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

NASA Astrophysics Data System (ADS)

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.

Molecular dynamics simulation study of hydrogen bonding in aqueous poly(ethylene oxide) solutions.

PubMed

Smith, G D; Bedrov, D; Borodin, O

2000-12-25

A molecular dynamics simulation study of hydrogen bonding in poly(ethylene oxide) (PEO)/water solutions was performed. PEO-water and water-water hydrogen bonding manifested complex dependence on both composition and temperature. Strong water clustering in concentrated solutions was seen. Saturation of hydrogen bonding at w(p) approximately equal to 0.5 and a dramatic decrease in PEO-water hydrogen bonding with increasing temperature, consistent with experimentally observed closed-loop phase behavior, were observed. Little tendency toward intermolecular bridging of PEO chains by water molecules was seen.

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

NASA Astrophysics Data System (ADS)

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.

Defect-induced local variation of crystal phase transition temperature in metal-halide perovskites.

PubMed

Dobrovolsky, Alexander; Merdasa, Aboma; Unger, Eva L; Yartsev, Arkady; Scheblykin, Ivan G

2017-06-26

Solution-processed organometal halide perovskites are hybrid crystalline semiconductors highly interesting for low-cost and efficient optoelectronics. Their properties are dependent on the crystal structure. Literature shows a variety of crystal phase transition temperatures and often a spread of the transition over tens of degrees Kelvin. We explain this inconsistency by demonstrating that the temperature of the tetragonal-to-orthorhombic phase transition in methylammonium lead triiodide depends on the concentration and nature of local defects. Phase transition in individual nanowires was studied by photoluminescence microspectroscopy and super-resolution imaging. We propose that upon cooling from 160 to 140 K, domains of the crystal containing fewer defects stay in the tetragonal phase longer than highly defected domains that readily transform to the high bandgap orthorhombic phase at higher temperatures. The existence of relatively pure tetragonal domains during the phase transition leads to drastic photoluminescence enhancement, which is inhomogeneously distributed across perovskite microcrystals.Understanding crystal phase transition in materials is of fundamental importance. Using luminescence spectroscopy and super-resolution imaging, Dobrovolsky et al. study the transition from the tetragonal to orthorhombic crystal phase in methylammonium lead triiodide nanowires at low temperature.

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

PubMed

Mosquera-Giraldo, Laura I; Taylor, Lynne S

2015-02-02

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

Does Warming a Lysozyme Solution Cook Ones Data?

NASA Technical Reports Server (NTRS)

Pusey, Marc; Burke, Michael; Judge, Russell

2000-01-01

Chicken egg white lysozyme has a well characterized thermally driven phase transition. Between pH 4.0 and 5.2, the transition temperature, as defined by the point where the tetragonal and orthorhombic solubility are equal, is a function of the pH, salt (precipitant) type and concentration, and most likely of the buffer concentration as well. This phase transition can be carried out with protein solution alone, prior to the initiation of the crystallization process. We have now measured the kinetics of this process and investigated its reversibility. An aliquot of a stock protein solution is held at a given temperature, and at periodic intervals used to set up batch crystallization experiments. The batch solutions were incubated at 20 C until macroscopic crystals were obtained, at which point the number of crystals in each well were counted. The transition effects increased with temperature, slowly falling off at 30 C with a half time (time to approx. 1/2 the t = 0 number of crystals) of approx. 5 hours, and an estimated half time of approx. 0.5 hours at 43 C. Further, the process was not reversible by simple cooling. After holding a lysozyme solution at 37 C (prior to addition of precipitant) for 16 hours, then cooling and holding it at 4 C, no return to the pre-warmed nucleation kinetics are observed after at least 4 weeks. Thus every thermal excursion above the phase transition point results in a further decrease in the nucleation rate of that solution, the extent being a function of the time and temperature. Orthorhombic lysozyme crystals apparently do not undergo the flow-induced growth cessation of tetragonal lysozyme crystals. We have previously shown that putting the protein in the orthorhombic form does not affect the averaged face growth kinetics, only nucleation, for tetragonal crystals. We may be able to use this differential behavior to elucidate how flow affects tile lysozyme crystal growth process.

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

Tao Zhu; Jack A. Walker; J. Liang

Due to increasing oil demand, oil companies are moving into arctic environments and deep-water areas for oil production. In these regions of lower temperatures, wax deposits begin to form when the temperature in the wellbore falls below wax appearance temperature (WAT). This condition leads to reduced production rates and larger pressure drops. Wax problems in production wells are very costly due to production down time for removal of wax. Therefore, it is necessary to develop a solution to wax deposition. In order to develop a solution to wax deposition, it is essential to characterize the crude oil and study phasemore » behavior properties. The main objective of this project was to characterize Alaskan North Slope crude oil and study the phase behavior, which was further used to develop a dynamic wax deposition model. This report summarizes the results of the various experimental studies. The subtasks completed during this study include measurement of density, molecular weight, viscosity, pour point, wax appearance temperature, wax content, rate of wax deposition using cold finger, compositional characterization of crude oil and wax obtained from wax content, gas-oil ratio, and phase behavior experiments including constant composition expansion and differential liberation. Also, included in this report is the development of a thermodynamic model to predict wax precipitation. From the experimental study of wax appearance temperature, it was found that wax can start to precipitate at temperatures as high as 40.6 C. The WAT obtained from cross-polar microscopy and viscometry was compared, and it was discovered that WAT from viscometry is overestimated. From the pour point experiment it was found that crude oil can cease to flow at a temperature of 12 C. From the experimental results of wax content, it is evident that the wax content in Alaskan North Slope crude oil can be as high as 28.57%. The highest gas-oil ratio for a live oil sample was observed to be 619.26 SCF/STB. The bubblepoint pressure for live oil samples varied between 1600 psi and 2100 psi. Wax precipitation is one of the most important phenomena in wax deposition and, hence, needs to be modeled. There are various models present in the literature. Won's model, which considers the wax phase as a non-ideal solution, and Pedersen's model, which considers the wax phase as an ideal solution, were compared. Comparison indicated that Pedersen's model gives better results, but the assumption of wax phase as an ideal solution is not realistic. Hence, Won's model was modified to consider different precipitation characteristics of the various constituents in the hydrocarbon fraction. The results obtained from the modified Won's model were compared with existing models, and it was found that predictions from the modified model are encouraging.« less

Molybdenum-titanium phase diagram evaluated from ab initio calculations

NASA Astrophysics Data System (ADS)

Barzilai, Shmuel; Toher, Cormac; Curtarolo, Stefano; Levy, Ohad

2017-07-01

The design of next generation β -type titanium implants requires detailed knowledge of the relevant stable and metastable phases at temperatures where metallurgical heat treatments can be performed. Recently, a standard specification for surgical implant applications was established for Mo-Ti alloys. However, the thermodynamic properties of this binary system are not well known and two conflicting descriptions of the β -phase stability have been presented in the literature. In this study, we use ab initio calculations to investigate the Mo-Ti phase diagram. These calculations predict that the β phase is stable over a wide concentration range, in qualitative agreement with one of the reported phase diagrams. In addition, they predict stoichiometric compounds, stable at temperatures below 300 ∘C , which have not yet been detected by experiments. The resulting solvus, which defines the transition to the β -phase solid solution, therefore occurs at lower temperatures and is more complex than previously anticipated.

Precipitation phases at different processes and heat treat ments as well as their effects on the mechanical properties of super-austenitic stainless steel

NASA Astrophysics Data System (ADS)

Sun, Hunying; Zhou, Zhangjian; Wang, Man; Li, Shaofu; Zhang, Liwei; Zou, Lei

2013-03-01

A new type lCr30Ni30Mo2TiZr super-austenitic stainless steel has been developed. The microstructures, precipitation phases and mechanical properties of the steel under different deformation processes and heat treatment (solution, stabilized treatment) were investigated using X-ray Diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) as well as mechanical tests. The results indicate that coarse carbides such as Cr-rich M23C6, sigma (σ), and little chi (χ) phases were formed in the steel, and large α' -Cr phases were also detected at three joint grain boundaries, and they were promoted by large strain. The precipitate phases were dissolved or transformed to intermetallic phase even at higher elevated temperature, and influenced the mechanical property obviously. These intermetallic compounds seriously reduced elongation of the rolled steel at room temperature and 700 °C, but increased the forged one at 700 °C. Impact absorbed energies of the stabilized specimens were lower than half of that solution status.

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

PubMed

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.

Fundamental incorporation of the density change during melting of a confined phase change material

NASA Astrophysics Data System (ADS)

Hernández, Ernesto M.; Otero, José A.

2018-02-01

The modeling of thermal diffusion processes taking place in a phase change material presents a challenge when the dynamics of the phase transition is coupled to the mechanical properties of the container. Thermo-mechanical models have been developed by several authors, however, it will be shown that these models only explain the phase transition dynamics at low pressures when the density of each phase experiences negligible changes. In our proposal, a new energy-mass balance equation at the interface is derived and found to be a consequence of mass conservation. The density change experienced in each phase is predicted by the proposed formulation of the problem. Numerical and semi-analytical solutions to the proposed model are presented for an example on a high temperature phase change material. The solutions to the models presented by other authors are observed to be well-behaved close to the isobaric limit. However, compared to the results obtained from our model, the change in the fusion temperature, latent heat, and absolute pressure is found to be greatly overestimated by other proposals when the phase transition is studied close to the isochoric regime.

A numerical analysis of phase-change problems including natural convection

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

Cao, Y.; Faghri, A.

1990-08-01

Fixed grid solutions for phase-change problems remove the need to satisfy conditions at the phase-change front and can be easily extended to multidimensional problems. The two most important and widely used methods are enthalpy methods and temperature-based equivalent heat capacity methods. Both methods in this group have advantages and disadvantages. Enthalpy methods (Shamsundar and Sparrow, 1975; Voller and Prakash, 1987; Cao et al., 1989) are flexible and can handle phase-change problems occurring both at a single temperature and over a temperature range. The drawback of this method is that although the predicted temperature distributions and melting fronts are reasonable, themore » predicted time history of the temperature at a typical grid point may have some oscillations. The temperature-based fixed grid methods (Morgan, 1981; Hsiao and Chung, 1984) have no such time history problems and are more convenient with conjugate problems involving an adjacent wall, but have to deal with the severe nonlinearity of the governing equations when the phase-change temperature range is small. In this paper, a new temperature-based fixed-grid formulation is proposed, and the reason that the original equivalent heat capacity model is subject to such restrictions on the time step, mesh size, and the phase-change temperature range will also be discussed.« less

Calculation of Gallium-metal-Arsenic phase diagrams

NASA Technical Reports Server (NTRS)

Scofield, J. D.; Davison, J. E.; Ray, A. E.; Smith, S. R.

1991-01-01

Electrical contacts and metallization to GaAs solar cells must survive at high temperatures for several minutes under specific mission scenarios. The determination of which metallizations or alloy systems that are able to withstand extreme thermal excursions with minimum degradation to solar cell performance can be predicted by properly calculated temperature constitution phase diagrams. A method for calculating a ternary diagram and its three constituent binary phase diagrams is briefly outlined and ternary phase diagrams for three Ga-As-X alloy systems are presented. Free energy functions of the liquid and solid phase are approximated by the regular solution theory. Phase diagrams calculated using this method are presented for the Ga-As-Ge and Ga-As-Ag systems.

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

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

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

2015-09-17

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

Synthesis and characterization of CoPt nanoparticles prepared by room temperature chemical reduction with PAMAM dendrimer as template.

PubMed

Wan, Haiying; Shi, Shifan; Bai, Litao; Shamsuzzoha, Mohammad; Harrell, J W; Street, Shane C

2010-08-01

We describe an approach to synthesize monodisperse CoPt nanoparticles with dendrimer as template by a simple chemical reduction method in aqueous solution using NaBH4 as reducing agent at room temperature. The as-made CoPt nanoparticles buried in the dendrimer matrix have the chemically disordered fcc structure and can be transformed to the fct phase after annealing at 700 degrees C. This is the first report of dendrimer-mediated room temperature synthesis of monodisperse magnetic nanoparticles in aqueous solution.

Growth of tungsten oxide nanostructures by chemical solution deposition

NASA Astrophysics Data System (ADS)

Jin, L. H.; Bai, Y.; Li, C. S.; Wang, Y.; Feng, J. Q.; Lei, L.; Zhao, G. Y.; Zhang, P. X.

2018-05-01

Tungsten oxide nanostructures were fabricated on LaAlO3 (00l) substrates by a simple chemical solution deposition. The decomposition behavior and phase formation of ammonium tungstate precursor were characterized by thermal analysis and X-ray diffraction. Moreover, the morphology and chemical state of nanostructures were analyzed by scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectra. The effects of crystallization temperature on the formation of nanodots and nanowires were investigated. The results indicated that the change of nanostructures had close relationship with the crystallization temperature during the chemical solution deposition process. Under higher crystallization temperature, the square-like dots transformed into the dome-like nanodots and nanowires. Moreover high density well-ordered nanodots could be obtained on the substrate with the further increase of crystallization temperature. It also suggested that this simple chemical solution process could be used to adjust the nanostructures of tungsten oxide compounds on substrate.

Ionic Conductivity of TlBr1-xIx(x = 0, 0.2, 1): Candidate Gamma Ray Detector

NASA Astrophysics Data System (ADS)

Bishop, S. R.; Ciampi, G.; Lee, C. D.; Kuhn, M.; Tuller, H. L.; Higgins, W.; Shah, K. S.

2012-10-01

The ionic conductivity of TlBr, TlI and their solid solutions, candidates for high energy radiation detection, was examined using impedance spectroscopy. The orthorhombic to cubic phase change in TlI was observed via a steep change in conductivity with increasing temperature, whereas the TlBr-TlI solid solution was cubic throughout the measured temperature range, in agreement with the literature. The intrinsic conductivity of the cubic phase of each material showed nearly identical behavior, indicating that I substitution for Br has little to no effect on the combined defect formation and transport parameters in the studied range. Additionally, optical transmission was correlated with I concentration.

Conditioning of carbonaceous material prior to physical beneficiation

DOEpatents

Warzinski, Robert P.; Ruether, John A.

1987-01-01

A carbonaceous material such as coal is conditioned by contact with a supercritical fluid prior to physical beneficiation. The solid feed material is contacted with an organic supercritical fluid such as cyclohexane or methanol at temperatures slightly above the critical temperature and pressures of 1 to 4 times the critical pressure. A minor solute fraction is extracted into critical phase and separated from the solid residuum. The residuum is then processed by physical separation such as by froth flotation or specific gravity separation to recover a substantial fraction thereof with reduced ash content. The solute in supercritical phase can be released by pressure reduction and recombined with the low-ash, carbonaceous material.

In vitro corrosion resistance of plasma source ion nitrided austenitic stainless steels.

PubMed

Le, M K; Zhu, X M

2001-04-01

Plasma source ion nitriding has emerged as a low-temperature, low-pressure nitriding approach for low-energy implanting nitrogen ions and then diffusing them into steel and alloy. In this work, a single high nitrogen face-centered-cubic (f.c.c.) phase (gammaN) formed on the 1Cr18Ni9Ti and AISI 316L austenitic stainless steels with a high nitrogen concentration of about 32 at % was characterized using Auger electron spectroscopy, electron probe microanalysis, glancing angle X-ray diffraction, and transmission electron microscopy. The corrosion resistance of the gammaN-phase layer was studied by the electrochemical cyclic polarization measurement in Ringer's solutions buffered to pH from 3.5 to 7.2 at a temperature of 37 degrees C. No pitting corrosion in the Ringer's solutions with pH = 7.2 and 5.5 was detected for the gammaN-phase layers on the two stainless steels. The high pitting potential for the gammaN-phase layers is higher, about 500 and 600 mV, above that of the two original stainless steels, respectively, in the Ringer's solution with pH = 3.5. The corroded surface morphologies of the gammaN-phase layers observed by scanning electron microscopy are consistent with the results of the electrochemical polarization measurement.

Deconfinement phase transition in a magnetic field in 2 + 1 dimensions from holographic models

NASA Astrophysics Data System (ADS)

M. Rodrigues, Diego; Capossoli, Eduardo Folco; Boschi-Filho, Henrique

2018-05-01

Using two different models from holographic quantum chromodynamics (QCD) we study the deconfinement phase transition in 2 + 1 dimensions in the presence of a magnetic field. Working in 2 + 1 dimensions lead us to exact solutions on the magnetic field, in contrast with the case of 3 + 1 dimensions where the solutions on the magnetic field are perturbative. As our main result we predict a critical magnetic field Bc where the deconfinement critical temperature vanishes. For weak fields meaning B Bc we find that the critical temperature raises with growing field showing a magnetic catalysis (MC). These results for IMC and MC are in agreement with the literature.

Simulation of radial solute segregation in vertical Bridgman growth of pyridine-doped benzene, a surrogate for binary organic nonlinear optical materials

NASA Astrophysics Data System (ADS)

Lee, Hanjie; Pearlstein, Arne J.

2000-09-01

We present steady axisymmetric computations of solute distributions and radial segregation for vertical Bridgman growth of pyridine-doped benzene, a binary aromatic system with anisotropic solid-phase thermal conductivity, that serves as a model of solute transport in crystal growth of organic nonlinear optical materials. The radial variation of solid-phase mass fraction ( Cs) of pyridine, which is rejected at the growing interface, depends strongly on growth conditions. High growth velocities tend to increase Cs near the centerline, the ampoule wall, or both, and low growth velocities give more nearly uniform radial distributions. The maximum ampoule-wall temperature gradient also affects radial segregation, with convex-to-the-liquid interfaces at small temperature gradients being associated with radially monotonic Cs distributions, and ridged interfaces at higher gradients being associated with nonmonotonic distributions having maxima at the centerline and ampoule wall. Nonuniformity is strongly determined by both interface shape and the nature of the flow near the interface. Solute is transported down to the interface by a large toroidal vortex, and swept radially inward to the centerline by a second, flattened toroidal cell. When the interface is depressed at its junction with the ampoule wall, rejected solute accumulates in the overlying liquid, where convection is relatively weak, resulting in local solute enrichment of the solid. Computations at normal and zero gravity show that for two very similar interface shapes, a maximum in the radial solid-phase solute distribution at the ampoule wall is associated with the interface shape, while the maximum on the centerline is associated with sweeping of solute to the centerline by a vortical flow on the interface. We also show that radial solute segregation depends significantly on whether account is taken of the anisotropy of the solid-phase thermal conductivity. Finally, the computations provide guidance as to the minimum ampoule length required to produce an axially uniform solute distribution over at least part of the length of a boule.

Modeling of glycine solubility in aqueous HCl-MgCl2 system and its application in phase transition of glycine by changing media and supersaturation

NASA Astrophysics Data System (ADS)

Ansari, Ziaul Haque; Zeng, Yan; Zhang, Yan; Demopoulos, George P.; Li, Zhibao

2017-06-01

The solubility of glycine in HCl and HCl-MgCl2 solutions was measured from 283.15 to 343.15 K and found to increase with temperature and increase linearly with the concentration of HCl. The MSE model integrated in the OLI platform was modified by regressing the experimental and literature solubility data through the adjustment of the middle-range interaction parameters. After parameterization, the model can accurately calculate the solubility with the average absolute deviation lower than 3.5% and thus be able to predict supersaturation of glycine. Crystallization of different polymorphs of glycine in water, HCl, NaOH, MgCl2, and HCl-MgCl2 aqueous solutions was performed. The effects of medium, temperature, supersaturation, and time on the crystallization were investigated. It was found that only in the HCl solution the formation of single α-glycine phase was achieved under all the investigated temperature and holding time. α-glycine or its mixture with γ-glycine or C4H18N2O4·HCl was produced in systems other than HCl solution depending on the conditions.

Phase relations in the system CuMoS

USGS Publications Warehouse

Dawei, H.; Chang, L.L.Y.; Knowles, C.R.

1990-01-01

Phase relations in the system CuMoS were studied in the temperature range 500-1000 ??C by using the conventional sealed, evacuated glass capsule technique. Reflected-light microscopy, X-ray powder diffraction and electron microprobe analysis were used for phase characterization. The chevrel-type phase, CuxMo3S4, is stable above 600??C, and forms equilibrium assemblages with the cubic Cu2S solid solution, copper, molybdenum, Mo2S3 and MoS2. Its solid solution ranges from Cu1.50-2.00Mo3S4 at 700??C to Cu1.22-2.00Mo3S4 at 1000 ??C. ?? 1990.

Miscibility as a factor for component crystallization in multisolute frozen solutions.

PubMed

Izutsu, Ken-Ichi; Shibata, Hiroko; Yoshida, Hiroyuki; Goda, Yukihiro

2014-07-01

The relationship between the miscibility of formulation ingredients and their crystallization during the freezing segment of the lyophilization process was studied. The thermal properties of frozen solutions containing myo-inositol and cosolutes were obtained by performing heating scans from -70 °C before and after heat treatment at -20 °C to -5 °C. Addition of dextran 40,000 reduced and prevented crystallization of myo-inositol. In the first scan, some frozen solutions containing an inositol-rich mixture with dextran showed single broad transitions (Tg's: transition temperatures of maximally freeze-concentrated solutes) that indicated incomplete mixing of the concentrated amorphous solutes. Heat treatment of these frozen solutions induced separation of the solutes into inositol-dominant and solute mixture phases (Tg' splitting) following crystallization of myo-inositol (Tg' shifting). The crystal growth involved myo-inositol molecules in the solute mixture phase. The amorphous-amorphous phase separation and resulting loss of the heteromolecular interaction in the freeze-concentrated inositol-dominant phase should allow ordered assembly of the solute molecules required for nucleation. Some dextran-rich and intermediate concentration ratio frozen solutions retained single Tg's of the amorphous solute mixture, both before and after heat treatments. The relevance of solute miscibility on the crystallization of myo-inositol was also indicated in the systems containing glucose or recombinant human albumin. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Scrutinization of thermal radiation, viscous dissipation and Joule heating effects on Marangoni convective two-phase flow of Casson fluid with fluid-particle suspension

NASA Astrophysics Data System (ADS)

Mahanthesh, B.; Gireesha, B. J.

2018-03-01

The impact of Marangoni convection on dusty Casson fluid boundary layer flow with Joule heating and viscous dissipation aspects is addressed. The surface tension is assumed to vary linearly with temperature. Physical aspects of magnetohydrodynamics and thermal radiation are also accounted. The governing problem is modelled under boundary layer approximations for fluid phase and dust particle phase and then Runge-Kutta-Fehlberg method based numeric solutions are established. The momentum and heat transport mechanisms are focused on the result of distinct governing parameters. The Nusselt number is also calculated. It is established that the rate of heat transfer can be enhanced by suspending dust particles in the base fluid. The temperature field of fluid phase and temperature of dust phase are quite reverse for thermal dust parameter. The radiative heat, viscous dissipation and Joule heating aspects are constructive for thermal fields of fluid and dust phases. The velocity of dusty Casson fluid dominates the velocity of dusty fluid while this trend is opposite in the case of temperature. Moreover qualitative behaviour of fluid phase and dust phase temperature/velocity are similar.

A CO2-Silica Geothermometer for Low Temperature Geothermal Resource Assessment, with Application to Resources in the Safford Basin, Arizona

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

Witcher, James C.; Stone, Claudia

1983-11-01

Geothermics is the study of the earth's heat energy, it's affect on subsurface temperature distribution, it's physical and chemical sources, and it's role in dynamic geologic processes. The term, geothermometry, is applied to the determination of equilibrium temperatures of natural chemical systems, including rock, mineral, and liquid phases. An assemblage of minerals or a chemical system whose phase composition is a function of temperature and pressure can be used as a geothermometer. Thus a geothermometer is useful to determine the formation temperature of rock or the last equilibrium temperature of a flowing aqueous solution such as ground water and hydrothermalmore » fluids.« less

High temperature coercive field behavior of Fe-Zr powder

NASA Astrophysics Data System (ADS)

Mishra, Debabrata; Perumal, A.; Srinivasan, A.

2009-04-01

We report the investigation of high temperature coercive field behavior of Fe80Zr20 nanocrystalline alloy powder having two-phase microstructure prepared by mechanical alloying process. Thermomagnetization measurement shows the presence of two different magnetic phase transitions corresponding to the amorphous matrix and nonequilibrium Fe(Zr) solid solution. Temperature dependent coercivity exhibits a sharp increase in its value close to the Curie temperature of the amorphous matrix. This feature is attributed to the loss of intergranular ferromagnetic exchange coupling between the nanocrystallites due to the paramagnetic nature of the amorphous matrix. The temperature dependent coercive field behavior is ascribed to the variations in both the effective anisotropy and the exchange stiffness constant with temperature.

Synthesis of mono-dispersed nanofluids using solution plasma

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

Heo, Yong Kang, E-mail: yk@rd.numse.nagoya-u.ac.jp; Bratescu, Maria Antoaneta, E-mail: maria@rd.numse.nagoya-u.ac.jp; Knowledge Hub Aichi, Yakusa-cho, Nagakute-ku, Toyota

2014-07-14

Small-sized and well-dispersed gold nanoparticles (NPs) for nanofluidics have been synthesized by electrical discharge in liquid environment using termed solution plasma processing (SPP). Electrons and the hydrogen radicals are reducing the gold ions to the neutral form in plasma gas phase and liquid phase, respectively. The gold NPs have the smallest diameter of 4.9 nm when the solution temperature was kept at 20 °C. Nucleation and growth theory describe the evolution of the NP diameter right after the reduction reaction in function of the system temperature, NP surface energy, dispersion energy barrier, and nucleation rate. Negative charges on the NPs surface duringmore » and after SPP generate repulsive forces among the NPs avoiding their agglomeration in solution. Increasing the average energy in the SPP determines a decrease of the zeta potential and an increase of the NPs diameter. An important enhancement of the thermal conductivity of 9.4% was measured for the synthesized nanofluids containing NPs with the smallest size.« less

Competition between Chaotic and Nonchaotic Phases in a Quadratically Coupled Sachdev-Ye-Kitaev Model.

PubMed

Chen, Xin; Fan, Ruihua; Chen, Yiming; Zhai, Hui; Zhang, Pengfei

2017-11-17

The Sachdev-Ye-Kitaev (SYK) model is a concrete solvable model to study non-Fermi liquid properties, holographic duality, and maximally chaotic behavior. In this work, we consider a generalization of the SYK model that contains two SYK models with a different number of Majorana modes coupled by quadratic terms. This model is also solvable, and the solution shows a zero-temperature quantum phase transition between two non-Fermi liquid chaotic phases. This phase transition is driven by tuning the ratio of two mode numbers, and a nonchaotic Fermi liquid sits at the critical point with an equal number of modes. At a finite temperature, the Fermi liquid phase expands to a finite regime. More intriguingly, a different non-Fermi liquid phase emerges at a finite temperature. We characterize the phase diagram in terms of the spectral function, the Lyapunov exponent, and the entropy. Our results illustrate a concrete example of the quantum phase transition and critical behavior between two non-Fermi liquid phases.

Surface activity of the triflate ion at the air/water interface and properties of N,N,N-trimethyl-N-dodecylammonium triflate aqueous solutions.

PubMed

Lima, F S; Maximiano, F A; Cuccovia, I M; Chaimovich, H

2011-04-19

The surface activity of salts added to water is orders of magnitude lower than that of surfactants. Sodium trifluoromethanesulfonate (NaTf) produced a change in surface tension with concentration, Δγ/Δc, of -13.2 mN·L/m·mol. This value is ca. 4-fold larger than those of simple salts and that of methanesulfonate. This unexpected surface effect suggested that positively charged micelles containing Tf could exhibit interesting properties. Dodecyltrimethylammonium triflate (DTATf) had a higher Kraft temperature (37 °C) and a lower cmc (5 × 10(-3) M) and degree of dissociation (0.11) than the chloride and bromide salts of DTA. Above the Kraft temperature, at a characteristic temperature t(1), the addition of NaTf above 0.05 M to a DTATf solution induced phase separation. By increasing the temperature of the two-phase system to above t(1), a homogeneous, transparent solution was obtained at a characteristic temperature t(2). These results, together with well-known triflate properties, led us to suggest that the Tf ion pairs with DTA and that the -CF(3) group may be dehydrated in the interfacial region, resulting in new and interesting self-aggregated structures. © 2011 American Chemical Society

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

NASA Astrophysics Data System (ADS)

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.

Analytical study of the liquid phase transient behavior of a high temperature heat pipe. M.S. Thesis

NASA Technical Reports Server (NTRS)

Roche, Gregory Lawrence

1988-01-01

The transient operation of the liquid phase of a high temperature heat pipe is studied. The study was conducted in support of advanced heat pipe applications that require reliable transport of high temperature drops and significant distances under a broad spectrum of operating conditions. The heat pipe configuration studied consists of a sealed cylindrical enclosure containing a capillary wick structure and sodium working fluid. The wick is an annular flow channel configuration formed between the enclosure interior wall and a concentric cylindrical tube of fine pore screen. The study approach is analytical through the solution of the governing equations. The energy equation is solved over the pipe wall and liquid region using the finite difference Peaceman-Rachford alternating direction implicit numerical method. The continuity and momentum equations are solved over the liquid region by the integral method. The energy equation and liquid dynamics equation are tightly coupled due to the phase change process at the liquid-vapor interface. A kinetic theory model is used to define the phase change process in terms of the temperature jump between the liquid-vapor surface and the bulk vapor. Extensive auxiliary relations, including sodium properties as functions of temperature, are used to close the analytical system. The solution procedure is implemented in a FORTRAN algorithm with some optimization features to take advantage of the IBM System/370 Model 3090 vectorization facility. The code was intended for coupling to a vapor phase algorithm so that the entire heat pipe problem could be solved. As a test of code capabilities, the vapor phase was approximated in a simple manner.

Method for low temperature preparation of a noble metal alloy

DOEpatents

Even, Jr., William R.

2002-01-01

A method for producing fine, essentially contamination free, noble metal alloys is disclosed. The alloys comprise particles in a size range of 5 to 500 nm. The method comprises 1. A method for preparing a noble metal alloy at low temperature, the method comprising the steps of forming solution of organometallic compounds by dissolving the compounds into a quantity of a compatible solvent medium capable of solvating the organometallic, mixing a portion of each solution to provide a desired molarity ratio of ions in the mixed solution, adding a support material, rapidly quenching droplets of the mixed solution to initiate a solute-solvent phase separation as the solvent freezes, removing said liquid cryogen, collecting and freezing drying the frozen droplets to produce a dry powder, and finally reducing the powder to a metal by flowing dry hydrogen over the powder while warming the powder to a temperature of about 150.degree. C.

Phase formation and UV luminescence of Gd{sup 3+} doped perovskite-type YScO{sub 3}

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

Shimizu, Yuhei; Ueda, Kazushige, E-mail: kueda@che.kyutech.ac.jp

Synthesis of pure and Gd{sup 3+}doped perovskite-type YScO{sub 3} was attempted by a polymerized complex (PC) method and solid state reaction (SSR) method. Crystalline phases and UV luminescence of samples were examined with varying heating temperatures. The perovskite-type single phase was not simply formed in the SSR method, as reported in some literatures, and two cubic C-type phases of starting oxide materials remained forming slightly mixed solid solutions. UV luminescence of Gd{sup 3+} doped samples increased with an increase in heating temperatures and volume of the perovskite-type phase. In contrast, a non-crystalline precursor was crystallized to a single C-type phasemore » at 800 °C in the PC method forming a completely mixed solid solution. Then, the phase of perovskite-type YScO{sub 3} formed at 1200 °C and its single phase was obtained at 1400 °C. It was revealed that high homogeneousness of cations was essential to generate the single perovskite-phase of YScO{sub 3}. Because Gd{sup 3+} ions were also dissolved into the single C-type phase in Gd{sup 3+} doped samples, intense UV luminescence was observed above 800 °C in both C-type phase and perovskite-type phase. - Graphical abstract: A pure perovskite-type YScO{sub 3} phase was successfully synthesized by a polymerized complex (PC) method. The perovskite-type YScO{sub 3} was generated through a solid solution of C-type (Y{sub 0.5}Sc{sub 0.5}){sub 2}O{sub 3} with drastic change of morphology. The PC method enabled a preparation of the single phase of the perovskite-type YScO{sub 3} at lower temperature and in shorter heating time. Gd{sup 3+} doped perovskite-type YScO{sub 3} was found to show a strong sharp UV emission at 314 nm. - Highlights: • Pure YScO{sub 3} phase was successfully synthesized by polymerized complex (PC) method. • Pure perovskite-type YScO{sub 3} phase was generated from pure C-type (Y{sub 0.5}Sc{sub 0.5}){sub 2}O{sub 3} one. • YScO{sub 3} was obtained at lower temperature and in shorter heating time by PC method. • Perovskite-type YScO{sub 3}:Gd{sup 3+} was found to show strong sharp UV emission at 314 nm.« less

Influence of creep damage on the low cycle thermal-mechanical fatigue behavior of two tantalum base alloys

NASA Technical Reports Server (NTRS)

Sheffler, K. D.; Doble, G. S.

1972-01-01

Low cycle fatigue tests have been performed on the tantalum base alloys T-111 and ASTAR 811C with synchronized, independently programmed temperature and strain cycling. The thermal-mechanical cycles applied fell into three basic categories: these were isothermal cycling, in-phase thermal cycling, and out-of-phase thermal cycling. In-phase cycling was defined as tensile deformation associated with high temperature and compressive deformation with low temperature, while out-of-phase thermal cycling was defined as the reverse case. The in-phase thermal cycling had a pronounced detrimental influence on the fatigue life of both alloys, with the life reduction being greater in the solid solution strengthened T-111 alloy than in the carbide strengthened ASTAR 811C alloy. The out-of-phase tests also showed pronounced effects on the fatigue life of both alloys, although not as dramatic.

Density fluctuations in aqueous solution of ionic liquid with lower critical solution temperature: Mixture of tetrabutylphosphonium trifluoroacetate and water

NASA Astrophysics Data System (ADS)

Nitta, Ayako; Morita, Takeshi; Saita, Shohei; Kohno, Yuki; Ohno, Hiroyuki; Nishikawa, Keiko

2015-05-01

Aqueous solutions of tetrabutylphosphonium trifluoroacetate ([P4444]CF3COO) exhibit a LCST-type phase transition with the critical point near 0.025 in mole fraction of [P4444]CF3COO at T = 302 K. The phase behavior of [P4444]CF3COO-water mixtures was investigated by evaluating their density fluctuations, which provide quantitative descriptions of the mixing states of the solutions. The concentration dependence of the density fluctuations was investigated at 293 and 301 K for the mixtures without distinguishing the components and for the individual components ([P4444]CF3COO and water). A drastic change in the mixing state was observed for the solution when the critical point was approached.

Nickel-Silver Monotectic in Alumina Crucible for Use with Contact Thermometry

NASA Astrophysics Data System (ADS)

Gotoh, M.; Dedyulin, S. N.

2017-07-01

Previously, the authors have published work describing a pure Ni fixed point within alumina crucibles. The success of this study stimulated working with the Ni-Ag monotectic point in alumina crucibles. Similar to eutectic points, the Ni-Ag monotectic temperature is an invariant point but it differs from a eutectic reaction in such a way that the monotectic phase change takes place from Ni-Ag liquid solution to Ni-Ag solid solution and Ag rich Ni-Ag liquid solution. In the phase diagram references, the Ni-Ag monotectic phase transition temperature is assigned to be about 20°C below the pure Ni melting/freezing point. As is the case for pure Ni, mechanical stability is one of the concerns. Therefore, proper cell design is necessary to avoid breakage of the alumina crucible. The techniques used for the fabrication and measurement of the pure Ni cell were applied to the Ni-Ag cell as well. The cells have been successfully fabricated and the temperature measurement at the fixed point was carried out for more than 20 thermal cycles in total. A Pt/Pd thermocouple was used to measure the temperature and was calibrated from the tin point to the gold point to measure the ITS-90. Freezing plateaus are realized with the technique of "recurrent offset freezing method with reserved solid". The duration of each freezing plateau is a minimum of 30 min. The monotectic transformation temperature for the best performed cell is determined as 1428.27°C with a combined uncertainty of ±0.06°C ({k}=1).

Homogeneous Liquid–Liquid Extraction of Rare Earths with the Betaine—Betainium Bis(trifluoromethylsulfonyl)imide Ionic Liquid System

PubMed Central

Hoogerstraete, Tom Vander; Onghena, Bieke; Binnemans, Koen

2013-01-01

Several fundamental extraction parameters such as the kinetics and loading were studied for a new type of metal solvent extraction system with ionic liquids. The binary mixture of the ionic liquid betainium bis(trifluoromethylsulfonyl)imide and water shows thermomorphic behavior with an upper critical solution temperature (UCST), which can be used to avoid the slower mass transfer due to the generally higher viscosity of ionic liquids. A less viscous homogeneous phase and mixing on a molecular scale are obtained when the mixture is heated up above 55 °C. The influence of the temperature, the heating and cooling times, were studied for the extraction of neodymium(III) with betaine. A plausible and equal extraction mechanism is proposed in bis(trifluoromethylsulfonyl)imide, nitrate, and chloride media. After stripping of the metals from the ionic liquid phase, a higher recovery of the ionic liquid was obtained by salting-out of the ionic liquid fraction lost by dissolution in the aqueous phase. The change of the upper critical solution temperature by the addition of HCl or betaine was investigated. In addition, the viscosity was measured below and above the UCST as a function of the temperature. PMID:24169434

The existence of a temperature-driven solid solution in LixFePO4 for 0 <= x <= 1

NASA Astrophysics Data System (ADS)

Delacourt, Charles; Poizot, Philippe; Tarascon, Jean-Marie; Masquelier, Christian

2005-03-01

Lithium-ion batteries have revolutionized the powering of portable electronics. Electrode reactions in these electrochemical systems are based on reversible insertion/deinsertion of Li+ ions into the host electrode material with a concomitant addition/removal of electrons into the host. If such batteries are to find a wider market such as the automotive industry, less expensive positive electrode materials will be required, among which LiFePO4 is a leading contender. An intriguing fundamental problem is to understand the fast electrochemical response from the poorly electronic conducting two-phase LiFePO4/FePO4 system. In contrast to the well-documented two-phase nature of this system at room temperature, we give the first experimental evidence of a solid solution LixFePO4 (0 <= x <= 1) at 450 °C, and two new metastable phases at room temperature with Li0.75FePO4 and Li0.5FePO4 composition. These experimental findings challenge theorists to improve predictive models commonly used in the field. Our results may also lead to improved performances of these electrodes at elevated temperatures.

Characterization of Polysulfone Membranes Prepared with Thermally Induced Phase Separation Technique

NASA Astrophysics Data System (ADS)

Tiron, L. G.; Pintilie, Ș C.; Vlad, M.; Birsan, I. G.; Baltă, Ș

2017-06-01

Abstract Membrane technology is one of the most used water treatment technology because of its high removal efficiency and cost effectiveness. Preparation techniques for polymer membranes show an important aspect of membrane properties. Generally, polysulfone (PSf) and polyethersulfone (PES) are used for the preparation of ultrafiltration (UF) membranes. Polysulfone (PSf) membranes have been widely used for separation and purification of different solutions because of their excellent chemical and thermal stability. Polymeric membranes were obtained by phase inversion method. The polymer solution introduced in the nonsolvent bath (distilled water) initiate the evaporation of the solvent from the solution, this phenomenon has a strong influence on the transport properties. The effect of the coagulation bath temperature on the membrane properties is of interest for this study. Membranes are characterized by pure water flux, permeability, porosity and retention of methylene blue. The low temperature of coagulation bath improve the membrane’s rejection and its influence was most notable.

Cultivation and energy efficient harvesting of microalgae using thermoreversible sol-gel transition

PubMed Central

Estime, Bendy; Ren, Dacheng; Sureshkumar, Radhakrishna

2017-01-01

Microalgae represent a promising source of renewable biomass for the production of biofuels and valuable chemicals. However, energy efficient cultivation and harvesting technologies are necessary to improve economic viability. A Tris-Acetate-Phosphate-Pluronic (TAPP) medium that undergoes a thermoreversible sol-gel transition is developed to efficiently culture and harvest microalgae without affecting the productivity as compared to that in traditional culture in a well-mixed suspension. After seeding microalgae in the TAPP medium in a solution phase at 15 °C, the temperature is increased by 7 °C to induce gelation. Within the gel, microalgae are observed to grow in large clusters rather than as isolated cells. The settling velocity of the microalgal clusters is approximately ten times larger than that of individual cells cultured in typical solution media. Such clusters are easily harvested gravimetrically by decreasing the temperature to bring the medium to a solution phase. PMID:28102313

Switchable vanadium dioxide (VO2) metamaterials fabricated from tungsten doped vanadia-based colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Paik, Taejong; Hong, Sung-Hoon; Gordon, Thomas; Gaulding, Ashley; Kagan, Cherie; Murray, Christopher

2013-03-01

We report the fabrication of thermochromic VO2-based metamaterials using solution-processable colloidal nanocrystals. Vanadium-based nanoparticles are prepared through a non-hydrolytic reaction, resulting in stable colloidal dispersions in solution. Thermochromic nanocrystalline VO2 thin-films are prepared via rapid thermal annealing of colloidal nanoparticles coated on a variety of substrates. Nanostructured VO2 can be patterned over large areas by nanoimprint lithography. Precise control of tungsten (W) doping concentration in colloidal nanoparticles enables tuning of the phase transition temperature of the nanocrystalline VO2 thin-films. W-doped VO2 films display a sharp temperature dependent phase transition, similar to the undoped VO2 film, but at lower temperatures tunable with the doping level. By sequential coating of doped VO2 with different doping concentrations, we fabricate ?smart? multi-layered VO2 films displaying multiple phase transition temperatures within a single structure, allowing for dynamic modulation of the metal-dielectric layered structure. The optical properties programmed into the layered structure are switchable with temperature, which provides additional degrees of freedom to design tunable optical metamaterials. This work is supported by the US Office of Naval Research Multidisciplinary University Research Initiative (MURI) program grant number ONR-N00014-10-1-0942.

Rapid nondestructive spectrometric measurement of temperature-dependent gas-liquid solubility equilibria.

PubMed

Ma, Jian; Dasgupta, Purnendu K; Yang, Bingcheng

2011-02-01

Gas-liquid solubility equilibria (Henry's Law behavior) are of basic interest to many different areas. Temperature-dependent aqueous solubilities of various organic compounds are of fundamental importance in many branches of environmental science. In a number of situations, the gas/dissolved solute of interest has characteristic spectroscopic absorption that is distinct from that of the solvent. For such cases, we report facile nondestructive rapid measurement of the temperature-dependent Henry's law constant (K(H)) in a static sealed spectrometric cell. Combined with a special cell design, multiwavelength measurement permits a large range of K(H) to be spanned. It is possible to derive the K(H) values from the absorbance measured in the gas phase only, the liquid phase only (preferred), and both phases. Underlying principles are developed, and all three approaches are illustrated for a solute like acetone in water. A thermostatic spectrophotometer cell compartment, widely used and available, facilitates rapid temperature changes and allows rapid temperature-dependent equilibrium measurements. Applicability is shown for both acetone and methyl isobutyl ketone. Very little sample is required for the measurement; the K(H) for 4-hydroxynonenal, a marker for oxidative stress, is measured to be 56.9 ± 2.6 M/atm (n = 3) at 37.4 °C with 1 mg of the material available.

Normal and anomalous nuclear spin-lattice relaxation at high temperatures in Sc-H(D), Y-H, and Lu-H solid solutions

NASA Astrophysics Data System (ADS)

Barnes, R. G.; Han, J.-W.; Torgeson, D. R.; Baker, D. B.; Conradi, M. S.; Norberg, R. E.

1995-02-01

We report the results of measurements of the proton (1H) spin-lattice relaxation rate R1 at high temperatures (to ~1400 K) in the hcp (α) solid-solution phases of the Sc-H, Y-H, and Lu-H systems, and of R1(45Sc) in Sc-H and Sc-D solid solutions. The latter measurements show unambiguous evidence of an anomalous increase at ~1000 K, whereas R1(1H) shows no such increase at any temperature. This behavior of R1(1H) contrasts with that in the bcc V-H, etc., solid solutions where anomalous relaxation occurs below ~1000 K, and in all investigated metal dihydride phases, MH2-x. The anomalous R1(1H) behavior in α-VHx, α-NbHx, etc., may be understood in terms of fast spin relaxation in the H2 gas in equilibrium with the solid, mediated by fast gas-solid exchange of hydrogen. However, in the present systems, α-ScHx, α-YHx, etc., the H2 gas pressure in equilibrium with the hcp systems is extremely low, resulting in negligible H2 concentration in the gas phase, and consequently a negligible contribution to R1(1H). In contrast, some of the present measurements indicate that the R1(45Sc) anomaly does result from the hydrogen content of the metal, but the mechanism remains unexplained.

Re Effects on Phase Stability and Mechanical Properties of MoSS+Mo3Si+Mo5SiB2 alloys

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

Yang, Ying; Bei, Hongbin; George, Easo P

2013-01-01

Because of their high melting points and good oxidation resistance Mo-Si-B alloys are of interest as potential ultrahigh-temperature structural materials. But their major drawbacks are poor ductility and fracture toughness at room temperature. Since alloying with Re has been suggested as a possible solution, we investigate here the effects of Re additions on the microstructure and mechanical properties of a ternary alloy with the composition Mo-12.5Si-8.5B (at.%). This alloy has a three-phase microstructure consisting of Mo solid-solution (MoSS), Mo3Si, and Mo5SiB2 and our results show that up to 8.4 at.% Re can be added to it without changing its microstructuremore » or forming any brittle phase at 1600 C. Three-point bend tests using chevron-notched specimens showed that Re did not improve fracture toughness of the three-phase alloy. Nanoindentation performed on the MoSS phase in the three-phase alloy showed that Re increases Young s modulus, but does not lower hardness as in some Mo solid solution alloys. Based on our thermodynamic calculations and microstructural analyses, the lack of a Re softening effect is attributed to the increased Si levels in the Re-containing MoSS phase since Si is known to increase its hardness. This lack of softening is possibly why there is no Re-induced improvement in fracture toughness.« less

Investigations on gel forming media use in low gravity bioseparations research

NASA Technical Reports Server (NTRS)

Todd, Paul; Szlag, David C.; Plank, Lindsay D.; Delcourt, Scott G.; Kunze, M. Elaine

1989-01-01

Research on gelling media and conditions suitable for the preservation of the spatial configuration of cell suspensions and macromolecular solutions after separation in free fluid during low gravity experiments is presented. The examples studied included free electrophoresis of cells in a cylindrical column and two-phase aqueous polymer separation. Microgravity electrophoresis experiments were simulated by separating model cell types (animal or human) in a vertical density gradient containing low-conductivity buffer, 1.7-6.5 percent Ficoll, 6.8-5.0 percent sucrose, and 1 percent SeaPrep low-melting temperature agarose. Upon cooling, a gel formed in the column and cells could be captured at the forming locations. Two-phase extraction experiments were simulated using two-polymer solutions in which phase separation occurs in normal saline at temperatures compatible with cell viability and in which one or both phases form a gel upon cooling. Suitable polymers included commercial agaroses (1-2 percent), maltodextrin (5-7 percent), and gelatin (5-20 percent).

Phase structure of NJL model with weak renormalization group

NASA Astrophysics Data System (ADS)

Aoki, Ken-Ichi; Kumamoto, Shin-Ichiro; Yamada, Masatoshi

2018-06-01

We analyze the chiral phase structure of the Nambu-Jona-Lasinio model at finite temperature and density by using the functional renormalization group (FRG). The renormalization group (RG) equation for the fermionic effective potential V (σ ; t) is given as a partial differential equation, where σ : = ψ bar ψ and t is a dimensionless RG scale. When the dynamical chiral symmetry breaking (DχSB) occurs at a certain scale tc, V (σ ; t) has singularities originated from the phase transitions, and then one cannot follow RG flows after tc. In this study, we introduce the weak solution method to the RG equation in order to follow the RG flows after the DχSB and to evaluate the dynamical mass and the chiral condensate in low energy scales. It is shown that the weak solution of the RG equation correctly captures vacuum structures and critical phenomena within the pure fermionic system. We show the chiral phase diagram on temperature, chemical potential and the four-Fermi coupling constant.

High-temperature phase relations and thermodynamics in the iron-lead-sulfur system

NASA Astrophysics Data System (ADS)

Eric, R. Hurman; Ozok, Hakan

1994-01-01

The PbS activities in FeS-PbS liquid mattes were obtained at 1100 °C and 1200 °C by the dew-point method. Negative deviations were observed, and the liquid-matte solutions were modeled by the Krupkowski formalism. The liquid boundaries of the FeS-PbS phase diagram were derived from the model equations yielding a eutectic temperature of 842 °C at X Pbs = 0.46. A phase diagram of the pseudobinary FeS-PbS was also verified experimentally by quenching samples equilibrated in evacuated and sealed silica capsules. No terminal solid solution ranges could be found. Within the Fe-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were established at 1200 °C. Activities of Pb were measured by the dew-point technique along the metal-rich boundary of the miscibility gap. Activities of Fe, Pb, and S, along the miscibility gap were also calculated by utilizing the bounding binary thermodynamics, phase equilibria, and tie-lines.

Electrical resistivity of the UAs 1- xSex solid solutions

NASA Astrophysics Data System (ADS)

Breandon, C.; Bartholin, H.; Tchapoutian, R.; Therond, P. G.; Schoenes, J.; Vogt, O.

1987-01-01

The electrical resistivity ϱ of UAs 1- xSex solid solutions has been measured between 13 K and room temperature. The magnetic phase diagram has been deduced. Effects of uniaxial stress on ϱ allow to understand some results and to reveal anisotropy of ϱ.

Molecular dynamics simulations of aqueous solutions of ethanolamines.

PubMed

López-Rendón, Roberto; Mora, Marco A; Alejandre, José; Tuckerman, Mark E

2006-08-03

We report on molecular dynamics simulations performed at constant temperature and pressure to study ethanolamines as pure components and in aqueous solutions. A new geometric integration algorithm that preserves the correct phase space volume is employed to study molecules having up to three ethanol chains. The most stable geometry, rotational barriers, and atomic charges were obtained by ab initio calculations in the gas phase. The calculated dipole moments agree well with available experimental data. The most stable conformation, due to intramolecular hydrogen bonding interactions, has a ringlike structure in one of the ethanol chains, leading to high molecular stability. All molecular dynamics simulations were performed in the liquid phase. The interaction parameters are the same for the atoms in the ethanol chains, reducing the number of variables in the potential model. Intermolecular hydrogen bonding is also analyzed, and it is shown that water associates at low water mole fractions. The force field reproduced (within 1%) the experimental liquid densities at different temperatures of pure components and aqueous solutions at 313 K. The excess and partial molar volumes are analyzed as a function of ethanolamine concentration.

Synthesis of formamidinium lead iodide perovskite bulk single crystal and its optical properties

NASA Astrophysics Data System (ADS)

Zheng, Hongge; Duan, Junjie; Dai, Jun

2017-07-01

Formamidinium lead iodide (FAPbI3) is a promising hybrid perovskite material for optoelectronic devices. We synthesized bulk single crystal FAPbI3 by a rapid solution crystallization method. X-ray diffraction (XRD) was performed to characterize the crystal structure. Temperature-dependent photoluminescence (PL) spectra of the bulk single crystal FAPbI3 were measured from 10 to 300 K to explain PL recombination mechanism. It shows that near band edge emission blueshifts with the temperature increasing from 10 to 120 K and from 140 K to room temperature, a sudden emission band redshift demonstrates near 140 K because of the phase transition from orthorhombic phase to cubic phase. From the temperature-dependent PL spectra, the temperature coefficients of the bandgap and thermal activation energies of FAPbI3 perovskite are fitted.

Effect of boundary heat flux on columnar formation in binary alloys: A phase-field study

NASA Astrophysics Data System (ADS)

Du, Lifei; Zhang, Peng; Yang, Shaomei; Chen, Jie; Du, Huiling

2018-02-01

A non-isothermal phase-field model was employed to simulate the columnar formation during rapid solidification in binary Ni-Cu alloy. Heat flux at different boundaries was applied to investigate the temperature gradient effect on the morphology, concentration and temperature distributions during directional solidifications. With the heat flux input/extraction from boundaries, coupling with latent heat release and initial temperature gradient, temperature distributions are significantly changed, leading to solute diffusion changes during the phase-transition. Thus, irregular columnar structures are formed during the directional solidification, and the concentration distribution in solid columnar arms could also be changed due to the different growing speeds and temperature distributions at the solid-liquid interfaces. Therefore, applying specific heat conditions at the solidifying boundaries could be an efficient way to control the microstructure during solidifications.

Monte Carlo and mean-field studies of phase evolution in concentrated surfactant solutions

NASA Astrophysics Data System (ADS)

Bohbot, Yardena; Ben-Shaul, Avinoam; Granek, Rony; Gelbart, William M.

1995-11-01

A two-dimensional lattice model, originally introduced by Granek et al. [J. Chem. Phys. 101, 4331 (1994)], is used to demonstrate the intricate coupling between the intramicellar interactions that determine the optimal aggregation geometry of surfactant molecules in dilute solution, and the intermicellar interactions that govern the phase behavior at higher concentrations. Three very different scenarios of self-assembly and phase evolution are analyzed in detail, based on Monte Carlo studies and theoretical interpretations involving mean-field, Landau-Ginzburg, Bethe-Peierls, and virial expansion schemes. The basic particles in the model are ``unit micelles'' which, due to spontaneous self-assembly or because of excluded area interactions, can fuse to form larger aggregates. These aggregates are envisaged as flat micelles composed of a bilayerlike body surrounded by a curved semitoroidal rim. The system's Hamiltonian involves one- through four-body potentials between the unit micelles, which account for their tendency to form aggregates of different shapes, e.g., elongated vs disklike micelles. Equivalently, the configurational energy of the system is a sum of micellar self-energies involving the packing free energies of the constituent molecules in the bilayer body and in rim segments of different local curvature. The rim energy is a sum of a line tension term and a 1D curvature energy which depends on the rim spontaneous curvature and bending rigidity. Different combinations of these molecular parameters imply different optimal packing geometries and hence different self-assembly and phase behaviors. The emphasis in this paper is on systems of ``curvature loving'' amphiphiles which, in our model, are characterized by negative line tension. The three systems studied are: (i) A dilute solution of stable disklike micelles which, upon increasing the concentration, undergoes a first-order phase transition to a continuous bilayer with isolated hole defects. An intermediate modulated ``checkerboard'' phase appears under certain conditions at low temperatures. (ii) A system of unit micelles which in dilute solution tend to associate into linear micelles. These micelles are rodlike at low temperatures, becoming increasingly more flexible as the temperature increases. Upon increasing the concentration the micelles grow and undergo (in 2D) a continuous transition into nematic and ``stripe'' phases of long rods. At still higher concentrations the micellar stripes fuse into continuous sheets with line defects. (iii) A system in which, already in dilute solution, the micelles favor the formation of branched aggregates, analogous to the branched cylindrical micelles recently observed in certain surfactant solutions. As the concentration increases the micelles associate into networks (``gels'') composed of a mesh of linear micelles linked by ``T-like'' intermicellar junctions. The network may span the entire system or phase separate and coexist with a dilute micellar phase, depending on the details of the molecular packing parameters.

Phase diagram, chemical stability and physical properties of the solid-solution Ba{sub 4}Nb{sub 2-x}Ta{sub x}O{sub 9}

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

Dunstan, Matthew T., E-mail: m.dunstan@chem.usyd.edu.au; Southon, Peter D.; Kepert, Cameron J.

Through the construction of the Ba{sub 4}Nb{sub 2-x}Ta{sub x}O{sub 9} phase diagram, it was discovered that the unique high-temperature {gamma} phase is a thermodynamic intermediate between the low-temperature {alpha} phase (Sr{sub 4}Ru{sub 2}O{sub 9}-type) and a 6H-perovskite. Refined site occupancies for the {gamma} phase across the Ba{sub 4}Nb{sub 2-x}Ta{sub x}O{sub 9} solid-solution indicate that Nb preferentially occupies the tetrahedral sites over the octahedral sites in the structure. When annealed in a CO{sub 2}-rich atmosphere, all of the phases studied absorb large amounts of CO{sub 2} at high temperatures between {approx}700 and 1300 K. In situ controlled-atmosphere diffraction studies show thatmore » this behaviour is linked to the formation of BaCO{sub 3} on the surface of the material, accompanied by a Ba{sub 5}(Nb,Ta){sub 4}O{sub 15} impurity phase. In situ diffraction in humid atmospheres also confirms that these materials hydrate below {approx}1273K, and that this plays a critical role in the various reconstructive phase transitions as well as giving rise to proton conduction. - Graphical abstract: Thermodynamic phase diagram of Ba{sub 4}Nb{sub 2-x}Ta{sub x}O{sub 9}. Highlights: > {gamma}-Ba{sub 4}Nb{sub 2}O{sub 9} phase is a structural intermediate between the {alpha} and 6H-perovskite phases. > Ba{sub 4}Nb{sub 2}O{sub 9} and Ba{sub 4}Ta{sub 2}O{sub 9} decompose at high temperatures in the presence of CO{sub 2}. > These materials all absorb between 5% and 6% of CO{sub 2} by mass between {approx}800 and 1200 K.« less

Dissolution and Separation of Aluminum and Aluminosilicates

DOE PAGES

McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; ...

2015-12-19

The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as amore » function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.« less

COMMERCIALLY PURE TITANIUM-ARSENIC ALLOYS. CONSTITUTION AND ROOM- TEMPERATURE TENSILE PROPERTIES

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

Haynes, R.

1960-02-01

Titanium--arsenic alloys undergo a peritectoid reaction at approximately 900 deg C, in which beta solid solution reacts with a compound, shown to be Ti/sub 4/As, to form alpha phase containing approximately 0.05 wt.% (0.03 at.%) arsenic. Solubility of arsenic in beta phase increases slowly with temperature, reaching a maximum of approximately 1.6 wt.% (1 at.%) at the eutectic temperature, 1351 plus or minus 15 deg C. The eutectic composition is approximately 17.5 wt.% (12 at.%) arsenic. Up to 1 wt.% arsenic exerts only a slight strengthening effect on commercially pure titanium, accompanied by a small loss in ductility. Solution-treatment atmore » temperatures in the beta field increases the strength above the level obtained by annealing in the ( alpha + Ti/ sub 4/As) field and this strengthening can be further enhanced by ageing at 550 deg C. Optimum properties obtainable are similar to those of low-strength titunium alloys. (auth)« less

Solid/liquid phase diagram of the ammonium sulfate/glutaric acid/water system.

PubMed

Beyer, Keith D; Pearson, Christian S; Henningfield, Drew S

2013-05-02

We have studied the low temperature phase diagram and water activities of the ammonium sulfate/glutaric acid/water system using differential scanning calorimetry, infrared spectroscopy of thin films, and a new technique: differential scanning calorimetry-video microscopy. Using these techniques, we have determined that there is a temperature-dependent kinetic effect to the dissolution of glutaric acid in aqueous solution. We have mapped the solid/liquid ternary phase diagram, determined the water activities based on the freezing point depression, and determined the ice/glutaric acid phase boundary as well as the ternary eutectic composition and temperature. We have also modified our glutaric acid/water binary phase diagram previously published based on these new results. We compare our results for the ternary system to the predictions of the Extended AIM Aerosol Thermodynamics Model (E-AIM), and find good agreement for the ice melting points in the ice primary phase field of this system; however, significant differences were found with respect to phase boundaries, concentration and temperature of the ternary eutectic, and glutaric acid dissolution.

Dielectric and Energy Storage Properties of the Heterogeneous P(VDF-HFP)/PC Composite Films

NASA Astrophysics Data System (ADS)

Zhao, Xiaojia; Peng, Guirong; Zhan, Zaiji

2017-12-01

Polymer-based materials with a high discharge energy and low energy loss have attracted considerable attention for energy storage applications. A new class of polymer-based composite films composed of amorphous polycarbonate (PC) and poly(vinylidene fluoride-hexafluoropropylene) [P(VDF-HFP)] has been fabricated by simply solution blending followed by thermal treatment under vacuum. The results show that the diameter of the spherical phase for PC and the melting temperature of P(VDF-HFP) increase, and the crystallinity and crystallization temperature of P(VDF-HFP) decrease with increasing PC content. The phase transition from the polar β phase to weak polarity γ phase is induced by PC addition. Moreover, the Curie temperature of the P(VDF-HFP)/PC composite films shifts to a lower temperature. With the addition of PC, the permittivity, polarization and discharge energy of the P(VDF-HFP)/PC composite films slightly decrease. However, the energy loss is significantly reduced.

Phase Diagram of HgTe -ZnTe Pseudobinary and Density, Heat Capacity, and Enthalphy of Mixing of Hg(sub 1-x)Zn(sub x)Te Pseudobinary Melts

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Sha, Yi-Gao; Mazuruk, K.; Lehoczky, S. L.

1996-01-01

In this article, the solidus temperatures of the Hg(sub 1-x) Zn(sub x)Te pseudobinary phase diagram for several compositions in the low x region were measured by differential thermal analysis and the HgTe-ZnTe pseudobinary phase diagram was constructed. The densities of two HgZnTe melts, x = 0.10 and 0.16, were determined by an in situ pycnometric technique in a transparent furnace over, respectively, 110 and 50 C ranges of temperature. The thermodynamic properties of the melts, such as the heat capacity and enthalpy of mixing, were calculated for temperatures between the liquidus and 1500 C by assuming an associated solution model for the liquid phase.

Hydrothermal synthesis of barium strontium titanate and bismuth titanate materials

NASA Astrophysics Data System (ADS)

Xu, Huiwen

Hydrothermal processing facilitates the synthesis of crystalline ceramic materials of varying composition or complex crystal structure. The present work can be divided into two parts. First is to study the low temperature hydrothermal synthesis of bismuth titanate. Second is to study both thermodynamic and kinetic aspects of the hydrothermally synthesized barium strontium titanate. A chelating agent was used to form a Bi-Ti gel precursor. By hydrothermally treating the Bi-Ti gel, crystalline bismuth titanate has been synthesized at 160°C for the first time. Microstructural evolution during the low temperature synthesis of bismuth titanate can be divided into two stages, including condensation of Bi-Ti gel particles and crystallization of bismuth titanate. Crystallization of bismuth titanate occurred by an in situ transformation mechanism at an early stage followed by a dissolution-reprecipitation mechanism. Phase separation was observed in hydrothermally synthesized barium strontium titanate (BST). By hydrothermally treating BST powders between 250°C--300°C, an asymmetrical miscibility gap was found in the BaTiO3-SrTiO 3 system at low temperatures (T ≤ 320°C). A subregular solid solution model was applied to calculate the equilibrium compositions and the Gibbs free energy of formation of BST solid solution at low temperatures (T ≤ 320°C). The Gibbs free energy of formation of Sr-rich BST phase is larger than that of Ba-rich BST phase. Kinetic studies of single phase BST solid solution at 80°C show that, compared to the BaTiO3 or Ba-rich BST, SrTiO3 and Sr-rich BST powders form at lower reaction rates.

Controlling block copolymer phase behavior using ionic surfactant

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

Ray, D.; Aswal, V. K.

2016-05-23

The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO{sub 26}PO{sub 39}EO{sub 26})] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle–surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at highermore » temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.« less

Organic aerogel microspheres

DOEpatents

Mayer, S.T.; Kong, F.M.; Pekala, R.W.; Kaschmitter, J.L.

1999-06-01

Organic aerogel microspheres are disclosed which can be used in capacitors, batteries, thermal insulation, adsorption/filtration media, and chromatographic packings, having diameters ranging from about 1 micron to about 3 mm. The microspheres can be pyrolyzed to form carbon aerogel microspheres. This method involves stirring the aqueous organic phase in mineral oil at elevated temperature until the dispersed organic phase polymerizes and forms nonstick gel spheres. The size of the microspheres depends on the collision rate of the liquid droplets and the reaction rate of the monomers from which the aqueous solution is formed. The collision rate is governed by the volume ratio of the aqueous solution to the mineral oil and the shear rate, while the reaction rate is governed by the chemical formulation and the curing temperature.

Organic aerogel microspheres

DOEpatents

Mayer, Steven T.; Kong, Fung-Ming; Pekala, Richard W.; Kaschmitter, James L.

1999-01-01

Organic aerogel microspheres which can be used in capacitors, batteries, thermal insulation, adsorption/filtration media, and chromatographic packings, having diameters ranging from about 1 micron to about 3 mm. The microspheres can be pyrolyzed to form carbon aerogel microspheres. This method involves stirring the aqueous organic phase in mineral oil at elevated temperature until the dispersed organic phase polymerizes and forms nonsticky gel spheres. The size of the microspheres depends on the collision rate of the liquid droplets and the reaction rate of the monomers from which the aqueous solution is formed. The collision rate is governed by the volume ratio of the aqueous solution to the mineral oil and the shear rate, while the reaction rate is governed by the chemical formulation and the curing temperature.

Organic aerogel microspheres and fabrication method therefor

DOEpatents

Mayer, S.T.; Kong, F.M.; Pekala, R.W.; Kaschmitter, J.L.

1996-04-16

Organic aerogel microspheres which can be used in capacitors, batteries, thermal insulation, adsorption/filtration media, and chromatographic packings, having diameters ranging from about 1 micron to about 3 mm. The microspheres can be pyrolyzed to form carbon aerogel microspheres. This method involves stirring the aqueous organic phase in mineral oil at elevated temperature until the dispersed organic phase polymerizes and forms nonsticky gel spheres. The size of the microspheres depends on the collision rate of the liquid droplets and the reaction rate of the monomers from which the aqueous solution is formed. The collision rate is governed by the volume ratio of the aqueous solution to the mineral oil and the shear rate, while the reaction rate is governed by the chemical formulation and the curing temperature.

Organic aerogel microspheres and fabrication method therefor

DOEpatents

Mayer, Steven T.; Kong, Fung-Ming; Pekala, Richard W.; Kaschmitter, James L.

1996-01-01

Organic aerogel microspheres which can be used in capacitors, batteries, thermal insulation, adsorption/filtration media, and chromatographic packings, having diameters ranging from about 1 micron to about 3 mm. The microspheres can be pyrolyzed to form carbon aerogel microspheres. This method involves stirring the aqueous organic phase in mineral oil at elevated temperature until the dispersed organic phase polymerizes and forms nonsticky gel spheres. The size of the microspheres depends on the collision rate of the liquid droplets and the reaction rate of the monomers from which the aqueous solution is formed. The collision rate is governed by the volume ratio of the aqueous solution to the mineral oil and the shear rate, while the reaction rate is governed by the chemical formulation and the curing temperature.

Understanding the mechanism of LCST phase separation of mixed ionic liquids in water by MD simulations.

PubMed

Zhao, Yuling; Wang, Huiyong; Pei, Yuanchao; Liu, Zhiping; Wang, Jianji

2016-08-17

Recently, it has been found experimentally that two different amino acid ionic liquids (ILs) can be mixed to show unique lowest critical solution temperature (LCST) phase separation in water. However, little is known about the mechanism of phase separation in these IL/water mixtures at the molecular level. In this work, five kinds of amino acid ILs were chosen to study the mechanism of LCST-type phase separation by molecular dynamics (MD) simulations. Toward this end, a series of all-atom MD simulations were carried out on the ternary mixtures consisting of two different ILs and water at different temperatures. The various interaction energies and radial distribution functions (RDFs) were calculated and analyzed for these mixed systems. It was found that for amino acid ILs, the -NH2 or -COOH group of one anion could have a hydrogen bonding interaction with the -COO(-) group of another anion. With the increase of temperature, this kind of hydrogen bonding interaction between anions was strengthened and then the anion-H2O electrostatic interaction was weakened, which led to the LCST-type phase separation of the mixed ILs in water. In addition, a series of MD simulations for [P6668]1[Lys]n[Asp]1-n/H2O systems were also performed to study the effect of the mixing ratio of ILs on phase separation. It was also noted that the experimental critical composition corresponding to the lowest critical solution temperature was well predicted from the total electrostatic interaction energies as a function of mole fraction of [P6668][Lys] in these systems. The conclusions drawn from this study may provide new insight into the LCST-type phase behavior of ILs in water, and motivate further studies on practical applications.

Solvent effects and polymorphic transformation of organic nonlinear optical crystal L-pyroglutamic acid in solution growth processes . I. Solvent effects and growth morphology

NASA Astrophysics Data System (ADS)

Wang, W. S.; Aggarwal, M. D.; Choi, J.; Gebre, T.; Shields, Angela D.; Penn, Benjamin G.; Frazier, Donald O.

1999-03-01

Single crystals of a new promising nonlinear optical material for the tunable UV harmonic generation, L-pyroglutamic acid 60×20×20 mm 3 in size were obtained from aqueous solution by using the temperature-lowering method. Solubility of L-pyroglutamic acid in different solvents was measured. The single crystals showed different morphological characteristics and growth rate in different solvents with different crystallographic orientations. Methanol or ethanol solutions yielded needle-like crystals. In mixed solution such as methanol/H 2O or ethanol/ H 2O plate-like crystals with a thickness in the direction [0 1 0] were observed. The water as a good solvent, however, produced long prism-like crystals. The two polymorphs of L-pyroglutamic acid (α and β phases) were found for the first time. The growth shapes of α-phase is mainly a prism and β phases is a rhombic plate.The growth rate of α and β phases is mainly a function of the supersaturation of the L-pyroglutamic acid in solution.

Lyotropic Phase Behavior of Polybutadiene-Poly(ethylene oxide) Diblock Copolymers in Ionic Liquids

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

Simone, Peter M.; Lodge, Timothy P.

2008-08-26

The lyotropic phase behavior of three poly(1,2-butadiene-b-ethylene oxide) diblock copolymers (PB-PEO) with different monomer volume fractions has been studied in two different ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF{sub 6}]), across the complete concentration range. The ordered microstructures present in the solutions were characterized via small-angle X-ray scattering (SAXS). The phase diagrams for the PB-PEO/ionic liquid solutions include regions corresponding to the classical copolymer microstructures: body-centered-cubic lattices of spheres, hexagonally ordered cylinders, and lamellae. Additionally, the phase diagrams also include wide regions of coexisting microstructures and regions apparently corresponding to a disordered network microstructure. The phase behavior ofmore » the PB-PEO copolymers in both ionic liquids was comparable to their previously reported aqueous solution behavior. The temperature dependence of the phase diagrams was very modest, indicative of a highly segregated system. The level of solvent selectivity was also investigated via cryogenic transmission electron microscopy (cryo-TEM) on dilute solutions. On the basis of the morphology of the dilute solution copolymer aggregate structures in the ionic liquid solvents, and on the structural length scales of the concentrated solutions, it was concluded that for PB-PEO [BMI][PF{sub 6}] behaves as a more selective solvent than [EMI][TFSI].« less

A Laboratory Study on the Phase Transition for Polar Stratospheric Cloud Particles

NASA Technical Reports Server (NTRS)

Teets, Edward H., Jr.

1997-01-01

The nucleation and growth of different phases of simulated polar stratospheric cloud (PSC) particles were investigated in the laboratory. Solutions and mixtures of solutions at concentrations 1 to 5 m (molality) of ammonium sulfate, ammonium bisulfate, sodium chloride, sulfuric acid, and nitric acid were supercooled to prescribed temperatures below their equilibrium melting point. These solutions were contained in small diameter glass tubing of volumes ranging from 2.6 to 0.04 ml. Samples were nucleated by insertion of an ice crystal, or in some cases by a liquid nitrogen cooled wire. Crystallization velocities were determined by timing the crystal growth front passages along the glass tubing. Solution mixtures containing aircraft exhaust (soot) were also examined. Crystallization rates increased as deltaT2, where deltaT is the supercooling for weak solutions (2 m or less). The higher concentrated solutions (greater than 3 m) showed rates significantly less than deltaT2. This reduced rate suggested an onset of a glass phase. Results were applied to the nucleation of highly concentrated solutions at various stages of polar stratospheric cloud development within the polar stratosphere.

Phase and structural behavior of SmAlO{sub 3}–RAlO{sub 3} (R = Eu, Gd) systems

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

Ohon, N.; Vasylechko, L., E-mail: crystal-lov@polynet.lviv.ua; Prots, Yu.

2014-02-01

Highlights: • Continuous solid solutions exist in the SmAlO{sub 3}–RAlO{sub 3} (R = Eu, Gd) systems. • Lattice parameter crossover was found in solid solutions Sm{sub 1−x}R{sub x}AlO{sub 3} (R = Eu, Gd). • Thermally induced lattice crossovers occur in Sm{sub 0.9}R{sub 0.1}AlO{sub 3} at elevated temperatures. • First-order structural phase transition Pbnm↔R3{sup ¯}c was found in Sm{sub 1−x}R{sub x}AlO{sub 3} (R = Eu, Gd). • Phase diagram of the systems SmAlO{sub 3}–EuAlO{sub 3} and SmAlO{sub 3}–GdAlO{sub 3} has been constructed. - Abstract: Phase and structural behavior in the SmAlO{sub 3}–RAlO{sub 3} (R = Eu, Gd) systems has been studiedmore » in a whole concentration range by means of laboratory X-ray diffraction, in situ synchrotron powder diffraction and differential thermal analysis techniques. Continuous solid solutions with orthorhombic perovskite structure have been found in both systems. Peculiarity of the solid solutions of Sm{sub 1−x}Eu{sub x}AlO{sub 3} and Sm{sub 1−x}Gd{sub x}AlO{sub 3} is the existence of two lattice parameter crossovers in each system occurred at x{sub Eu} = 0.07 and 0.62 and at x{sub Gd} = 0.04 and 0.33, respectively. The temperature induced lattice crossovers in the Sm{sub 0.9}Eu{sub 0.1}AlO{sub 3} and Sm{sub 0.9}Gd{sub 0.1}AlO{sub 3} samples have been found at 387 and 922 K and at 501 and 894 K. First-order reversible structural phase transformations Pbnm↔R3{sup ¯}c have been detected in both systems at the elevated temperatures. The temperatures of these transitions increase linearly with the decreasing of the samarium content. Phase diagrams of the pseudo-binary systems SmAlO{sub 3}–EuAlO{sub 3} and SmAlO{sub 3}–GdAlO{sub 3} have been constructed.« less

Gradient Augmented Level Set Method for Two Phase Flow Simulations with Phase Change

NASA Astrophysics Data System (ADS)

Anumolu, C. R. Lakshman; Trujillo, Mario F.

2016-11-01

A sharp interface capturing approach is presented for two-phase flow simulations with phase change. The Gradient Augmented Levelset method is coupled with the two-phase momentum and energy equations to advect the liquid-gas interface and predict heat transfer with phase change. The Ghost Fluid Method (GFM) is adopted for velocity to discretize the advection and diffusion terms in the interfacial region. Furthermore, the GFM is employed to treat the discontinuity in the stress tensor, velocity, and temperature gradient yielding an accurate treatment in handling jump conditions. Thermal convection and diffusion terms are approximated by explicitly identifying the interface location, resulting in a sharp treatment for the energy solution. This sharp treatment is extended to estimate the interfacial mass transfer rate. At the computational cell, a d-cubic Hermite interpolating polynomial is employed to describe the interface location, which is locally fourth-order accurate. This extent of subgrid level description provides an accurate methodology for treating various interfacial processes with a high degree of sharpness. The ability to predict the interface and temperature evolutions accurately is illustrated by comparing numerical results with existing 1D to 3D analytical solutions.

Thermodynamics of concentrated solid solution alloys

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

Gao, Michael C.; Zhang, C.; Gao, P.

This study reviews the three main approaches for predicting the formation of concentrated solid solution alloys (CSSA) and for modeling their thermodynamic properties, in particular, utilizing the methodologies of empirical thermo-physical parameters, CALPHAD method, and first-principles calculations combined with hybrid Monte Carlo/Molecular Dynamics (MC/MD) simulations. In order to speed up CSSA development, a variety of empirical parameters based on Hume-Rothery rules have been developed. Herein, these parameters have been systematically and critically evaluated for their efficiency in predicting solid solution formation. The phase stability of representative CSSA systems is then illustrated from the perspectives of phase diagrams and nucleation drivingmore » force plots of the σ phase using CALPHAD method. The temperature-dependent total entropies of the FCC, BCC, HCP, and σ phases in equimolar compositions of various systems are presented next, followed by the thermodynamic properties of mixing of the BCC phase in Al-containing and Ti-containing refractory metal systems. First-principles calculations on model FCC, BCC and HCP CSSA reveal the presence of both positive and negative vibrational entropies of mixing, while the calculated electronic entropies of mixing are negligible. Temperature dependent configurational entropy is determined from the atomic structures obtained from MC/MD simulations. Current status and challenges in using these methodologies as they pertain to thermodynamic property analysis and CSSA design are discussed.« less

Thermodynamics of concentrated solid solution alloys

DOE PAGES

Gao, Michael C.; Zhang, C.; Gao, P.; ...

2017-10-12

This study reviews the three main approaches for predicting the formation of concentrated solid solution alloys (CSSA) and for modeling their thermodynamic properties, in particular, utilizing the methodologies of empirical thermo-physical parameters, CALPHAD method, and first-principles calculations combined with hybrid Monte Carlo/Molecular Dynamics (MC/MD) simulations. In order to speed up CSSA development, a variety of empirical parameters based on Hume-Rothery rules have been developed. Herein, these parameters have been systematically and critically evaluated for their efficiency in predicting solid solution formation. The phase stability of representative CSSA systems is then illustrated from the perspectives of phase diagrams and nucleation drivingmore » force plots of the σ phase using CALPHAD method. The temperature-dependent total entropies of the FCC, BCC, HCP, and σ phases in equimolar compositions of various systems are presented next, followed by the thermodynamic properties of mixing of the BCC phase in Al-containing and Ti-containing refractory metal systems. First-principles calculations on model FCC, BCC and HCP CSSA reveal the presence of both positive and negative vibrational entropies of mixing, while the calculated electronic entropies of mixing are negligible. Temperature dependent configurational entropy is determined from the atomic structures obtained from MC/MD simulations. Current status and challenges in using these methodologies as they pertain to thermodynamic property analysis and CSSA design are discussed.« less

Critical Intermediate Structure That Directs the Crystalline Texture and Surface Morphology of Organo-Lead Trihalide Perovskite.

PubMed

Chia, Hao-Chung; Sheu, Hwo-Shuenn; Hsiao, Yu-Yun; Li, Shao-Sian; Lan, Yi-Kang; Lin, Chung-Yao; Chang, Je-Wei; Kuo, Yen-Chien; Chen, Chia-Hao; Weng, Shih-Chang; Su, Chun-Jen; Su, An-Chung; Chen, Chun-Wei; Jeng, U-Ser

2017-10-25

We have identified an often observed yet unresolved intermediate structure in a popular processing with dimethylformamide solutions of lead chloride and methylammonium iodide for perovskite solar cells. With subsecond time-resolved grazing-incidence X-ray scattering and X-ray photoemission spectroscopy, supplemental with ab initio calculation, the resolved intermediate structure (CH 3 NH 3 ) 2 PbI 2 Cl 2 ·CH 3 NH 3 I features two-dimensional (2D) perovskite bilayers of zigzagged lead-halide octahedra and sandwiched CH 3 NH 3 I layers. Such intermediate structure reveals a hidden correlation between the intermediate phase and the composition of the processing solution. Most importantly, the 2D perovskite lattice of the intermediate phase is largely crystallographically aligned with the [110] planes of the three-dimensional perovskite cubic phase; consequently, with sublimation of Cl ions from the organo-lead octahedral terminal corners in prolonged annealing, the zigzagged octahedral layers of the intermediate phase can merge with the intercalated methylammonium iodide layers for templated growth of perovskite crystals. Regulated by annealing temperature and the activation energies of the intermediate and perovskite, deduced from analysis of temperature-dependent structural kinetics, the intermediate phase is found to selectively mature first and then melt along the layering direction for epitaxial conversion into perovskite crystals. The unveiled epitaxial conversion under growth kinetics controls might be general for solution-processed and intermediate-templated perovskite formation.

Superalloy for high-temperature hydrogen environmental applications

NASA Technical Reports Server (NTRS)

McKannan, Eugene C. (Inventor); McPherson, William B. (Inventor); Ahmed, Shaffiq (Inventor); Chandler, Shirley S. (Inventor)

1991-01-01

A nickel-based superalloy is provided which is resistant to deterioration in hydrogen at high operating temperatures and pressures, and which thus can be used in hydrogen-fueled spacecraft such as the Space Shuttle. The superalloy is characterized by a two-phase microstructure and consists of a gamma-prime precipitated phase in a gamma matrix. The gamma matrix phase is a primary solid solution and the gamma precipitated phase will be an intermetallic compound of the type A.sub.3 B, such as nickel aluminide or titanide. Both phases are coherent, ordered, and compatible, and thus will retain most of their strength at elevated temperatures. The alloy consists essentially of (by weight): Ni 50-60%, Cr 10-20%, Al 2-6%, Co 2-5%, Ti 3-8%, W 5-12%, Mo 5-10%, Nb 1-3%, wherein the ratio W/MO is approximately equal to 1, and Ti/Al ranges from about 1 to about 2.

Thermoelectric properties of a doped LaNiO3 perovskite system prepared using a spark-plasma sintering process

NASA Astrophysics Data System (ADS)

Tak, Jang-Yeul; Choi, Soon-Mok; Seo, Won-Seon; Cho, Hyung Koun

2013-07-01

Both perovskites LaNiO3 and LaCuO3 have a limitation associated with phase transitions for high-temperature thermoelectric applications. The optimized conditions were investigated to obtain the LaNi1- x Cu x O3- δ perovskite single phase showing a Cu-doping effect into Ni sites against unintended deoxidized phases. Three advantages of synergetic effects due to the simultaneous presence of nickel and copper were investigated: a low melting temperature of CuO as compared to that of NiO, the absence of intermediated deoxidized phases in the LaCuO3 system, and the Cu doping effect, which suppresses the formation of intermediate secondary phases. A solid solution was also fabricated using a spark-plasma sintering (SPS) process for the purpose of sintering LaNi1- x Cu x O3- δ compositions at a low sintering temperature.

Influences on Distribution of Solute Atoms in Cu-8Fe Alloy Solidification Process Under Rotating Magnetic Field

NASA Astrophysics Data System (ADS)

Zou, Jin; Zhai, Qi-Jie; Liu, Fang-Yu; Liu, Ke-Ming; Lu, De-Ping

2018-05-01

A rotating magnetic field (RMF) was applied in the solidification process of Cu-8Fe alloy. Focus on the mechanism of RMF on the solid solution Fe(Cu) atoms in Cu-8Fe alloy, the influences of RMF on solidification structure, solute distribution, and material properties were discussed. Results show that the solidification behavior of Cu-Fe alloy have influenced through the change of temperature and solute fields in the presence of an applied RMF. The Fe dendrites were refined and transformed to rosettes or spherical grains under forced convection. The solute distribution in Cu-rich phase and Fe-rich phase were changed because of the variation of the supercooling degree and the solidification rate. Further, the variation in solute distribution was impacted the strengthening mechanism and conductive mechanism of the material.

Heat capacities and entropies of sillimanite, fibrolite, andalusite, kyanite, and quartz and the Al2SiO5 phase diagram

USGS Publications Warehouse

Hemingway, B.S.; Robie, R.A.; Evans, H.T.; Kerrick, Derrill M.

1991-01-01

Low-temperature heat capacities for sillimanite, fibrolite, and both fine-grained and coarse-grained quartz have been measured. Superambient heat capacities have been measured for four sillimanite, two andalusite, one kyanite, and two fibrolite samples. Equations are recommended for the temperature dependence of the heat capacities of kyanite, andalusite, sillimanite, and fibrolite. The heat capacity functions have been combined with thermal expansion (fibrolite and sillimanite reported here), enthalpy of solution, and phase equilibrium data in order to construct a phase diagram for the Al2SiO5 polymorphs. -from Authors

Oxidation of U-20 at% Zr alloy in air at 423 1063 K

NASA Astrophysics Data System (ADS)

Matsui, Tsuneo; Yamada, Takanobu; Ikai, Yasushi; Naito, Keiji

1993-01-01

The oxidation behavior of U 0.80Zr 0.20 alloy (two-phase mixture of U and UZr 2 below 878 K and single solid solution above 1008 K) was studied by thermogravimetry in the temperature range from 423 to 1063 K in air. During oxidation in the low temperature region (423-503 K), the sample kept its initial shape (a rectangular rod) and the surface of the sample was covered by a black thin adherent UO2 + x oxide layer. On the other hand, by oxidation in the middle temperature region, the sample broke to several pieces of thin plates and blocks, and fine powder at 643-723 K and entirely to fine powder at 775-878 K, all of which were analyzed to be a mixture of U 3O 8 and ZrO 2. By oxidation in the high temperature region (1008-1063 K) the sample broke to very fine powder, which consisted of U 3O 8 and ZrO 2. Based on the sample shape, the oxide phase identified after oxidation and the slope value of the bilogarithmic plots of the weight gain against time, the oxidation kinetics was analyzed with a paralinear equation in the low temperature region below 503 K and a linear equation in the middle and high temperature regions above 643 K. Oxidation rates of U 0.80Zr 0.20 (two-phase mixture) in the low and middle temperature regions were smaller than those of uranium metal. A discontinuity in the plot of the linear oxidation rate constant versus reciprocal temperature was found to be present between 723 and 838 K, similarly to the case of uranium metal previously reported. The linear rate constants of single-phase solid solution in the high temperature region above 1008 K seemed to be a little smaller than those estimated by the extrapolation of the values in the middle temperature region.

The Investigation of Perchlorate/Iron Phase Mixtures as A Possible Source of Oxygen Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Sutter, B.; Heil, E.; Morris, R. V.; Archer, P. D.; Ming, D. W.; Niles, P. B.; Eigenbrode, J. L.; Franz, H.; Freissinet C.; Glavin, D. P.;

Zero field splitting fluctuations induced phase relaxation of Gd3+ in frozen solutions at cryogenic temperatures

NASA Astrophysics Data System (ADS)

Raitsimring, A.; Dalaloyan, A.; Collauto, A.; Feintuch, A.; Meade, T.; Goldfarb, D.

2014-11-01

Distance measurements using double electron-electron resonance (DEER) and Gd3+ chelates for spin labels (GdSL) have been shown to be an attractive alternative to nitroxide spin labels at W-band (95 GHz). The maximal distance that can be accessed by DEER measurements and the sensitivity of such measurements strongly depends on the phase relaxation of Gd3+ chelates in frozen, glassy solutions. In this work, we explore the phase relaxation of Gd3+-DOTA as a representative of GdSL in temperature and concentration ranges typically used for W-band DEER measurements. We observed that in addition to the usual mechanisms of phase relaxation known for nitroxide based spin labels, GdSL are subjected to an additional phase relaxation mechanism that features an increase in the relaxation rate from the center to the periphery of the EPR spectrum. Since the EPR spectrum of GdSL is the sum of subspectra of the individual EPR transitions, we attribute this field dependence to transition dependent phase relaxation. Using simulations of the EPR spectra and its decomposition into the individual transition subspectra, we isolated the phase relaxation of each transition and found that its rate increases with |ms|. We suggest that this mechanism is due to transient zero field splitting (tZFS), where its magnitude and correlation time are scaled down and distributed as compared with similar situations in liquids. This tZFS induced phase relaxation mechanism becomes dominant (or at least significant) when all other well-known phase relaxation mechanisms, such as spectral diffusion caused by nuclear spin diffusion, instantaneous and electron spin spectral diffusion, are significantly suppressed by matrix deuteration and low concentration, and when the temperature is sufficiently low to disable spin lattice interaction as a source of phase relaxation.

The activity-composition relationship of oxygen and hydrogen isotopes in aqueous salt solutions: III. Vapor-liquid water equilibration of NaCl solutions to 350°C

NASA Astrophysics Data System (ADS)

Horita, Juske; Cole, David R.; Wesolowski, David J.

1995-03-01

The effect of dissolved NaCl on equilibrium oxygen and hydrogen isotope fractionation factors between liquid water and water vapor was precisely determined in the temperature range from 130-350°C, using two different types of apparatus with static or dynamic sampling techniques of the vapor phase. The magnitude of the oxygen and hydrogen isotope effects of NaCl is proportional to the molality of liquid NaCl solutions at a given temperature. Dissolved NaCl lowers appreciably the hydrogen isotope fractionation factor between liquid water and water vapor over the entire temperature range. NaCl has little effect on the oxygen isotope fractionation factor at temperatures below about 200°C, with the magnitude of the salt effect gradually increasing from 200-350°C. Our results are at notable variance with those of Truesdell (1974) and Kazahaya (1986), who reported large oxygen and hydrogen isotope effects of NaCl with very complex dependencies on temperature and NaCl molality. Our high-temperature results have been regressed along with our previous results between 50 and 100°C (Horita et al., 1993a) and the low-temperature literature data to simple equations which are valid for NaCl solutions from 0 to at least 5 molal NaCl in the temperature range from 10-350°C. Our preliminary results of oxygen isotope fractionation in the system CaCO3-water ± NaCl at 300°C and 1 kbar are consistent with those obtained from the liquid-vapor equilibration experiments, suggesting that the isotope salt effects are common to systems involving brines and any other coexisting phases or species (gases, minerals, dissolved species, etc.). The observed NaCl isotope effects at elevated temperatures should be taken into account in the interpretation of isotopic data of brine-dominated natural systems.

Phase study of titanium dioxide nanoparticle prepared via sol-gel process

NASA Astrophysics Data System (ADS)

Oladeji Araoyinbo, Alaba; Bakri Abdullah, Mohd Mustafa Al; Salleh, Mohd Arif Anuar Mohd; Aziz, Nurul Nadia Abdul; Iskandar Azmi, Azwan

2018-03-01

In this study, titanium dioxide nanoparticles have been prepared via sol-gel process using titanium tetraisopropoxide as a precursor with hydrochloric acid as a catalyst, and ethanol with deionized water as solvents. The value of pH used is set to 3, 7 and 8. The sols obtained were dried at 100 °C for 1 hr and calcined at 350, 550, and 750 °C for 3 hrs to observe the phase transformation of titanium dioxide nanoparticle. The samples were characterized by x-ray diffraction and field emission scanning electron microscope. The morphology analysis is obtained from field emission scanning electron microscope. The phase transformation was investigated by x-ray diffraction. It was found that the pH of the solution affect the agglomeration of titanium dioxide particle. The x-ray diffraction pattern of titanium dioxide shows the anatase phase most abundant at temperature of 350 °C. At temperature of 550 °C the anatase and rutile phase were present. At temperature of 750 °C the rutile phase was the most abundant for pH 3, 7 and 8. It was confirmed that at higher temperature the rutile phase which is the stable phase are mostly present.

Generalized thermoelastic problem of an infinite body with a spherical cavity under dual-phase-lags

NASA Astrophysics Data System (ADS)

Karmakar, R.; Sur, A.; Kanoria, M.

2016-07-01

The aim of the present contribution is the determination of the thermoelastic temperatures, stress, displacement, and strain in an infinite isotropic elastic body with a spherical cavity in the context of the mechanism of the two-temperature generalized thermoelasticity theory (2TT). The two-temperature Lord-Shulman (2TLS) model and two-temperature dual-phase-lag (2TDP) model of thermoelasticity are combined into a unified formulation with unified parameters. The medium is assumed to be initially quiescent. The basic equations are written in the form of a vector matrix differential equation in the Laplace transform domain, which is then solved by the state-space approach. The expressions for the conductive temperature and elongation are obtained at small times. The numerical inversion of the transformed solutions is carried out by using the Fourier-series expansion technique. A comparative study is performed for the thermoelastic stresses, conductive temperature, thermodynamic temperature, displacement, and elongation computed by using the Lord-Shulman and dual-phase-lag models.

Accelerated exploration of multi-principal element alloys with solid solution phases

PubMed Central

Senkov, O.N.; Miller, J.D.; Miracle, D.B.; Woodward, C.

2015-01-01

Recent multi-principal element, high entropy alloy (HEA) development strategies vastly expand the number of candidate alloy systems, but also pose a new challenge—how to rapidly screen thousands of candidate alloy systems for targeted properties. Here we develop a new approach to rapidly assess structural metals by combining calculated phase diagrams with simple rules based on the phases present, their transformation temperatures and useful microstructures. We evaluate over 130,000 alloy systems, identifying promising compositions for more time-intensive experimental studies. We find the surprising result that solid solution alloys become less likely as the number of alloy elements increases. This contradicts the major premise of HEAs—that increased configurational entropy increases the stability of disordered solid solution phases. As the number of elements increases, the configurational entropy rises slowly while the probability of at least one pair of elements favouring formation of intermetallic compounds increases more rapidly, explaining this apparent contradiction. PMID:25739749

Epitaxial layers of 2122 BCSCO superconductor thin films having single crystalline structure

NASA Technical Reports Server (NTRS)

Pandey, Raghvendra K. (Inventor); Raina, Kanwal K. (Inventor); Solayappan, Narayanan (Inventor)

1995-01-01

A substantially single phase, single crystalline, highly epitaxial film of Bi.sub.2 CaSr.sub.2 Cu.sub.2 O.sub.8 superconductor which has a T.sub.c (zero resistance) of 83K is provided on a lattice-matched substrate with no intergrowth. This film is produced by a Liquid Phase Epitaxy method which includes the steps of forming a dilute supercooled molten solution of a single phase superconducting mixture of oxides of Bi, Ca, Sr, and Cu having an atomic ratio of about 2:1:2:2 in a nonreactive flux such as KCl, introducing the substrate, e.g., NdGaO.sub.3, into the molten solution at 850.degree. C., cooling the solution from 850.degree. C. to 830.degree. C. to grow the film and rapidly cooling the substrate to room temperature to maintain the desired single phase, single crystalline film structure.

New anatase-type Til-2xNbxAlxO2 solid solution nanoparticles: direct formation, phase stability, and photocatalytic performance.

PubMed

Hirano, Masanori; Ito, Takaharu

2006-12-01

New anatase-type titania solid solutions co-doped with niobium and aluminum (Til-2xNbxAIlxO2 (X = 0 -0.20)) were synthesized as nanoparticles from precursor solutions of TiOSO4, NbCl5, and Al(NO3)3 under mild hydrothermal conditions at 180 degrees C for 5 h using the hydrolysis of urea. The lattice parameters a0 and c0 of anatase slightly and gradually increased, when the content of niobium and aluminum increased from X = 0 to 0.20. The crystallite size of anatase increased from 12 to 28 nm with increasing the value of X from 0 to 0.20. 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 adsorptivity of TiO2 was improved by the formation of anatase-type Til-2xNbxAlxO2 solid solutions. The photocatalytic activity of anatase-type Til-2xNbxAlxO2 solid solutions was superior to that of commercially available anatase-type pure TiO2 (ST-01) and anatase-type pure TiO2 hydrothermally prepared. The new anatase phase of Til-2xNbxAlxO2 (X = 0-0.20) solid solutions existed stably up to 850 0C during heat treatment in air. In comparison with hydrothermal pure TiO2, the starting temperature of anatase-to-rutile phase transformation was delayed by the formation of Ti1-2xNbxAlxO, (X = 0-0.20) solid solutions, although its completing temperature was accelerated.

Development and Characterization of Improved NiTiPd High-Temperature Shape-Memory Alloys by Solid-Solution Strengthening and Thermomechanical Processing

NASA Technical Reports Server (NTRS)

Bigelow, Glen; Noebe, Ronald; Padula, Santo, II; Garg, Anita; Olson, David

2006-01-01

The need for compact, solid-state actuation systems for use in the aerospace, automotive, and other transportation industries is currently motivating research in high-temperature shape-memory alloys (HTSMA) with transformation temperatures greater than 100 C. One of the basic high-temperature alloys investigated to fill this need is Ni(19.5)Ti(50.5)Pd30. Initial testing has indicated that this alloy, while having acceptable work characteristics, suffers from significant permanent deformation (or ratcheting) during thermal cycling under load. In an effort to overcome this deficiency, various solid-solution alloying and thermomechanical processing schemes were investigated. Solid-solution strengthening was achieved by substituting 5at% gold or platinum for palladium in Ni(19.5)Ti(50.5)Pd30, the so-called baseline alloy, to strengthen the martensite and austenite phases against slip processes and improve thermomechanical behavior. Tensile properties, work behavior, and dimensional stability during repeated thermal cycling under load for the ternary and quaternary alloys were compared. The relative difference in yield strength between the martensite and austenite phases and the dimensional stability of the alloy were improved by the quaternary additions, while work output was only minimally impacted. The three alloys were also thermomechanically processed by cycling repeatedly through the transformation range under a constant stress. This so-called training process dramatically improved the dimensional stability in these samples and also recovered the slight decrease in work output caused by quaternary alloying. An added benefit of the solid-solution strengthening was maintenance of enhanced dimensional stability of the trained material to higher temperatures compared to the baseline alloy, providing a greater measure of over-temperature capability.

Sequence Directionality Dramatically Affects LCST Behavior of Elastin-Like Polypeptides.

PubMed

Li, Nan K; Roberts, Stefan; Quiroz, Felipe Garcia; Chilkoti, Ashutosh; Yingling, Yaroslava G

2018-04-30

Elastin-like polypeptides (ELP) exhibit an inverse temperature transition or lower critical solution temperature (LCST) transition phase behavior in aqueous solutions. In this paper, the thermal responsive properties of the canonical ELP, poly(VPGVG), and its reverse sequence poly(VGPVG) were investigated by turbidity measurements of the cloud point behavior, circular dichroism (CD) measurements, and all-atom molecular dynamics (MD) simulations to gain a molecular understanding of mechanism that controls hysteretic phase behavior. It was shown experimentally that both poly(VPGVG) and poly(VGPVG) undergo a transition from soluble to insoluble in aqueous solution upon heating above the transition temperature ( T t ). However, poly(VPGVG) resolubilizes upon cooling below its T t , whereas the reverse sequence, poly(VGPVG), remains aggregated despite significant undercooling below the T t . The results from MD simulations indicated that a change in sequence order results in significant differences in the dynamics of the specific residues, especially valines, which lead to extensive changes in the conformations of VPGVG and VGPVG pentamers and, consequently, dissimilar propensities for secondary structure formation and overall structure of polypeptides. These changes affected the relative hydrophilicities of polypeptides above T t , where poly(VGPVG) is more hydrophilic than poly(VPGVG) with more extended conformation and larger surface area, which led to formation of strong interchain hydrogen bonds responsible for stabilization of the aggregated phase and the observed thermal hysteresis for poly(VGPVG).

Fluorescence probe of polypeptide conformational dynamics in gas phase and in solution

NASA Astrophysics Data System (ADS)

Iavarone, Anthony T.; Meinen, Jan; Schulze, Susanne; Parks, Joel H.

2006-07-01

Fluorescence measurements of polypeptides derivatized with the fluorescent dye BODIPY TMR have been used to probe the polypeptide conformational dynamics as a function of temperature and charge state. Measurements of (BODIPY TMR)-[Pro]n-Arg-Trp and (BODIPY TMR)-[Gly-Ser]m-Arg-Trp have been performed for charge states 1+ and 2+ of n = 4 and 10 and m = 2 and 5. The 2+ charge states of both of these polypeptides exhibit similar temperature dependences for equal chain lengths (n = 4, m = 2 and n = 10, m = 5) and suggest conformations dominated by Coulomb repulsion. In the absence of such Coulomb repulsion, the 1+ charge state conformations appear to be characterized by the flexibility of the polypeptide chain for which [Gly-Ser]m > [Pro]n. Comparisons of these gas phase polypeptide measurements with corresponding measurements in solution provide a direct measure of the effects of solvent on the conformational dynamics. The change in fluorescence as a function of temperature in the gas phase is two orders of magnitude greater than that in solution, a dramatic result we attribute to the restrictions on intramolecular dynamics imposed by diffusion-limited kinetics and the lack of shielding by solvent. Measurements were also made of unsolvated Pron peptides without the tryptophan (Trp) residue to isolate the interaction of the fluorescent dye with charges.

DISTRIBUTION OF URANIUM, ZIRCONIUM, NIOBIUM, RUTHENIUM AND CERIUM BETWEEN NITRIC ACID SOLUTIONS AND 10% TLA-5% OCTYL ALCOHOL/SHELL SOL-T

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

Lopez-Menchero, E.; Centeno, J.; Magni, G.

1962-03-01

The extraction of traces of Ru, Zr, Nb, Ce, and U at low concentrations (5 mg/l in aqueous solution) from nitric acid solutions using trilauryl amine (TLA) has been experimentally studied. TLA will eventually be used for final purification of plutonium. Room-temperature data on plutonium contaminant distribution between aqueous solutions of varying nitric acid concentrations and a Shellsol-T solution containing l0% TlA and 5% octyl alcohol are presented. Within the temperature and nitric acid concentration ranges tested, the extractability of uranium increased with increased acid concentrations, although acid concentration in the aqueous phase had no effect on the decontamination factorsmore » for the main fission products. (H.G.G.)« less

A novel approach to model the transient behavior of solid-oxide fuel cell stacks

NASA Astrophysics Data System (ADS)

Menon, Vikram; Janardhanan, Vinod M.; Tischer, Steffen; Deutschmann, Olaf

2012-09-01

This paper presents a novel approach to model the transient behavior of solid-oxide fuel cell (SOFC) stacks in two and three dimensions. A hierarchical model is developed by decoupling the temperature of the solid phase from the fluid phase. The solution of the temperature field is considered as an elliptic problem, while each channel within the stack is modeled as a marching problem. This paper presents the numerical model and cluster algorithm for coupling between the solid phase and fluid phase. For demonstration purposes, results are presented for a stack operated on pre-reformed hydrocarbon fuel. Transient response to load changes is studied by introducing step changes in cell potential and current. Furthermore, the effect of boundary conditions and stack materials on response time and internal temperature distribution is investigated.

Influence of Step Annealing Temperature on the Microstructure and Pitting Corrosion Resistance of SDSS UNS S32760 Welds

NASA Astrophysics Data System (ADS)

Yousefieh, M.; Shamanian, M.; Saatchi, A.

2011-12-01

In the present work, the influence of step annealing heat treatment on the microstructure and pitting corrosion resistance of super duplex stainless steel UNS S32760 welds have been investigated. The pitting corrosion resistance in chloride solution was evaluated by potentiostatic measurements. The results showed that step annealing treatments in the temperature ranging from 550 to 1000 °C resulted in a precipitation of sigma phase and Cr2N along the ferrite/austenite and ferrite/ferrite boundaries. At this temperature range, the metastable pits mainly nucleated around the precipitates formed in the grain boundary and ferrite phase. Above 1050 °C, the microstructure contains only austenite and ferrite phases. At this condition, the critical pitting temperature of samples successfully arrived to the highest value obtained in this study.

Identification and characterization of the intermediate phase in hybrid organic-inorganic MAPbI3 perovskite.

PubMed

Guo, Xin; McCleese, Christopher; Kolodziej, Charles; Samia, Anna C S; Zhao, Yixin; Burda, Clemens

2016-03-07

Perovskite films were prepared using single step solution deposition at different annealing temperatures and annealing times. The crystal structure, phases and grain size were investigated with XRD, XPS and SEM/EDX. The prepared films show a typical orientation of tetragonal perovskite phase and a gradual transition at room temperature from the yellow intermediate phase to the black perovskite phase. Films with high purity were obtained by sintering at 100 °C. In addition, the chemical composition and crystal structure of intermediate phase were investigated in detail. FTIR, UV-vis and NMR spectra revealed the occurance of DMF complexes. Interestingly, the intermediate phase could be transformed to the black perovskite phase upon X-ray irradiation. In addition, the recovery of the aged perovskite films from a yellow intermediate phase back to the black perovskite was shown to be viable via heating and X-ray irradiation.

An Investigation into the Polymorphism and Crystallization of Levetiracetam and the Stability of its Solid Form.

PubMed

Xu, Kailin; Xiong, Xinnuo; Guo, Liuqi; Wang, Lili; Li, Shanshan; Tang, Peixiao; Yan, Jin; Wu, Di; Li, Hui

2015-12-01

Levetiracetam (LEV) crystals were prepared using different solvents at different temperatures. The LEV crystals were systematically characterized by X-ray powder diffraction (XRPD) and morphological analysis. The results indicated that many kinds of crystal habits exist in a solid form of LEV. To investigate the effects of LEV concentration, crystallization temperature, and crystallization type on crystallization and solid phase transformation of LEV, multiple methods were performed for LEV aqueous solution to determine if a new solid form exists in solid-state LEV. However, XRPD data demonstrate that the LEV solid forms possess same spatial arrangements that are similar to the original solid form. This result indicates that the LEV concentration, crystallization temperature, and crystallization type in aqueous solution have no influence on the crystallization and solid phase transformation of LEV. Moreover, crystallization by sublimation, melt cooling, and quench cooling, as well as mechanical effect, did not result in the formation of new LEV solid state. During melt cooling, the transformation of solid form LEV is a direct process from melting amorphous phase to the original LEV crystal phase, and the conversion rate is very quick. In addition, stability investigation manifested that LEV solid state is very stable under various conditions. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

In Situ Observations of Thermoreversible Gelation and Phase Separation of Agarose and Methylcellulose Solutions under High Pressure.

PubMed

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.

Natural occurrence and significance of fluids indicating high pressure and temperature

USGS Publications Warehouse

Roedder, E.

1981-01-01

Most natural minerals have formed from a fluid phase such as a silicate melt or a saline aqueous solution. Fluid inclusions are tiny volumes of such fluids that were trapped within the growing crystals. These inclusions can provide valuable but sometimes ambiguous data on the temperature, pressure, and composition of these fluids, many of which are not available from any other source. They also provide "visual autoclaves" in which it is possible to watch, through the microscope, the actual phase changes take place as the inclusions are heated. This paper reviews the methods of study and the results obtained, mainly on inclusions formed from highly concentrated solutions, at temperatures ???500??C. Many such fluids have formed as a result of immiscibility with silicate melt in igneous or high-temperature metamorphic rocks. These include fluids consisting of CO2, H2O, or hydrosaline melts that were <50% H2O. From the fluid inclusion evidence it is clear that a boiling, very hot, very saline fluid was present during the formation of most of the porphyry copper deposits in the world. Similarly, from the inclusion evidence it is clear that early (common) pegmatites formed from essentially silicate melts and that the late, rare-element-bearing and chamber-type pegmatites formed from a hydrosaline melt or a more dilute water solution. The evidence on whether this change in composition from early to late solutions was generally continuous or involved immiscibility is not as clear. ?? 1981.

Retention behavior of neutral solutes in pressurized flow-driven capillary electrochromatography using an ODS column.

PubMed

Nakagawa, Hiroyuki; Kitagawa, Shinya; Araki, Shuki; Ohtani, Hajime

2006-02-01

Several alkyl benzenes are separated by pressurized flow-driven capillary electrochromatography using a temperature-controlled capillary column packed with octadecyl siloxane-modified silica gel, and the effect of applied voltage on the retention is investigated. The van't Hoff plot shows good linearity at the column temperature between 305 and 330 K under applications from -6 to +6 kV. The applied voltage causes a relatively large variation in the enthalpy and the entropy of transfer of the solute from the mobile phase to the stationary phase (> 20%). However, the direction of variation in the enthalpy is almost opposite to that in the entropy, both of which might compensate each other. Therefore, the retention factor is not significantly varied (< 4%) by the application of voltage.

Mott-to-Goodenough insulator-insulator transition in LiVO2

NASA Astrophysics Data System (ADS)

Subedi, Alaska

2017-06-01

I critically examine Goodenough's explanation for the experimentally observed phase transition in LiVO2 using microscopic calculations based on density functional and dynamical mean field theories. The high-temperature rhombohedral phase exhibits both magnetic and dynamical instabilities. Allowing a magnetic solution for the rhombohedral structure does not open an insulating gap, and an explicit treatment of the on-site Coulomb U interaction is needed to stabilize an insulating rhombohedral phase. The non-spin-polarized phonon dispersions of the rhombohedral phase show two unstable phonon modes at the wave vector (1/3 ,-1/3 ,0 ) that corresponds to the experimentally observed trimer forming instability. A full relaxation of the supercell corresponding to this instability yields a nonmagnetic state containing V3 trimers. These results are consistent with Goodenough's suggestion that the high-temperature phase is in the localized-electron regime and the transition to the low-temperature phase in the itinerant-electron regime is driven by V-V covalency.

Equilibrium polymerization models of re-entrant self-assembly

NASA Astrophysics Data System (ADS)

Dudowicz, Jacek; Douglas, Jack F.; Freed, Karl F.

2009-04-01

As is well known, liquid-liquid phase separation can occur either upon heating or cooling, corresponding to lower and upper critical solution phase boundaries, respectively. Likewise, self-assembly transitions from a monomeric state to an organized polymeric state can proceed either upon increasing or decreasing temperature, and the concentration dependent ordering temperature is correspondingly called the "floor" or "ceiling" temperature. Motivated by the fact that some phase separating systems exhibit closed loop phase boundaries with two critical points, the present paper analyzes self-assembly analogs of re-entrant phase separation, i.e., re-entrant self-assembly. In particular, re-entrant self-assembly transitions are demonstrated to arise in thermally activated equilibrium self-assembling systems, when thermal activation is more favorable than chain propagation, and in equilibrium self-assembly near an adsorbing boundary where strong competition exists between adsorption and self-assembly. Apparently, the competition between interactions or equilibria generally underlies re-entrant behavior in both liquid-liquid phase separation and self-assembly transitions.

Phase change in CoTi2 induced by MeV electron irradiation

NASA Astrophysics Data System (ADS)

Zensho, Akihiro; Sato, Kazuhisa; Yasuda, Hidehiro; Mori, Hirotaro

2018-07-01

The phase change induced by MeV electron irradiation in the intermetallic compound E93-CoTi2 was investigated using high-voltage electron microscopy. Under MeV electron irradiation, CoTi2 was first transformed into an amorphous phase and, with continued irradiation, crystallite formation in the amorphous phase (i.e. formation of crystallites of a solid-solution phase within the amorphous phase) was induced. The critical temperature for amorphisation was around 250 K. The total dose (dpa) required for crystallite formation (i.e. that required for partial crystallisation) was high (i.e. 27-80 dpa) and, even after prolonged irradiation, the amorphous phase was retained in the irradiated sample. Such partial crystallisation behaviour of amorphous Co33Ti67 was clearly different from the crystallisation behaviour (i.e. amorphous-to-solid solution, polymorphous transformation) of amorphous Cr67Ti33 reported in the literature. A possible cause of the difference is discussed.

Sequence heuristics to encode phase behaviour in intrinsically disordered protein polymers

PubMed Central

Quiroz, Felipe García; Chilkoti, Ashutosh

2015-01-01

Proteins and synthetic polymers that undergo aqueous phase transitions mediate self-assembly in nature and in man-made material systems. Yet little is known about how the phase behaviour of a protein is encoded in its amino acid sequence. Here, by synthesizing intrinsically disordered, repeat proteins to test motifs that we hypothesized would encode phase behaviour, we show that the proteins can be designed to exhibit tunable lower or upper critical solution temperature (LCST and UCST, respectively) transitions in physiological solutions. We also show that mutation of key residues at the repeat level abolishes phase behaviour or encodes an orthogonal transition. Furthermore, we provide heuristics to identify, at the proteome level, proteins that might exhibit phase behaviour and to design novel protein polymers consisting of biologically active peptide repeats that exhibit LCST or UCST transitions. These findings set the foundation for the prediction and encoding of phase behaviour at the sequence level. PMID:26390327

Kinetic Phase Diagrams of Ternary Al-Cu-Li System during Rapid Solidification: A Phase-Field Study

PubMed Central

Yang, Xiong; Zhang, Lijun; Sobolev, Sergey; Du, Yong

2018-01-01

Kinetic phase diagrams in technical alloys at different solidification velocities during rapid solidification are of great importance for guiding the novel alloy preparation, but are usually absent due to extreme difficulty in performing experimental measurements. In this paper, a phase-field model with finite interface dissipation was employed to construct kinetic phase diagrams in the ternary Al-Cu-Li system for the first time. The time-elimination relaxation scheme was utilized. The solute trapping phenomenon during rapid solidification could be nicely described by the phase-field simulation, and the results obtained from the experiment measurement and/or the theoretical model were also well reproduced. Based on the predicted kinetic phase diagrams, it was found that with the increase of interface moving velocity and/or temperature, the gap between the liquidus and solidus gradually reduces, which illustrates the effect of solute trapping and tendency of diffusionless solidification. PMID:29419753

Temperature-dependent structure and phase variation of nickel silicide nanowire arrays prepared by in situ silicidation

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

Liu, Hailong; She, Guangwei, E-mail: shegw@mail.ipc.ac.cn; Mu, Lixuan

Graphical abstract: Display Omitted Highlight: ► Nickel silicides nanowire arrays prepared by a simple in situ silicidation method. ► Phases of nickel silicides could be varied by tuning the reaction temperature. ► A growth model was proposed for the nickel silicides nanowires. ► Diffusion rates of Ni and Si play a critical role for the phase variation. -- Abstract: In this paper, we report an in situ silicidizing method to prepare nickel silicide nanowire arrays with varied structures and phases. The in situ reaction (silicidation) between Si and NiCl{sub 2} led to conversion of Si nanowires to nickel silicide nanowires.more » Structures and phases of the obtained nickel silicides could be varied by changing the reaction temperature. At a relatively lower temperature of 700 °C, the products are Si/NiSi core/shell nanowires or NiSi nanowires, depending on the concentration of NiCl{sub 2} solution. At a higher temperature (800 °C and 900 °C), other phases of the nickel silicides, including Ni{sub 2}Si, Ni{sub 31}Si{sub 12}, and NiSi{sub 2}, were obtained. It is proposed that the different diffusion rates of Ni and Si atoms at different temperatures played a critical role in the formation of nickel silicide nanowires with different phases.« less

Si-Ge-metal ternary phase diagram calculations

NASA Technical Reports Server (NTRS)

Fleurial, J. P.; Borshchevsky, A.

1990-01-01

Solution crystal growth and doping conditions of Si-Ge alloys used for high-temperature thermoelectric generation are determined here. Liquid-phase epitaxy (LPE) has been successfully employed recently to obtain single-crystalline homogeneous layers of Si-Ge solid solutions from a liquid metal solvent. Knowledge of Si-Ge-metallic solvent ternary phase diagrams is essential for further single-crystal growth development. Consequently, a thermodynamic equilibrium model was used to calculate the phase diagrams of the Si-Ge-M systems, including solid solubilities, where M is Al, Ga, In, Sn, Pb, Sb, or Bi. Good agreement between calculated liquidus and solidus data and experimental DTA and microprobe results was obtained. The results are used to compare the suitability of the different systems for crystal growth (by LPE-type process).

Resolving phase stability in the Ti-O binary with first-principles statistical mechanics methods

NASA Astrophysics Data System (ADS)

Gunda, N. S. Harsha; Puchala, Brian; Van der Ven, Anton

2018-03-01

The Ti-O system consists of a multitude of stable and metastable oxides that are used in wide ranging applications. In this work we investigate phase stability in the Ti-O binary from first principles. We perform a systematic search for ground state structures as a function of oxygen concentration by considering oxygen-vacancy and/or titanium-vacancy orderings over four parent crystal structures: (i) hcp Ti, (ii) ω -Ti, (iii) rocksalt, and (iv) hcp oxygen containing interstitial titanium. We explore phase stability at finite temperature using cluster expansion Hamiltonians and Monte Carlo simulations. The calculations predict a high oxygen solubility in hcp Ti and the stability of suboxide phases that undergo order-disorder transitions upon heating. Vacancy ordered rocksalt phases are also predicted at low temperature that disorder to form an extended solid solution at high temperatures. Predicted stable and metastable phase diagrams are qualitatively consistent with experimental observations, however, important discrepancies are revealed between first-principles density functional theory predictions of phase stability and the current understanding of phase stability in this system.

Numerical modeling of the elution peak profiles of retained solutes in supercritical fluid chromatography

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

Kaczmarski, Krzysztof; Guiochon, Georges A

2011-01-01

In supercritical fluid chromatography (SFC), the significant expansion of the mobile phase along the column causes the formation of axial and radial gradients of temperature. Due to these gradients, the mobile phase density, its viscosity, its velocity, its diffusion coefficients, etc. are not constant throughout the column. This results in a nonuniform flow velocity distribution, itself causing a loss of column efficiency in certain cases, even at low flow rates, as they do in HPLC. At high flow rates, an important deformation of the elution profiles of the sample components may occur. The model previously used to account satisfactorily formore » the retention of an unsorbed solute in SFC is applied to the modeling of the elution peak profiles of retained compounds. The numerical solution of the combined heat and mass balance equations provides the temperature and the pressure profiles inside the column and values of the retention time and the band profiles of retained compounds that are in excellent agreement with independent experimental data for large value of mobile phase reduced density. At low reduced densities, the band profiles can strongly depend on the column axial distribution of porosity.« less

Molecular Dynamics Simulations of Strain-Induced Phase Transition of Poly(ethylene oxide) in Water.

PubMed

Donets, Sergii; Sommer, Jens-Uwe

2018-01-11

We study the dilute aqueous solutions of poly(ethylene oxide) (PEO) oligomers that are subject to an elongating force dipole acting on both chain ends using atomistic molecular dynamics. By increasing the force, liquid-liquid demixing can be observed at room temperature far below the lower critical solution temperature. For forces above 35 pN, fibrillar nanostructures are spontaneously formed related to a decrease in hydrogen bonding between PEO and water. Most notable is a rapid decrease in the bifurcated hydrogen bonds during stretching, which can also be observed for isolated single chains. The phase-segregated structures display signs of chain ordering, but a clear signature of the crystalline order is not obtained during the simulation time, indicating a liquid-liquid phase transition induced by chain stretching. Our results indicate that the solvent quality of the aqueous solution of PEO depends on the conformational state of the chains, which is most likely related to the specific hydrogen-bond-induced solvation of PEO in water. The strain-induced demixing of PEO opens the possibility to obtain polymer fibers with low energy costs because crystallization starts via the strain-induced demixing in the extended state only.

Continuous surface force based lattice Boltzmann equation method for simulating thermocapillary flow

NASA Astrophysics Data System (ADS)

Zheng, Lin; Zheng, Song; Zhai, Qinglan

2016-02-01

In this paper, we extend a lattice Boltzmann equation (LBE) with continuous surface force (CSF) to simulate thermocapillary flows. The model is designed on our previous CSF LBE for athermal two phase flow, in which the interfacial tension forces and the Marangoni stresses as the results of the interface interactions between different phases are described by a conception of CSF. In this model, the sharp interfaces between different phases are separated by a narrow transition layers, and the kinetics and morphology evolution of phase separation would be characterized by an order parameter via Cahn-Hilliard equation which is solved in the frame work of LBE. The scalar convection-diffusion equation for temperature field is resolved by thermal LBE. The models are validated by thermal two layered Poiseuille flow, and two superimposed planar fluids at negligibly small Reynolds and Marangoni numbers for the thermocapillary driven convection, which have analytical solutions for the velocity and temperature. Then thermocapillary migration of two/three dimensional deformable droplet are simulated. Numerical results show that the predictions of present LBE agreed with the analytical solution/other numerical results.

The effect of solute additions on the steady-state creep behavior of dispersion-strengthened aluminum.

NASA Technical Reports Server (NTRS)

Reynolds, G. H.; Lenel, F. V.; Ansell, G. S.

1971-01-01

The effect of solute additions on the steady-state creep behavior of coarse-grained dispersion-strengthened aluminum alloys was studied. Recrystallized dispersion-strengthened solid solutions were found to have stress and temperature sensitivities quite unlike those observed in single-phase solid solutions having the same composition and grain size. The addition of magnesium or copper to the matrix of a recrystallized dispersion-strengthened aluminum causes a decrease in the steady-state creep rate which is much smaller than that caused by similar amounts of solute in single-phase solid solutions. All alloys exhibited essentially a 4.0 power stress exponent in agreement with the model of Ansell and Weertman. The activation energy for steady-state creep in dispersion-strengthened Al-Mg alloys, as well as the stress dependence, was in agreement with the physical model of dislocation climb over the dispersed particles.

Structural and low temperature dielectric studies on Pb0.8Bi0.2Fe0.6Nb0.4O3 multiferroic solid solution

NASA Astrophysics Data System (ADS)

Dadami, Sunanda T.; Matteppanvar, Shidaling; Shivaraja, I.; Rayaprol, Sudhindra; Deshapande, S. K.; Angadi, Basavaraj

2018-05-01

In this paper the structural and low temperature dielectric properties of Pb0.8Bi0.2Fe0.6Nb0.4O3 (PBFNO) multiferroic solid solution were reported. PBFNO multiferroic was synthesized by single step solid state reaction method. Calcination was carried out at 700 °/2hr with different sintering temperature (800 °C, 850 °C, 900 °C, 950 °C, 1000 °C and 1050 °C for 1 hr) and time duration (800 °C for 1 to 5 hr). Single phase was confirmed through room temperature (RT) X-ray Diffraction (XRD). It was found that sintering carried out at 800°C/3 hr gives single phase. Rietveld refined lattice parameters using monoclinic structure are: a = 5.6663(1) Å, b = 5.6694(1) Å, c = 4.0112(1) Å and β = 90.038(1)° with the average grain size as 2.987 µm. The dielectric properties studied over a wide range of frequency (100 Hz - 5 MHz) and temperature (133 K - 293 K). Dielectric constant and loss tangent exhibits frequency dispersion nature at low frequency region. AC conductivity increases with increase in temperature corresponds to negative temperature coefficient of resistance (NTCR) behaviour.

Dissociation of Heme–Globin Complexes by Blackbody Infrared Radiative Dissociation: Molecular Specificity in the Gas Phase?

PubMed Central

Gross, Deborah S.; Zhao, Yuexing; Williams, Evan R.

2005-01-01

The temperature dependence of the unimolecular kinetics for dissociation of the heme group from holo-myoglobin (Mb) and holo-hemoglobin α-chain (Hb-α) was investigated with blackbody infrared radiative dissociation (BIRD). The rate constant for dissociation of the 9 + charge state of Mb formed by electrospray ionization from a “pseudo-native” solution is 60% lower than that of Hb-α at each of the temperatures investigated. In solutions of pH 5.5–8.0, the thermal dissociation rate for Mb is also lower than that of HB-α (Hargrove, M. S. et al. J. Biol. Chem. 1994, 269, 4207–4214). Thus, Mb is thermally more stable with respect to heme loss than Hb-α both in the gas phase and in solution. The Arrhenius activation parameters for both dissociation processes are indistinguishable within the current experimental error (activation energy 0.9 eV and pre-exponential factor of 108–10 s−1). The 9+ to 12+ charge states of Mb have similar Arrhenius parameters when these ions are formed from pseudo-native solutions. In contrast, the activation energies and pre-exponential factors decrease from 0.8 to 0.3 eV and 107 to 102 s−1, respectively, for the 9 + to 12 + charge states formed from acidified solutions in which at least 50% of the secondary structure is lost. These results demonstrate that gas-phase Mb ions retain clear memory of the composition of the solution from which they are formed and that these differences can be probed by BIRD. PMID:16479269

Dissociation of heme-globin complexes by blackbody infrared radiative dissociation: molecular specificity in the gas phase?

PubMed

Gross, D S; Zhao, Y; Williams, E R

1997-05-01

The temperature dependence of the unimolecular kinetics for dissociation of the heme group from holo-myoglobin (Mb) and holo-hemoglobin alpha-chain (Hb-alpha) was investigated with blackbody infrared radiative dissociation (BIRD). The rate constant for dissociation of the 9 + charge state of Mb formed by electrospray ionization from a "pseudo-native" solution is 60% lower than that of Hb-alpha at each of the temperatures investigated. In solutions of pH 5.5-8.0, the thermal dissociation rate for Mb is also lower than that of HB-alpha (Hargrove, M. S. et al. J. Biol. Chem.1994, 269, 4207-4214). Thus, Mb is thermally more stable with respect to heme loss than Hb-alpha both in the gas phase and in solution. The Arrhenius activation parameters for both dissociation processes are indistinguishable within the current experimental error (activation energy 0.9 eV and pre-exponential factor of 10(8-10) s(-1)). The 9+ to 12+ charge states of Mb have similar Arrhenius parameters when these ions are formed from pseudo-native solutions. In contrast, the activation energies and pre-exponential factors decrease from 0.8 to 0.3 eV and 10(7) to 10(2) s(-1), respectively, for the 9 + to 12 + charge states formed from acidified solutions in which at least 50% of the secondary structure is lost. These results demonstrate that gas-phase Mb ions retain clear memory of the composition of the solution from which they are formed and that these differences can be probed by BIRD.

Magnetic self-orientation of lyotropic hexagonal phases based on long chain alkanoic (fatty) acids.

PubMed

Douliez, Jean-Paul

2010-07-06

It is presently shown that long chain (C14, C16, and C18) alkanoic (saturated fatty) acids can form magnetically oriented hexagonal phases in aqueous concentrated solutions in mixtures with tetrabutylammonium (TBAOH) as the counterion. The hexagonal phase occurred for a molar ratio, alkanoic acid/TBAOH, higher than 1, i.e., for an excess of fatty acid. The hexagonal phase melted to an isotropic phase (micelles) upon heating at a given temperature depending on the alkyl chain length. The self-orientation of the hexagonal phase occurred upon cooling from the "high-temperature" isotropic phase within the magnetic field. The long axis of the hexagonal phase was shown to self-orient parallel to the magnetic field as evidenced by deuterium solid-state NMR. This finding is expected to be of interest in the field of structural biology and materials chemistry for the synthesis of oriented materials.

Kinetics of diffusional droplet growth in a liquid/liquid two-phase system

NASA Technical Reports Server (NTRS)

Baird, James K.; Cain, Judith B.

1993-01-01

This report contains experimental results for the interdiffusion coefficient of the system, succinonitrile plus water, at a number of compositions and temperatures in the single phase region of the phase diagram. The concentration and temperature dependence of the measured diffusion coefficient has been analyzed in terms of Landau - Ginzburg theory, which assumes that the Gibb free energy is an analytic function of its variables, and can be expanded in a Taylor series about any point in the phase diagram. At most points in the single phase region this is adequate. Near the consolute point (critical point of solution), however, the free energy is non-analytic, and the Landau - Ginzburg theory fails. The solution to this problem dictates that the Landau - Ginzburg form of the free energy be replaced by Widom scaling functions with irrational values for the scaling exponents. As our measurements of the diffusion coefficient near the critical point reflect this non-analytic character, we are preparing for publication in a refereed journal a separate analysis of some of the data contained herein as well as some additional measurements we have just completed. When published, reprints of this article will be furnished to NASA.

Room-temperature NaI/H2O compression icing: solute-solute interactions.

PubMed

Zeng, Qingxin; Yao, Chuang; Wang, Kai; Sun, Chang Q; Zou, Bo

2017-10-11

In situ Raman spectroscopy revealed that transiting the concentrated NaI/H 2 O solutions to an ice VI phase and then into an ice VII phase at 298 K proceeds in a way different from that activated by the solute type. Unlike the solute type that raises both the critical pressures P C1 and P C2 , for the liquid-VI, the VI-VII transition simultaneously occurs in the Hofmeister series order: I > Br > Cl > F ∼ 0; concentration increase raises the P C1 faster than the P C2 that remains almost constant at higher NaI/H 2 O molecular number ratios. Concentration increase moves the P C1 along the liquid-VI phase boundary and it finally merges with P C2 at the triple-phase junction featured at 350 K and 3.05 GPa. The highly-deformed H-O bond is less sensitive to the concentration because of the involvement of anion-anion repulsion that weakens the electric field in the hydration shells. Observations confirm that the salt solvation lengthens the O:H nonbond and softens its phonon but relaxes the H-O bond contrastingly. Compression, however, has the opposite effect from that of salt solvation. Therefore, compression recovers the polarization-deformed O:H-O bond first and then proceeds to the phase transitions. The anion-anion interaction discriminates the effect of NaI/H 2 O concentration from that of the solute type at an identical concentration on the phase transitions.

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

Warner-Schmid, D.; Hoshi, Suwaru; Armstrong, D.W.

Aqueous solutions of nonionic surfactants are known to undergo phase separations at elevated temperatures. This phenomenon is known as clouding,' and the temperature at which it occurs is refereed to as the cloud point. Permethylhydroxypropyl-[beta]-cyclodextrin (PMHP-[beta]-CD) was synthesized and aqueous solutions containing it were found to undergo similar cloud-point behavior. Factors that affect the phase separation of PMHP-[beta]-CD were investigated. Subsequently, the cloud-point extractions of several aromatic compounds (i.e., acetanilide, aniline, 2,2[prime]-dihydroxybiphenyl, N-methylaniline, 2-naphthol, o-nitroaniline, m-nitroaniline, p-nitroaniline, nitrobenzene, o-nitrophenol, m-nitrophenol, p-nitrophenol, 4-phenazophenol, 3-phenylphenol, and 2-phenylbenzimidazole) from dilute aqueous solution were evaluated. Although the extraction efficiency of the compounds varied, mostmore » can be quantitatively extracted if sufficient PMHP-[beta]-CD is used. For those few compounds that are not extracted (e.g., o-nitroacetanilide), the cloud-point procedure may be an effective one-step isolation or purification method. 18 refs., 2 figs., 3 tabs.« less

CO.sub.2 separation from low-temperature flue gases

DOEpatents

Dilmore, Robert; Allen, Douglas; Soong, Yee; Hedges, Sheila

2010-11-30

Two methods are provide for the separation of carbon dioxide from the flue gases. The first method utilizes a phase-separating moiety dissolved in an aqueous solution of a basic moiety to capture carbon dioxide. The second method utilizes a phase-separating moiety as a suspended solid in an aqueous solution of a basic moiety to capture carbon dioxide. The first method takes advantage of the surface-independent nature of the CO.sub.2 absorption reactions in a homogeneous aqueous system. The second method also provides permanent sequestration of the carbon dioxide. Both methods incorporate the kinetic rate enhancements of amine-based scrubbing while eliminating the need to heat the entire amine solution (80% water) in order to regenerate and release CO.sub.2. Both methods also take advantage of the low-regeneration temperatures of CO.sub.2-bearing mineral systems such as Na.sub.2CO.sub.3/NaHCO.sub.3 and K.sub.2CO.sub.3/KHCO.sub.3.

Revisiting the formation of cyclic clusters in liquid ethanol

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

Balanay, Mannix P.; Fan, Haiyan, E-mail: haiyan.fan@nu.edu.kz; Kim, Dong Hee

2016-04-21

The liquid phase of ethanol in pure and in non-polar solvents was studied at room temperature using Fourier transform infrared (FT-IR) and {sup 1}H nuclear magnetic resonance (NMR) spectroscopies together with theoretical approach. The FT-IR spectra for pure ethanol and solution in cyclohexane at different dilution stages are consistent with {sup 1}H NMR results. The results from both methods were best explained by the results of the density functional theory based on a multimeric model. It is suggested that cyclic trimers and tetramers are dominated in the solution of cyclohexane/hexane with the concentration greater than 0.5M at room temperature. Inmore » liquid ethanol, while the primary components at room temperature are cyclic trimers and tetramers, there is a certain amount (∼14%) of open hydroxide group representing the existence of chain like structures in the equilibria. The cyclic cluster model in the liquid and concentrated solution phase (>0.5M) can be used to explain the anomalously lower freezing point of ethanol (159 K) than that of water (273 K) at ambient conditions. In addition, {sup 1}H NMR at various dilution stages reveals the dynamics for the formation of cyclic clusters.« less

High Temperature Surface Interactions

DTIC Science & Technology

1989-11-01

and importance. To predict the parabolic scaling rate for a pure metal forming a dense, adherent one-phase scale, Wagner (1) needed only to assume that...coefficient for the acidic Ca(V03) 4 solute. Thus, limited measurements of CeO2 in the 0.7 Na2SO4-0.3NaVO3 solution can be interpolated to predict the...solutions can be predicted , as shown in Fig. 13. Obviously, these assumptions about the solution thermodynamics should receive experimental testing. In any

Synthesis and characterization of LTA nanozeolite using barley husk silica: Mercury removal from standard and real solutions

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

Azizi, Seyed Naser, E-mail: azizi@umz.ac.ir; Dehnavi, Ahmad Roozbehani, E-mail: Roozbehanisulfur@yahoo.com; Joorabdoozha, Amir

2013-05-15

Highlights: ► Silica extraction from barley husk with high purity for the synthesis of A nanozeolite. ► Free template A nanozeolite synthesized via new source of silica at low temperature. ► Optimization of SiO{sub 2}/Al{sub 2}O{sub 3}, Na{sub 2}O/SiO{sub 2} ratios, temperature and time of the synthesis. ► Utilizing of synthesized A nanozeolite for mercury removal from aqueous solutions. ► Mercury removal at optimized pH, contact time and adsorbent dose from real solution. - Abstract: In this study, synthesized Lined Type A (LTA) nanozeolite from barley husk silica (BHS) was used for mercury removal from standard and real aqueous solutions.more » The BHS in amorphous phase with 80% purity was extracted from barley husk ash (BHA), and used effectively as a new source of silica for the synthesis of NaA nanozeolite. The NaA nanocrystal in pure phase has been synthesized at low temperature, without adding any organic additives. The effects of heating time, reaction temperature, SiO{sub 2}/Al{sub 2}O{sub 3}, and Na{sub 2}O/SiO{sub 2} mole ratios on the crystallization of NaA nanozeolite were studied. The adsorption capacity of mercury (II) was studied as a function of pH, contact time, and amount of adsorbent. The crystallization of NaA nanozeolite from BHS was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), Brunauer–Emmett–Teller (BET), and FTIR techniques. Moreover, concentration of Hg{sup 2+} ions in the aqueous solutions was analyzed by hydride generation atomic absorption spectroscopy method (HG-AAS). The standard and real samples analysis showed that NaA nanozeolite is capable of Hg{sup 2+} ions removal from the aqueous solutions. Efficiency of mercury (II) adsorption from real solutions onto the nano-sized NaA zeolite was 98%.« less

DE-FOA-EE0005502 Advanced Percussive Drilling Technology for Geothermal Exploration and Development Phase II Report.

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

Su, Jiann-Cherng; Raymond, David W.; Prasad, Somuri V.

Percussive hammers are a promising advance in drilling technology for geothermal since they rely upon rock reduction mechanisms that are well-suited for use in the hard, brittle rock characteristic of geothermal formations. The project research approach and work plan includes a critical path to development of a high-temperature (HT) percussive hammer using a two- phase approach. The work completed in Phase I of the project demonstrated the viability of percussive hammers and that solutions to technical challenges in design, material technology, and performance are likely to be resolved. Work completed in Phase II focused on testing the findings from Phasemore » I and evaluating performance of the materials and designs at high- operating temperatures. A high-operating temperature (HOT) drilling facility was designed, built, and used to test the performance of the DTH under extreme conditions. Results from the testing indicate that a high-temperature capable hammer can be developed and is a viable alternative for user in the driller's toolbox.« less

α-Phase transformation kinetics of U – 8 wt% Mo established by in situ neutron diffraction

DOE PAGES

Garlea, Elena; Steiner, M. A.; Calhoun, C. A.; ...

2016-05-08

The α-phase transformation kinetics of as-cast U - 8 wt% Mo below the eutectoid temperature have been established by in situ neutron diffraction. α-phase weight fraction data acquired through Rietveld refinement at five different isothermal hold temperatures can be modeled accurately utilizing a simple Johnson-Mehl-Avrami-Kolmogorov impingement-based theory, and the results are validated by a corresponding evolution in the γ-phase lattice parameter during transformation that follows Vegard’s law. Neutron diffraction data is used to produce a detailed Time-Temperature-Transformation diagram that improves upon inconsistencies in the current literature, exhibiting a minimum transformation start time of 40 min at temperatures between 500 °Cmore » and 510 °C. Lastly, the transformation kinetics of U – 8 wt% Mo can vary significantly from as-cast conditions after extensive heat treatments, due to homogenization of the typical dendritic microstructure which possesses non-negligible solute segregation.« less

Exact solutions for unsteady free convection flow over an oscillating plate due to non-coaxial rotation.

PubMed

Mohamad, Ahmad Qushairi; Khan, Ilyas; Ismail, Zulkhibri; Shafie, Sharidan

2016-01-01

Non-coaxial rotation has wide applications in engineering devices, e.g. in food processing such as mixer machines and stirrers with a two-axis kneader, in cooling turbine blades, jet engines, pumps and vacuum cleaners, in designing thermal syphon tubes, and in geophysical flows. Therefore, this study aims to investigate unsteady free convection flow of viscous fluid due to non-coaxial rotation and fluid at infinity over an oscillating vertical plate with constant wall temperature. The governing equations are modelled by a sudden coincidence of the axes of a disk and the fluid at infinity rotating with uniform angular velocity, together with initial and boundary conditions. Some suitable non-dimensional variables are introduced. The Laplace transform method is used to obtain the exact solutions of the corresponding non-dimensional momentum and energy equations with conditions. Solutions of the velocity for cosine and sine oscillations as well as for temperature fields are obtained and displayed graphically for different values of time ( t ), the Grashof number ( Gr ), the Prandtl number ([Formula: see text]), and the phase angle ([Formula: see text]). Skin friction and the Nusselt number are also evaluated. The exact solutions are obtained and in limiting cases, the present solutions are found to be identical to the published results. Further, the obtained exact solutions also validated by comparing with results obtained by using Gaver-Stehfest algorithm. The interested physical property such as velocity, temperature, skin friction and Nusselt number are affected by the embedded parameters time ( t ), the Grashof number ( Gr ), the Prandtl number ([Formula: see text]), and the phase angle ([Formula: see text]).

Strengthening by Substitutional Solutes and the Temperature Dependence of the Flow Stress in Ni3Al

DTIC Science & Technology

1989-05-26

stoichiometric composition in polycrystalline Ni3AI and Ni3Ga. 29 Fig. 3.1 The Ni-Al binary-alloy phase diagram in vacinity of Ni3A1 phase, as verified in...I <I- iai / I I- I I I I000 - - II 21 25 29 33 37 ATOMIC % Al Fig. 3.1 The Ni-Al binary-alloy phase diagram in vacinity of Ni3Al phase, as verified

The formation of supercooled brines, viscous liquids, and low-temperature perchlorate glasses in aqueous solutions relevant to Mars

NASA Astrophysics Data System (ADS)

Toner, J. D.; Catling, D. C.; Light, B.

2014-05-01

Salt solutions on Mars can stabilize liquid water at low temperatures by lowering the freezing point of water. The maximum equilibrium freezing-point depression possible, known as the eutectic temperature, suggests a lower temperature limit for liquid water on Mars; however, salt solutions can supercool below their eutectic before crystallization occurs. To investigate the magnitude of supercooling and its variation with salt composition and concentration, we performed slow cooling and warming experiments on pure salt solutions and saturated soil-solutions of MgSO4, MgCl2, NaCl, NaClO4, Mg(ClO4)2, and Ca(ClO4)2. By monitoring solution temperatures, we identified exothermic crystallization events and determined the composition of precipitated phases from the eutectic melting temperature. Our results indicate that supercooling is pervasive. In general, supercooling is greater in more concentrated solutions and with salts of Ca and Mg. Slowly cooled MgSO4, MgCl2, NaCl, and NaClO4 solutions investigated in this study typically supercool 5-15 °C below their eutectic temperature before crystallizing. The addition of soil to these salt solutions has a variable effect on supercooling. Relative to the pure salt solutions, supercooling decreases in MgSO4 soil-solutions, increases in MgCl2 soil-solutions, and is similar in NaCl and NaClO4 soil-solutions. Supercooling in MgSO4, MgCl2, NaCl, and NaClO4 solutions could marginally extend the duration of liquid water during relatively warm daytime temperatures in the martian summer. In contrast, we find that Mg(ClO4)2 and Ca(ClO4)2 solutions do not crystallize during slow cooling, but remain in a supercooled, liquid state until forming an amorphous glass near -120 °C. Even if soil is added to the solutions, a glass still forms during cooling. The large supercooling effect in Mg(ClO4)2 and Ca(ClO4)2 solutions has the potential to prevent water from freezing over diurnal and possibly annual cycles on Mars. Glasses are also potentially important for astrobiology because of their ability to preserve pristine cellular structures intact compared to solutions that crystallize.

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

Brgoch, Jakoah; Klob, Simon D.; Denault, Kristin A.

The preparation of Eu 2+-substituted barium aluminum silicates is achieved using a rapid microwave-assisted preparation. The phase evolution of two BaAl 2Si 2O 8:Eu 2+ polymorphs, the higher temperature hexagonal phase (hexacelsian), and the lower temperature monoclinic phase (celsian), is explored by varying the ramp time and soak time. This preparation method significantly reduces the reaction time needed to form these phases compared to conventional solid state routes. The luminescent properties of the two phases are identified under UV excitation with the hexagonal phase emitting in the UV region (λ em = 372 nm) and the monoclinic phase emitting inmore » the blue region (λ em = 438 nm). The differences in optical properties of the two polymorphs are correlated to the coordination number and arrangement of the alkali earth site. The optical properties of the monoclinic phase can be further tuned through the substitution of Sr 2+, forming the solid solution (Ba 1–xSr x)Al 2Si 2O 8:Eu 2+. Changes in the crystal structure due to Sr 2+ substitution produce a surprising blue-shift in the emission spectrum, which is explained by a greater dispersion of bond lengths in the (Ba/Sr)–O polyhedra. The entire monoclinic solid solution exhibits excellent quantum yields of nearly 90 %, owing to the structural rigidity provided by the highly connected tetrahedral network.« less

Triclinic-monoclinic-orthorhombic (T-M-O) structural transitions in phase diagram of FeVO4-CrVO4 solid solutions

NASA Astrophysics Data System (ADS)

Bera, Ganesh; Reddy, V. R.; Rambabu, P.; Mal, P.; Das, Pradip; Mohapatra, N.; Padmaja, G.; Turpu, G. R.

2017-09-01

Phase diagram of FeVO4-CrVO4 solid solutions pertinent with structural and magnetic phases is presented with unambiguous experimental evidences. Solid solutions Fe1-xCrxVO4 (0 ≤ x ≤ 1.0) were synthesized through the standard solid state route and studied by X-ray diffraction, scanning electron microscopy, energy dispersive spectra of X-rays, Raman spectroscopy, d.c. magnetization, and 57Fe Mössbauer spectroscopic studies. FeVO4 and CrVO4 were found to be in triclinic (P-1 space group) and orthorhombic structures (Cmcm space group), respectively. Cr incorporation into the FeVO4 lattice leads to the emergence of a new monoclinic phase dissimilar to the both end members of the solid solutions. In Fe1-xCrxVO4 up to x = 0.10, no discernible changes in the triclinic structure were found. A new structural monoclinic phase (C2/m space group) emerges within the triclinic phase at x = 0.125, and with the increase in Cr content, it gets stabilized with clear single phase signatures in the range of x = 0.175-0.25 as evidenced by the Rietveld analysis of the structures. Beyond x = 0.33, orthorhombic phase similar to CrVO4 (Cmcm space group) emerges and coexists with a monoclinic structure up to x = 0.85, which finally tends to stabilize in the range of x = 0.90-1.00. The Raman spectroscopic studies also confirm the structural transition. FeVO4 Raman spectra show the modes related to three nonequivalent V ions in the triclinic structure, where up to 42 Raman modes are observed in the present study. With the stabilization of structures having higher symmetry, the number of Raman modes decreases and the modes related to symmetry inequivalent sites collate into singular modes from the doublet structure. A systematic crossover from two magnetic transitions in FeVO4, at 21.5 K and 15.4 K to single magnetic transition in CrVO4, at 71 K (antiferromagnetic transition), is observed in magnetization studies. The intermediate solid solution with x = 0.15 shows two magnetic transitions, whereas in the compound with x = 0.33 one of the magnetic transitions disappears. 57Fe Mössbauer spectroscopic studies show a finger print evidence for disappearance of non-equivalent sites of Fe as the structure changes from Triclinic-Monoclinic-Orthorhombic phases with the increasing Cr content in Fe1-xCrxVO4. Comprehensive studies related to the structural changes in Fe1-xCrxVO4 solid solutions lead us to detailed phase diagrams which shall be characteristic for room temperature structural and temperature dependent magnetic transitions in these solid solutions, respectively.

Electrochemically Induced Insulator-Metal-Insulator Transformations of Vanadium Dioxide Nanocrystal Films

NASA Astrophysics Data System (ADS)

Milliron, Delia; Dahlman, Clayton; Leblanc, Gabriel; Bergerud, Amy

Vanadium dioxide (VO2) undergoes significant optical, electronic, and structural changes as it transforms between the low-temperature monoclinic and high-temperature rutile phases. The low-temperature state is insulating and transparent, while the high-temperature state is metallic and IR blocking. Alternative stimuli have been utilized to trigger insulator-to-metal transformations in VO2, including electrochemical gating. Here, VO2 nanocrystal films have been prepared by solution deposition of V2O3 nanocrystals followed by oxidative annealing. Nanocrystalline VO2 films are electrochemically reduced, inducing changes in their electronic and optical properties. We observe a reversible transition between infrared transparent insulating phases and a darkened metallic phase by in situ visible-near-infrared spectroelectrochemistry and correlate these observations with structural and electronic changes monitored by X-ray absorption spectroscopy, X-ray diffraction, Raman spectroscopy, and conductivity measurements. Reduction causes an initial transformation to a metallic, IR-colored distorted monoclinic phase. However, an unexpected reversible transition from conductive, reduced monoclinic VO2 to an infrared-transparent insulating phase is observed upon further reduction.

Microstructure and Rheology of a Flow-Induced Structured Phase in Wormlike Micellar Solutions

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

Cardiel Rivera, Joshua J.; Dohnalkova, Alice; Dubash, Neville

2013-04-30

Surfactant molecules found in soaps and detergents can self-assemble into a great variety of morphologies (e.g., spherical micelles, cylindrical micelles, and lamellar phases). The resulting morphology is highly affected by ionic strength, temperature, and flow conditions. In particular, cylindrical micelles in the presence of inorganic or organic salts can self-assemble into large flexible and elongated wormlike micelles. In equilibrium, the wormlike micelles transition from slightly entangled to branched and, finally, to multi-connected structures with increasing salt concentration. In our work, by introducing external flow conditions via microfluidics, these micellar structures can follow very different trajectories on the phase map andmore » new nanoporous structures can be created. This flow induced approach offers great potential to create novel materials and nanoporous scaffolds from wormlike micelles under ambient temperature and pressure, without any chemical and thermal means (1). As a result, this work provides attractive solutions for synthesizing new biocompatible materials under ambient conditions with biosensing, encapsulation, catalysis, photonics, and self-healing applications.« less

Atom Probe Tomography Analysis of the Distribution of Rhenium in Nickel Alloys

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

Mottura, A.; Warnken, N; Miller, Michael K

2010-01-01

Atom probe tomography (APT) is used to characterise the distributions of rhenium in a binary Ni-Re alloy and the nickel-based single-crystal CMSX-4 superalloy. A purpose-built algorithm is developed to quantify the size distribution of solute clusters, and applied to the APT datasets to critique the hypothesis that rhenium is prone to the formation of clusters in these systems. No evidence is found to indicate that rhenium forms solute clusters above the level expected from random fluctuations. In CMSX-4, enrichment of Re is detected in the matrix phase close to the matrix/precipitate ({gamma}/{gamma}{prime}) phase boundaries. Phase field modelling indicates that thismore » is due to the migration of the {gamma}/{gamma}{prime} interface during cooling from the temperature of operation. Thus, neither clustering of rhenium nor interface enrichments can be the cause of the enhancement in high temperature mechanical properties conferred by rhenium alloying.« less

Ti{sub 2}AlN thin films synthesized by annealing of (Ti+Al)/AlN multilayers

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

Cabioch, Thierry, E-mail: Thierry.cabioch@univ-poitiers.fr; Alkazaz, Malaz; Beaufort, Marie-France

2016-08-15

Highlights: • Epitaxial thin films of the MAX phase Ti{sub 2}AlN are obtained by thermal annealing. • A new metastable (Ti,Al,N) solid solution with the structure of α-T is evidenced. • The formation of the MAX phase occurs at low temperature (600 °C). - Abstract: Single-phase Ti{sub 2}AlN thin films were obtained by annealing in vacuum of (Ti + Al)/AlN multilayers deposited at room temperature by magnetron sputtering onto single-crystalline (0001) 4H-SiC and (0001) Al{sub 2}O{sub 3} substrates. In-situ X-ray diffraction experiments combined with ex-situ cross-sectional transmission electron microscopy observations reveal that interdiffusion processes occur in the multilayer at amore » temperature of ∼400 °C leading to the formation of a (Ti, Al, N) solid solution, having the hexagonal structure of α-Ti, whereas the formation of Ti{sub 2}AlN occurs at 550–600 °C. Highly oriented (0002) Ti{sub 2}AlN thin films can be obtained after an annealing at 750 °C.« less

Resolving Confined 7Li Dynamics of Uranyl Peroxide Capsule U 24

DOE PAGES

Xie, Jing; Neal, Harrison A.; Szymanowski, Jennifer; ...

2018-04-18

Here, we obtained a kerosene-soluble form of the lithium salt [UO 2(O 2)(OH) 2] 24 phase (Li-U 24), by adding cetyltrimethylammonium bromide surfactant to aqueous Li-U 24. Interestingly, its variable-temperature solution 7Li NMR spectroscopy resolves two narrowly spaced resonances down to –10 °C, which shift upfield with increasing temperature, and finally coalesce at temperatures > 85 °C. Comparison with solid-state NMR demonstrates that the Li dynamics in the Li-U 24-CTA phase involves only exchange between different local encapsulated environments. This behavior is distinct from the rapid Li exchange dynamics observed between encapsulated and external Li environments for Li-U 24 inmore » both the aqueous and the solid-state phases. Density functional theory calculations suggest that the two experimental 7Li NMR chemical shifts are due to Li cations coordinated within the square and hexagonal faces of the U 24 cage, and they can undergo exchange within the confined environment, as the solution is heated. Very different than U 24 in aqueous media, there is no evidence that the Li cations exit the cage, and therefore, this represents a truly confined space.« less

Hydrogels with a Memory: Dual-Responsive, Organometallic Poly(ionic liquid)s with Hysteretic Volume-Phase Transition

PubMed Central

2017-01-01

We report on the synthesis and structure–property relations of a novel, dual-responsive organometallic poly(ionic liquid) (PIL), consisting of a poly(ferrocenylsilane) backbone of alternating redox-active, silane-bridged ferrocene units and tetraalkylphosphonium sulfonate moieties in the side groups. This PIL is redox responsive due to the presence of ferrocene in the backbone and also exhibits a lower critical solution temperature (LCST)-type thermal responsive behavior. The LCST phase transition originates from the interaction between water molecules and the ionic substituents and shows a concentration-dependent, tunable transition temperature in aqueous solution. The PIL’s LCST-type transition temperature can also be influenced by varying the redox state of ferrocene in the polymer main chain. As the polymer can be readily cross-linked and is easily converted into hydrogels, it represents a new dual-responsive materials platform. Interestingly, the as-formed hydrogels display an unusual, strongly hysteretic volume-phase transition indicating useful thermal memory properties. By employing the dispersing abilities of this cationic PIL, CNT-hydrogel composites were successfully prepared. These hybrid conductive composite hydrogels showed bi-stable states and tunable resistance in heating–cooling cycles. PMID:28654756

Hydrothermal Diamond Anvil Cell (HDAC): From Visual Observation to X-ray Absorption Spectroscopy

NASA Astrophysics Data System (ADS)

Bassett, W. A.; Mibe, K.

2006-05-01

A fluid sample contained in a Re gasket between two diamond anvils can be subjected to pressures up to 2.5 GPa and temperatures up to 1200°C in a resistively heated hydrothermal diamond anvil cell (HDAC). Thermocouples are used to measure temperature. The constant-volume sample chamber permits isochoric measurements that can be used to determine pressure from the equation of state of H2O and to map phases and properties in P-T space. A movie of reactions between K-feldspar and water up to 2.5 GPa and 880°C illustrates the use of visual observations for mapping coexisting solution, melt, and solid phases. X-ray absorption spectroscopy of ZnBr2 in solution up to 500°C and 500 MPa shows hydrogen bond breaking in the hydration shells of the ZnBr42- and Br- ions with increasing temperature. In other studies the stability field of ikaite (CaCO3·6H2O) has been mapped by visual observation and Raman spectroscopy; the phases of montmorillonite have been mapped by X-ray diffraction; and the leaching of Pb from zircon has been measured by X-ray microprobe.

Microstructural Evolution and Mechanical Properties of Ti-22Al-25Nb (At.%) Orthorhombic Alloy with Three Typical Microstructures

NASA Astrophysics Data System (ADS)

Wang, Wei; Zeng, Weidong; Liu, Yantao; Xie, Guoxin; Liang, Xiaobo

2018-01-01

Microstructural evolution, tensile and creep behavior of Ti-22Al-25Nb (at.%) orthorhombic alloy with three typical microstructures were investigated. The three typical microstructures were obtained by different solution and age treatment temperatures and analyzed by the BSE technique. The tensile strengths of the alloy at room temperature and 650 °C were investigated. The creep behaviors of the three typical microstructures were also studied at 650 °C/150 MPa for 100 h in air. The phase transformation mechanisms in creep deformation were also found. The experimental results showed that the formations of the three typical microstructures were decided by the isothermal forging and heat treatment. It was supposed that the high-temperature solution treatment might be dominant for the volume fraction and diameter of the equiaxed particles. While the double age treatment would lead to lamellar O phases. Due to grain refinement strengthening, the equiaxed microstructure presented the best tensile strength and ductility. The fully lamellar microstructure had the best creep resistance than that of other microstructures. In this paper, the phenomenon of creep-induced α 2 phase decomposition was occurred during creep deformation of the equiaxed microstructure.

Resolving Confined 7Li Dynamics of Uranyl Peroxide Capsule U 24

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

Xie, Jing; Neal, Harrison A.; Szymanowski, Jennifer

Here, we obtained a kerosene-soluble form of the lithium salt [UO 2(O 2)(OH) 2] 24 phase (Li-U 24), by adding cetyltrimethylammonium bromide surfactant to aqueous Li-U 24. Interestingly, its variable-temperature solution 7Li NMR spectroscopy resolves two narrowly spaced resonances down to –10 °C, which shift upfield with increasing temperature, and finally coalesce at temperatures > 85 °C. Comparison with solid-state NMR demonstrates that the Li dynamics in the Li-U 24-CTA phase involves only exchange between different local encapsulated environments. This behavior is distinct from the rapid Li exchange dynamics observed between encapsulated and external Li environments for Li-U 24 inmore » both the aqueous and the solid-state phases. Density functional theory calculations suggest that the two experimental 7Li NMR chemical shifts are due to Li cations coordinated within the square and hexagonal faces of the U 24 cage, and they can undergo exchange within the confined environment, as the solution is heated. Very different than U 24 in aqueous media, there is no evidence that the Li cations exit the cage, and therefore, this represents a truly confined space.« less

New model system in radiation cryochemistry:. hyperquenched glassy water

NASA Astrophysics Data System (ADS)

Bednarek, Janusz; Plonka, Andrzej; Hallbrucker, Andreas; Mayer, Erwin

1999-08-01

Radicals generated by high-energy irradiation of liquid water, short-lived at ambient temperature, can be studied at cryogenic temperatures after irradiating water and dilute aqueous solutions in their glassy states which can be obtained by so-called hyperquenching of the liquids at cooling rates of ˜10 6-10 7 K s -1. In the glassy states of hyperquenched dilute aqueous solutions there is no problem with phase separation and radiolysis of glassy water is quite distinct from radiolysis of polycrystalline ice obtained from liquid water on slow-cooling in liquid nitrogen.

FAST TRACK COMMUNICATION: A closer look at arrested spinodal decomposition in protein solutions

NASA Astrophysics Data System (ADS)

Gibaud, Thomas; Schurtenberger, Peter

2009-08-01

Concentrated aqueous solutions of the protein lysozyme undergo a liquid-solid transition upon a temperature quench into the unstable spinodal region below a characteristic arrest temperature of Tf = 15 °C. We use video microscopy and ultra-small angle light scattering in order to investigate the arrested structures as a function of initial concentration, quench temperature and rate of the temperature quench. We find that the solid-like samples show all the features of a bicontinuous network that is formed through an arrested spinodal decomposition process. We determine the correlation length ξ and demonstrate that ξ exhibits a temperature dependence that closely follows the critical scaling expected for density fluctuations during the early stages of spinodal decomposition. These findings are in agreement with an arrest scenario based on a state diagram where the arrest or gel line extends far into the unstable region below the spinodal line. Arrest then occurs when during the early stage of spinodal decomposition the volume fraction phi2 of the dense phase intersects the dynamical arrest threshold phi2,Glass, upon which phase separation gets pinned into a space-spanning gel network with a characteristic length ξ.

Effect of Preparation Methods on Crystallization Behavior and Tensile Strength of Poly(vinylidene fluoride) Membranes

PubMed Central

Liu, Jie; Lu, Xiaolong; Wu, Chunrui

2013-01-01

Poly(vinylidene fluoride) (PVDF) membranes were prepared by non solvent induced phase separation (NIPS), melt spinning and the solution-cast method. The effect of preparation methods with different membrane formation mechanisms on crystallization behavior and tensile strength of PVDF membranes was investigated. Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) and X-ray diffraction (XRD) were employed to examine the crystal form of the surface layers and the overall membranes, respectively. Spherulite morphologies and thermal behavior of the membranes were studied by polarized light optical microscopy (PLO) and differential scanning calorimetry (DSC) separately. It was found that the crystallization behavior of PVDF membranes was closely related to the preparation methods. For membranes prepared by the NIPS method, the skin layers had a mixture of α and β phases, the overall membranes were predominantly α phase, and the total crystallinity was 60.0% with no spherulite. For melt spinning membranes, the surface layers also showed a mixture of α and β phases, the overall membranes were predominantly α phase. The total crystallinity was 48.7% with perfect spherulites. Whereas the crystallization behavior of solution-cast membranes was related to the evaporation temperature and the additive, when the evaporation temperature was 140 °C with a soluble additive in the dope solution, obvious spherulites appeared. The crystalline morphology of PVDF exerted a great influence on the tensile strength of the membranes, which was much higher with perfect spherulites. PMID:24957064

Investigating surface chemistry-controlled dolomite precipitation in saline, alkaline, and dilute waters

NASA Astrophysics Data System (ADS)

Yoerg, A.; Roberts, J. A.

2017-12-01

Previous experiments have shown carboxylated organic matter facilitates dolomite precipitation at low temperature (< 80°C) in both modern and ancient seawater geochemistries. The efficacy of this mechanism in alternative chemical environments, particularly those typical of modern dolomitic environments, remains unclear. We investigated this question using a series of batch laboratory experiments ranging in duration from hours to several months. Experiments were conducted using fluids representative of environments where dolomite is found/thought to form in the modern, such as evaporative, alkaline lakes, sabkhas, and dilute mixing zones. Results indicate that while carboxylated organic matter promotes mineral precipitation in a variety of chemistries, the resultant mineralogy is primarily a function solution chemistry (i.e. saturation state). Specifically, our results suggest elevated alkalinity may be required to produce a high-Mg phase. In solutions where alkalinity is scarce, only amorphous carbonate phases form in association with organic matter, contrasting the Mg-bearing crystalline phases that result from highly alkaline solutions. Results of high-alkalinity, short-term experiments suggest that initially amorphous material is rapidly transformed into high and low-Mg phases in the presence of carboxylated organic matter, but that within days this mineralogy evolves. Longer timescales or elevated temperature may be necessary to produce an ordered dolomite phase. Additional results from longer term, steady-state experiments and additional analyses (Raman spectroscopy and tender energy spectroscopy) will shed further light on resultant mineralogy and this mechanism of dolomite precipitation.

Transient phases during fast crystallization of organic thin films from solution

NASA Astrophysics Data System (ADS)

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.

Effect of ageing time and temperature on corrosion behaviour of aluminum alloy 2014

NASA Astrophysics Data System (ADS)

Gadpale, Vikas; Banjare, Pragya N.; Manoj, Manoranjan Kumar

2018-03-01

In this paper, the effect of corrosion behaviour of aluminium alloy 2014 were studied by potentiodynamic polarization in 1 mole of NaCl solution of aged sample. The experimental testing results concluded that, corrosion resistance of Aluminum alloy 2014 degraded with the increasing the temperature (150°C & 200°C) and time of ageing. Corroded surface of the aged specimens was tested under optical microscopes for microstructures for phase analysis. Optical micrographs of corroded surfaces showed general corrosion and pitting corrosion. The corrosion resistance of lower ageing temperature and lower ageing time is higher because of its fine distribution of precipitates in matrix phase.

Structure and anomalous solubility for hard spheres in an associating lattice gas model.

PubMed

Szortyka, Marcia M; Girardi, Mauricio; Henriques, Vera B; Barbosa, Marcia C

2012-08-14

In this paper we investigate the solubility of a hard-sphere gas in a solvent modeled as an associating lattice gas. The solution phase diagram for solute at 5% is compared with the phase diagram of the original solute free model. Model properties are investigated both through Monte Carlo simulations and a cluster approximation. The model solubility is computed via simulations and is shown to exhibit a minimum as a function of temperature. The line of minimum solubility (TmS) coincides with the line of maximum density (TMD) for different solvent chemical potentials, in accordance with the literature on continuous realistic models and on the "cavity" picture.

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

NASA Astrophysics Data System (ADS)

Zhao, Yue; Tang, Xiao; Wu, Wei; Grivel, Jean-Claude

2014-05-01

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/NiW. 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-MOD cases. Moreover, we found that the formation of impurities (mainly BaCeO3, NiWO4 and NiO) is strongly related to the annealing temperature, i.e., the diffusion controlled reactions become intensive from 760 oC, which might be connected with the poor structural and superconducting properties of the films deposited at high sintering temperatures. Based on these results, the optimized growth conditions of YBCO films were established, and a high critical current density (Jc) of about 2 MA/cm2 (77 K, self field) is achieved in a 200 nm thick YBCO film in the architecture made by our all CSD route.

Complementary experimental-simulational study of surfactant micellar phase in the extraction process of metallic ions: Effects of temperature and salt concentration

NASA Astrophysics Data System (ADS)

Soto-Ángeles, Alan Gustavo; Rodríguez-Hidalgo, María del Rosario; Soto-Figueroa, César; Vicente, Luis

2018-02-01

The thermoresponsive micellar phase behaviour that exhibits the Triton-X-100 micelles by temperature effect and addition of salt in the extraction process of metallic ions was explored from mesoscopic and experimental points. In the theoretical study, we analyse the formation of Triton-X-100 micelles, load and stabilization of dithizone molecules and metallic ions extraction inside the micellar core at room temperature; finally, a thermal analysis is presented. In the experimental study, the spectrophotometric outcomes confirm the solubility of the copper-dithizone complex in the micellar core, as well as the extraction of metallic ions of aqueous environment via a cloud-point at 332.2 K. The micellar solutions with salt present a low absorbance value compared with the micellar solutions without salt. The decrease in the absorbance value is attributed to a change in the size of hydrophobic region of colloidal micelles. All transitory stages of extraction process are discussed and analysed in this document.

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

Garlea, Elena; Steiner, M. A.; Calhoun, C. A.

The α-phase transformation kinetics of as-cast U - 8 wt% Mo below the eutectoid temperature have been established by in situ neutron diffraction. α-phase weight fraction data acquired through Rietveld refinement at five different isothermal hold temperatures can be modeled accurately utilizing a simple Johnson-Mehl-Avrami-Kolmogorov impingement-based theory, and the results are validated by a corresponding evolution in the γ-phase lattice parameter during transformation that follows Vegard’s law. Neutron diffraction data is used to produce a detailed Time-Temperature-Transformation diagram that improves upon inconsistencies in the current literature, exhibiting a minimum transformation start time of 40 min at temperatures between 500 °Cmore » and 510 °C. Lastly, the transformation kinetics of U – 8 wt% Mo can vary significantly from as-cast conditions after extensive heat treatments, due to homogenization of the typical dendritic microstructure which possesses non-negligible solute segregation.« less

Large scale synthesis of nanostructured zirconia-based compounds from freeze-dried precursors

NASA Astrophysics Data System (ADS)

Gómez, A.; Villanueva, R.; Vie, D.; Murcia-Mascaros, S.; Martínez, E.; Beltrán, A.; Sapiña, F.; Vicent, M.; Sánchez, E.

2013-01-01

Nanocrystalline zirconia powders have been obtained at the multigram scale by thermal decomposition of precursors resulting from the freeze-drying of aqueous acetic solutions. This technique has equally made possible to synthesize a variety of nanostructured yttria or scandia doped zirconia compositions. SEM images, as well as the analysis of the XRD patterns, show the nanoparticulated character of those solids obtained at low temperature, with typical particle size in the 10-15 nm range when prepared at 673 K. The presence of the monoclinic, the tetragonal or both phases depends on the temperature of the thermal treatment, the doping concentration and the nature of the dopant. In addition, Rietveld refinement of the XRD profiles of selected samples allows detecting the coexistence of the tetragonal and the cubic phases for high doping concentration and high thermal treatment temperatures. Raman experiments suggest the presence of both phases also at relatively low treatment temperatures.

Glass ceramic toughened with tetragonal zirconia

DOEpatents

Keefer, K.D.

1984-02-10

A phase transformation-toughened glass ceramic and a process for making it are disclosed. A mixture of particulate network-forming oxide, network-modifying oxide, and zirconium oxide is heated to yield a homogeneous melt, and this melt is then heat treated to precipitate an appreciable quantity of tetragonal zirconia, which is retained at ambient temperature to form a phase transformation-toughened glass ceramic. Nuclearing agents and stabilizing agents may be added to the mixture to facilitate processing and improve the ceramic's properties. Preferably, the mixture is first melted at a temperature from 1200 to 1700/sup 0/C and is then heat-treated at a temperature within the range of 800 to 1200/sup 0/C in order to precipitate tetragonal ZrO/sub 2/. The composition, as well as the length and temperature of the heat treatment, must be carefully controlled to prevent solution of the precipitated tetragonal zirconia and subsequent conversion to the monoclinic phase.

Glass ceramic toughened with tetragonal zirconia

DOEpatents

Keefer, Keith D.; Michalske, Terry A.

1986-01-01

A phase transformation-toughened glass ceramic and a process for making it are disclosed. A mixture of particulate network-forming oxide, network-modifying oxide, and zirconium oxide is heated to yield a homogeneous melt, and this melt is then heat-treated to precipitate an appreciable quantity of tetragonal zirconia, which is retained at ambient temperature to form a phase transformation-toughened glass ceramic. Nucleating agents and stabilizing agents may be added to the mixture to facilitate processing and improve the ceramic's properties. Preferably, the mixture is first melted at a temperature from 1200.degree. to 1700.degree. C. and is then heat-treated at a temperature within the range of 800.degree. to 1200.degree. C. in order to precipitate tetragonal ZrO.sub.2. The composition, as well as the length and temperature of the heat-treatment, must be carefully controlled to prevent solution of the precipitated tetragonal zirconia and subsequent conversion to the monoclinic phase.

Effect of Channel Geometry and Properties of a Vapor-Gas Mixture on Volume Condensation in a Flow through a Nozzle

NASA Astrophysics Data System (ADS)

Sidorov, A. A.; Yastrebov, A. K.

2018-01-01

A method of direct numerical solution of the kinetic equation for the droplet size distribution function was used for the numerical investigation of volume condensation in a supersonic vapor-gas flow. Distributions of temperature for the gas phase and droplets, degree of supersaturation, pressure, fraction of droplets by weight, the number of droplets per unit mass, and of the nucleation rate along the channel were determined. The influence of nozzle geometry, mixture composition, and temperature dependence of the mixture properties on the investigated process was evaluated. It has been found that the nozzle divergence angle determines the vapor-gas mixture expansion rate: an increase in the divergence angle enhances the temperature decrease rate and the supersaturation degree raise rate. With an increase or decrease in the partial pressure of incondensable gas, the droplet temperature approaches the gas phase temperature or the saturation temperature at the partial gas pressure, respectively. A considerable effect of the temperature dependence of the liquid surface tension and properties on gas phase parameters and the integral characteristics of condensation aerosol was revealed. However, the difference in results obtained with or without considering the temperature dependence of evaporation heat is negligible. The predictions are compared with experimental data of other investigations for two mixtures: a mixture of heavy water vapor with nitrogen (incondensable gas) or n-nonane vapor with nitrogen. The predictions agree quite well qualitatively and quantitatively with the experiment. The comparison of the predictions with numerical results from other publications obtained using the method of moments demonstrates the usefulness of the direct numerical solution method and the method of moments in a wide range of input data.

A revised Pitzer model for low-temperature soluble salt assemblages at the Phoenix site, Mars

NASA Astrophysics Data System (ADS)

Toner, J. D.; Catling, D. C.; Light, B.

2015-10-01

The Wet Chemistry Laboratory (WCL) on the Mars Phoenix Lander measured ions in a soil-water extraction and found Na+, K+, H+ (pH), Ca2+, Mg2+, SO42-, ClO4-, and Cl-. Equilibrium models offer insights into salt phases that were originally present in the Phoenix soil, which dissolved to form the measured WCL solution; however, there are few experimental datasets for single cation perchlorates (ClO4-), and none for mixed perchlorates, at low temperatures, which are needed to build models. In this study, we measure ice and salt solubilities in binary and ternary solutions in the Na-Ca-Mg-ClO4 system, and then use this data, along with existing data, to construct a low-temperature Pitzer model for perchlorate brines. We then apply our model to a nominal WCL solution. Previous studies have modeled either freezing of a WCL solution or evaporation at a single temperature. For the first time, we model evaporation at subzero temperatures, which is relevant for dehydration conditions that might occur at the Phoenix site. Our model indicates that a freezing WCL solution will form ice, KClO4, hydromagnesite (3MgCO3·Mg(OH)2·3H2O), calcite (CaCO3), meridianiite (MgSO4·11H2O), MgCl2·12H2O, NaClO4·2H2O, and Mg(ClO4)2·6H2O at the eutectic (209 K). The total water held in hydrated salt phases at the eutectic is ∼1.2 wt.%, which is much greater than hydrated water contents when evaporation is modeled at 298.15 K (∼0.3 wt.%). Evaporation of WCL solutions at lower temperatures (down to 210 K) results in lower water activities and the formation of more dehydrated minerals, e.g. kieserite (MgSO4·H2O) instead of meridianiite. Potentially habitable brines, with water activity aw > 0.6, can occur when soil temperatures are above 220 K and when the soil liquid water content is greater than 0.4 wt.% (100 ×gH2O gsoil-1). In general, modeling indicates that mineral assemblages derived from WCL-type solutions are characteristic of the soil temperature, water content, and water activity conditions under which they formed, and are useful indicators of past environmental conditions.

Structural Changes in PEO-PPO-PEO Gels Induced by Methylparaben and Dexamethasone Observed Using Time-Resolved SAXS

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

Meznarich, Norman A.K.; Juggernauth, K Anne; Batzli, Kiersten M

2011-11-17

Aqueous solutions of polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) triblock copolymers (commercially available as Pluronic surfactants) micellize and structurally arrange into cubic quasicrystalline lattices as their temperature is raised. This structural evolution is seen macroscopically as a gelation, and the presence of these ordered phases can be controlled through both polymer concentration and temperature. The presence of added solutes within the dispersions can also affect the onset and kinetics of structure formation. Here we investigate the structures formed in Pluronic F127 solutions ranging from 20 to 30% with two pharmaceutical additives [methylparaben (MP) and dexamethasone (DX)] using small-angle X-ray scattering (SAXS). We observe bothmore » the progressive evolution and breakdown of these structures as the temperature is increased from 0 to 80 °C. Additionally, we conducted time-resolved SAXS measurements to elucidate the kinetics of the structural evolution. On the basis of the evolution of scattering peaks as the samples were being heated, we suggest that added MP changes the nucleation behavior of fcc phases within the sample from a heterogeneous process to a more homogeneous distribution of nucleated species. MP and DX also stabilize the micelle lattices, allowing them to persevere at higher temperatures. We observed the unusual result that the presence of DX caused the primary peaks of the structure factor to be suppressed, while preserving the higher order peaks. The primary peaks reappeared at the highest temperatures tested.« less

Temperature-dependent formation of NaCl dihydrate in levitated NaCl and sea salt aerosol particles.

PubMed

Peckhaus, Andreas; Kiselev, Alexei; Wagner, Robert; Duft, Denis; Leisner, Thomas

2016-12-28

Recent laboratory studies indicate that the hydrated form of crystalline NaCl is potentially important for atmospheric processes involving depositional ice nucleation on NaCl dihydrate particles under cirrus cloud conditions. However, recent experimental studies reported a strong discrepancy between the temperature intervals where the efflorescence of NaCl dihydrate has been observed. Here we report the measurements of the volume specific nucleation rate of crystalline NaCl in the aqueous solution droplets of pure NaCl suspended in an electrodynamic balance at constant temperature and humidity in the range from 250 K to 241 K. Based on these measurements, we derive the interfacial energy of crystalline NaCl dihydrate in a supersaturated NaCl solution and determined its temperature dependence. Taking into account both temperature and concentration dependence of nucleation rate coefficients, we explain the difference in the observed fractions of NaCl dihydrate reported in the previous studies. Applying the heterogeneous classical nucleation theory model, we have been able to reproduce the 5 K shift of the NaCl dihydrate efflorescence curve observed for the sea salt aerosol particles, assuming the presence of super-micron solid inclusions (hypothetically gypsum or hemihydrate of CaSO 4 ). These results support the notion that the phase transitions in microscopic droplets of supersaturated solution should be interpreted by accounting for the stochastic nature of homogeneous and heterogeneous nucleation and cannot be understood on the ground of bulk phase diagrams alone.

Temperature-dependent formation of NaCl dihydrate in levitated NaCl and sea salt aerosol particles

NASA Astrophysics Data System (ADS)

Peckhaus, Andreas; Kiselev, Alexei; Wagner, Robert; Duft, Denis; Leisner, Thomas

2016-12-01

Recent laboratory studies indicate that the hydrated form of crystalline NaCl is potentially important for atmospheric processes involving depositional ice nucleation on NaCl dihydrate particles under cirrus cloud conditions. However, recent experimental studies reported a strong discrepancy between the temperature intervals where the efflorescence of NaCl dihydrate has been observed. Here we report the measurements of the volume specific nucleation rate of crystalline NaCl in the aqueous solution droplets of pure NaCl suspended in an electrodynamic balance at constant temperature and humidity in the range from 250 K to 241 K. Based on these measurements, we derive the interfacial energy of crystalline NaCl dihydrate in a supersaturated NaCl solution and determined its temperature dependence. Taking into account both temperature and concentration dependence of nucleation rate coefficients, we explain the difference in the observed fractions of NaCl dihydrate reported in the previous studies. Applying the heterogeneous classical nucleation theory model, we have been able to reproduce the 5 K shift of the NaCl dihydrate efflorescence curve observed for the sea salt aerosol particles, assuming the presence of super-micron solid inclusions (hypothetically gypsum or hemihydrate of CaSO4). These results support the notion that the phase transitions in microscopic droplets of supersaturated solution should be interpreted by accounting for the stochastic nature of homogeneous and heterogeneous nucleation and cannot be understood on the ground of bulk phase diagrams alone.

Multi-scaling in the critical phenomena in the quenched disordered systems

NASA Astrophysics Data System (ADS)

Wu, X. T.

2018-04-01

The Landau-Ginzburg-Wilson Hamiltonian with random temperature for the phase transition in disordered systems from the Griffiths phase to ordered phase is reexamined. From the saddle point solutions, especially the excited state solutions, it is shown that the system self-organizes into blocks coupled with their neighbors like superspins, which are emergent variables. Taking the fluctuation around these saddle point solutions into account, we get an effective Hamiltonian, including the emergent superspins of the blocks, the fluctuation around the saddle point solutions, and their couplings. Applying Stratonovich-Hubbard transformation to the part of superspins, we get a Landau-Ginzburg-Wilson Hamiltonian for the blocks. From the saddle point equations for the blocks, we can get the second generation blocks, of which sizes are much larger than the first generation blocks. Repeating this procedure again and again, we get many generations of blocks to describe the asymptotic behavior. If a field is applied, the effective field on the superspins is multiplied greatly and proportional to the block size. For a very small field, the effective field on the higher generation superspins can be so strong to cause the superspins polarized radically. This can explain the extra large critical isotherm exponent discovered in the experiments. The phase space of reduced temperature vs. field is divided into many layers , in which different generation blocks dominate the critical behavior. The sizes of the different generation emergent blocks are new relevant length scales. This can explain a lot of puzzles in the experiments and the Monte Carlo simulation.

The Investigation of Chlorate/Iron-Phase Mixtures as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Clark, J.; Sutter, B.; Morris, R. V.; Archer, P. D.; Ming, D. W.; Niles, P.; Mahaffy, P.; Navarro-Gonzalez, R.

2016-01-01

The Sample Analysis at Mars (SAM) instrument on board the Curiosity Rover has detected oxygen and HCl gas releases from all analyzed Gale Crater sediments. The presence of perchlorate ClO4(sup-) and/or chlorates ClO3(sup-) are potential sources of the aforementioned O2 releases. The detections of O2 and HCl gas releases and chlorinated hydrocarbons by SAM coupled with the detection of perchlorates by Phoenix Lander's 2008 Wet Chemistry Laboratory all suggest that perchlorates, and possibly chorates, may be present in the Gale Crater sediments. Previous laboratory studies have attempted to replicate these O2 releases by heating perchlorates and chlorates in instruments operated similarly to those in the SAM instrument. Early studies found that pure perchlorates release O2 at temperatures higher than those observed in SAM data. Subsequently, studies were done to test the effects of mixing iron-phase minerals, analogous to those detected on Mars by ChemMin, with perchlorates. The iron in these minerals acts as a catalyst and causes O2 to be released from the perchlorate at a lower temperature. These studies found that perchlorate solutions mixed with either Hawaii palagonite or ferrihydrite produce O2 releases at temperatures similar to the Rocknest (RN) windblown deposit and the John Klein (JK) drill sample from the Sheepbed mudstone. The study also determined that perchlorate mixtures with magnetite, hematite, fayalite-magnetite, ilmentite, and pyrrhotite produce O2 releases at temperatures similar to the Confidence Hills (CH) drill sample from the Murray mudstone. Oxygen re-leases from pure chlorates were recently compared with the SAM data. Laboratory analyses determined that Ca-chlorate produces O2 and HCl peaks that are similar to those detected in RN and JK materials. Currently, no perchlorate/chlorate mixture with iron-phase minerals can explain the O2 releases from either the Cumberland (CB) drill sample from the Sheepbed mudstone or Windjana (WJ) drill sample from the Kimberly sandstone. Mixtures of chlorate solutions with iron-phase minerals may produce O2 peaks at temperatures that match those from CB and WJ materials. The goal of this work is to determine if heating chlorate solutions mixed with iron-phase minerals will produce O2 and HCl peak temperatures similar to O2 and HCl peak temperatures of sediments analyzed by SAM, particularly the WJ and CB materials.

Smart membranes: Hydroxypropyl cellulose for flavor delivery

NASA Astrophysics Data System (ADS)

Heitfeld, Kevin A.

2007-12-01

This work focuses on the use of temperature responsive gels (TRGs) (polymeric hydrogels with a large temperature-dependent change in volume) for flavor retention at cooking temperatures. Specifically, we have studied a gel with a lower critical solution temperature (LCST) that swells at low temperatures and collapses at high temperatures. In the collapsed state, the polymer acts as a transport barrier, keeping the volatile flavors inside. An encapsulation system was designed to utilize the solution (phase separation) behavior of a temperature responsive gel. The gel morphology was understood and diffusive properties were tailored through morphology manipulation. Heterogeneous and homogeneous gels were processed by understanding the effect of temperature on gel morphology. A morphology model was developed linking bulk diffusive properties to molecular morphology. Flavor was encapsulated within the gel and the emulsifying capability was determined. The capsules responded to temperature similarly to the pure polymer. The release kinetcs were compared to commercial gelatin capsules and the temperature responsive polymer took longer to release.

Cloud point extraction: an alternative to traditional liquid-liquid extraction for lanthanides(III) separation.

PubMed

Favre-Réguillon, Alain; Draye, Micheline; Lebuzit, Gérard; Thomas, Sylvie; Foos, Jacques; Cote, Gérard; Guy, Alain

2004-06-17

Cloud point extraction (CPE) was used to extract and separate lanthanum(III) and gadolinium(III) nitrate from an aqueous solution. The methodology used is based on the formation of lanthanide(III)-8-hydroxyquinoline (8-HQ) complexes soluble in a micellar phase of non-ionic surfactant. The lanthanide(III) complexes are then extracted into the surfactant-rich phase at a temperature above the cloud point temperature (CPT). The structure of the non-ionic surfactant, and the chelating agent-metal molar ratio are identified as factors determining the extraction efficiency and selectivity. In an aqueous solution containing equimolar concentrations of La(III) and Gd(III), extraction efficiency for Gd(III) can reach 96% with a Gd(III)/La(III) selectivity higher than 30 using Triton X-114. Under those conditions, a Gd(III) decontamination factor of 50 is obtained.

Effects of solvent density on retention in gas-liquid chromatography. I. Alkanes solutes in polyethylene glycol stationary phases.

PubMed

González, F R; Pérez-Parajón, J; García-Domínguez, J A

2002-04-12

Gas-liquid chromatographic columns were prepared coating silica capillaries with poly(oxyethylene) polymers of different molecular mass distributions, in the range of low number-average molar masses, where the density still varies significantly. A novel, high-temperature, rapid evaporation method was developed and applied to the static coating of the low-molecular-mass stationary phases. The analysis of alkanes retention data from these columns reveals that the dependence of the partition coefficient with the solvent macroscopic density is mainly due to a variation of entropy. Enthalpies of solute transfer contribute poorly to the observed variations of retention. Since the alkanes solubility diminishes with the increasing solvent density, and this variation is weakly dependent with temperature, it is concluded that the decrease of free-volume in the liquid is responsible for this behavior.

Photochemical solution processing of films of metastable phases for flexible devices: the β-Bi2O3 polymorph

PubMed Central

Pérez-Mezcua, Dulce; Bretos, Iñigo; Jiménez, Ricardo; Ricote, Jesús; Jiménez-Rioboó, Rafael J.; da Silva, Cosmelina Gonçalves; Chateigner, Daniel; Fuentes-Cobas, Luis; Sirera, Rafael; Calzada, M. Lourdes

2016-01-01

The potential of UV-light for the photochemical synthesis and stabilization of non-equilibrium crystalline phases in thin films is demonstrated for the β-Bi2O3 polymorph. The pure β-Bi2O3 phase is thermodynamically stable at high temperature (450–667 °C), which limits its applications in devices. Here, a tailored UV-absorbing bismuth(III)-N-methyldiethanolamine complex is selected as an ideal precursor for this phase, in order to induce under UV-light the formation of a –Bi–O–Bi– continuous network in the deposited layers and the further conversion into the β-Bi2O3 polymorph at a temperature as low as 250 °C. The stabilization of the β-Bi2O3 films is confirmed by their conductivity behavior and a thorough characterization of their crystal structure. This is also supported by their remarkable photocatalytic activity. Besides, this processing method has allowed us for the first time the preparation of β-Bi2O3 films on flexible plastic substrates, which opens new opportunities for using these materials in potential applications not available until now (e.g., flexible photocatalytic reactors, self-cleaning surfaces or wearable antimicrobial fabrics). Therefore, photochemical solution deposition (PCSD) demonstrates to be not only an efficient approach for the low temperature processing of oxide films, but also an excellent alternative for the stabilization of metastable phases. PMID:27996042

Stepwise positional-orientational order and the multicritical-multistructural global phase diagram of the s=3/2 Ising model from renormalization-group theory.

PubMed

Yunus, Çağın; Renklioğlu, Başak; Keskin, Mustafa; Berker, A Nihat

2016-06-01

The spin-3/2 Ising model, with nearest-neighbor interactions only, is the prototypical system with two different ordering species, with concentrations regulated by a chemical potential. Its global phase diagram, obtained in d=3 by renormalization-group theory in the Migdal-Kadanoff approximation or equivalently as an exact solution of a d=3 hierarchical lattice, with flows subtended by 40 different fixed points, presents a very rich structure containing eight different ordered and disordered phases, with more than 14 different types of phase diagrams in temperature and chemical potential. It exhibits phases with orientational and/or positional order. It also exhibits quintuple phase transition reentrances. Universality of critical exponents is conserved across different renormalization-group flow basins via redundant fixed points. One of the phase diagrams contains a plastic crystal sequence, with positional and orientational ordering encountered consecutively as temperature is lowered. The global phase diagram also contains double critical points, first-order and critical lines between two ordered phases, critical end points, usual and unusual (inverted) bicritical points, tricritical points, multiple tetracritical points, and zero-temperature criticality and bicriticality. The four-state Potts permutation-symmetric subspace is contained in this model.

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

PubMed

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.

Deformation and Damage Mechanisms in High Temperature Composits with Ductile Matrices

DTIC Science & Technology

1992-06-01

Models 2 2.1.2 Uniform Fields and Phase Eigenstrains 4 in Heterogeneous Media 6 2.1.3 Constitutive Equations of the Phases 10 2.1.4 Comparison with...systems, but the FDM model assumptions may no longer hold and the PHA model is again indicated. 3 I 2.1.2 Uniform Fields and Phase Eigenstrains in...mechanical and eigenstrain -induced local fields, and regard plastic strains as phase eigenstrains . A solution scheme for the PHA and FDM models was

The structure, thermal expansion and phase transition properties of Ho{sub 2}Mo{sub 3−x}W{sub x}O{sub 12} (x = 0, 1.0, 2.0) solid solutions

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

Liu, X.Z.; Hao, L.J.; Wu, M.M.

Graphical abstract: A polymorph with Gd{sub 2}Mo{sub 3}O{sub 12}-type structure (space group: Pba2) for negative thermal expansion material Ho{sub 2}Mo{sub 3}O{sub 12} is observed above 700 °C, this polymorphism could be effectively supressed by W-substiution for Mo, the give the temperature dependence of Pba2 phase contents for Ho{sub 2}Mo{sub 3−x}W{sub x}O{sub 12} (x = 0.0, 1.0, 2.0). - Highlights: • The solid solution Ho{sub 2}Mo{sub 3−x}W{sub x}O{sub 12} was investigated by in situ X-ray diffraction. • It is found that the substitution slightly influence thermal expansion property. • A polymorph of Ho{sub 2}Mo{sub 3}O{sub 12} with Pba2 space group wasmore » observed above 700 °C. • The W-substitution for Mo effectively suppresses this transformation. - Abstract: Three solid solutions of Ho{sub 2}Mo{sub 3−x}W{sub x}O{sub 12}(x = 0, 1.0, 2.0) were prepared by solid state reaction method, the temperature dependent in-situ X-ray diffraction and thermal analysis were performed to investigate their structure and thermal expansion. All samples have orthorhombic structure(space group Pbcn# 60) with negative thermal expansion at the room temperature. the substitution of W for Mo enlarges the lattice constant and slightly influences the negative thermal expansion. An irreversible phase transformation to the Pba2 phase(Tb{sub 2}Mo{sub 3}O{sub 12} structure) was observed at high temperature for Mo-rich samples. This ploymorphism could be effectively suppressed by the W-substitution for Mo, this phenomenon could be explained by the lower electronegativity of W{sup 6+} than Mo{sup 6+}.« less

Solvothermal method as a green chemistry solution for micro-encapsulation of phase change materials for high temperature thermal energy storage

NASA Astrophysics Data System (ADS)

Tudor, Albert Ioan; Motoc, Adrian Mihail; Ciobota, Cristina Florentina; Ciobota, Dan. Nastase; Piticescu, Radu Robert; Romero-Sanchez, Maria Dolores

2018-05-01

Thermal energy storage systems using phase change materials (PCMs) as latent heat storage are one of the main challenges at European level in improving the performances and efficiency of concentrated solar power energy generation due to their high energy density. PCM with high working temperatures in the temperature range 300-500 °C are required for these purposes. However their use is still limited due to the problems raised by the corrosion of the majority of high temperature PCMs and lower thermal transfer properties. Micro-encapsulation was proposed as one method to overcome these problems. Different micro-encapsulation methods proposed in the literature are presented and discussed. An original process for the micro-encapsulation of potassium nitrate as PCM in inorganic zinc oxide shells based on a solvothermal method followed by spray drying to produce microcapsules with controlled phase composition and distribution is proposed and their transformation temperatures and enthalpies measured by differential scanning calorimetry are presented.

Convective flows in enclosures with vertical temperature or concentration gradients

NASA Technical Reports Server (NTRS)

Wang, L. W.; Chai, A. T.; Sun, D. J.

1988-01-01

The transport process in the fluid phase during the growth of a crystal has a profound influence on the structure and quality of the solid phase. In vertical growth techniques the fluid phase is often subjected to vertical temperature and concentration gradients. The main objective is to obtain more experimental data on convective flows in enclosures with vertical temperature or concentration gradients. Among actual crystal systems the parameters vary widely. The parametric ranges studied for mass transfer are mainly dictated by the electrochemical system employed to impose concentration gradients. Temperature or concentration difference are maintained between two horizontal end walls. The other walls are kept insulated. Experimental measurements and observations were made of the heat transfer or mass transfer, flow patterns, and the mean and fluctuating temperature distribution. The method used to visualize the flow pattern in the thermal cases is an electrochemical pH-indicator method. Laser shadowgraphs are employed to visualize flow patterns in the solutal cases.

Convective flows in enclosures with vertical temperature or concentration gradients

NASA Technical Reports Server (NTRS)

Wang, L. W.; Chai, A. T.; Sun, D. J.

1989-01-01

The transport process in the fluid phase during the growth of a crystal has a profound influence on the structure and quality of the solid phase. In vertical growth techniques the fluid phase is often subjected to vertical temperature and concentration gradients. The main objective is to obtain more experimental data on convective flows in enclosures with vertical temperature or concentration gradients. Among actual crystal systems the parameters vary widely. The parametric ranges studied for mass transfer are mainly dictated by the electrochemical system employed to impose concentration gradients. Temperature or concentration difference are maintained between two horizontal end walls. The other walls are kept insulated. Experimental measurements and observations were made of the heat transfer or mass transfer, flow patterns, and the mean and fluctuating temperature distribution. The method used to visualize the flow pattern in the thermal cases is an electrochemical pH-indicator method. Laser shadowgraphs are employed to visualize flow patterns in the solutal cases.

Stability of exact solutions describing two-layer flows with evaporation at the interface

NASA Astrophysics Data System (ADS)

Bekezhanova, V. B.; Goncharova, O. N.

2016-12-01

A new exact solution of the equations of free convection has been constructed in the framework of the Oberbeck-Boussinesq approximation of the Navier-Stokes equations. The solution describes the joint flow of an evaporating viscous heat-conducting liquid and gas-vapor mixture in a horizontal channel. In the gas phase the Dufour and Soret effects are taken into account. The consideration of the exact solution allows one to describe different classes of flows depending on the values of the problem parameters and boundary conditions for the vapor concentration. A classification of solutions and results of the solution analysis are presented. The effects of the external disturbing influences (of the liquid flow rates and longitudinal gradients of temperature on the channel walls) on the stability characteristics have been numerically studied for the system HFE7100-nitrogen in the common case, when the longitudinal temperature gradients on the boundaries of the channel are not equal. In the system both monotonic and oscillatory modes can be formed, which damp or grow depending on the values of the initial perturbations, flow rates and temperature gradients. Hydrodynamic perturbations are most dangerous under large gas flow rates. The increasing oscillatory perturbations are developed due to the thermocapillary effect under large longitudinal gradients of temperature. The typical forms of the disturbances are shown.

Microstructural studies of hydrogen damage in metastable stainless steels. Ph.D. Thesis

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

Chen, S.

1994-12-31

The primary objective of this dissertation is to determine the role of microstructure in hydrogen-induced damage in austenitic stainless steels. Specific attention was focused on the interactions between hydrogen and the austenitic grain, twin boundaries and the matrix, and the associated phase transformations. An experimental program of research was conducted to determine the phase transformation and cracking path in hydrogen charged stainless steels. Normal-purity AISI 304 (Fe18CrYNi) and high-purity 305 (Fe18Cr12Ni) solution-annealet stainless steels were examined. The steels were cathodically charged with hydrogen at 1, 10 and 100 mA/sq cm at room temperature for 5 min. to 32 hours, inmore » an 1N H2SO4 solution with 0.25 g/l of NaAsO2 added as a hydrogen recombination poison. Resultant changes in microstructure and hydrogen damage due to charging and subsequent room temperature aging were studied by x-ray diffraction, optical microscope (in the Nomarski mode), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). A new phase in 305 stainless steel was observed, and was identified as an epsilon(*) (hcp) hydride due to hydrogen charging. Two new phases in 304 stainless steel were found as gamma(*) (fcc) and epsilon(*) hydrides from hydrogen charging. The hydride formation mechanisms during charging were: (1) gamma yields gamma(*) hydride and (2) gamma yields epsilon yields epsilon(*) hydride. These hydrides are unstable and decomposed during room temperature aging in air. The decomposition mechanisms were: (1) epsilon(*) hydride (hcp) yields expanded epsilon (hcp) phase yields a (bcc) phase; (2) gamma(*) hydride yields gamma phase. The grain and twin boundary cracks were the results of charging and identified as the preferred cracking sites. Transgranular crack initiation and growth accompanied the decomposition of hydrides and were controlled by hydrogen outgassing during room temperature aging.« less

Investigation on structural and electrical properties of Fe doped ZnO nanoparticles synthesized by solution combustion method

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

Ram, Mast, E-mail: mastram1999@yahoo.com; Bala, Kanchan; Sharma, Hakikat

In the present study, nanoparticles of Fe doped zinc oxide (ZnO) [Zn{sub 1-x}Fe{sub x}O where x=0.0, 0.01, 0.02, 0.03 and 0.05] were prepared by cost effective solution combustion method. The powder X-ray diffractometry confirms the formation of single phase wurtzite structure. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to investigate the micrsostructure of Fe-doped ZnO nanoparticles. The DC electrical conductivity was found to increase with temperature and measurement was carried out in the temperature range of 300-473K. DC electrical conductivity increases with temperature and decreases with Fe doping concentration.

Exploration Of `Click' Chemistry For Microelectronic Applications

NASA Astrophysics Data System (ADS)

Musa, Osama M.; Sridhar, Laxmisha M.

The ‘Click’ chemistry was explored for low temperature snap cure and for possible use as an adhesion promoter in electronic applications. Several azide and alkyne resins were synthesized and their curing potential was evaluated with a special emphasis on exploring Cu(I) catalyst effect. The preliminary curing study in the absence of catalysts showed a strong dependence of cure temperatures on the electronic nature of alkynes. The cure temperatures showed a tendency to increase with decreasing electronegativity of the substituent on alkynes. The capability of Cu(I) catalysts to accelerate the ‘Click’ chemistry was demonstrated for the first time in bulk phase. Using several Cu(I) catalysts, the cure temperatures could be lowered by as much as 40-100°C compared to the control, depending on the nature of catalyst and the catalyst loading. We discovered a novel synergistic effect between Cu(I) and silver filler in lowering the cure temperatures. Using this combination, lower cure temperatures could be obtained than using either alone. Among several resins screened, one resin system has shown promise for 80°C snap-cure in which the aforementioned synergistic effect is operative. Solution phase ‘Click’ chemistry was employed for the synthesis of a hybrid triazole-epoxy resin system. This system was found to cure without added amine curative. The triazole group here serves as a linker as well as an internal adhesion promoter. To address the incompatibility and volatility issues, which arose during evaluation, a controlled oligomerization method has been developed using controlled heating of azides and alkynes in solution phase.

Development of a new microextraction method based on elevated temperature dispersive liquid-liquid microextraction for determination of triazole pesticides residues in honey by gas chromatography-nitrogen phosphorus detection.

PubMed

Farajzadeh, Mir Ali; Mogaddam, Mohammad Reza Afshar; Ghorbanpour, Houshang

2014-06-20

In the present study, a rapid, highly efficient, and reliable sample preparation method named "elevated temperature dispersive liquid-liquid microextraction" followed by gas chromatography-nitrogen-phosphorus detection was developed for the extraction, preconcentration, and determination of five triazole pesticides (penconazole, hexaconazole, diniconazole, tebuconazole, and difenoconazole) in honey samples. In this method the temperature of high-volume aqueous phase was adjusted at an elevated temperature and then a disperser solvent containing an extraction solvent was rapidly injected into the aqueous phase. After cooling to room temperature, the phase separation was accelerated by centrifugation. Various parameters affecting the extraction efficiency such as type and volume of the extraction and disperser solvents, temperature, salt addition, and pH were evaluated. Under the optimum extraction conditions, the method resulted in low limits of detection and quantification within the range 0.05-0.21ngg(-1) in honey (15-70ngL(-1) in solution) and 0.15-1.1ngg(-1) in honey (45-210ngL(-1) in solution), respectively. Enrichment factors and extraction recoveries were in the ranges of 1943-1994 and 97-100%, respectively. The method precision was evaluated at 1.5ngg(-1) of each analyte, and the relative standard deviations were found to be less than 4% for intra-day (n=6) and less than 6% for inter-days. The method was successfully applied to the analysis of honey samples and difenoconazole was determined at ngg(-1) levels. Copyright © 2014 Elsevier B.V. All rights reserved.

Exploring connections between statistical mechanics and Green's functions for realistic systems: Temperature dependent electronic entropy and internal energy from a self-consistent second-order Green's function

NASA Astrophysics Data System (ADS)

Welden, Alicia Rae; Rusakov, Alexander A.; Zgid, Dominika

2016-11-01

Including finite-temperature effects from the electronic degrees of freedom in electronic structure calculations of semiconductors and metals is desired; however, in practice it remains exceedingly difficult when using zero-temperature methods, since these methods require an explicit evaluation of multiple excited states in order to account for any finite-temperature effects. Using a Matsubara Green's function formalism remains a viable alternative, since in this formalism it is easier to include thermal effects and to connect the dynamic quantities such as the self-energy with static thermodynamic quantities such as the Helmholtz energy, entropy, and internal energy. However, despite the promising properties of this formalism, little is known about the multiple solutions of the non-linear equations present in the self-consistent Matsubara formalism and only a few cases involving a full Coulomb Hamiltonian were investigated in the past. Here, to shed some light onto the iterative nature of the Green's function solutions, we self-consistently evaluate the thermodynamic quantities for a one-dimensional (1D) hydrogen solid at various interatomic separations and temperatures using the self-energy approximated to second-order (GF2). At many points in the phase diagram of this system, multiple phases such as a metal and an insulator exist, and we are able to determine the most stable phase from the analysis of Helmholtz energies. Additionally, we show the evolution of the spectrum of 1D boron nitride to demonstrate that GF2 is capable of qualitatively describing the temperature effects influencing the size of the band gap.

Iron-titanium oxyhydroxides which transport water into the deep upper mantle and mantle transition zone

NASA Astrophysics Data System (ADS)

Matsukage, K. N.; Nishihara, Y.

2015-12-01

We experimentally discovered a new hydrous phase in the system FeOOH-TiO2 at pressures of 10-16 GPa and temperatures of 1000-1600°C which corresponds to conditions of the deep upper mantle and the Earth's mantle transition zone. Seven different compositions in the FeOOH-TiO2 system having molar ratios of x = Ti/(Fe + Ti) = 0, 0.125, 0.25, 0.375, 0.5, 0.75 that were prepared by mixing reagent grade a-FeOOH (goethite) and TiO2 (anatase) powders were used as starting materials. High-pressure and high-temperature experiments were carried out using Kawai-type multi-anvil apparatus (Orange-1000 at Ehime University and SPI-1000 at Tokyo Institute of Technology). In this system, we identified two stable iron-titanium oxyhydroxide phases whose estimated composition is expressed by (FeH)1 - xTixO2 . One is the Fe-rich solid solution (x < 0.23) with e-FeOOH type crystal structure (e-phase, orthorhombic, P21nm) that was described by the previous studies (e.g., Suzuki 2010), and the other is the more Ti-rich solid solution (x > 0.35) with a-PbO2 type structure (a-phase, orthorhombic, Pbcn). The a-phase is stable up to 1500ºC for a composition of x = 0.5 and at least to 1600ºC for x = 0.75. Our result means that this phase is stable at average mantle temperature in the Earth's mantle transition zone. The Iron-titanium-rich hydrous phases was possible to stable in basalt + H2O system (e.g., Hashimoto and Matsukage 2013). Therefore our findings suggest that water transport in the Earth's deep interior is probably much more efficient than had been previously thought.

Classical mutual information in mean-field spin glass models

NASA Astrophysics Data System (ADS)

Alba, Vincenzo; Inglis, Stephen; Pollet, Lode

2016-03-01

We investigate the classical Rényi entropy Sn and the associated mutual information In in the Sherrington-Kirkpatrick (S-K) model, which is the paradigm model of mean-field spin glasses. Using classical Monte Carlo simulations and analytical tools we investigate the S-K model in the n -sheet booklet. This is achieved by gluing together n independent copies of the model, and it is the main ingredient for constructing the Rényi entanglement-related quantities. We find a glassy phase at low temperatures, whereas at high temperatures the model exhibits paramagnetic behavior, consistent with the regular S-K model. The temperature of the paramagnetic-glassy transition depends nontrivially on the geometry of the booklet. At high temperatures we provide the exact solution of the model by exploiting the replica symmetry. This is the permutation symmetry among the fictitious replicas that are used to perform disorder averages (via the replica trick). In the glassy phase the replica symmetry has to be broken. Using a generalization of the Parisi solution, we provide analytical results for Sn and In and for standard thermodynamic quantities. Both Sn and In exhibit a volume law in the whole phase diagram. We characterize the behavior of the corresponding densities, Sn/N and In/N , in the thermodynamic limit. Interestingly, at the critical point the mutual information does not exhibit any crossing for different system sizes, in contrast with local spin models.

Investigation of the phase relations in the U-Al-Ge ternary system: Influence of the Al/Ge substitution on the properties of the intermediate phases

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

Moussa, C.; El Sayah, Z.; Chajewski, G.

The phase relations within the U-Al-Ge ternary system were studied for two isothermal sections, at 673 K for the whole Gibbs triangle and at 1173 K for the concentration range 25–100 at% U. The identification of the phases, their composition ranges and stability were determined by x-ray powder diffraction, scanning electron microscopy coupled to energy dispersive spectroscopy and differential thermal analysis. The tie-lines and the solubility domains were determined for the U-Ge and U-Al binaries, the UAl{sub 3}-UGe{sub 3} solid-solution and for the unique ternary intermediate phase U{sub 3}Al{sub 2−x}Ge{sub 3+x}. The experimental isopleth section of the pseudo-binary UAl{sub 3}-UGe{submore » 3} reveals an isomorphous solid solution based on the Cu{sub 3}Au-type below the solidus. The U{sub 3}Al{sub 2−x}Ge{sub 3+x} solid solution extends for −0.1≤x≤1.35 and −0.2≤x≤1.5 at 673 K and 1173 K respectively. It crystallizes in the I-centered tetragonal symmetry. The reciprocal lattice of several compositions of the U{sub 3}Al{sub 2−x}Ge{sub 3+x} solid solution was examined by electron diffraction at room temperature, revealing the presence of a c-glide plane. Their crystal structure was refined by single crystal x-ray diffraction suggesting an isomorphous solid solution best described with the non-centrosymmetric space group I4cm in the paramagnetic domain. The magnetic measurements confirm the ferromagnetic ordering of the solid solution U{sub 3}Al{sub 2−x}Ge{sub 3+x} with an increase of Tc with the Al content. The thermal variation of the specific heat bear out the magnetic transitions with some delocalized character of the uranium 5f electrons. - Graphical abstract: The phase relations within the U-Al-Ge ternary system were experimentally assessed for two isothermal sections, at 673 K for the whole Gibbs triangle and at 1173 K for the concentration range 25–100 at% U. A complete UAl{sub 3}-UGe{sub 3} solid-solution based on the Cu{sub 3}Au-type forms below the solidus. A unique ternary phase showing a large homogeneity domain, U{sub 3}Al{sub 2−x}Ge{sub 3+x} for −0.1≤x≤1.35 and −0.2≤x≤1.5 at 673 K and 1173 K respectively has been evidenced. It is best described with the non-centrosymmetric space group I4cm above room temperature. A linear increase of the ferromagnetic ordering is observed with the Al content. - Highlights: • Isothermal sections of the U-Al-Ge system were investigated for 673 K and 1173 K. • An isomorphous solid-solution UAl{sub 3}-UGe{sub 3} forms for the whole composition range. • U{sub 3}Al{sub 2−x}Ge{sub 3+x} the unique ternary phase to form exists for a large homogeneity domain. • U{sub 3}Al{sub 2−x}Ge{sub 3+x} is best described in I4cm space group above room temperature. • The ferromagnetic transition of U{sub 3}Al{sub 2−x}Ge{sub 3+x} linearly increases with the Al content.« less

Evidence for transbilayer, tail-to-tail cholesterol dimers in dipalmitoylglycerophosphocholine liposomes.

PubMed

Harris, J S; Epps, D E; Davio, S R; Kézdy, F J

1995-03-21

The behavior of multilamellar liposomes of 2,3-dipalmitoyl-sn-glycero-1-phosphocholine (DPPC) was studied by differential scanning calorimetry (DSC) in the presence of < or = 5 mol % of the amphiphilic solutes methyl oleate, cholesterol, pregnenolone, and dehydroandrosterone. The DSC thermograms indicate that the solutes are miscible only with the liquid-disordered (Id) phase, and not with the solid-ordered (so) phase. The slopes of the Tm vs solute concentration curves confirm this conclusion: It appears that the so-1d phase transition of DPPC, which corresponds to the melting of the phospholipid chains, can be treated as a simple melting process and, thus, could be used as a cryoscopic system. In that case, its melting point depression constant, Kf, can be calculated a priori from the experimentally measured heat of fusion per gram of DPPC, lf, and the temperature of the phase transition of pure DPPC, T(o), by the equation Kf = RTo2/(1000lf) = 12.3 +/- 0.9 K g M-1 cm3. With methyl oleate as the solute, the Tm vs methyl oleate concentration plot is linear, and from the slope we calculate Kf = 12.9 +/- 0.8 K g M-1 cm3. Thus, methyl oleate appears to form an ideal cryoscopic system with dipalmitoyllecithin liposomes: It is fully miscible with the 1d phase but is apparently insoluble in the s(o) phase. Pregnenolone and dehydroandrosterone also form ideal cryoscopic systems with dipalmitoyllecithin liposomes: The Tm vs solute concentration plots are linear and yield the correct MWs for these solutes.(ABSTRACT TRUNCATED AT 250 WORDS)

Simultaneous extraction and HPLC determination of 3-indole butyric acid and 3-indole acetic acid in pea plant by using ionic liquid-modified silica as sorbent.

PubMed

Sheikhian, Leila; Bina, Sedigheh

2016-01-15

In this study, ionic liquid-modified silica was used as sorbent for simultaneous extraction and preconcentration of 3-indole butyric acid and 3-indole acetic acid in pea plants. The effect of some parameters such as pH and ionic strength of sample solution, amount of sorbent, flow rate of aqueous sample solution and eluent solution, concentration of eluent solution, and temperature were studied for each hormone solution. Percent extraction of 3-indole butyric acid and 3-indole acetic acid was strongly affected by pH of aqueous sample solution. Ionic strength of aqueous phase and temperature showed no serious effects on extraction efficiency of studied plant hormones. Obtained breakthrough volume was 200mL for each of studied hormones. Preconcentration factor for spectroscopic and chromatographic determination of studied hormones was 100 and 4.0×10(3) respectively. Each solid sorbent phase was reusable for almost 10 times of extraction/stripping procedure. Relative standard deviations of extraction/stripping processes of 3-indole butyric acid and 3-indole acetic acid were 2.79% and 3.66% respectively. The calculated limit of detections for IBA and IAA were 9.1×10(-2)mgL(-1) and 1.6×10(-1)mgL(-1) respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Extraction of cesium, strontium and the platinium group metals from acidic high activity nuclear waste using a Purex process compatible organic extractant. Final report, December 15, 1980-August 15, 1983

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

Davis, M.W. Jr.; Van Brunt, V.

1984-09-14

Purex process compatible organic systems which selectively and reversibly extract cesium, strontium, and palladium from synthetic mixed fission product solutions containing 3M HNO/sub 3/ have been developed. This advance makes the development of continuous solvent extraction processes for their recovery more likely. The most favorable cesium and strontium complexing solutions have been tested for radiation stability to 10/sup 7/ rad using a 0.4 x 10/sup 7/ rad/h /sup 60/Co source. The distribution coefficients dropped somewhat but remained above unity. For cesium the complexing organic solution is 5 vol % (0.1M) NNS, 27 vol % TBP and 68 vol % kerosenemore » containing 0.05m Bis 4,4',(5')(1-hydroxy 2-ethylhexyl)-benzo 18-crown-6 (Crown XVII). The NNS is a sulfonic acid cation exchanger. With an aqueous phase containing 0.006M Cs/sup +1/ in contact with an equal volume of extractant the D org/aq = 1.6 at a temperature of 25 to 35/sup 0/C. For strontium the complexing organic solution is 5 vol % (0.1M) NNS, 27 vol % TBP and 68 vol % Kerosene containing 0.02M Bis 4,4'(5') (1-hydroxyheptyl)cyclohexo 18-crown-6 (Crown XVI). With an aqueous phase containing 0.003M Sr/sup +2/ in contact with an equal volume of extractant the D org/aq = 1.98 at a temperature of 25 to 35/sup 0/C. For palladium the complexing organic solution consisted of a ratio of TBP/kerosene of 0.667 containing 0.3M Alamine 336 which is a tertiary amine anion exchanger. With an aqueous phase containing 0.0045M Pd/sup +/ in contact with an equal volume of extractant the D org/aq = 1.95 at a temperature of 25 to 35/sup 0/C.« less

Solid-phase microextraction for qualitative and quantitative determination of migrated degradation products of antioxidants in an organic aqueous solution.

PubMed

Burman, Lina; Albertsson, Ann-Christine; Höglund, Anders

2005-07-08

Low molecular weight aromatic substances may migrate out from plastic packaging to their contents, especially if they consist of organic aqueous solutions or oils. It is, therefore, extremely important to be able to identify and quantify any migrated substances in such solutions, even at very low concentrations. We have in this work investigated and evaluated the use of solid-phase microextraction for the specific task of extraction from an organic aqueous solution such as a simulated pharmaceutical solution consisting of 10 vol.% ethanol in water. The goal was furthermore to investigate the possibility of simultaneously identifying and quantifying the substances in spite of differences in their chemical structures. Methods were developed and evaluated for extraction both with direct sampling and with headspace sampling. Difficulties appeared due to the ethanol in the solution and the minute amounts of substances present. We have shown that a simultaneous quantification of migrated low molecular weight degradation products of antioxidants using only one fibre is possible if the extraction method and temperature are adjusted in relation to the concentration levels of the analytes. Comparions were made with solid-phase extraction.

Viscometric and misting properties of polymer-modified fuel

NASA Technical Reports Server (NTRS)

Grens, E. A., II; Williams, M. C.

1982-01-01

Solutions of polyisobutylenes L160, L200, B200, and B230 in Jet-A were prepared at concentrations up to 3000 ppm. These polymers have molecular weights in the range 5 to 9 x 1,00,000 and have previously been shown to induce anti-misting properties in Jet-A. In connection with the pumpability of such solutions, especially at low temperatures, the shear viscosity, eta, of these solutions was measured at temperatures 25 C, 0 C, and -25 C. Concentration-dependence of eta was very similar for all four polymer solutes, the increase of eta(c) at 3000 ppm being roughly four-fold (relative to Jet-A) for the L-series and five-fold for the B-series. This behavior prevailed at all temperatures, and there was no evidence of phase separation or other chemical instability at -25 C at any concentration. In the more practical c-range for anti-misting applications, say within 1000 ppm, the increase of eta(c) was only twofold.

Postdoc Proposal

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

Dorhout, Jacquelyn Marie

2017-11-21

The goal of this project is to determine whether variables such as the molarity of nitric acid (HNO 3), temperature, and surface characteristics of uranium materials have an effect on the fractionation of 15N between the solution and vapor phases.

Features of the adsoprtion of naproxen on the chiral stationary phase (S,S)-Whelk-O1 under reversed-phase conditions

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

Asnin, Leonid; Gritti, Fabrice; Kaczmarski, Krzysztof

Using elution chromatography, we studied the adsorption mechanism of the Naproxen enantiomers on the chiral stationary phase (S,S)-Whelk-O1, from buffered methanol-water solutions. We propose an adsorption mechanism that assumes monolayer adsorption of the more retained enantiomer and the associative adsorption of the less retained one. The effects of the mobile phase composition on the adsorption of Naproxen are discussed. The combination of an elevated column temperature and of the use of an acidic mobile phase led to the degradation of the column and caused a major loss of its separation ability. The use of a moderately acidic mobile phase atmore » temperature slightly above ambient did not produce rapid severe damages but, nevertheless, hampered the experiments and caused a slow gradual deterioration of the column.« less

Formation mechanism of axial macrosegregation of primary phases induced by a static magnetic field during directional solidification

PubMed Central

Li, Xi; Fautrelle, Yves; Ren, Zhongming; Moreau, Rene

2017-01-01

Understanding the macrosegregation formed by applying magnetic fields is of high commercial importance. This work investigates how static magnetic fields control the solute and primary phase distributions in four directionally solidified alloys (i.e., Al-Cu, Al-Si, Al-Ni and Zn-Cu alloys). Experimental results demonstrate that significant axial macrosegregation of the solute and primary phases (i.e., Al2Cu, Si, Al3Ni and Zn5Cu phases) occurs at the initial solidification stage of the samples. This finding is accompanied by two interface transitions in the mushy zone: quasi planar → sloping → quasi planar. The amplitude of the macrosegregation of the primary phases under the magnetic field is related to the magnetic field intensity, temperature gradient and growth speed. The corresponding numerical simulations present a unidirectional thermoelectric (TE) magnetic convection pattern in the mushy zone as a consequence of the interaction between the magnetic field and TE current. Furthermore, a model is proposed to explain the peculiar macrosegregation phenomenon by considering the effect of the forced TE magnetic convection on the solute distribution. The present study not only offers a new approach to control the solute distribution by applying a static magnetic field but also facilitates the understanding of crystal growth in the solute that is controlled by the static magnetic field during directional solidification. PMID:28367991

A novel perovskite oxide chemically designed to show multiferroic phase boundary with room-temperature magnetoelectricity

NASA Astrophysics Data System (ADS)

Fernández-Posada, Carmen M.; Castro, Alicia; Kiat, Jean-Michel; Porcher, Florence; Peña, Octavio; Algueró, Miguel; Amorín, Harvey

2016-09-01

There is a growing activity in the search of novel single-phase multiferroics that could finally provide distinctive magnetoelectric responses at room temperature, for they would enable a range of potentially disruptive technologies, making use of the ability of controlling polarization with a magnetic field or magnetism with an electric one (for example, voltage-tunable spintronic devices, uncooled magnetic sensors and the long-searched magnetoelectric memory). A very promising novel material concept could be to make use of phase-change phenomena at structural instabilities of a multiferroic state. Indeed, large phase-change magnetoelectric response has been anticipated by a first-principles investigation of the perovskite BiFeO3-BiCoO3 solid solution, specifically at its morphotropic phase boundary between multiferroic polymorphs of rhombohedral and tetragonal symmetries. Here, we report a novel perovskite oxide that belongs to the BiFeO3-BiMnO3-PbTiO3 ternary system, chemically designed to present such multiferroic phase boundary with enhanced ferroelectricity and canted ferromagnetism, which shows distinctive room-temperature magnetoelectric responses.

A novel perovskite oxide chemically designed to show multiferroic phase boundary with room-temperature magnetoelectricity.

PubMed

Fernández-Posada, Carmen M; Castro, Alicia; Kiat, Jean-Michel; Porcher, Florence; Peña, Octavio; Algueró, Miguel; Amorín, Harvey

2016-09-28

There is a growing activity in the search of novel single-phase multiferroics that could finally provide distinctive magnetoelectric responses at room temperature, for they would enable a range of potentially disruptive technologies, making use of the ability of controlling polarization with a magnetic field or magnetism with an electric one (for example, voltage-tunable spintronic devices, uncooled magnetic sensors and the long-searched magnetoelectric memory). A very promising novel material concept could be to make use of phase-change phenomena at structural instabilities of a multiferroic state. Indeed, large phase-change magnetoelectric response has been anticipated by a first-principles investigation of the perovskite BiFeO 3 -BiCoO 3 solid solution, specifically at its morphotropic phase boundary between multiferroic polymorphs of rhombohedral and tetragonal symmetries. Here, we report a novel perovskite oxide that belongs to the BiFeO 3 -BiMnO 3 -PbTiO 3 ternary system, chemically designed to present such multiferroic phase boundary with enhanced ferroelectricity and canted ferromagnetism, which shows distinctive room-temperature magnetoelectric responses.

Density functional theory of freezing of a system of highly elongated ellipsoidal oligomer solutions

NASA Astrophysics Data System (ADS)

Dwivedi, Shikha; Mishra, Pankaj

2017-05-01

We have used the density functional theory of freezing to study the liquid crystalline phase behavior of a system of highly elongated ellipsoidal conjugated oligomers dispersed in three different solvents namely chloroform, toluene and their equimolar mixture. The molecules are assumed to interact via solvent-implicit coarse-grained Gay-Berne potential. Pair correlation functions needed as input in the density functional theory have been calculated using the Percus-Yevick (PY) integral equation theory. Considering the isotropic and nematic phases, we have calculated the isotropic-nematic phase transition parameters and presented the temperature-density and pressure-temperature phase diagrams. Different solvent conditions are found not only to affect the transition parameters but also determine the capability of oligomers to form nematic phase in various thermodynamic conditions. In principle, our results are verifiable through computer simulations.

Effectiveness of the Surfactant Dioctyl Sodium Sulfosuccinate (DOSS) to Disperse Oil in a Changing Marine Environment

NASA Astrophysics Data System (ADS)

Steffy, D. A.; Nichols, A.; Kiplagat, G.

2011-12-01

We investigated the surfactant which was used to disperse the oil spill which occurred in the Gulf of Mexico during the summer 2010. The surfactant DOSS is an organic sulfonic acid salt which is a synthetic detergent that disrupts the interfacial tension between the saltwater and crude oil phases. The disruption becomes maximum at or above the critical micelle concentration (CMC). The CMC for the surfactant was determined to be at 0.13 % solution in deionized water at a pH of 7.2 and a temperature of 70oF. The CMC is lower at 0.09% solution in salt water. The effect has been identified as a "salting out" effect (Somasundaran, 2006). The CMC of DOSS in both saline and deionized water occurred at lower percent solutions at higher temperatures. The surface tension versus % solution plots are modeled by a power equation, with correlation coefficients consistently over 0.94. Surface tension versus percent solution plots are scalable to fit a temperature desired by the function f(x)= (1/(1+X^α)), where α = T1/T2.

Regular expansion solutions for small Peclet number heat or mass transfer in concentrated two-phase particulate systems

NASA Technical Reports Server (NTRS)

Yaron, I.

1974-01-01

Steady state heat or mass transfer in concentrated ensembles of drops, bubbles or solid spheres in uniform, slow viscous motion, is investigated. Convective effects at small Peclet numbers are taken into account by expanding the nondimensional temperature or concentration in powers of the Peclet number. Uniformly valid solutions are obtained, which reflect the effects of dispersed phase content and rate of internal circulation within the fluid particles. The dependence of the range of Peclet and Reynolds numbers, for which regular expansions are valid, on particle concentration is discussed.

Characterization of solution-phase and gas-phase reactions in on-line electrochemistry-thermospray tandem mass spectrometry.

PubMed

Volk, K J; Yost, R A; Brajter-Toth, A

1989-07-14

Electrochemistry was used on-line with high-performance liquid chromatography-thermospray tandem mass spectrometry to provide insight into the solution-phase decomposition reactions of electrochemically generated oxidation products. Products formed during electrooxidation were monitored as the electrode potential was varied. The solution reactions which follow the initial electron transfer at the electrode are affected by the vaporizer tip temperature of the thermospray probe and the composition of the thermospray buffer. Either hydrolysis or ammonolysis reactions of the initial electrochemical oxidation products can occur with pH 7 ammonium acetate buffer. Both the electrochemically generated and the synthesized disulfide of 6-thiopurine decompose under thermospray conditions to produce 6-thiopurine and purine-6-sulfinate. Solution-phase studies indicate that nucleophilic and electrophilic substitution reactions with purine-6-sulfinate result in the formation of purine, adenine, and hypoxanthine. Products were identified and characterized by tandem mass spectrometry. This work shows the first example of high-performance liquid chromatography used on-line with electrochemistry to separate stable oxidation products prior to analysis by thermospray tandem mass spectrometry. In addition, solution-phase and gas-phase studies with methylamine show that the site of the nucleophilic and electrophilic reactions is probably inside the thermospray probe. Most importantly, these results also show that the on-line combination of electrochemistry with thermospray tandem mass spectrometry provides valuable information about redox and associated chemical reactions of biological molecules such as the structures of intermediates or products as well as providing insight into reaction pathways.

Ductile tungsten-nickel alloy and method for making same

DOEpatents

Snyder, Jr., William B.

1976-01-01

The present invention is directed to a ductile, high-density tungsten-nickel alloy which possesses a tensile strength in the range of 100,000 to 140,000 psi and a tensile elongation of 3.1 to 16.5 percent in 1 inch at 25.degree.C. This alloy is prepared by the steps of liquid phase sintering a mixture of tungsten-0.5 to 10.0 weight percent nickel, heat treating the alloy at a temperature above the ordering temperature of approximately 970.degree.C. to stabilize the matrix phase, and thereafter rapidly quenching the alloy in a suitable liquid to maintain the matrix phase in a metastable, face-centered cubic, solid- solution of tungsten in nickel.

Kinetics of the cellular decomposition of supersaturated solid solutions

NASA Astrophysics Data System (ADS)

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

2014-09-01

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

Liquid-liquid separation in solutions of normal and sickle cell hemoglobin

NASA Astrophysics Data System (ADS)

Galkin, Oleg; Chen, Kai; Nagel, Ronald L.; Elison Hirsch, Rhoda; Vekilov, Peter G.

2002-06-01

We show that in solutions of human hemoglobin (Hb)oxy- and deoxy-Hb A or Sof near-physiological pH, ionic strength, and Hb concentration, liquid-liquid phase separation occurs reversibly and reproducibly at temperatures between 35 and 40°C. In solutions of deoxy-HbS, we demonstrate that the dense liquid droplets facilitate the nucleation of HbS polymers, whose formation is the primary pathogenic event for sickle cell anemia. In view of recent results that shifts of the liquid-liquid separation phase boundary can be achieved by nontoxic additives at molar concentrations up to 30 times lower than the protein concentrations, these findings open new avenues for the inhibition of the HbS polymerization.

Free energy change of off-eutectic binary alloys on solidification

NASA Technical Reports Server (NTRS)

Ohsaka, K.; Trinh, E. H.; Lin, J.-C.; Perepezko, J. H.

1991-01-01

A formula for the free energy difference between the undercooled liquid phase and the stable solid phase is derived for off-eutectic binary alloys in which the equilibrium solid/liquid transition takes place over a certain temperature range. The free energy change is then evaluated numerically for a Bi-25 at. pct Cd alloy modeled as a sub-subregular solution.

Optimization of the crystal growth of the superconductor CaKFe4As4 from solution in the FeAs -CaFe2As2-KFe2As2 system

NASA Astrophysics Data System (ADS)

Meier, W. R.; Kong, T.; Bud'ko, S. L.; Canfield, P. C.

2017-06-01

Measurements of the anisotropic properties of single crystals play a crucial role in probing the physics of new materials. Determining a growth protocol that yields suitable high-quality single crystals can be particularly challenging for multicomponent compounds. Here we present a case study of how we refined a procedure to grow single crystals of CaKFe4As4 from a high temperature, quaternary liquid solution rich in iron and arsenic ("FeAs self-flux"). Temperature dependent resistance and magnetization measurements are emphasized, in addition to the x-ray diffraction, to detect intergrown CaKFe4As4 , CaFe2As2 , and KFe2As2 within what appear to be single crystals. Guided by the rules of phase equilibria and these data, we adjusted growth parameters to suppress formation of the impurity phases. The resulting optimized procedure yielded phase-pure single crystals of CaKFe4As4 . This optimization process offers insight into the growth of quaternary compounds and a glimpse of the four-component phase diagram in the pseudoternary FeAs -CaFe2As2-KFe2As2 system.

Structural and ferroelectric phase evolution in [KNbO3]1-x[BaNi1/2Nb1/2O3-δ]x (x = 0, 0.1)

NASA Astrophysics Data System (ADS)

Hawley, Christopher; Wu, Liyan; Xiao, Geoffrey; Grinberg, Ilya; Rappe, Andrew; Davies, Peter; Spanier, Jonathan

The phase transition evolution for [KNbO3]1-x[BaNi1/2Nb1/2O3-δ]x (x=0, 0.1) is determined via complementary dielectric constant and Raman scattering measurements. Raman scattering by optical phonons over the range of 100-1000 cm-1 for -190°C < T < 600°C reveals six discernible zone-center optical phonon modes. They are assigned to structural and ferroelectric phases in the solid solution x = 0.1 and compared with those for end member x = 0 and with the results of temperature-dependent dielectric permittivity. Rigorous peak fitting analyses of spectra collected from the solid solution and end member indicate structural and ferroelectric phase transition temperatures that are quite close to those for the KNbO3 end member. Remarkably, despite the inclusion of 5 atomic Work supported by US ARO under W911NF-14-1-0500, NSF 1123696, and DoE BES under DE-FG02-07ER46431. Equipment acquisitions and computational support under DURIP and DoE NERSCC.

Transient phases during crystallization of solution-processed organic thin films

NASA Astrophysics Data System (ADS)

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.

The effect of an external electric field on the growth of incongruent-melting material

NASA Astrophysics Data System (ADS)

Uda, Satoshi; Huang, Xinming; Wang, Shou-Qi

2005-02-01

The significance of an electric field on the crystallization process is differentiated into two consequences; (i) thermodynamic effect and (ii) growth-dynamic effect. The former modifies the chemical potential of the associated phases which changes the equilibrium phase relationship while the latter influences the solute transport, growth kinetics, surface creation and defect generation during growth. The intrinsic electric field generating during growth is attributed to the crystallization-related electromotive force and the thermoelectric power driven by the temperature gradient at the interface which influences the solute transport and solute partitioning. The external electric field was applied to the growth apparatus in the ternary system of La2O3- Ga2O3- SiO2 so that the chemical potential of both solid and liquid phases changed leading to the variation of the equilibrium phase relationship. Imposing a 500 V/cm electric field on the system moved the boundary of primary phase field of lanthanum gallate ( LaGaO3) and Ga-bearing lanthanum silicate ( La14GaxSi9-xO) toward the SiO2 apex by 5 mol% which clearly demonstrated the change of the phase relationship by the external electric field.

Development of tropine-salt aqueous two-phase systems and removal of hydrophilic ionic liquids from aqueous solution.

PubMed

Wu, Haoran; Yao, Shun; Qian, Guofei; Song, Hang

2016-08-26

A novel aqueous two-phase systems (ATPS) composed of a small molecule organic compound tropine and an organic or inorganic salt aqueous solution has been developed for the first time. The phase behavior of tropine-salt ATPS was systemically investigated and the phase equilibrium data were measured in different temperatures and concentrations and correlated by the Merchuk equation with satisfactory results. The detection of the conductivity and particle size proved the formation of micelle in the process of forming tropine-salt ATPS. The separation application of the ATPS was assessed with the removal of hydrophilic benzothiazolium-based ionic liquids (ILs) from aqueous solution. The result showed that ILs were effectively extracted into the top tropine-rich phase. Finally, ILs in the top tropine-rich phase were further separated by the means of adsorption-desorption with DM301 macroporous resin and ethanol. The method of novel tropine-salt ATPS combined with adsorption-desorption is demonstrated a promising alternative thought and approach for the removal or recovery of hydrophilic compounds from aqueous media and also could provide a potential application for bio-separation. Copyright © 2016. Published by Elsevier B.V.

Aspects of wellbore heat transfer during two-phase flow

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

Hasan, A.R.; Kabir, C.S.

1994-08-01

Wellbore fluid temperature is governed by the rate of heat loss from the wellbore to the surrounding formation, which in turn is a function of depth and production/injection time. The authors present an approach to estimate wellbore fluid temperature during steady-state two-phase flow. The method incorporates a new solution of the thermal diffusivity equation and the effect of both conductive and convective heat transport for the wellbore/formation system. For the multiphase flow in the wellbore, the Hasan-Kabir model has been adapted, although other mechanistic models may be used. A field example is used to illustrate the fluid temperature calculation proceduremore » and shows the importance of accounting for convection in the tubing/casing annulus. A sensitivity study shows that significant differences exist between the predicted wellhead temperature and the formation surface temperature and that the fluid temperature gradient is nonlinear. This study further shows that increased free gas lowers the wellhead temperature as a result of the Joule-Thompson effect. In such cases, the expression for fluid temperature developed earlier for single-phase flow should not be applied when multiphase flow is encountered. An appropriate expression is presented in this work for wellbores producing multiphase fluids.« less

Microstructures responsible for the invar and permalloy effects in Fe-Ni alloys

NASA Astrophysics Data System (ADS)

Ustinovshchikov, Yu. I.; Shabanova, I. N.; Lomova, N. V.

2015-05-01

The experimental studies of Fe68Ni32 and Fe23Ni77 alloys by transmission electron microscopy and X-ray electron spectroscopy show that the ordering-separation phase transition in these alloys occurs in a temperature range near 600°C. At temperatures higher than the transition temperature, the ordering energy of the alloy is positive, and the structures contain clusters enriched in one of the components. After heat treatment at the temperatures where the invar effect in the Fe68Ni32 alloy is maximal, a modulated microstructure forms. Below the transition temperature, the ordering energy is negative, which provides a tendency to formation of chemical compounds. After aging at these temperatures (where the Fe23Ni77 alloy exhibits high permalloy properties), highly dispersed completely coherent particles of the FeNi3 phase with structure L12 precipitate in a solid solution.

Silicon nitride-aluminum oxide solid solution (SiAION) formation and densification by pressure sintering

NASA Technical Reports Server (NTRS)

Yeh, H. C.; Sanders, W. A.; Fiyalko, J. L.

1975-01-01

Stirred-ball-mill-blended Si3N4 and Al2O3 powders were pressure sintered in order to investigate the mechanism of solid solution formation and densification in the Si3N4-Al2O3 system. Powder blends with Si3N4:Al2O3 mole ratios of 4:1, 3:2, and 2:3 were pressure sintered at 27.6-MN/sq m pressure at temperatures to 17000 C (3090 F). The compaction behavior of the powder blends during pressure sintering was determined by observing the density of the powder compact as a function of temperature and time starting from room temperature. This information, combined with the results of X-ray diffraction and metallographic analyses regarding solutioning and phase transformation phenomena in the Si3N4-Al2O3 system, was used to describe the densification behavior.

Skylab near-infrared observations of clouds indicating supercooled liquid water droplets

NASA Technical Reports Server (NTRS)

Curran, R. J.; Wu, M.-L. C.

1982-01-01

Orographically-induced lee-wave clouds were observed over New Mexico by a multichannel scanning radiometer on Skylab during December 1973. Channels centered at 0.83, 1.61 and 2.125 microns were used to determine the cloud optical thickness, thermodynamic phase and effective particle size. An additional channel centered at 11.4 microns was used to determine cloud-top temperature, which was corroborated through comparison with the stereographically determined cloud top altitudes and conventional temperature soundings. Analysis of the measured near-infrared reflection functions at 1.61 and 2.125 microns are most easily interpreted as indicating the presence of liquid-phase water droplets. This interpretation is not conclusive even after considerable effort to understand possible sources for misinterpretation. However, if accepted the resulting phase determination is considered anomalous due to the inferred cloud-top temperatures being in the -32 to -47 C range. Theory for the homogeneous nucleation of pure supercooled liquid water droplets predicts very short lifetimes for the liquid phase at these cold temperatures. A possible explanation for the observations is that the wave-clouds are composed of solution droplets. Impurities in the cloud droplets could decrease the homogeneous freezing rate for these droplets, permitting them to exist for a longer time in the liquid phase, at the cold temperatures found.

Solutions for the diurnally forced advection-diffusion equation to estimate bulk fluid velocity and diffusivity in streambeds from temperature time series

NASA Astrophysics Data System (ADS)

Luce, C.; Tonina, D.; Gariglio, F. P.; Applebee, R.

2012-12-01

Differences in the diurnal variations of temperature at different depths in streambed sediments are commonly used for estimating vertical fluxes of water in the streambed. We applied spatial and temporal rescaling of the advection-diffusion equation to derive two new relationships that greatly extend the kinds of information that can be derived from streambed temperature measurements. The first equation provides a direct estimate of the Peclet number from the amplitude decay and phase delay information. The analytical equation is explicit (e.g. no numerical root-finding is necessary), and invertable. The thermal front velocity can be estimated from the Peclet number when the thermal diffusivity is known. The second equation allows for an independent estimate of the thermal diffusivity directly from the amplitude decay and phase delay information. Several improvements are available with the new information. The first equation uses a ratio of the amplitude decay and phase delay information; thus Peclet number calculations are independent of depth. The explicit form also makes it somewhat faster and easier to calculate estimates from a large number of sensors or multiple positions along one sensor. Where current practice requires a priori estimation of streambed thermal diffusivity, the new approach allows an independent calculation, improving precision of estimates. Furthermore, when many measurements are made over space and time, expectations of the spatial correlation and temporal invariance of thermal diffusivity are valuable for validation of measurements. Finally, the closed-form explicit solution allows for direct calculation of propagation of uncertainties in error measurements and parameter estimates, providing insight about error expectations for sensors placed at different depths in different environments as a function of surface temperature variation amplitudes. The improvements are expected to increase the utility of temperature measurement methods for studying groundwater-surface water interactions across space and time scales. We discuss the theoretical implications of the new solutions supported by examples with data for illustration and validation.

Large scale synthesis of nanostructured zirconia-based compounds from freeze-dried precursors

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

Gomez, A.; Villanueva, R.; Vie, D.

2013-01-15

Nanocrystalline zirconia powders have been obtained at the multigram scale by thermal decomposition of precursors resulting from the freeze-drying of aqueous acetic solutions. This technique has equally made possible to synthesize a variety of nanostructured yttria or scandia doped zirconia compositions. SEM images, as well as the analysis of the XRD patterns, show the nanoparticulated character of those solids obtained at low temperature, with typical particle size in the 10-15 nm range when prepared at 673 K. The presence of the monoclinic, the tetragonal or both phases depends on the temperature of the thermal treatment, the doping concentration and themore » nature of the dopant. In addition, Rietveld refinement of the XRD profiles of selected samples allows detecting the coexistence of the tetragonal and the cubic phases for high doping concentration and high thermal treatment temperatures. Raman experiments suggest the presence of both phases also at relatively low treatment temperatures. - Graphical abstract: Zr{sub 1-x}A{sub x}O{sub 2-x/2} (A=Y, Sc; 0{<=}x{<=}0.12) solid solutions have been prepared as nanostructured powders by thermal decomposition of precursors obtained by freeze-drying, and this synthetic procedure has been scaled up to the 100 g scale. Highlights: Black-Right-Pointing-Pointer Zr{sub 1-x}A{sub x}O{sub 2-x/2} (A=Y, Sc; 0{<=}x{<=}0.12) solid solutions have been prepared as nanostructured powders. Black-Right-Pointing-Pointer The synthetic method involves the thermal decomposition of precursors obtained by freeze-drying. Black-Right-Pointing-Pointer The temperature of the thermal treatment controls particle sizes. Black-Right-Pointing-Pointer The preparation procedure has been scaled up to the 100 g scale. Black-Right-Pointing-Pointer This method is appropriate for the large-scale industrial preparation of multimetallic systems.« less

Electrochemical synthesis of a surface-porous Mg70.5Al29.5 eutectic alloy in a neutral aqueous NaCl solution

NASA Astrophysics Data System (ADS)

Yang, Feng; Li, Yong-gang; Wei, Ying-hui; Wei, Huan; Yan, Ze-ying; Hou, Li-feng

2018-03-01

A surface-porous Mg-Al eutectic alloy was fabricated at room temperature via electrochemical dealloying in a neutral, aqueous 0.6 M NaCl solution by controlling the applied potential and processing duration. Selective dissolution occurred on the alloy surface. The surface-porous formation mechanism is governed by the selective dissolution of the α-Mg phase, which leaves the Mg17Al12 phase as the porous layer framework. The pore characteristics (morphology, size, and distribution) of the dealloyed samples are inherited from the α-Mg phases of the precursor Mg70.5Al29.5 (at.%) alloy. Size control in the porous layer can be achieved by regulating the synthesis parameters.

Phase equilibria of the magnesium sulfate-water system to 4 kbars

NASA Technical Reports Server (NTRS)

Hogenboom, D. L.; Kargel, J. S.; Ganasan, J. P.; Lee, L.

1993-01-01

Magnesium sulfate is the most abundant salt in carbonaceous chondrites, and it may be important in the low-temperature igneous evolution and aqueous differentiation of icy satellites and large chondritic asteroids. Accordingly, we are investigating high-pressure phase equilibria in MgSO4-H2O solutions under pressures up to four kbars. An initial report was presented two years ago. This abstract summarizes our results to date including studies of solutions containing 15.3 percent, 17 percent, and 22 percent MgSO4. Briefly, these results demonstrate that increasing pressure causes the eutectic and peritectic compositions to shift to much lower concentrations of magnesium sulfate, and the existence of a new low-density phase of magnesium sulfate hydrate.

Separation and concentration of lower alcohols from dilute aqueous solutions

DOEpatents

Moore, Raymond H.; Eakin, David E.; Baker, Eddie G.; Hallen, Richard T.

1991-01-01

A process for producing, from a dilute aqueous solution of a lower (C.sub.1 -C.sub.5) alcohol, a concentrated liquid solution of the alcohol in an aromatic organic solvent is disclosed. Most of the water is removed from the dilute aqueous solution of alcohol by chilling sufficiently to form ice crystals. Simultaneously, the remaining liquid is extracted at substantially the same low temperature with a liquid organic solvent that is substantially immiscible in aqueous liquids and has an affinity for the alcohol at that temperature, causing the alcohol to transfer to the organic phase. After separating the organic liquid from the ice crystals, the organic liquid can be distilled to enrich the concentration of alcohol therein. Ethanol so separated from water and concentrated in an organic solvent such as toluene is useful as an anti-knock additive for gasoline.

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

DOEpatents

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

2007-08-14

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

Melt coaxial electrospinning: a versatile method for the encapsulation of solid materials and fabrication of phase change nanofibers.

PubMed

McCann, Jesse T; Marquez, Manuel; Xia, Younan

2006-12-01

We have developed a method based on melt coaxial electrospinning for fabricating phase change nanofibers consisting of long-chain hydrocarbon cores and composite sheaths. This method combines melt electrospinning with a coaxial spinneret and allows for nonpolar solids such as paraffins to be electrospun and encapsulated in one step. Shape-stabilized, phase change nanofibers have many potential applications as they are able to absorb, hold, and release large amounts of thermal energy over a certain temperature range by taking advantage of the large heat of fusion of long-chain hydrocarbons. We have focused on compounds with melting points near room temperature (octadecane) and body temperature (eicosane) as these temperature ranges are most valuable in practice. We have produced thermally stable, phase change materials up to 45 wt % octadecane, as measured by differential scanning calorimetry. In addition, the resultant fibers display novel segmented morphologies for the cores due to the rapid solidification of the hydrocarbons driven by evaporative cooling of the carrier solution. Aside from the fabrication of phase change nanofibers, the melt coaxial method is promising for applications related to microencapsulation and controlled release of drugs.

Method for stabilizing low-level mixed wastes at room temperature

DOEpatents

Wagh, A.S.; Singh, D.

1997-07-08

A method to stabilize solid and liquid waste at room temperature is provided comprising combining solid waste with a starter oxide to obtain a powder, contacting the powder with an acid solution to create a slurry, said acid solution containing the liquid waste, shaping the now-mixed slurry into a predetermined form, and allowing the now-formed slurry to set. The invention also provides for a method to encapsulate and stabilize waste containing cesium comprising combining the waste with Zr(OH){sub 4} to create a solid-phase mixture, mixing phosphoric acid with the solid-phase mixture to create a slurry, subjecting the slurry to pressure; and allowing the now pressurized slurry to set. Lastly, the invention provides for a method to stabilize liquid waste, comprising supplying a powder containing magnesium, sodium and phosphate in predetermined proportions, mixing said powder with the liquid waste, such as tritium, and allowing the resulting slurry to set. 4 figs.

Method for stabilizing low-level mixed wastes at room temperature

DOEpatents

Wagh, Arun S.; Singh, Dileep

1997-01-01

A method to stabilize solid and liquid waste at room temperature is provided comprising combining solid waste with a starter oxide to obtain a powder, contacting the powder with an acid solution to create a slurry, said acid solution containing the liquid waste, shaping the now-mixed slurry into a predetermined form, and allowing the now-formed slurry to set. The invention also provides for a method to encapsulate and stabilize waste containing cesium comprising combining the waste with Zr(OH).sub.4 to create a solid-phase mixture, mixing phosphoric acid with the solid-phase mixture to create a slurry, subjecting the slurry to pressure; and allowing the now pressurized slurry to set. Lastly, the invention provides for a method to stabilize liquid waste, comprising supplying a powder containing magnesium, sodium and phosphate in predetermined proportions, mixing said powder with the liquid waste, such as tritium, and allowing the resulting slurry to set.

A low temperature solution phases synthesis for silicon quantum dots

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

Bley, R.A.; Yang, Chung-Sung; Kauzlarich, S.M.

Silicon nanoparticles are of interest because of their optoelectronic properties. This warrants finding new methods for making these clusters which are more economical and allow for greater versatility in their mechanical and chemical manipulation. We have produced silicon nanoclusters using a low temperature solution phase method. Our approach uses the Zintl salts KSi, NaSi or Mg{sub 2}Si as the source of silicon anion, This is reacted with tetrachlorosilane, the silicon cation source, in appropriate solvents. These nanoclusters have been terminated with various organic groups via reaction with alkyl-Li or alkylgrignard reagents. High resolution TEM, FTIR, and Raman spectroscopy have beenmore » used to establish the size, structure and surface composition of the particles. UV-vis and photoluminescence have been used to investigate their optical properties. The effect of termination on the photoluminescence will be discussed in detail.« less

Model of two-temperature convective transfer in porous media

NASA Astrophysics Data System (ADS)

Gruais, Isabelle; Poliševski, Dan

2017-12-01

In this paper, we study the asymptotic behaviour of the solution of a convective heat transfer boundary problem in an ɛ -periodic domain which consists of two interwoven phases, solid and fluid, separated by an interface. The fluid flow and its dependence with respect to the temperature are governed by the Boussinesq approximation of the Stokes equations. The tensors of thermal diffusion of both phases are ɛ -periodic, as well as the heat transfer coefficient which is used to describe the first-order jump condition on the interface. We find by homogenization that the two-scale limits of the solutions verify the most common system used to describe local thermal non-equilibrium phenomena in porous media (see Nield and Bejan in Convection in porous media, Springer, New York, 1999; Rees and Pop in Transport phenomena in porous media III, Elsevier, Oxford, 2005). Since now, this system was justified only by volume averaging arguments.

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

NASA Technical Reports Server (NTRS)

Holanda, R.

1984-01-01

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

Temperature-responsive chromatography for the separation of biomolecules.

PubMed

Kanazawa, Hideko; Okano, Teruo

2011-12-09

Temperature-responsive chromatography for the separation of biomolecules utilizing poly(N-isopropylacrylamide) (PNIPAAm) and its copolymer-modified stationary phase is performed with an aqueous mobile phase without using organic solvent. The surface properties and function of the stationary phase are controlled by external temperature changes without changing the mobile-phase composition. This analytical system is based on nonspecific adsorption by the reversible transition of a hydrophilic-hydrophobic PNIPAAm-grafted surface. The driving force for retention is hydrophobic interaction between the solute molecules and the hydrophobized polymer chains on the stationary phase surface. The separation of the biomolecules, such as nucleotides and proteins was achieved by a dual temperature- and pH-responsive chromatography system. The electrostatic and hydrophobic interactions could be modulated simultaneously with the temperature in an aqueous mobile phase, thus the separation system would have potential applications in the separation of biomolecules. Additionally, chromatographic matrices prepared by a surface-initiated atom transfer radical polymerization (ATRP) exhibit a strong interaction with analytes, because the polymerization procedure forms a densely packed polymer, called a polymer brush, on the surfaces. The copolymer brush grafted surfaces prepared by ATRP was an effective tool for separating basic biomolecules by modulating the electrostatic and hydrophobic interactions. Applications of thermally responsive columns for the separations of biomolecules are reviewed here. Copyright © 2011 Elsevier B.V. All rights reserved.

In situ neutron scattering study of nanoscale phase evolution in PbTe-PbS thermoelectric material

DOE PAGES

Ren, Fei; Schmidt, Robert; Keum, Jong K.; ...

2016-08-24

Introducing nanostructural second phases has been proved to be an effective approach to reduce the lattice thermal conductivity and thus enhance the figure of merit for many thermoelectric materials. Furthermore studies of the formation and evolution of these second phases are central to understanding temperature dependent material behavior, improving thermal stabilities, as well as designing new materials. We examined powder samples of PbTe-PbS thermoelectric material using in situ neutron diffraction and small angle neutron scattering (SANS) techniques from room temperature to elevated temperature up to 663 K, to explore quantitative information on the structure, weight fraction, and size of themore » second phase. Neutron diffraction data showed the as-milled powder was primarily solid solution before heat treatment. During heating, PbS second phase precipitated out of the PbTe matrix around 480 K, while re-dissolution started around 570 K. The second phase remained separated from the matrix upon cooling. Furthermore, SANS data indicated there are two populations of nanostructures. The size of the smaller nanostructure increased from initially 5 nm to approximately 25 nm after annealing at 650 K, while the size of the larger nanostructure remained unchanged. Our study demonstrated that in situ neutron techniques are effective means to obtain quantitative information to study temperature dependent nanostructural behavior of thermoelectrics and likely other high-temperature materials.« less

Mechanisms to Detoxify Selected Organic Contaminants in Higher Plants and Microbes, and Their Potential Use in Landscape Management

DTIC Science & Technology

2004-10-01

presence of plants. The plants were cultivated in hydroponics . Five-day old seedlings were exposed to 0.1 mM TNT solution and the TNT concentration in the...compound in the soil or nutrient solution . In the second phase, they accumulate slowly in the tissues. The intensity of the absorption process...absorption rate is directly proportional to the concentration of the compound in the soil or nutrient solution . Temperature strongly influences the

The formation and structure of Fe-Mn-Ni-Si solute clusters and G-phase precipitates in steels

NASA Astrophysics Data System (ADS)

King, D. J. M.; Burr, P. A.; Middleburgh, S. C.; Whiting, T. M.; Burke, M. G.; Wenman, M. R.

2018-07-01

Solute clustering and G-phase precipitation cause hardening phenomena observed in some low alloy and stainless steels, respectively. Density functional theory was used to investigate the energetic driving force for the formation of these precipitates, capturing temperature effects through analysis of the system's configurational and magnetic entropies. It is shown that enrichment of Mn, Ni and Si is thermodynamically favourable compared to the dilute ferrite matrix of a typical A508 low alloy steel. We predict the ordered G-phase to form preferentially rather than a structure with B2-type ordering when the Fe content of the system falls below 10-18 at. %. The B2 → G-phase transformation is predicted to occur spontaneously when vacancies are introduced into the B2 structure in the absence of Fe.

Thermal properties of spinel based solid solutions

NASA Astrophysics Data System (ADS)

O'Hara, Kelley Rae

Solid solution formation in spinel based systems proved to be a viable approach to decreasing thermal conductivity. Samples with systematically varied additions of MgGa2O4 to MgAl2O 4 were prepared and thermal diffusivity was measured using the laser flash technique. Additionally, heat capacity was measured using differential scanning calorimetry and modeled for the MgAl2O4-MgGa 2O4 system. At 200°C thermal conductivity decreased 24% with a 5 mol% addition of MgGa2O4 to the system. The solid solution continued to decrease the thermal conductivity by 13% up to 1000°C with 5 mol% addition. The decrease in thermal conductivity ultimately resulted in a decrease in heat flux when applied to a theoretical furnace lining, which could lead to energy savings in industrial settings. The MgAl2O4-Al2O3 phase equilibria was investigated to fully understand the system and the thermal properties at elevated temperatures. The solvus line between MgAl2O4 and Al2O3 has been defined at 79.6 wt% Al 2O3 at 1500°C, 83.0 wt% Al2O4 at 1600°C, and 86.5 wt% Al2O3 at 1700°C. A metastable region has been identified at temperatures up to 1700°C which could have significant implications for material processing and properties. The spinel solid solution region has been extended to form an infinite solid solution with Al2O3 at elevated temperatures. A minimum in melting at 1975°C and a chemistry of 96 wt% Al2O3 rather than a eutectic is present. Thermal properties in the MgAl2O4-Al2O 3 system were investigated in both the single phase solid solution region and the two phase region. The thermal diffusivity decreased through the MgAl 2O4 solid solution region and was at a minimum through the entire metastable (nucleation and growth) region. As Al2O 3 became present as a second phase the thermal diffusivity increased with Al2O3 content. There was an 11.7% increase in thermal diffusivity with a change in overall chemistry of 85.20 wt% Al2O 3 to 87.71 wt% Al2O3, due to the drastic change in final chemistry (38.3 wt% Al20 3) caused by the nucleation and growth region in the system.

The enhancement and suppression of immersion mode heterogeneous ice-nucleation by solutes.

PubMed

Whale, Thomas F; Holden, Mark A; Wilson, Theodore W; O'Sullivan, Daniel; Murray, Benjamin J

2018-05-07

Heterogeneous nucleation of ice from aqueous solutions is an important yet poorly understood process in multiple fields, not least the atmospheric sciences where it impacts the formation and properties of clouds. In the atmosphere ice-nucleating particles are usually, if not always, mixed with soluble material. However, the impact of this soluble material on ice nucleation is poorly understood. In the atmospheric community the current paradigm for freezing under mixed phase cloud conditions is that dilute solutions will not influence heterogeneous freezing. By testing combinations of nucleators and solute molecules we have demonstrated that 0.015 M solutions (predicted melting point depression <0.1 °C) of several ammonium salts can cause suspended particles of feldspars and quartz to nucleate ice up to around 3 °C warmer than they do in pure water. In contrast, dilute solutions of certain alkali metal halides can dramatically depress freezing points for the same nucleators. At 0.015 M, solutes can enhance or deactivate the ice-nucleating ability of a microcline feldspar across a range of more than 10 °C, which corresponds to a change in active site density of more than a factor of 10 5 . This concentration was chosen for a survey across multiple solutes-nucleant combinations since it had a minimal colligative impact on freezing and is relevant for activating cloud droplets. Other nucleators, for instance a silica gel, are unaffected by these 'solute effects', to within experimental uncertainty. This split in response to the presence of solutes indicates that different mechanisms of ice nucleation occur on the different nucleators or that surface modification of relevance to ice nucleation proceeds in different ways for different nucleators. These solute effects on immersion mode ice nucleation may be of importance in the atmosphere as sea salt and ammonium sulphate are common cloud condensation nuclei (CCN) for cloud droplets and are internally mixed with ice-nucleating particles in mixed-phase clouds. In addition, we propose a pathway dependence where activation of CCN at low temperatures might lead to enhanced ice formation relative to pathways where CCN activation occurs at higher temperatures prior to cooling to nucleation temperature.

Thermophysical properties of Ni-containing single-phase concentrated solid solution alloys

DOE PAGES

Jin, Ke; Mu, Sai; An, Ke; ...

2016-12-27

For this research temperature dependent thermophysical properties, including specific heat capacity, lattice thermal expansion, thermal diffusivity and conductivity, have been systematically studied in Ni and eight Ni-containing single-phase face-centered-cubic concentrated solid solution alloys, at elevated temperatures up to 1273 K. The alloys have similar specific heat values of 0.4–0.5 J·g -1·K -1 at room temperature, but their temperature dependence varies greatly due to Curie and K-state transitions. The lattice, electronic, and magnetic contributions to the specific heat have been separated based on first-principles methods in NiCo, NiFe, Ni-20Cr and NiCoFeCr. The alloys have similar thermal expansion behavior, with the exceptionmore » that NiFe and NiCoFe have much lower thermal expansion coefficient in their ferromagnetic state due to magnetostriction effects. Calculations based on the quasi-harmonic approximation accurately predict the temperature dependent lattice parameter of NiCo and NiFe with < 0.2% error, but underestimated that of Ni-20Cr by 1%, compared to the values determined from neutron diffraction. In addition, all the alloys containing Cr have very similar thermal conductivity, which is much lower than that of Ni and the alloys without Cr, due to the large magnetic disorder.« less

Mechanical Alloying of W-Mo-V-Cr-Ta High Entropy Alloys

NASA Astrophysics Data System (ADS)

Das, Sujit; Robi, P. S.

2018-04-01

Recent years have seen the emergence of high-entropy alloys (HEAs) consisting of five or more elements in equi-atomic or near equi-atomic ratios. These alloys in single phase solid solution exhibit exceptional mechanical properties viz., high strength at room and elevated temperatures, reasonable ductility and stable microstructure over a wide range of temperatures making it suitable for high temperature structural materials. In spite of the attractive properties, processing of these materials remains a challenge. Reports regarding fabrication and characterisation of a few refractory HEA systems are available. The processing of these alloys have been carried out by arc melting of small button sized materials. The present paper discusses the development of a novel refractory W-Mo-V-Cr-Ta HEA powder based on a new alloy design concept. The powder mixture was milled for time periods up to 64 hours. Single phase alloy powder having body centred cubic structure was processed by mechanical alloying. The milling characteristics and extent of alloying during the ball milling were characterized using X-ray diffractiometre (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM). A single phase solid solution alloy powder having body-centred cubic (BCC) structure with a lattice parameter of 3.15486 Å was obtained after milling for 32 hours.

Thermoresponsive light scattering device utilizing surface behavior effects between polyimide and an ionic liquid-water mixture exhibiting lower critical solution temperature (LCST)-type phase separation

NASA Astrophysics Data System (ADS)

Goda, Kazuya; Takatoh, Kohki; Funasako, Yusuke; Inokuchi, Makoto

2018-06-01

We proposed a thermoresponsive light scattering device that utilizes the surface behavior between polyimide and an ionic liquid-water mixture exhibiting lower critical solution temperature (LCST)-type phase separation. The LCST behavior for an ionic liquid device utilizing the polyimide with and without alkyl side chains was investigated. In the here-reported ionic liquid device that utilized the polyimide with alkyl side chains, [nBu4P][CF3COO] droplets were generated by phase separation—they were predominantly formed at the alkyl surface by a surface pinning effect. A stable transmittance in the opaque state could be obtained with this device. In contrast, an ionic liquid device using polyimide without alkyl side chains deteriorated transmittance in the opaque state because there was no surface pinning effect. Additionally, the viewing angle, contrast ratio, and heat cycle testing of this ionic liquid device with polyimide with alkyl side chains were also investigated. The results indicated that no parallax was obtained and that the ionic liquid device has a stable transmittance (verified by heat cycle testing). This unique device is expected to find use in the smart window applications that are activated by temperature changes.

Liquefaction processes and systems and liquefaction process intermediate compositions

DOEpatents

Schmidt, Andrew J.; Hart, Todd R.; Billing, Justin M.; Maupin, Gary D.; Hallen, Richard T.; Anderson, Daniel B.

2014-07-12

Liquefaction processes are provided that can include: providing a biomass slurry solution having a temperature of at least 300.degree. C. at a pressure of at least 2000 psig; cooling the solution to a temperature of less than 150.degree. C.; and depressurizing the solution to release carbon dioxide from the solution and form at least part of a bio-oil foam. Liquefaction processes are also provided that can include: filtering the biomass slurry to remove particulates; and cooling and depressurizing the filtered solution to form the bio-oil foam. Liquefaction systems are provided that can include: a heated biomass slurry reaction zone maintained above 300.degree. C. and at least 2000 psig and in continuous fluid communication with a flash cooling/depressurization zone maintained below 150.degree. C. and between about 125 psig and about atmospheric pressure. Liquefaction systems are also provided that can include a foam/liquid separation system. Liquefaction process intermediate compositions are provided that can include a bio-oil foam phase separated from an aqueous biomass solids solution.

Formation Mechanism and Control of Perovskite Films from Solution to Crystalline Phase Studied by in Situ Synchrotron Scattering.

PubMed

Chang, Chun-Yu; Huang, Yu-Ching; Tsao, Cheng-Si; Su, Wei-Fang

2016-10-12

Controlling the crystallization and morphology of perovskite films is crucial for the fabrication of high-efficiency perovskite solar cells. For the first time, we investigate the formation mechanism of the drop-cast perovskite film from its precursor solution, PbCl 2 and CH 3 NH 3 I in N,N-dimethylformamide, to a crystalline CH 3 NH 3 PbI 3-x Cl x film at different substrate temperatures from 70 to 180 °C in ambient air and humidity. We employed an in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) technique for this study. When the substrate temperature is at or below 100 °C, the perovskite film is formed in three stages: the initial solution stage, transition-to-solid film stage, and transformation stage from intermediates into a crystalline perovskite film. In each stage, the multiple routes for phase transformations are preceded concurrently. However, when the substrate temperature is increased from 100 to 180 °C, the formation mechanism of the perovskite film is changed from the "multistage formation mechanism" to the "direct formation mechanism". The proposed mechanism has been applied to understand the formation of a perovskite film containing an additive. The result of this study provides a fundamental understanding of the functions of the solvent and additive in the solution and transition states to the crystalline film. It provides useful knowledge to design and fabricate crystalline perovskite films for high-efficiency solar cells.

One-dimensional zinc oxide nanomaterials synthesis and photovoltaic applications

NASA Astrophysics Data System (ADS)

Weintraub, Benjamin A.

As humanly engineered materials systems approach the atomic scale, top-down manufacturing approaches breakdown and following nature's example, bottom-up or self-assembly methods have the potential to emerge as the dominant paradigm. Synthesis of one-dimensional nanomaterials takes advantage of such self-assembly manufacturing techniques, but until now most efforts have relied on high temperature vapor phase schemes which are limited in scalability and compatibility with organic materials. The solution-phase approach is an attractive low temperature alternative to overcome these shortcomings. To this end, this thesis is a study of the rationale solution-phase synthesis of ZnO nanowires and applications in photovoltaics. The following thesis goals have been achieved: rationale synthesis of a single ZnO nanowire on a polymer substrate without seeding, design of a wafer-scale technique to control ZnO nanowire array density using layer-by-layer polymers, determination of optimal nanowire field emitter density to maximize the field enhancement factor, design of bridged nanowires across metal electrodes to order to circumvent post-synthesis manipulation steps, electrical characterization of bridged nanowires, rationale solution-phase synthesis of long ZnO nanowires on optical fibers, fabrication of ZnO nanowire dye-sensitized solar cells on optical fibers, electrical and optical characterization of solar cell devices, comparison studies of 2-D versus 3-D nanowire dye-sensitized solar cell devices, and achievement of 6-fold solar cell power conversion efficiency enhancement using a 3-D approach. The thesis results have implications in nanomanufacturing scale-up and next generation photovoltaics.

Magnetite solubility and phase stability in alkaline media at elevated temperatures

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

Ziemniak, S.E.; Jones, M.E.; Combs, K.E.S.

Magnetite, Fe{sub 3}O{sub 4}, is the dominant oxide constituent of the indigenous corrosion layers that form on iron base alloys in high purity, high temperature water. The apparent simultaneous stability of two distinct oxidation states of iron in this metal oxide is responsible for its unique solubility behavior. The present work was undertaken to extend the experimental and theoretical bases for estimating solubilities of an iron corrosion product (Fe{sub 3}O{sub 4}/Fe(OH){sub 2}) over a broader temperature range and in the presence of complexing, pH-controlling reagents. These results indicate that a surface layer of ferrous hydroxide controls magnetite solubility behavior atmore » low temperatures in much the same manner as a surface layer of nickel(II) hydroxide was previously reported to control the low temperature solubility behavior of NiO. The importance of Fe(III) ion complexes implies not only that most previously-derived thermodynamic properties of the Fe(OH){sub 3}{sup {minus}} ion are incorrect, but that magnetite phase stability probably shifts to favor a sodium ferric hydroxyphosphate compound in alkaline sodium phosphate solutions at elevated temperatures. The test methodology involved pumping alkaline solutions of known composition through a bed of Fe{sub 3}O{sub 4} granules and analyzing the emerging solution for Fe. Two pH-controlling reagents were tested: sodium phosphate and ammonia. Equilibria for the following reactions were described in thermodynamic terms: (a) Fe(OH){sub 2}/Fe{sub 3}O{sub 4} dissolution and transformation, (b) Fe(II) and Fe(III) ion hydroxocomplex formation (hydrolysis), (c) Fe(II) ion amminocomplex formation, and (d) Fe(II) and Fe(III) ion phosphatocomplex formation. 36 refs.« less

Method transfer from high-pressure liquid chromatography to ultra-high-pressure liquid chromatography. II. Temperature and pressure effects.

PubMed

Åsberg, Dennis; Samuelsson, Jörgen; Leśko, Marek; Cavazzini, Alberto; Kaczmarski, Krzysztof; Fornstedt, Torgny

2015-07-03

The importance of the generated temperature and pressure gradients in ultra-high-pressure liquid chromatography (UHPLC) are investigated and compared to high-pressure liquid chromatography (HPLC). The drug Omeprazole, together with three other model compounds (with different chemical characteristics, namely uncharged, positively and negatively charged) were used. Calculations of the complete temperature profile in the column at UHPLC conditions showed, in our experiments, a temperature difference between the inlet and outlet of 16 °C and a difference of 2 °C between the column center and the wall. Through van't Hoff plots, this information was used to single out the decrease in retention factor (k) solely due to the temperature gradient. The uncharged solute was least affected by temperature with a decrease in k of about 5% while for charged solutes the effect was more pronounced, with k decreases up to 14%. A pressure increase of 500 bar gave roughly 5% increase in k for the uncharged solute, while omeprazole and the other two charged solutes gave about 25, 20 and 15% increases in k, respectively. The stochastic model of chromatography was applied to estimate the dependence of the average number of adsorption/desorption events (n) and the average time spent by a molecule in the stationary phase (τs) on temperature and pressure on peak shape for the tailing, basic solute. Increasing the temperature yielded an increase in n and decrease in τs which resulted in less skew at high temperatures. With increasing pressure, the stochastic modeling gave interesting results for the basic solute showing that the skew of the peak increased with pressure. The conclusion is that pressure effects are more pronounced for both retention and peak shape than the temperature effects for the polar or charged compounds in our study. Copyright © 2015 Elsevier B.V. All rights reserved.

The crystal structure of lueshite at 298 K resolved by high-resolution time-of-flight neutron powder diffraction

NASA Astrophysics Data System (ADS)

Mitchell, Roger H.; Kennedy, Brendan J.; Knight, Kevin S.

2018-01-01

Refinement of time-of-flight high-resolution neutron powder diffraction data for lueshite (Na, Ca)(Nb, Ta, Ti)O3, the natural analogue of synthetic NaNbO3, demonstrates that lueshite at room temperature (298 K) adopts an orthorhombic structure with a 2 a p × 2 a p × 4 a p superlattice described by space group Pmmn [#59: a = 7.8032(4) Å; b = 7.8193(4) Å; c = 15.6156(9) Å]. This structure is analogous to that of phase S of synthetic NaNbO3 observed at 753-783 K (480-510 °C). In common with synthetic NaNbO3, lueshite exhibits a series of phase transitions with decreasing temperature from a cubic (Pm\\bar{3}m) aristotype through tetragonal ( P4/ mbm) and orthorhombic ( Cmcm) structures. However, the further sequence of phase transitions differs in that for lueshite the series terminates with the room temperature S ( Pmmn) phase, and the R ( Pmmn or Pnma) and P ( Pbcm) phases of NaNbO3 are not observed. The appearance of the S phase in lueshite at a lower temperature, relative to that of NaNbO3, is attributable to the effects of solid solution of Ti, Ta and Ca in lueshite.

Phase stability and magnetic behavior of FeCrCoNiGe high-entropy alloy

NASA Astrophysics Data System (ADS)

Huang, Shuo; Vida, Ádám; Molnár, Dávid; Kádas, Krisztina; Varga, Lajos Károly; Holmström, Erik; Vitos, Levente

2015-12-01

We report an alternative FeCrCoNiGe magnetic material based on FeCrCoNi high-entropy alloy with Curie point far below the room temperature. Investigations are done using first-principles calculations and key experimental measurements. Results show that the equimolar FeCrCoNiGe system is decomposed into a mixture of face-centered cubic and body-centered cubic solid solution phases. The increased stability of the ferromagnetic order in the as-cast FeCrCoNiGe composite, with measured Curie temperature of 640 K, is explained using the exchange interactions.

Solution properties of almandine-pyrope garnet as determined by phase equilibrium experiments

USGS Publications Warehouse

Koziol, A.M.; Bohlen, S.R.

1992-01-01

The thermodynamic mixing properties of almandine-pyrope garnet were derived from phase equilibrium experiments at temperatures of 900 and 1000??C and pressures from 8 to 14 kbar. Almandine has essentially ideal behavior in almandine-pyrope garnet over the composition range Alm89-Alm61 at the above experimental conditions. In all experimental products a systematic partitioning of Fe and Mg between garnet and ilmenite was seen with ln Kd ??? 1.59 which was not temperature sensitive. The results support the use of garnet mixing models that incorporate ideal or nearly ideal Fe-Mg parameters. -from Authors

On the stability of the exact solutions of the dual-phase lagging model of heat conduction.

PubMed

Ordonez-Miranda, Jose; Alvarado-Gil, Juan Jose

2011-04-13

The dual-phase lagging (DPL) model has been considered as one of the most promising theoretical approaches to generalize the classical Fourier law for heat conduction involving short time and space scales. Its applicability, potential, equivalences, and possible drawbacks have been discussed in the current literature. In this study, the implications of solving the exact DPL model of heat conduction in a three-dimensional bounded domain solution are explored. Based on the principle of causality, it is shown that the temperature gradient must be always the cause and the heat flux must be the effect in the process of heat transfer under the dual-phase model. This fact establishes explicitly that the single- and DPL models with different physical origins are mathematically equivalent. In addition, taking into account the properties of the Lambert W function and by requiring that the temperature remains stable, in such a way that it does not go to infinity when the time increases, it is shown that the DPL model in its exact form cannot provide a general description of the heat conduction phenomena.

Nonequilibrium segregation and phase instability in alloy films during elevated-temperature irradiation in a high-voltage electron microscope

NASA Astrophysics Data System (ADS)

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

1984-05-01

The effects of defect-production rate gradients, caused by the radial nonuniformity in the electron flux distribution, on solute segregation and phase stability in alloy films undergoing high-voltage electron-microscope (HVEM) irradiation at high temperatures are assessed. Two-dimensional (axially symmetric) compositional redistributions were calculated, taking into account both axial and transverse radial defect fluxes. It was found that when highly focused beams were employed radiation-induced segregation consisted of two stages: dominant axial segregation at the film surfaces at short irradiation times and competitive radial segregation at longer times. The average alloy composition within the irradiated region could differ greatly from that irradiated with a uniform beam, because of the additional atom transport from or to the region surrounding the irradiated zone under the influence of radial fluxes. Damage-rate gradient effects must be taken into account when interpreting in-situ HVEM observations of segregation-induced phase instabilities. The theoretical predictions are compared with experimental observations of the temporal and spatial dependence of segregation-induced precipitation in thin films of Ni-Al, Ni-Ge and Ni-Si solid solutions.

Extraction and separation of tungsten (VI) from aqueous media with Triton X-100-ammonium sulfate-water aqueous two-phase system without any extractant.

PubMed

Yongqiang Zhang; Tichang Sun; Tieqiang Lu; Chunhuan Yan

2016-11-25

An aqueous two-phase system composed of Triton X-100-(NH 4 ) 2 SO 4 -H 2 O was proposed for extraction and separation of tungsten(VI) from aqueous solution without using any extractant. The effects of aqueous pH, concentration of ammonium sulfate, Triton X-100 and tungsten, extracting temperature on the extraction of tungsten were investigated. The extraction of tungsten has remarkable relationship with aqueous pH and are to above 90% at pH=1.0-3.0 under studied pH range (pH=1.0-7.0) and increases gradually with increasing Triton X-100 concentration, but decreases slightly with increasing ammonium sulfate concentration. The extraction percentage of tungsten is hardly relevant to temperature but its distribution coefficient linearly increases with increasing temperature within 303.15-343.15K. The distribution coefficient of tungsten increases with the increase of initial tungsten concentration (0.1-3%) and temperature (303.15 K-333.15K). The solubilization capacity of tungsten in Triton X-100 micellar phase is independent of temperature. FT-IR analysis reveals that there is no evident interaction between polytungstate anion and ether oxygen unit in Triton X-100, and DLS analysis indicates that zeta potential of Triton X-100 micellar phase have a little change from positive to negative after extracting tungsten. Based on the above-mentioned results, it can be deduced that polytungstate anions are solubilized in hydrophilic outer shell of Triton X-100 micelles by electrostatic attraction depending on its relatively high hydrophobic nature. The stripping of tungsten is mainly influenced by temperature and can be easily achieved to 95% in single stage stripping. The tungsten (VI) is separated out from solution containing Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Al(III), Cr(III) and Mn(II) under the suitable conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Solid-liquid phase equilibria in the ternary system (LiBO2 + Li2CO3 + H2O) at 288.15 and 298.15 K

NASA Astrophysics Data System (ADS)

Wang, Shi-qiang; Guo, Ya-fei; Yang, Jian-sen; Deng, Tian-long

2015-12-01

Experimental studies on the solubilities and physicochemical properties including density, refractive index and pH value in the ternary systems (LiBO2 + Li2CO3 + H2O) at 288.15 and 298.15 K were determined with the method of isothermal dissolution equilibrium. Based on the experimental results, the phase diagrams and their corresponding physicochemical properties versus composition diagram in the system were plotted. In the phase diagrams of the ternary system at 288.15 and 298.15 K, there are one eutectic point and two crystallization regions corresponding to lithium metaborate octahydrate (LiBO2 · 8H2O) and lithium carbonate (Li2CO3), respectively. This system at both temperatures belongs to hydrate type I, and neither double salt nor solid solution was found. A comparison of the phase diagrams for this ternary system at 288.15 and 298.15 K shows that the solid phase numbers and exist minerals are the same, and the area of crystallization region of Li2CO3 is increased obviously with the increasing temperature while that of LiBO2 · 8H2O is decreased. The physicochemical properties (density, pH value and refractive index) of the solutions of the ternary system at two temperatures changes regularly with the increasing lithium carbonate concentration. The calculated values of density and refractive index using empirical equations of the ternary system are in good agreement with the experimental values.

Retention behavior of hydrophobic organic chemicals as a function of temperature in soil leaching column chromatography.

PubMed

Liang, Xinmiao; Xu, Feng; Lin, Bingcheng; Su, Fan; Schramm, Karl-Werner; Kettrup, Antonius

2002-11-01

To study the transport mechanism of hydrophobic organic chemicals (HOCs) and the energy change in soil/solvent system, a soil leaching column chromatographic (SLCC) experiment at an environmental temperature range of 20-40 degrees C was carried out, which utilized a reference soil (SP 14696) packed column and a methanol-water (1:4 by volume ratio) eluent. The transport process quickens with the increase of column temperature. The ratio of retention factors at 30 and 40 degrees C (k'30/k'40) ranged from 1.08 to 1.36. The lower enthalpy change of the solute transfer in SLCC (from eluent to soil) than in conventional reversed-phase liquid chromatography (e.g., from eluent to C18) is consistent with the hypothesis that HOCs were dominantly and physically partitioned between solvent and soil. The results were also verified by the linear solvation energy relationships analysis. The chief factor controlling the retention was found to be the solute solvophobic partition, and the second important factor was the solute hydrogen-bond basicity, while the least important factors were the solute polarizability-dipolarity and hydrogen-bond acidity. With the increase of temperature, the contributions of the solute solvophobic partition and hydrogen-bond basicity gradually decrease, and the latter decreases faster than the former.

Extraction of Oil from Flaxseed (Linum usitatissimum L.) Using Enzyme-Assisted Three-Phase Partitioning.

PubMed

Tan, Zhi-Jian; Yang, Zi-Zhen; Yi, Yong-Jian; Wang, Hong-Ying; Zhou, Wan-Lai; Li, Fen-Fang; Wang, Chao-Yun

2016-08-01

In this study, enzyme-assisted three-phase partitioning (EATPP) was used to extract oil from flaxseed. The whole procedure is composed of two parts: the enzymolysis procedure in which the flaxseed was hydrolyzed using an enzyme solution (the influencing parameters such as the type and concentration of enzyme, temperature, and pH were optimized) and three-phase partitioning (TPP), which was conducted by adding salt and t-butanol to the crude flaxseed slurry, resulting in the extraction of flaxseed oil into alcohol-rich upper phase. The concentration of t-butanol, concentration of salt, and the temperature were optimized to maximize the extraction yield. Under optimized conditions of a 49.29 % t-butanol concentration, 30.43 % ammonium sulfate concentration, and 35 °C extraction temperature, a maximum extraction yield of 71.68 % was obtained. This simple and effective EATPP can be used to achieve high extraction yields and oil quality, and thus, it is potential for large-scale oil production.

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

DOE PAGES

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

2018-02-23

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

Point defect disorder in high-temperature solution grown Sr6Tb0.94Fe1.06(BO3)6 single crystals

NASA Astrophysics Data System (ADS)

Velázquez, M.; Péchev, S.; Duttine, M.; Wattiaux, A.; Labrugère, C.; Veber, Ph.; Buffière, S.; Denux, D.

2018-08-01

New Sr6Tb0.94Fe1.06(BO3)6 single crystals were obtained from lithium borate high-temperature solution growth under controlled atmosphere. Their average crystal structure was found to adopt the trigonal R-3 space group with lattice parameters a = 12.2164 Å and c = 9.1934 Å. A combined multiscale characterization approach, involving diffuse reflectance, X-ray photoelectron (XPS) and Mössbauer spectroscopies, was undertaken to establish the exact nature of the point defect disorder in this crystal structure. The FeTb× antisite disorder in the Sr6Tb0.94Fe1.06(BO3)6 single crystals is different from the kind of point defect disorder known to exist in the powder phase material counterpart. The absence of Tb4+ cations in the crystal lattice was established by XPS, and that of any phase transition down to 4 K was checked by specific heat measurements. The magnetic susceptibility curve was found to follow a Curie-Weiss behaviour in the 4-354 K temperature range.

The design of an Fe-12Mn-O.2Ti alloy steel for low temperature use

NASA Technical Reports Server (NTRS)

Hwang, S. K.; Morris, J. W., Jr.

1977-01-01

An investigation was made to improve the low temperature mechanical properties of Fe-8 approximately 12% Mn-O 2Ti alloy steels. A two-phase(alpha + gamma) tempering in combination with cold working or hot working was identified as an effective treatment. A potential application as a Ni-free cryogenic steel was shown for this alloy. It was also shown that an Fe-8Mn steel could be grain-refined by a purely thermal treatment because of its dislocated martensitic structure and absence of epsilon phase. A significant reduction of the ductile-brittle transition temperature was obtained in this alloy. The nature and origin of brittle fracture in Fe-Mn alloys were also investigated. Two embrittling regions were found in a cooling curve of an Fe-12Mn-O 2Ti steel which was shown to be responsible for intergranular fracture. Auger electron spectroscopy identified no segregation during solution-annealing treatment. Avoiding the embrittling zones by controlled cooling led to a high cryogenic toughness in a solution-annealed condition.

Advanced Percussive Drilling Technology for Geothermal Exploration and Development

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

Su, Jiann; Raymond, David; Prasad, Somuri

Percussive hammers are a promising advance in drilling technology for geothermal since they rely upon rock reduction mechanisms that are well-suited for use in the hard, brittle rock characteristic of geothermal formations. The project research approach and work plan includes a critical path to development of a high-temperature (HT) percussive hammer using a two phase approach. The work completed in Phase I of the project demonstrated the viability of percussive hammers and that solutions to technical challenges in design, material technology, and performance are likely to be resolved. Work completed in Phase II focused on testing the findings from Phasemore » I and evaluating performance of the materials and designs at high operating temperatures. A high-operating temperature (HOT) drilling facility was designed, built, and used to test the performance of the DTH under extreme conditions. Results from the testing indicate that a high-temperature capable hammer can be developed and is a viable alternative for use in the driller’s toolbox.« less

High-pressure synthesis and structural, physical properties of CaIr1-xPtxO3 and CaIr1-xRhxO3

NASA Astrophysics Data System (ADS)

Hirai, S.; Bromiley, G. D.; Klemme, S.; Irifune, T.; Ohfuji, H.; Attfield, P.; Nishiyama, N.

2010-12-01

Since the discovery of the perovskite to post-perovskite transition in MgSiO3 in a laser-heated DAC, wide attention has been focussed on the post-perovskite phase of MgSiO3. This is because the post-perovskite phase is likely to play a key role in Earth’s lowermost mantle, and because the perovskite to post-perovskite transition can explain many features of the D” seismic discontinuity. While it is meaningful to conduct further studies of MgSiO3, the post-perovskite phase of MgSiO3 cannot be quenched to ambient pressure/temperature conditions. Thus, further studies must be conducted using analogue compounds of MgSiO3 post-perovskite, which are quenchable to ambient pressure/temperature conditions. The post-perovskite phase of MgSiO3 crystallizes in a layered structure with CaIrO3-structure. Therefore, it is useful to investigate compounds with CaIrO3-structure. There are only four quenchable oxides with CaIrO3-structure reported to date: CaIrO3, CaPtO3, CaRhO3 and CaRuO3. CaIrO3 can be synthesized at ambient pressure, whilst the other three oxides can only be obtained at high pressure/temperature conditions using a multi-anvil apparatus. Further studies on these materials have revealed structural phase transitions at high P-T and a metal-insulator transition by hole doping. In the case of CaIrO3, The post-perovskite phase of CaIrO3 synthesized at 2GPa, 1373K transforms into a perovskite phase at 2GPa, 1673K. In other words, the perovskite phase can be synthesized at temperatures higher than those needed for synthesizing the post-perovskite phase. This is also the case for CaRhO3 (6GPa, 1873K) and CaRuO3 (23GPa, 1343K), while CaPtO3 remained post-perovskite at higher temperatures. We have succeeded in synthesizing solid solutions between CaIrO3, CaPtO3 and CaRhO3. We have found the systematic change in structural and physical properties of post-perovskite oxides, with composition and P-T, which broadens the future opportunity for studying post-perovskite systems in terms of materials science applications. To our knowledge, this will be the first report on structural, magnetic and charge-transport properties of B-site substituted solid solutions of post-perovskite oxides with 4d/5d transition metals. High-quality polycrystalline samples of CaIr1-xPtxO3 and CaIr1-xRhxO3 have been obtained at high pressures, and structural, magnetic and charge-transport properties of the compounds will be reported. ODF analysis reveals that solutions of CaIrO3, CaPtO3 and CaRhO3 exhibit similar grain growth features to the mother compound, although growth in [0 1 0] plays a more dominant role than the growth in [0 0 1] for the solid solutions. CaIrO3 is a characteristic hard magnet suitable for applications such as magnetic recording, with TN = 108K. A new phase of CaIr1-xPtxO3 synthesized at a high P/T condition has Raman modes which resemble those of CaIrO3 perovskite, suggesting this phase has a perovskite structure.The instability of the perovskite phase of CaIr1-xPtxO3 reveals why the post-perovskite to peovskite phase transition has not been observed for CaPtO3 unlike the case for CaIrO3, CaRhO3 and CaRuO3.

Kinematic dust viscosity effect on linear and nonlinear dust-acoustic waves in space dusty plasmas with nonthermal ions

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

El-Hanbaly, A. M.; Sallah, M., E-mail: msallahd@mans.edu.eg; El-Shewy, E. K.

2015-10-15

Linear and nonlinear dust-acoustic (DA) waves are studied in a collisionless, unmagnetized and dissipative dusty plasma consisting of negatively charged dust grains, Boltzmann-distributed electrons, and nonthermal ions. The normal mode analysis is used to obtain a linear dispersion relation illustrating the dependence of the wave damping rate on the carrier wave number, the dust viscosity coefficient, the ratio of the ion temperature to the electron temperatures, and the nonthermal parameter. The plasma system is analyzed nonlinearly via the reductive perturbation method that gives the KdV-Burgers equation. Some interesting physical solutions are obtained to study the nonlinear waves. These solutions aremore » related to soliton, a combination between a shock and a soliton, and monotonic and oscillatory shock waves. Their behaviors are illustrated and shown graphically. The characteristics of the DA solitary and shock waves are significantly modified by the presence of nonthermal (fast) ions, the ratio of the ion temperature to the electron temperature, and the dust kinematic viscosity. The topology of the phase portrait and the potential diagram of the KdV-Burgers equation is illustrated, whose advantage is the ability to predict different classes of traveling wave solutions according to different phase orbits. The energy of the soliton wave and the electric field are calculated. The results in this paper can be generalized to analyze the nature of plasma waves in both space and laboratory plasma systems.« less

Room temperature metastable monoclinic phase in BaTiO3 crystals

NASA Astrophysics Data System (ADS)

Lummen, Tom; Wang, Jianjun; Holt, Martin; Kumar, Amit; Vlahos, Eftihia; Denev, Sava; Chen, Long-Qing; Gopalan, Venkatraman

2011-03-01

Low-symmetry monoclinic phases in ferroelectric materials are of considerable interest, due to their associated enhanced electromechanical coupling. Such phases have been found in Pb-based perovskite solid solutions such as lead zirconate titanate (PZT), where they form structural bridges between the rhombohedral and tetragonal ground states in compositional space. In this work, we directly image such a monoclinic phase in BaTi O3 crystals at room-temperature, using optical second harmonic generation, Raman, and X-ray microscopic imaging techniques. Phase-field modeling indicates that ferroelectric domain microstructures in BaTi O3 induce local inhomogeneous stresses in the crystals, which can effectively trap the transient intermediate monoclinic structure that occurs across the thermal orthorhombic-tetragonal phase boundary. The induced metastable monoclinic domains are ferroelectrically soft, being easily moved by electric fields as low as 0.5 kV cm-1 . Stabilizing such intermediate low-symmetry phases could very well lead to Pb-free materials with enhanced piezoelectric properties.

Effect of dope solution temperature on the membrane structure and membrane distillation performance

NASA Astrophysics Data System (ADS)

Nawi, N. I. M.; Bilad, M. R.; Nordin, N. A. H. M.

2018-04-01

Membrane distillation (MD) is a non-isothermal process applicable to purify water using hydrophobic membrane. Membrane in MD is hydrophobic, permeable to water vapor but repels liquid water. MD membrane is expected to pose high flux, high fouling and scaling resistances and most importantly high wetting resistance. This study develops flat-sheet polyvinylidene fluoride (PVDF) membrane by exploring both liquid-liquid and liquid-solid phase inversion technique largely to improve its wetting resistance and flux performance. We hypothesize that temperature of dope solution play roles in solid-liquid separation during membrane formation and an optimum balance between liquid-liquid and liquid-solid (crystallization) separation leads to highly performance PVDF membrane. Findings obtained from differential scanning calorimeter test show that increasing dope solution temperature reduces degree of PVDF crystallinity and suppresses formation of crystalline structure. The morphological images of the resulting membranes show that at elevated dope solution temperature (40, 60, 80 and 100°C), the spherulite-like structures are formed across the thickness of membranes ascribed from due to different type of crystals. The performance of direct-contact MD shows that the obtained flux of the optimum dope temperature (60°C) of 10.8 L/m2h is comparable to commercial PTFE-based MD membrane.

Amino acid ionic liquids.

PubMed

Ohno, Hiroyuki; Fukumoto, Kenta

2007-11-01

The preparation of ionic liquids derived from amino acids, and their properties, are outlined. Since amino acids have both a carboxylic acid residue and an amino group in a single molecule, they can be used as either anions or cations. These groups are also useful in their ability to introduce functional group(s). Twenty different natural amino acids were used as anions, to couple with the 1-ethyl-3-methylimidazolium cation. The salts obtained were all liquid at room temperature. The properties of the resulting ionic liquids (AAILs) depend on the side groups of the amino acids involved. These AAILs, composed of an amino acid with some functional groups such as a hydrogen bonding group, a charged group, or an aromatic ring, had an increased glass transition (or melting) temperature and/or higher viscosity as a result of additional interactions among the ions. Viscosity is reduced and the decomposition temperature of imidazolium-type salts is improved by using the tetrabutylphosphonium cation. The chirality of AAILs was maintained even upon heating to 150 degrees C after acetylation of the free amino group. The amino group was also modified to introduce a strong acid group so as to form hydrophobic and chiral ionic liquids. Unique phase behavior of the resulting hydrophobic ionic liquids and water mixture is found; the mixture is clearly phase separated at room temperature, but the solubility of water in this IL increases upon cooling, to give a homogeneous solution. This phase change is reversible, and separation occurs again by raising the temperature a few degrees. It is extraordinary for an IL/water mixture to display such behavior with a lower critical solution temperature. Some likely applications are proposed for these amino acid derived ionic liquids.

Formation of bubbly horizon in liquid-saturated porous medium by surface temperature oscillation.

PubMed

Goldobin, Denis S; Krauzin, Pavel V

2015-12-01

We study nonisothermal diffusion transport of a weakly soluble substance in a liquid-saturated porous medium in contact with a reservoir of this substance. The surface temperature of the porous medium half-space oscillates in time, which results in a decaying solubility wave propagating deep into the porous medium. In this system, zones of saturated solution and nondissolved phase coexist with ones of undersaturated solution. The effect is first considered for the case of annual oscillation of the surface temperature of water-saturated ground in contact with the atmosphere. We reveal the phenomenon of formation of a near-surface bubbly horizon due to temperature oscillation. An analytical theory of the phenomenon is developed. Further, the treatment is extended to the case of higher frequency oscillations and the case of weakly soluble solids and liquids.

Strain, temperature, and electric-field effects on the phase transition and piezoelectric responses of K0.5Na0.5NbO3 thin films

NASA Astrophysics Data System (ADS)

Zhou, Meng-Jun; Wang, Jian-Jun; Chen, Long-Qing; Nan, Ce-Wen

2018-04-01

A KNbO3-based solid solution system is environmentally friendly with good electromechanical performance. This work established the misfit strain-strain and temperature-strain phase diagrams for K0.5Na0.5NbO3 thin films and calculated the polarization switching, phase transition, and piezoelectric responses of K0.5Na0.5NbO3 thin films under various strains, temperatures, and electric fields. The results show that the piezoelectric coefficient d33 can be enhanced near the phase boundaries. For the ferroelectric phase with a nonzero out-of-plane polarization component, an optimal electric field is identified for maximizing d33, which is desired in applications such as thin-film piezoelectric micro-electromechanical systems, transducers for ultrasound medical imaging, and energy harvesting. The present results are expected to provide guidance for the future experimental study of KxNa1-xNbO3 thin films and the optimization of ferroelectric thin film-based devices.

On the bad metallicity and phase diagrams of Fe1+δX (X =Te, Se, S, solid solutions): an electrical resistivity study

NASA Astrophysics Data System (ADS)

El Massalami, M.; Deguchi, K.; Machida, T.; Takeya, H.; Takano, Y.

2014-12-01

Based on a systematic analysis of the thermal evolution of the resistivities of Fe-based chalcogenides Fe1+δTe1-xXx (X = Se, S), it is inferred that their often observed nonmetallic resistivities are related to a presence of two resistive channels: one is a high- temperature thermally-activated process while the other is a low-temperature log-in-T process. On lowering temperature, there are often two metal-to-nonmetall crossover events: one from the high-T thermally-activated nonmetallic regime into a metal-like phase and the other from the log-in-T regime into a second metal-like phase. Based on these events, together with the magnetic and superconducting transitions, a phase diagram is constructed for each series. We discuss the origin of both processes as well as the associated crossover events. We also discuss how these resistive processes are being influenced by pressure, intercalation, disorder, doping, or sample condition and, in turn, how these modifications are shaping the associated phase diagrams.

The enhancement and suppression of immersion mode heterogeneous ice-nucleation by solutes

PubMed Central

Holden, Mark A.; Wilson, Theodore W.; O'Sullivan, Daniel; Murray, Benjamin J.

2018-01-01

Heterogeneous nucleation of ice from aqueous solutions is an important yet poorly understood process in multiple fields, not least the atmospheric sciences where it impacts the formation and properties of clouds. In the atmosphere ice-nucleating particles are usually, if not always, mixed with soluble material. However, the impact of this soluble material on ice nucleation is poorly understood. In the atmospheric community the current paradigm for freezing under mixed phase cloud conditions is that dilute solutions will not influence heterogeneous freezing. By testing combinations of nucleators and solute molecules we have demonstrated that 0.015 M solutions (predicted melting point depression <0.1 °C) of several ammonium salts can cause suspended particles of feldspars and quartz to nucleate ice up to around 3 °C warmer than they do in pure water. In contrast, dilute solutions of certain alkali metal halides can dramatically depress freezing points for the same nucleators. At 0.015 M, solutes can enhance or deactivate the ice-nucleating ability of a microcline feldspar across a range of more than 10 °C, which corresponds to a change in active site density of more than a factor of 105. This concentration was chosen for a survey across multiple solutes–nucleant combinations since it had a minimal colligative impact on freezing and is relevant for activating cloud droplets. Other nucleators, for instance a silica gel, are unaffected by these ‘solute effects’, to within experimental uncertainty. This split in response to the presence of solutes indicates that different mechanisms of ice nucleation occur on the different nucleators or that surface modification of relevance to ice nucleation proceeds in different ways for different nucleators. These solute effects on immersion mode ice nucleation may be of importance in the atmosphere as sea salt and ammonium sulphate are common cloud condensation nuclei (CCN) for cloud droplets and are internally mixed with ice-nucleating particles in mixed-phase clouds. In addition, we propose a pathway dependence where activation of CCN at low temperatures might lead to enhanced ice formation relative to pathways where CCN activation occurs at higher temperatures prior to cooling to nucleation temperature. PMID:29780544

Characterization of rarefaction waves in van der Waals fluids

NASA Astrophysics Data System (ADS)

Yuen, Albert; Barnard, John J.

2015-12-01

We calculate the isentropic evolution of an instantaneously heated foil, assuming a van der Waals equation of state with the Maxwell construction. The analysis by Yuen and Barnard [Phys. Rev. E 92, 033019 (2015), 10.1103/PhysRevE.92.033019] is extended for the particular case of three degrees of freedom. We assume heating to temperatures in the vicinity of the critical point. The self-similar profiles of the rarefaction waves describing the evolution of the foil display plateaus in density and temperature due to a phase transition from the single-phase to the two-phase regime. The hydrodynamic equations are expressed in a dimensionless form and the solutions form a set of universal curves, depending on a single parameter: the dimensionless initial entropy. We characterize the rarefaction waves by calculating how the plateau length, density, pressure, temperature, velocity, internal energy, and sound speed vary with dimensionless initial entropy.

A study of the diffusional behavior of a two-phase metal matrix composite exposed to a high temperature environment

NASA Technical Reports Server (NTRS)

Tenney, D. R.

1974-01-01

The progress of diffusion-controlled filament-matrix interaction in a metal matrix composite where the filaments and matrix comprise a two-phase binary alloy system was studied by mathematically modeling compositional changes resulting from prolonged elevated temperature exposure. The analysis treats a finite, diffusion-controlled, two-phase moving-interface problem by means of a variable-grid finite-difference technique. The Ni-W system was selected as an example system. Modeling was carried out for the 1000 to 1200 C temperature range for unidirectional composites containing from 6 to 40 volume percent tungsten filaments in a Ni matrix. The results are displayed to show both the change in filament diameter and matrix composition as a function of exposure time. Compositional profiles produced between first and second nearest neighbor filaments were calculated by superposition of finite-difference solutions of the diffusion equations.

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

Guo, Peijun; Xia, Yi; Gong, Jue

Solution-processable metal-halide perovskites (MHPs) offer great promise for efficient light harvesting and emitting devices due to their long carrier lifetime and superior carrier transport characteristics. Ferroelectric effects, a hallmark of traditional oxide perovskites, was proposed to be a mechanism to suppress carrier recombination and enhance charge transport in MHPs, but the existence and influence of such polar order is still of considerable debate. Here we performed transient reflection measurements on single crystals of both inorganic and organic-inorganic (hybrid) MHPs over a range of temperatures, and demonstrate significant phonon softening in the cubic phases close to the cubic-to-tetragonal phase transition temperatures.more » Such phonon softening indicates the formation of polar domains, which grow in size upon cooling and can persist in the low-temperature tetragonal and orthorhombic phases. Our results link the extraordinary electronic properties of MHPs to the spontaneous polarizations which can contribute to more efficient charge separation and characteristics of an indirect bandgap.« less

Aqueous Two Phase System Assisted Self-Assembled PLGA Microparticles

NASA Astrophysics Data System (ADS)

Yeredla, Nitish; Kojima, Taisuke; Yang, Yi; Takayama, Shuichi; Kanapathipillai, Mathumai

2016-06-01

Here, we produce poly(lactide-co-glycolide) (PLGA) based microparticles with varying morphologies, and temperature responsive properties utilizing a Pluronic F127/dextran aqueous two-phase system (ATPS) assisted self-assembly. The PLGA polymer, when emulsified in Pluronic F127/dextran ATPS, forms unique microparticle structures due to ATPS guided-self assembly. Depending on the PLGA concentration, the particles either formed a core-shell or a composite microparticle structure. The microparticles facilitate the simultaneous incorporation of both hydrophobic and hydrophilic molecules, due to their amphiphilic macromolecule composition. Further, due to the lower critical solution temperature (LCST) properties of Pluronic F127, the particles exhibit temperature responsiveness. The ATPS based microparticle formation demonstrated in this study, serves as a novel platform for PLGA/polymer based tunable micro/nano particle and polymersome development. The unique properties may be useful in applications such as theranostics, synthesis of complex structure particles, bioreaction/mineralization at the two-phase interface, and bioseparations.

Effect of Heat Treatment on the Microstructure and Wear Properties of Al-Zn-Mg-Cu/In-Situ Al-9Si-SiCp/Pure Al Composite by Powder Metallurgy

NASA Astrophysics Data System (ADS)

Yu, Byung Chul; Bae, Ki-Chang; Jung, Je Ki; Kim, Yong-Hwan; Park, Yong Ho

2018-05-01

This study examined the effects of heat treatment on the microstructure and wear properties of Al-Zn-Mg-Cu/in-situ Al-9Si-SiCp/pure Al composites. Pure Al powder was used to increase densification but it resulted in heterogeneous precipitation as well as differences in hardness among the grains. Heat treatment was conducted to solve this problem. The heat treatment process consisted of three stages: solution treatment, quenching, and aging treatment. After the solution treatment, the main dissolved phases were η'(Mg4Zn7), η(MgZn2), and Al2Cu phase. An aging treatment was conducted over the temperature range, 100-240 °C, for various times. The GP zone and η'(Mg4Zn7) phase precipitated at a low aging temperature of 100-160 °C, whereas the η(MgZn2) phase precipitated at a high aging temperature of 200-240 °C. The hardness of the sample aged at 100-160 °C was higher than that aged at 200-240 °C. The wear test was conducted under various linear speeds with a load of 100 N. The aged composite showed a lower wear rate than that of the as-sintered composite under all conditions. As the linear speed was increased to 1.0 m/s, the predominant wear behavior changed from abrasive to adhesive wear in all composites.

Cyclic phase change in a cylindrical thermal energy storage capsule

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

Hasan, M.; Mujumdar, A.S.; Weber, M.E.

1983-12-01

This paper is concerned with a practical melting/freezing problem in conjunction with the more realistic case of a cyclic phase change thermal energy storage device. In this model the phase change medium is encapsulated in long cylindrical tubes, the surface temperature of which is allowed to vary sinusoidally with time about the discrete freezing temperature. Initial temperature of the medium is assumed to be constant at a temperature above or below the freezing/melting temperature. Natural convection in the melt is assumed to be negligible and the variations in the depth of freezing and/or melting in each half cycle is ignored.more » Depending on the half-cycle parameters the problem is simplified to either freezing or melting. The governing one-dimensional heat diffusion equations for both phases are solved by the Finite Integral Transform techniques. The kernels for the transformation are the time-dependent eigen functions separately defined for each phases. This extended transform method can accomodate any time-dependent surface temperature variation. The application of the transform generated a series of coupled, nonlinear first order differential equations, which are solved by Runge Kutta-Verner fifth and sixth order method. Dimensionless solutions of temperature variations in both phases, fusion front position and the fraction solidified (or melted) are displayed graphically to aid in practical calculations. For the special case of a constant surface temperature, comparisons are made between the present results and the existing integral and purely numerical results. The results are found to compare favourably. Results for fractional solidification (or melting and interface position are also compared with the simple Conduction Shape Factor method, after allowing for the time-dependent boundary conditions. Once again the results agree reasonably well.« less

Injectable CMC/PEI gel as an in vivo scaffold for demineralized bone matrix.

PubMed

Kim, Kyung Sook; Kang, Yun Mi; Lee, Ju Young; Kim, E Sle; Kim, Chun Ho; Min, Byoung Hyun; Lee, Hai Bang; Kim, Jae Ho; Kim, Moon Suk

2009-01-01

A number of materials have been considered as sources of grafts to repair bone defects. Here, we examined the possibility of creating in situ-forming gels from sodium carboxymethylcellulose (CMC) and poly(ethyleneimine) (PEI) for use as an in vivo carrier of demineralized bone matrix (DBM). The interaction between anionic CMC and cationic PEI was examined by evaluating phase transition behavior and viscosity of CMC solutions containing 0-30 wt% PEI. CMC solutions containing 10 wt% PEI exhibited a sol-to-gel phase transition at temperatures greater than 35 degrees C. The phase transition is caused by electrostatic crosslinking of the CMC/PEI solution to form a gel with a three-dimensional network structure. In situ-formed gel implants were successfully fabricated in vivo by simple subcutaneous injection of the CMC/PEI (90/10) solution (with and without DBM) into Fisher rats. The resulting in situ-formed implant maintained its shape for 28 days in vitro and in vivo. Our results show that in situ-forming CMC/PEI gels can serve as a DBM carrier that can be delivered with a minimally invasive procedure.

Preparation of stationary phases for reversed-phase high-performance liquid chromatography using thermal treatments at high temperature.

PubMed

Vigna, Camila R M; Bottoli, Carla B G; Collins, Kenneth E; Collins, Carol H

2007-07-13

Batches of poly(methyloctylsiloxane) (PMOS)-loaded silica were prepared by deposition from a solution of PMOS into the pores of HPLC silica. Portions of PMOS-loaded silica were subjected to a thermal treatment at 100 degrees C for 24h (condition 1) in a tube furnace under a nitrogen atmosphere. After that, the material was heated for 4h at higher temperatures (150-400 degrees C) (condition 2). Heating at higher temperatures produces polymer bilayers. Non-immobilized and thermally treated stationary phases were characterized by percent carbon, (29)Si cross-polarization magic angle spinning nuclear magnetic resonance spectroscopy and reversed-phase chromatographic performance. The results show that thermal treatment between 150 and 300 degrees C accelerates the immobilization process, possibly due to some bond breaking of the polysiloxane, with formation of strong linkages to the surface of the support, resulting in more complete coverage of the silica. The chromatographic results show an improvement of efficiency with the increase of the temperature of condition 2 up to 300 degrees C and an increase in the resolution of the components, mainly for the phase heated at 300 degrees C. Such results demonstrate that a two-step thermal treatment (100 degrees C then 150-300 degrees C) produces stationary phases with good properties for use in reversed-phase high-performance liquid chromatography.

Ferromagnetic superconductors: A vortex phase in ternary rare-earth compounds

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

Kuper, C.G.; Revzen, M.; Ron, A.

1980-06-09

It is shown that the generalized Ginzburg-Landau free-energy functional of Blount and Varma admits self-consistent solutions with quantized-flux vortices, magnetized in a region about the cores. There is a temperature range where the new phase has a lower free energy than either the pure superconducting or ferromagnetic phases; it represents true coexistence of ferromagnetism and superconductivity. The main features of the specific heat and magnetic properties of some rare-earth ternary compounds can be explained qualitatively.

Describing the strongly interacting quark-gluon plasma through the Friedberg-Lee model

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

Shu Song; Li Jiarong; Institute of Particle Physics, Hua-Zhong Normal University, Wuhan 430079

2010-10-15

The Friedberg-Lee (FL) model is studied at finite temperature and density. The soliton solutions of the FL model in the deconfinement phase transition are solved and thoroughly discussed for certain boundary conditions. We indicate that the solitons before and after the deconfinement have different physical meanings: the soliton before deconfinement represents hadrons, while the soliton after the deconfinement represents the bound state of quarks which leads to a strongly interacting quark-gluon plasma phase. The corresponding phase diagram is given.

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

PubMed

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.

Liquid-phase deposition of thin Si films by ballistic electro-reduction

NASA Astrophysics Data System (ADS)

Ohta, T.; Gelloz, B.; Kojima, A.; Koshida, N.

2013-01-01

It is shown that the nanocryatalline silicon ballistic electron emitter operates in a SiCl4 solution without using any counter electrodes and that thin amorphous Si films are efficiently deposited on the emitting surface with no contaminations and by-products. Despite the large electrochemical window of the SiCl4 solution, electrons injected with sufficiently high energies preferentially reduce Si4+ ions at the interface. Using an emitter with patterned line emission windows, a Si-wires array can be formed in parallel. This low-temperature liquid-phase deposition technique provides an alternative clean process for power-effective fabrication of advanced thin Si film structures and devices.

Rotaxane liquid crystals with variable length: The effect of switching efficiency on the isotropic-nematic transition

NASA Astrophysics Data System (ADS)

He, Hao; Sevick, Edith M.; Williams, David R. M.

2018-04-01

We examine a solution of non-adaptive two-state rotaxane molecules which can switch from a short state of length L to a long state of length qL, using statistical thermodynamics. This molecular switching is externally driven and can result in an isotropic-nematic phase transition without altering temperature and concentration. Here we concentrate on the limitation imposed by switching inefficiency, i.e., on the case where molecular switching is not quantitative, leading to a solution of rotaxanes in different states. We present switching diagrams that can guide in the design of rotaxanes which affect a macroscopic phase change.

Closed Form Solutions for Unsteady Free Convection Flow of a Second Grade Fluid over an Oscillating Vertical Plate

PubMed Central

Ali, Farhad; Khan, Ilyas; Shafie, Sharidan

2014-01-01

Closed form solutions for unsteady free convection flows of a second grade fluid near an isothermal vertical plate oscillating in its plane using the Laplace transform technique are established. Expressions for velocity and temperature are obtained and displayed graphically for different values of Prandtl number Pr, thermal Grashof number Gr, viscoelastic parameter α, phase angle ωτ and time τ. Numerical values of skin friction τ 0 and Nusselt number Nu are shown in tables. Some well-known solutions in literature are reduced as the limiting cases of the present solutions. PMID:24551033

Dissolution of spent nuclear fuel in carbonate-peroxide solution

NASA Astrophysics Data System (ADS)

Soderquist, Chuck; Hanson, Brady

2010-01-01

This study shows that spent UO2 fuel can be completely dissolved in a room temperature carbonate-peroxide solution apparently without attacking the metallic Mo-Tc-Ru-Rh-Pd fission product phase. In parallel tests, identical samples of spent nuclear fuel were dissolved in nitric acid and in an ammonium carbonate, hydrogen peroxide solution. The resulting solutions were analyzed for strontium-90, technetium-99, cesium-137, europium-154, plutonium, and americium-241. The results were identical for all analytes except technetium, where the carbonate-peroxide dissolution had only about 25% of the technetium that the nitric acid dissolution had.

Magnetic studies of nickel hydride nanoparticles embedded in chitosan matrix

NASA Astrophysics Data System (ADS)

Araújo-Barbosa, S.; Morales, M. A.

2017-11-01

In this work we present a method to produce NiH (β-NiH phase) nanoparticles from Ni-Cu solid solution. The reduction of Ni2+ and Cu2+ occurred at high temperatures and in presence of glutaraldehyde, citric acid and chitosan biopolymer. The samples are mainly composed of Ni and NiH phases with particles sizes ranging from 9 to 27 nm. DC magnetization studies reveal the presence of hydrogen-poor nickel hydride phase (α-NiH phase) which enhances the saturation magnetization at temperatures below 50 K. Stability of samples stored in air after 8 months was verified, and thermal treatment at 350 oC in presence of air transformed the samples to Ni and Cu oxides. Furthermore, we present a discussion regarding the mechanism of Ni2+ and Cu2+ chemical reduction.

Effect of annealing temperature on the properties of copper oxide films prepared by dip coating technique

NASA Astrophysics Data System (ADS)

Raship, N. A.; Sahdan, M. Z.; Adriyanto, F.; Nurfazliana, M. F.; Bakri, A. S.

2017-01-01

Copper oxide films were grown on silicon substrates by sol-gel dip coating method. In order to study the effects of annealing temperature on the properties of copper oxide films, the temperature was varied from 200 °C to 450 °C. In the process of dip coating, the substrate is withdrawn from the precursor solution with uniform velocity to obtain a uniform coating before undergoing an annealing process to make the copper oxide film polycrystalline. The physical properties of the copper oxide films were measured by an X-ray diffraction (XRD), a field emission scanning electron microscope (FESEM), an atomic force microscopy (AFM) and a four point probe instrument. From the XRD results, we found that pure cuprite (Cu2O) phase can be obtained by annealing the films annealed at 200 °C. Films annealed at 300 °C had a combination phase which consists of tenorite (CuO) and cuprite (Cu2O) phase while pure tenorite (CuO) phase can be obtained at 450 °C annealing temperature. The surface microstructure showed that the grains size is increased whereas the surface roughness is increased and then decreases by increasing in annealing temperature. The films showed that the resistivity decreased with increasing annealing temperature. Consequently, it was observed that annealing temperature has strong effects on the structural, morphological and electrical properties of copper oxide films.

A high-performance protocol for extraction of microplastics in fish.

PubMed

Karami, Ali; Golieskardi, Abolfazl; Choo, Cheng Keong; Romano, Nicholas; Ho, Yu Bin; Salamatinia, Babak

2017-02-01

So far, several classes of digesting solutions have been employed to extract microplastics (MPs) from biological matrices. However, the performance of digesting solutions across different temperatures has never been systematically investigated. In the first phase of the present study, we measured the efficiency of different oxidative agents (NaClO or H 2 O 2 ), bases (NaOH or KOH), and acids [HCl or HNO 3 ; concentrated and diluted (5%)] in digesting fish tissues at room temperature (RT, 25°C), 40, 50, or 60°C. In the second phase, the treatments that were efficient in digesting the biological materials (>95%) were evaluated for their compatibility with eight major plastic polymers (assessed through recovery rate, Raman spectroscopy analysis, and morphological changes). Among the tested solutions, NaClO, NaOH, and diluted acids did not result in a satisfactory digestion efficiency at any of the temperatures. The H 2 O 2 treatment at 50°C efficiently digested the biological materials, although it decreased the recovery rate of nylon-6 (NY6) and nylon-66 (NY66) and altered the colour of polyethylene terephthalate (PET) fragments. Similarly, concentrated HCl and HNO 3 treatments at RT fully digested the fish tissues, but also fully dissolved NY6 and NY66, and reduced the recovery rate of most or all of the polymers, respectively. Potassium hydroxide solution fully eliminated the biological matrices at all temperatures. However, at 50 and 60°C, it degraded PET, reduced the recovery rate of PET and polyvinyl chloride (PVC), and changed the colour of NY66. According to our results, treating biological materials with a 10% KOH solution and incubating at 40°C was both time and cost-effective, efficient in digesting biological materials, and had no impact on the integrity of the plastic polymers. Furthermore, coupling this treatment with NaI extraction created a promising protocol to isolate MPs from whole fish samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Lattice thermal expansion of the solid solutions (La{sub 1−x}Sm{sub x}){sub 2}Ce{sub 2}O{sub 7}

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

Wu, Hongdan; Lei, Xinrong; Zhang, Jinhua, E-mail: jhzhang1212@126.com

2014-09-15

Highlights: • Sm-doped La{sub 2}Ce{sub 2}O{sub 7} was prepared by the coprecipitation–calcination method. • In situ HT-XRD measurements revealed that is much stable than 8YSZ. • Its thermal expansion is better than 8YSZ. - Abstract: A series of solid solutions with the general formula (La{sub 1−x}Sm{sub x}){sub 2}Ce{sub 2}O{sub 7} (0.0 ≤ x ≤ 1.0) were prepared by the coprecipitation–calcination method. The products obtained were characterized by powder X-ray diffraction for phase purity. It was observed that La{sup 3+} and Sm{sup 3+} can form complete solid solution in (La,Sm){sub 2}Ce{sub 2}O{sub 7} with defect-fluorite-type phase. The unit cell parameters ofmore » these solutions were calculated by a least squares method and the lattice parameters decreased linearly as x increased. The lattice thermal expansion behavior of (La{sub 1−x}Sm{sub x}){sub 2}Ce{sub 2}O{sub 7} (0.0 ≤ x ≤ 1.0) was investigated by high-temperature X-ray diffraction in the temperature range 298–1623 K. The lattice parameters a{sub T} of all the solutions at different temperature can be expressed as a{sub T} = a + bT + cT{sup 2}. As x < 1, the thermal expansion has a sudden decrease at ca. 473 K. The coefficients of lattice thermal expansion of Sm{sub 2}Ce{sub 2}O{sub 7} were 10.2–13.6 × 10{sup −6} K{sup −1} from 298 to 1623 K, and without the thermal contraction at low temperature. The materials show positive or negative thermal expansion due to the asymmetric anharmonic vibration.« less

The origin of the initial heat associated with a single impulse in mammalian non-myelinated nerve fibres

PubMed Central

Howarth, J. V.; Keynes, R. D.; Ritchie, J. M.

1968-01-01

1. A study has been made of the temperature changes associated with the passage of a single impulse in rabbit desheated vagus nerves. 2. The initial changes consist of an evolution of positive heat followed by a reabsorption of most of it; i.e. there is a phase of positive and a phase of negative heat production. 3. The size of the positive heat, its time of onset, and the time of onset of the negative heat have been measured by an analogue method of analysis. In addition, these parameters, together with the size of the negative heat and the duration of both phases of initial heat, have been studied with the aid of a computer, and also by conventional heat block analysis. 4. At about 5° C the measured positive heat is 7·2 μcal/g. impulse. It starts as soon as the compound action potential reaches the thermopile and lasts for about 107 msec. 5. This positive heat decreases with increasing temperature, the ratio of heat at 4° C to that at 14° C being 1·86. 6. The measured negative heat at about 5° C is 4·9 μcal/g. impulse. It starts 102 msec after the onset of positive heat, and lasts for about 240 msec. 7. When the sodium of Locke solution is replaced by lithium the positive heat is reduced by 19%, but the negative heat is increased by 22%. 8. In potassium-free solutions the positive heat is hardly affected (increase of 5%), but the negative heat is more than doubled. As a result the nerve may become briefly colder than its initial temperature by about 2 μ° C. 9. The effect of sodium-deficient solutions on the positive heat is somewhat variable, but the negative heat is consistently diminished. 10. Replacement of the chloride of Locke solution by sulphate or nitrate has little effect on the positive heat. The negative heat is reduced in size by 26% and in duration by 22%. 11. Replacement of most of the sodium of Locke solution by barium reduces or abolishes the negative heat, and increases the measured size of the positive heat nearly threefold. 12. Veratrine (10-5 g/ml.) produces a nearly tenfold increase in the net positive heat. 13. Ouabain (1 mM) and antimycin A (1 μg/ml.) applied for 30-60 min have little effect on the initial heat production. 14. Over the temperature range 5-15° C, and for the ionic solution changes described above, there is close agreement in timing between the positive heat and the rising phase of the action potential, and between the negative heat and the falling phase. 15. Because of the inevitable temporal dispersion of the action potential over the face of the thermopile, the observed temperature changes are smaller than those which occur at a single point in the nerve close to a stimulating electrode. The corrected value of the positive heat at 5° C is 24·5 μcal/g. impulse, while that of the negative heat is 22·2 μcal/g. impulse. 16. The heats of mixing of the ions in solution that interchange during the action potential are much too small to account for the observed initial heats, but an exchange of ions associated with fixed charges might make a significant contribution to the heats. 17. The condenser theory, according to which the positive heat represents the dissipation of electrical energy stored in the membrane capacity, while the negative heat results from the recharging of the capacity, appears unable to account for more than half of the observed temperature changes. 18. It seems probable that the greater part of the initial heat results from changes in the entropy of the nerve membrane when it is depolarized and repolarized. PMID:5636997

Heterogeneous interactions of chlorine nitrate, hydrogen chloride, and nitric acid with sulfuric acid surfaces at stratospheric temperatures

NASA Technical Reports Server (NTRS)

Tolbert, Margaret A.; Rossi, Michel J.; Golden, David M.

1988-01-01

The heterogeneous interactions of ClONO2, HCl, and HNO3 with sulfuric acid surfaces were studied using a Knudsen cell flow reactor. The surfaces studied, chosen to simulate global stratospheric particulate, were composed of 65-75 percent H2SO4 solutions at temperatures in the range -63 to -43 C. Heterogeneous loss, but not reaction, of HNO3 and HCl occurred on these surfaces; the measured sticking coefficients are reported. Chlorine nitrate reacted on the cold sulfuric acid surfaces, producing gas-phase HOCl and condensed HNO3. CLONO2 also reacted with HCl dissolved in the 65-percent H2SO4 solution at -63 C, forming gaseous Cl2. In all cases studied, the sticking and/or reaction coefficients were much larger for the 65-percent H2SO4 solution at -63 C than for the 75-percent solution at -43 C.

Solution-Phase Synthesis of Cesium Lead Halide Perovskite Nanowires.

PubMed

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.

A mass-balanced definition of corrected retention volume in gas chromatography.

PubMed

Kurganov, A

2007-05-25

The mass balance equation of a chromatographic system using a compressible moving phase has been compiled for mass flow of the mobile phase instead of traditional volumetric flow allowing solution of the equation in an analytical form. The relation obtained correlates retention volume measured under ambient conditions with the partition coefficient of the solute. Compared to the relation in the ideal chromatographic system the equation derived contains an additional correction term accounting for the compressibility of the moving phase. When the retention volume is measured under the mean column pressure and column temperature the correction term is reduced to unit and the relation is simplified to those known for the ideal system. This volume according to International Union of Pure and Applied Chemistry (IUPAC) is called the corrected retention volume.

Inorganic Corrosion-Inhibitive Pigments for High-Temperature Alkali-activated Well Casing Foam Cement

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

Sugama, T.; Pyatina, T.

2014-11-01

This study evaluates inorganic pigments for improving carbon steel (CS) brine-corrosion protection by the sodium metasilicate-activated calcium aluminate cement/Fly Ash blend at 300°C. Calcium borosilicate (CBS) and zinc phosphate, significantly improved CS corrosion-protection by decreasing cement’s permeability for corrosive ions and inhibiting anodic corrosion. An amorphous Na 2O-Al 2O 3-SiO 2-H 2O phase tightly attached to CS surface formed at 300oC in CBS-modified cement pore solution. The corrosion rate of the CS covered with this phase was nearly 4-fold lower than in the case of nonmodified cement pore solution where the major phase formed on the surface of CS wasmore » crystalline analcime.« less

Inorganic Corrosion-Inhibitive Pigments for High-Temperature Alkali-activated Well Casing Foam Cement

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

Sugama, T.; Pyatina, T.

2014-11-14

This study evaluates inorganic pigments for improving carbon steel (CS) brine-corrosion protection by the sodium metasilicate-activated calcium aluminate cement/Fly Ash blend at 300°C. Calcium borosilicate (CBS) and zinc phosphate, significantly improved CS corrosion-protection by decreasing cement’s permeability for corrosive ions and inhibiting anodic corrosion. An amorphous Na 2O-Al 2O 3-SiO 2-H 2O phase tightly attached to CS surface formed at 300oC in CBS-modified cement pore solution. The corrosion rate of the CS covered with this phase was nearly 4-fold lower than in the case of nonmodified cement pore solution where the major phase formed on the surface of CS wasmore » crystalline analcime.« less

As-Cast Icosashedral Quasicrystals in Ti-Zr-Ni Alloys

NASA Astrophysics Data System (ADS)

Lee, Geun Woo; Gangopadhyay, Anup K.; Kelton, Kenneth F.

2002-03-01

Most Ti-based icosahedral quasicrystals (i-phase) obtained by rapid quenching from the melt are metastable and disordered. In contrast, the Ti-Zr-Ni i-phase prepared by low temperature annealing is stable and better ordered. This i-phase is formed by a solid-state transformation from C14 Laves phase and α (Ti/Zr) solid-solution phase. It has not been possible previously to grow this i-phase directly from the liquid. Here, the nucleation and growth of the i-phase from the liquid in as-cast Ti-Zr-Ni alloys is reported. Pentagonal growth ledges in as-cast Ti-Zr-Ni ingots are clearly observed. Transmission electron microscopy and x-ray diffraction studies confirm the phase identity. Differential scanning calorimetry measurements show an endothermic transformation from the i-phase to a phase mixture of the C14 Laves and solid-solution phases, demonstrating that this i-phase is also stable. The short time that the liquid remains in the Laves phase-forming-field and the higher nucleation rate of the i-phase, owing to the presumed similarity between the local atomic structures of the i-phase and liquid, allows the i-phase to nucleate and grow directly from the liquid. Container-less solidification studies using electrostatic levitation (ESL) techniques support this conclusion.

Solubility of carbon dioxide in aqueous solutions of 2-amino-2-methyl-1-propanol and N-methyldiethanolamine and their mixtures in the temperature range of 313 to 353 K and pressures up to 2.7 MPa

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

Silkenbaeumer, D.; Lichtenthaler, R.N.; Rumpf, B.

1998-08-01

The solubility of carbon dioxide in aqueous solutions containing 2-amino-2-methyl-1-propanol (AMP) was measured in the temperature range from 313 to 353 K at total pressures up to 2.7 MPa using an analytical method. A model taking into account chemical reactions in the liquid phase as well as physical interactions is used to correlate the new data. To test the predictive capability of the model, the solubility of carbon dioxide in an aqueous solution containing AMP and N-methyldiethanolamine (MDEA) was measured at 313 K. Experimental results are reported and compared to literature data and calculations.

Kinetics of radiation-induced precipitation at the alloy surface

NASA Astrophysics Data System (ADS)

Lam, N. Q.; Nguyen, T.; Leaf, G. K.; Yip, S.

1988-05-01

Radiation-induced precipitation of a new phase at the surface of an alloy during irradiation at elevated temperatures was studied with the aid of a kinetic model of segregation. The preferential coupling of solute atoms with the defect fluxes gives rise to a strong solute enrichment at the surface, which, if surpassing the solute solubility limit, leads to the formation of a precipitate layer. The moving precipitate/matrix interface was accommodated by means of a mathematical scheme that transforms spatial coordinates into a reference frame in which the boundaries are immobile. Sample calculations were performed for precipitation of the γ'-Ni 3Si layer on Ni-Si alloys undergoing electron irradiation. The dependences of the precipitation kinetics on the defect-production rate, irradiation temperature, internal defect sink concentration and alloy composition were investigated systematically.

Oxidation kinetics of a continuous carbon phase in a nonreactive matrix

NASA Technical Reports Server (NTRS)

Eckel, Andrew J.; Cawley, James D.; Parthasarathy, Triplicane A.

1995-01-01

Analytical solutions of and experimental results on the oxidation kinetics of carbon in a pore are presented. Reaction rate, reaction sequence, oxidant partial pressure, total system pressure, pore/crack dimensions, and temperature are analyzed with respect to the influence of each on an overall linear-parabolic rate relationship. Direct measurement of carbon recession is performed using two microcomposite model systems oxidized in the temperature range of 700 to 1200 C, and for times to 35 h. Experimental results are evaluated using the derived analytical solutions. Implications on the oxidation resistance of continuous-fiber-reinforced ceramic-matrix composites containing a carbon constituent are discussed.

Improved ferroelectric and pyroelectric parameters in iminodiacetic acid doped TGS crystal

NASA Astrophysics Data System (ADS)

Rai, Chitharanjan; Sreenivas, K.; Dharmaprakash, S. M.

2010-01-01

Single crystals of Iminodiacetic acid (HN(CH 2COOH) 2) doped Triglycine sulphate (IDATGS) has been grown from aqueous solution at constant temperature by slow evaporation technique. The concentration of the dopant in the TGS solution was 2 mol%. The X-ray diffraction analysis indicates that there is significant change in the lattice parameters compared to pure TGS crystal. The IDATGS crystal has larger transition temperature and observed higher and uniform figure of merit over most part of the ferroelectric phase. These crystals also exhibit higher internal bias field and micro-hardness number compared to pure TGS. Therefore IDATGS may be a potential material for IR detectors.

X-ray study of mesomorphism of bent-core and chromonic mesogens

NASA Astrophysics Data System (ADS)

Joshi, Leela Pradhan

The discovery of thermotropic biaxial nematic phase in bent-core mesogens, have engendered interest in these systems. Also, it undergoes optical switching about 100 times faster than conventional uniaxial nematic liquid crystal. Azo-substituted bent-core compounds, A131 and A103, were investigated as both offer an opportunity to observe their structures and phase transitions from the uniaxial nematic (Nu) to biaxial nematic (Nb) phase and from Nb to the underlying smectic-C (SmC) phase. Plank-like molecular systems are also expected to form Nb phase. Chromonic liquid crystals formed by aqueous solutions of plank-like dye molecules are interesting for their unique self-assembly and structural evolution. They have applications in optical element, coloring in food and textiles, and etc. Both systems were investigated with synchrotron x-ray scattering, polarizing optical microscopy, and differential scanning calorimetry. Temperature dependence of d-spacing and positional order correlations along the director clearly mark the phase boundaries where Nu-Nb transition was approximately 27° below the clearing point. Positional order correlation length of A131 increased from 1.5 in Nu to 3.3 molecular lengths in Nb phase, before it jumps by a factor of at least 5 in SmC phase. The lack of large discontinuous changes in the structural parameters and the subtle signatures in heat capacity establish the second order nature of Nu-Nb and Nb-SmC phase transitions. The chromonic system investigation results provide quantitative information of structural properties in nematic and columnar mesophases. We studied water solutions of (achiral) sunset yellow dye and (chiral and achiral) dihydrochloride salts of perylenebis-dicarboxydiimide. Positional order correlation lengths measurements, parallel and perpendicular to the aggregate axis, revealed that they increase with concentration and decrease with temperature. Temperature dependence of correlation lengths yielded the scission energy to be 1.8 (+/-0.1) x10-20J and 1.5 (+/-0.08) x10-20J in the nematic and columnar phases. The aggregates' small aspect ratio (2.5) is inconsistent with the Onsager model for the formation of an orientationally ordered phase, which strongly suggests more complicated aggregate-shape than simple cylindrical objects as postulated by Laventovich, et al.

Antiferromagnetic Potts Model on the Erdős-Rényi Random Graph

NASA Astrophysics Data System (ADS)

Contucci, Pierluigi; Dommers, Sander; Giardinà, Cristian; Starr, Shannon

2013-10-01

We study the antiferromagnetic Potts model on the Poissonian Erdős-Rényi random graph. By identifying a suitable interpolation structure and an extended variational principle, together with a positive temperature second-moment analysis we prove the existence of a phase transition at a positive critical temperature. Upper and lower bounds on the temperature critical value are obtained from the stability analysis of the replica symmetric solution (recovered in the framework of Derrida-Ruelle probability cascades) and from an entropy positivity argument.

Structure-property relationships of new bismuth and lead oxide based perovskite ternary solid solutions

NASA Astrophysics Data System (ADS)

Dwivedi, Akansha

Two new bismuth and lead oxide based perovskite ternary solid solutions, namely xBi(Zn1/2Ti1/2)O3-yPbZrO3-zPbTiO3 [xBZT-yPZ-zPT] and xBi(Mg1/2Ti1/2)O3-yBi(Zn 1/2Ti1/2)O3-zPbTiO3 [xBMT-yBZT-zPT] have been developed and their structural and electrical properties have been determined. Various characterization techniques such as X-ray diffraction, calorimetery, electron microscopy, dielectric and piezoelectric measurements have been performed to determine the details of the phase diagram, crystal structure, and domain structure. The selection of these materials is based on the hypothesis that the presence of BZT-PT (Case I ferroelectric (FE)) will increase the transition temperature of MPB systems BMT-PT (Case II FE), and PZ-PT (Case III FE), and subsequently a MPB will be observed in the ternary phase diagrams. The Case I, II, and III classification has been outlined by Stringer et al., is on the basis of the transition temperatures (TC) behavior with composition in the Bi and Pb oxide based binary systems. Several pseudobinary lines have been investigated across the xBZT-yPZ-zPT ternary phase diagram which exhibit varied TC behavior with composition, showing both Case I- and Case III-like TC trends in different regions. A MPB between rhombohedral to tetragonal phases has been located on a pseudobinary line 0.1BZT-0.9[xPT-(1-x)PZ]. Compositions near MPB exhibit mainly soft PZT-like properties with the TC around 60°C lower than the unmodified PZT near its MPB. Electrical properties are reported for the MPB composition, TC = 325°C, Pr = 35 microC/cm2, d33 = 300 pC/N and kP =0.45. Rhombohedral compositions show diffuse phase transition with small frequency dispersion, similar to relaxors. Two transition peaks in the permittivity as well as in the latent heat has been observed in some compositions near the BZT-PT binary. This leads to the speculation for the existence of miscibility gap in the solid solutions in these regions. Transmission electron microscopy (TEM) performed on these compositions show subdomain modulation contrast suggesting the presence of localized and correlated spatial fluctuations in the spontaneous strain. In the xBMT-yBZT-zPT system, very small rhombohedral region in the room temperature phase diagram has been observed. Owing to the limited solid solubility, only a part of the phase diagram could be explored. Compositions on pseudobinary xPT-(1-x)[0.9BMT-0.1BZT] has been successfully fabricated and characterized. High c/a ratio of 1.04 has been observed for a surprisingly low tolerance factor of 0.9732. Transition temperature trends have been established from DSC and dielectric data along this pseudobinary line. The following trend in the TC has been observed with the increase in non PT end member that has been divided into three zones: in Zone I TC increases, in Zone II it decreases, and in the Zone III, two transition temperatures are observed. From the TEM investigation, it has been noted that these compositions exhibit subdomain modulations which reflects the presence of spontaneous strain. These modulations increase with the increase in non PT end member, and at certain composition along pseudobinary, both macro and micro domains structure can be observed. Compositions in the rhombohedral phase of xBMT-yBZT-zPT show dramatic changes in dielectric and piezoelectric properties when quenched from high temperature. Samples quenched from temperature range 650°C-900°C show classical ferroelectric switching behavior, which is not observed on either side of this temperature range. These quenched states are however, unstable in nature and lose their ferroelectric properties when heated to a temperature as low as 400°C. Structural analysis by TEM shows varied domain structures for samples quenched from different temperatures. Evidences of tilt transitions and intermediate phases have also been observed in the TEM study. New insights into solid solution development and defect metastability are gained and discussed in relation to relaxor based ferroelectric phenomena. Complex domains and intermediate displacive phase transitions are all considered to consistently account for the structure-property-process relations in these novel systems.

Schizophrenic Diblock-Copolymer-Functionalized Nanoparticles as Temperature-Responsive Pickering Emulsifiers.

PubMed

Ranka, Mikhil; Katepalli, Hari; Blankschtein, Daniel; Hatton, T Alan

2017-11-21

Stimuli-responsive pickering emulsions have received considerable attention in recent years, and the utilization of temperature as a stimulus has been of particular interest. Previous efforts have led to responsive systems that enable the formation of stable emulsions at room temperature, which can subsequently be triggered to destabilize with an increase in temperature. The development of a thermoresponsive system that exhibits the opposite response, however, i.e., one that can be triggered to form stable emulsions at elevated temperatures and subsequently be induced to phase separate at lower temperatures, has so far been lacking. Here, we describe a system that accomplishes this goal by leveraging a schizophrenic diblock copolymer that exhibits both an upper and a lower critical solution temperature. The diblock copolymer was conjugated to 20 nm silica nanoparticles, which were subsequently demonstrated to stabilize O/W emulsions at 65 °C and trigger phase separation upon cooling to 25 °C. The effects of particle concentration, electrolyte concentration, and polymer architecture were investigated, and facile control of emulsion stability was demonstrated for multiple oil types. Our approach is likely to be broadly adaptable to other schizophrenic diblock copolymers and find significant utility in applications such as enhanced oil recovery and liquid-phase heterogeneous catalysis, where stable emulsions are desired only at elevated temperatures.

Phase diagrams and physicochemical properties of Li+,K+(Rb+)//borate-H2O systems at 323 K

NASA Astrophysics Data System (ADS)

Feng, Shan; Yu, Xudong; Cheng, Xinglong; Zeng, Ying

2017-11-01

The phase and physicochemical properties diagrams of Li+,K+(Rb+)//borate-H2O systems at 323 K were constructed using the experimentally measured solubilities, densities, and refractive indices. The Schreinemakers' wet residue method and the X-ray diffraction were used for the determination of the compositions of solid phase. Results show that these two systems belong to the hydrate I type, with no solid solution or double salt formation. The borate phases formed in our experiments are RbB5O6(OH)4 · 2H2O, Li2B4O5(OH)4 · H2O, and K2B4O5(OH)4 · 2H2O. Comparison between the stable phase diagrams of the studied system at 288, 323, and 348 K show that in this temperature range, the crystallization form of salts do not changed. With the increase in temperature, the crystallization field of Li2B4O5(OH)4 · H2O salt at 348 K is obviously larger than that at 288 K. In the Li+,K+(Rb+)//borate-H2O systems, the densities and refractive indices of the solutions (at equilibrium) increase along with the mass fraction of K2B4O7 (Rb2B4O7), and reach the maximum values at invariant point E.

Buckling of a circular plate made of a shape memory alloy due to a reverse thermoelastic martensite transformation

NASA Astrophysics Data System (ADS)

Movchan, A. A.; Sil'chenko, L. G.

2008-02-01

We solve the axisymmetric buckling problem for a circular plate made of a shape memory alloy undergoing reverse martensite transformation under the action of a compressing load, which occurs after the direct martensite transformation under the action of a generally different (extending or compressing) load. The problem was solved without any simplifying assumptions concerning the transverse dimension of the supplementary phase transition region related to buckling. The mathematical problem was reduced to a nonlinear eigenvalue problem. An algorithm for solving this problem was proposed. It was shown that the critical buckling load under the reverse transition, which is obtained by taking into account the evolution of the phase strains, can be many times lower than the same quantity obtained under the assumption that the material behavior is elastic even for the least (martensite) values of the elastic moduli. The critical buckling force decreases with increasing modulus of the load applied at the preliminary stage of direct transition and weakly depends on whether this load was extending or compressing. In shape memory alloys (SMA), mutually related processes of strain and direct (from the austenitic into the martensite phase) or reverse thermoelastic phase transitions may occur. The direct transition occurs under cooling and (or) an increase in stresses and is accompanied by a significant decrease (nearly by a factor of three in titan nickelide) of the Young modulus. If the direct transition occurs under the action of stresses with nonzero deviator, then it is accompanied by accumulation of macroscopic phase strains, whose intensity may reach 8%. Under the reverse transition, which occurs under heating and (or) unloading, the moduli increase and the accumulated strain is removed. For plates compressed in their plane, in the case of uniform temperature distribution over the thickness, one can separate trivial processes under which the strained plate remains plane and the phase ratio has a uniform distribution over the thickness. For sufficiently high compressing loads, the trivial process of uniform compression may become unstable in the sense that, for small perturbations of the plate deflection, temperature, the phase ratio, or the load, the difference between the corresponding perturbed process and the unperturbed process may be significant. The results of several experiments concerning the buckling of SMA elements are given in [1, 2], and the statement and solution of the corresponding boundary value problems can be found in [3-11]. The experimental studies [2] and several analytic solutions obtained for the Shanley column [3, 4], rods [5-7], rectangular plates under direct [8] and reverse [9] transitions showed that the processes of thermoelastic phase transitions can significantly (by several times) decrease the critical buckling loads compared with their elastic values calculated for the less rigid martensite state of the material. Moreover, buckling does not occur in the one-phase martensite state in which the elastic moduli are minimal but in the two-phase state in which the values of the volume fractions of the austenitic and martensite phase are approximately equal to each other. This fact is most astonishing for buckling, studied in the present paper, under the reverse transition in which the Young modulus increases approximately half as much from the beginning of the phase transition to the moment of buckling. In [3-9] and in the present paper, the static buckling criterion is used. Following this criterion, the critical load is defined to be the load such that a nontrivial solution of the corresponding quasistatic problem is possible under the action of this load. If, in the problems of stability of rods and SMA plates, small perturbations of the external load are added to small perturbations of the deflection (the critical force is independent of the amplitude of the latter), then the critical forces vary depending on the value of perturbations of the external load [5, 8, 9]. Thus, in the case of small perturbations of the load, the problem of stability of SMA elements becomes indeterminate. The solution of the stability problem for SMA elements also depends on whether the small perturbations of the phase ratio and the phase strain tensor are taken into account. According to this, the problem of stability of SMA elements can be solved in the framework of several statements (concepts, hypotheses) which differ in the set of quantities whose perturbations are admissible (taken into account) in the process of solving the problem. The variety of these statements applied to the problem of buckling of SMA elements under direct martensite transformation is briefly described in [4, 5]. But, in the problem of buckling under the reverse transformation, some of these statements must be changed. The main question which we should answer when solving the problem of stability of SMA elements is whether small perturbations of the phase ratio (the volume fraction of the martensite phase q) are taken into account, because an appropriate choice significantly varies the results of solving the stability problem. If, under the transition to the adjacent form of equilibrium, the phase ratio of all points of the body is assumed to remain the same, then we deal with the "fixed phase atio" concept. The opposite approach can be classified as the "supplementary phase transition" concept (which occurs under the transition to the adjacent form of equilibrium). It should be noted that, since SMA have temperature hysteresis, the phase ratio in SMA can endure only one-sided small variations. But if we deal with buckling under the inverse transformation, then the variation in the volume fraction of the martensite phase cannot be positive. The phase ratio is not an independent variable, like loads or temperature, but, due to the constitutive relations, its variations occur together with the temperature variations and, in the framework of connected models for a majority of SMA, together with variations in the actual stresses. Therefore, the presence or absence of variations in q is determined by the presence or absence of variations in the temperature, deflection, and load, as well as by the system of constitutive relations used in this particular problem. In the framework of unconnected models which do not take the influence of actual stresses on the phase ratio into account, the "fixed phase ratio" concept corresponds to the case of absence of temperature variations. The variations in the phase ratio may also be absent in connected models in the case of specially chosen values of variations in the temperature and (or) in the external load, as well as in the case of SMA of CuMn type, for which the influence of the actual stresses on the phase compound is absent or negligible. In the framework of the "fixed phase ratio" hypothesis, the stability problem for SMA elements has a solution coinciding in form with the solution of the corresponding elastic problem, with the elastic moduli replaced by the corresponding functions of the phase ratio. In the framework of the supplementary phase transition" concept, the result of solving the stability problem essentially depends on whether the small perturbations of the external loads are taken into account in the process of solving the problem. The point is that, when solving the problem in the connected setting, the supplementary phase transition region occupies, in general, not the entire cross-section of the plate but only part of it, and the location of the boundary of this region depends on the existence and the value of these small perturbations. More precisely, the existence of arbitrarily small perturbations of the actual load can result in finite changes of the configuration of the supplementary phase transition region and hence in finite change of the critical values of the load. Here we must distinguish the "fixed load" hypothesis where no perturbations of the external loads are admitted and the "variable load" hypothesis in the opposite case. The conditions that there no variations in the external loads imply additional equations for determining the boundary of the supplementary phase transition region. If the "supplementary phase transition" concept and the "fixed load" concept are used together, then the solution of the stability problem of SMA is uniquely determined in the same sense as the solution of the elastic stability problem under the static approach. In the framework of the "variable load" concept, the result of solving the stability problem for SMA ceases to be unique. But one can find the upper and lower bounds for the critical forces which correspond to the cases of total absence of the supplementary phase transition: the upper bound corresponds to the critical load coinciding with that determined in the framework of the "fixed phase ratio" concept, and the lower bound corresponds to the case where the entire cross-section of the plate experiences the supplementary phase transition. The first version does not need any additional name, and the second version can be called as the "all-round supplementary phase transition" hypothesis. In the present paper, the above concepts are illustrated by examples of solving problems about axisymmetric buckling of a circular freely supported or rigidly fixed plate experiencing reverse martensite transformation under the action of an external force uniformly distributed over the contour. We find analytic solutions in the framework of all the above-listed statements except for the case of free support in the "fixed load" concept, for which we obtain a numerical solution.

Hot and cold water as a supercritical solvent

NASA Astrophysics Data System (ADS)

Fuentevilla, Daphne Anne

This dissertation addresses the anomalous properties of water at high temperatures near the vapor-liquid critical point and at low temperatures in the supercooled liquid region. The first part of the dissertation is concerned with the concentration dependence of the critical temperature, density, and pressure of an aqueous sodium chloride solution. Because of the practical importance of an accurate knowledge of critical parameters for industrial, geochemical, and biological applications, an empirical equation for the critical locus of aqueous sodium chloride solutions was adopted in 1999 by the International Association for the Properties of Water and Steam (IAPWS) as a guideline. However, since this original Guideline on the Critical Locus of Aqueous Solutions of Sodium Chloride was developed, two new theoretical developments occurred, motivating the first part of this dissertation. Here, I present a theory-based formulation for the critical parameters of aqueous sodium chloride solutions as a proposed replacement for the empirical formulation currently in use. This formulation has been published in the International Journal of Thermophysics and recommended by the Executive Committee of IAPWS for adoption as a Revised Guideline on the Critical Locus of Aqueous Solutions of Sodium Chloride. The second part of the dissertation addresses a new concept, considering cold water as a supercritical solvent. Based on the idea of a second, liquid-liquid, critical point in supercooled water, we explore the possibility of supercooled water as a novel supercooled solvent through the thermodynamics of critical phenomena. In 2006, I published a Physical Review letter presenting a parametric scaled equation of state for supercooled-water. Further developments based on this work led to a phenomenological mean-field "two-state" model, clarifying the nature of the phase separation in a polyamorphic single-component liquid. In this dissertation, I modify this two-state model to incorporate solutes. Critical lines emanating from the pure-water critical point show how even small additions of solute may significantly affect the thermodynamic properties and phase behavior of supercooled aqueous solutions. Some solutes, such as glycerol, can prevent spontaneous crystallization, thus making liquid-liquid separation in supercooled water experimentally accessible. This work will help in resolving the question on liquid polyamorphism in supercooled water.

Precursor preparation for Ca-Al layered double hydroxide to remove hexavalent chromium coexisting with calcium and magnesium chlorides

NASA Astrophysics Data System (ADS)

Zhong, Lihua; He, Xiaoman; Qu, Jun; Li, Xuewei; Lei, Zhiwu; Zhang, Qiwu; Liu, Xinzhong

2017-01-01

Al(OH)3 and Ca(OH)2 powders are co-ground to prepare a precursor which hydrates into a layered double hydroxide (LDH) phase by agitation in aqueous solution with target hexavalent chromium (Cr(VI)) at room temperature, to achieve an obvious improvement in removal efficiency of Cr(VI) through an easy incorporation into the structure. Although the prepared precursor transforms into LDH phases also when agitated in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. The adsorption isotherm and kinetic studies show that the phenomena occurring on the Al-Ca precursor fit a pseudo-second-order kinetics with a Langmuir adsorption capacity of 59.45 mg/g. Besides, characterizations of the prepared precursor and the samples after adsorption are also performed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscope (TEM) to understand the reason of the preferential incorporation of Cr(VI) to the coexisting chloride salts during the LDH phase formation. Ca-Al precursor (C3A) was agitated in a hexavalent chromium (Cr(VI)) solution to form Al-Ca-CrO4 LDH product. Ca-Al-CrO4 LDH phase occurred preferentially to Ca-Al-MCl2 LDH phases in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist.

In situ neutron scattering study of nanoscale phase evolution in PbTe-PbS thermoelectric material

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

Ren, Fei, E-mail: renfei@temple.edu, E-mail: kean@ornl.gov; Qian, Bosen; Schmidt, Robert

2016-08-22

Introducing nanostructural second phases has proved to be an effective approach to reduce the lattice thermal conductivity and thus enhances the figure of merit for many thermoelectric materials. Studies of the formation and evolution of these second phases are essential to understanding material temperature dependent behaviors, improving thermal stabilities, as well as designing new materials. In this study, powder samples of the PbTe-PbS thermoelectric material were examined using in situ neutron diffraction and small angle neutron scattering (SANS) techniques between room temperature and elevated temperature up to 663 K, to explore quantitative information on the structure, weight fraction, and size ofmore » the second phase. Neutron diffraction data showed that the as-milled powder was primarily a solid solution prior to heat treatment. During heating, a PbS second phase precipitated out of the PbTe matrix around 500 K, while re-dissolution started around 600 K. The second phase remained separated from the matrix upon cooling. Furthermore, SANS data indicated that there are two populations of nanostructures. The size of the smaller nanostructure increased from initially 5 nm to approximately 25 nm after annealing at 650 K, while the size of the larger one remained unchanged. This study demonstrated that in situ neutron techniques are effective means to obtain quantitative information on temperature-dependent nanostructural behavior of thermoelectrics and likely other high-temperature materials.« less

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

Clark, Williams; Zhao, Ji-Cheng

Cost effective and high performance alloys that are capable of operating at 760 °C or higher for extended periods of time under a very aggressive environment are critically required for the design and development of advanced ultrasupercritical (AUSC) boilers and steam turbines. Finely dispersed Laves phase precipitates have been shown by Takeyama and co-workers to be a viable strengthening mechanism in high temperature austenitic steels. There is currently no straightforward theory that can predict what other intermetallic phases can serve as potent precipitation-strengthening phases for steels; thus we employed a highly effective dual-anneal diffusion multiple (DADM) approach to screen formore » viable strengthening precipitates over a wide range of compositions. From the Fe-Co-Cr-Ni-Mo DADMs, the Fe-Cr-Mo based Chi phase was identified as a new strengthening phase for high temperature ferritic steels; and from the Fe-Mn-Cr-Nb-Ni-Mo-FeAl DADMs, the Laves phase was identified as a viable strengthening precipitate in Fe-Mn and Fe-Ni based austenitic steels. After identification of viable strengthening phases from the DADMs that covered compositions in the basic ternary and quaternary systems, we employed computation thermodynamics to perform multicomponent alloy design and optimization. For the new the Chi-phase strengthened steels, we performed thermodynamic calculations to vary the volume fraction of the Chi phase and introduced Nb and carbon to promote the formation of stable carbides for grain size control during solution heat treatment. For the Fe-Ni-Mn based austenitic steels, we performed extensive parametric optimization of compositions in order to reduce the expensive Ni content, add Cr and Al for oxidation resistance, and balance the alloying contents (Ni, Mn, Cr, Al, Mo) to suppress the ferritic phase and promote the austenitic matrix phase. Four steels (two ferritic + two austenitic) were designed and tested. The two Chi-phase strengthened ferritic steels exhibited excellent oxidation resistance and good creep-rupture strength at moderate temperatures, considering their ferritic matrix that usually results in lower creep resistance than austenitic steels. These steels showed brittleness and sample-to-sample variability in ductility. The low ductility might be due to the macro segregation during solidification or the significant grain growth during the solution heat treatments. We believe there is no inherent brittleness based on the chemistry of the steels. The creep-rupture performance of the steels is comparable to the 9Cr steels. Due to their ferritic matrix, the new Chi-phase strengthened ferritic steels may not be suited for the 760 °C AUSC applications, but they are very good candidates for intermediate temperature applications due to their outstanding oxidation resistance and high strength. Further study is required to find the source of low and highly variable ductility. We believe the compositions of the Chi-phase strengthened steels are not inherently brittle. The Chi-phase strengthened ferritic steels may also be excellent candidates for intermediate-temperature and room-temperature cast stainless steels, thus we highly recommend further investigations. The two Mn-containing austenitic steels based on the Laves phase showed good ductility, excellent oxidation resistance (slightly inferior to the two ferritic steels) at high temperatures and moderate creep strength. The creep-strength of the two austenitic steels based on the Larson-Miller parameters is higher than that of the traditional 316 stainless steels, but lower than the alumina-forming alloys (AFAs) developed at Oak Ridge National Laboratories. We do not recommend high priority in further studying these compositions unless higher Cr alloys are required for hot-corrosion resistance.« less

Programmable pH buffers

DOEpatents

Gough, Dara Van; Huber, Dale L.; Bunker, Bruce C.; Roberts, Mark E.

2017-01-24

A programmable pH buffer comprises a copolymer that changes pK.sub.a at a lower critical solution temperature (LCST) in water. The copolymer comprises a thermally programmable polymer that undergoes a hydrophobic-to-hydrophilic phase change at the LCST and an electrolytic polymer that exhibits acid-base properties that are responsive to the phase change. The programmable pH buffer can be used to sequester CO.sub.2 into water.

Core-softened potentials, multiple liquid-liquid critical points, and density anomaly regions: An exact solution

NASA Astrophysics Data System (ADS)

Rizzatti, Eduardo O.; Barbosa, Marco Aurélio A.; Barbosa, Marcia C.

2018-02-01

The pressure versus temperature phase diagram of a system of particles interacting through a multiscale shoulder-like potential is exactly computed in one dimension. The N-shoulder potential exhibits N density anomaly regions in the phase diagram if the length scales can be connected by a convex curve. The result is analyzed in terms of the convexity of the Gibbs free energy.

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

Yudoyono, Gatut, E-mail: gyudoyono@physics.its.ac.id; Zharvan, Vicran; Ichzan, Nur

Titanium dioxide (titania) nanoparticle were synthesized by coprecipitation process of titanium trichloride (TiCl{sub 3}) in aqueous medium, with NH{sub 4}OH as pH regulator. The pH solution was varied during the synthesis process between pH 3-8.4, and all samples were calcined temperature at 400°C for 3 hours. Characteristics and properties of the TiO{sub 2} powder were investigated using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM). XRD results show that the single-phase rutile formed when the pH is less than 5, anatase single phase formed began pH 8, and the pH of the solution between 5-8 formed mixed phase rutile-anatase-brookite, rutile-brookite ormore » anatase-brookite. Methylene Blue (MB) photodegradation test were performed in order to evaluate photocatalytic activity. Nanoparticles TiO{sub 2} rutile, anatase phase, and mixed phase rutile-brookite, anatase-brookite used to test the photocatalytic activity by measuring the absorbance spectrum photodegradation using UV-Vis spectrometer. The test results showed that the mixture phase of rutile-brookite provide the greatest photodegradation than other phases.« less

Optimization of the crystal growth of the superconductor CaKFe 4 As 4 from solution in the FeAs - CaFe 2 As 2 - KFe 2 As 2 system

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

Meier, W. R.; Kong, T.; Bud'ko, S. L.

Measurements of the anisotropic properties of single crystals play a crucial role in probing the physics of new materials. Determining a growth protocol that yields suitable high-quality single crystals can be particularly challenging for multicomponent compounds. Here we present a case study of how we refined a procedure to grow single crystals of CaKFe 4As 4 from a high temperature, quaternary liquid solution rich in iron and arsenic (“FeAs self-flux”). Temperature dependent resistance and magnetization measurements are emphasized, in addition to the x-ray diffraction, to detect intergrown CaKFe 4As 4, CaFe 2As 2, and KFe 2As 2 within what appearmore » to be single crystals. Guided by the rules of phase equilibria and these data, we adjusted growth parameters to suppress formation of the impurity phases. The resulting optimized procedure yielded phase-pure single crystals of CaKFe 4As 4. In conclusion, this optimization process offers insight into the growth of quaternary compounds and a glimpse of the four-component phase diagram in the pseudoternary FeAs–CaFe 2As 2–KFe 2As 2 system.« less

Unlocking the potential of supported liquid phase catalysts with supercritical fluids: low temperature continuous flow catalysis with integrated product separation

PubMed Central

Franciò, Giancarlo; Hintermair, Ulrich; Leitner, Walter

2015-01-01

Solution-phase catalysis using molecular transition metal complexes is an extremely powerful tool for chemical synthesis and a key technology for sustainable manufacturing. However, as the reaction complexity and thermal sensitivity of the catalytic system increase, engineering challenges associated with product separation and catalyst recovery can override the value of the product. This persistent downstream issue often renders industrial exploitation of homogeneous catalysis uneconomical despite impressive batch performance of the catalyst. In this regard, continuous-flow systems that allow steady-state homogeneous turnover in a stationary liquid phase while at the same time effecting integrated product separation at mild process temperatures represent a particularly attractive scenario. While continuous-flow processing is a standard procedure for large volume manufacturing, capitalizing on its potential in the realm of the molecular complexity of organic synthesis is still an emerging area that requires innovative solutions. Here we highlight some recent developments which have succeeded in realizing such systems by the combination of near- and supercritical fluids with homogeneous catalysts in supported liquid phases. The cases discussed exemplify how all three levels of continuous-flow homogeneous catalysis (catalyst system, separation strategy, process scheme) must be matched to locate viable process conditions. PMID:26574523

Unlocking the potential of supported liquid phase catalysts with supercritical fluids: low temperature continuous flow catalysis with integrated product separation.

PubMed

Franciò, Giancarlo; Hintermair, Ulrich; Leitner, Walter

2015-12-28

Solution-phase catalysis using molecular transition metal complexes is an extremely powerful tool for chemical synthesis and a key technology for sustainable manufacturing. However, as the reaction complexity and thermal sensitivity of the catalytic system increase, engineering challenges associated with product separation and catalyst recovery can override the value of the product. This persistent downstream issue often renders industrial exploitation of homogeneous catalysis uneconomical despite impressive batch performance of the catalyst. In this regard, continuous-flow systems that allow steady-state homogeneous turnover in a stationary liquid phase while at the same time effecting integrated product separation at mild process temperatures represent a particularly attractive scenario. While continuous-flow processing is a standard procedure for large volume manufacturing, capitalizing on its potential in the realm of the molecular complexity of organic synthesis is still an emerging area that requires innovative solutions. Here we highlight some recent developments which have succeeded in realizing such systems by the combination of near- and supercritical fluids with homogeneous catalysts in supported liquid phases. The cases discussed exemplify how all three levels of continuous-flow homogeneous catalysis (catalyst system, separation strategy, process scheme) must be matched to locate viable process conditions. © 2015 The Authors.

Optimization of the crystal growth of the superconductor CaKFe 4 As 4 from solution in the FeAs - CaFe 2 As 2 - KFe 2 As 2 system

DOE PAGES

Meier, W. R.; Kong, T.; Bud'ko, S. L.; ...

2017-06-19

Measurements of the anisotropic properties of single crystals play a crucial role in probing the physics of new materials. Determining a growth protocol that yields suitable high-quality single crystals can be particularly challenging for multicomponent compounds. Here we present a case study of how we refined a procedure to grow single crystals of CaKFe 4As 4 from a high temperature, quaternary liquid solution rich in iron and arsenic (“FeAs self-flux”). Temperature dependent resistance and magnetization measurements are emphasized, in addition to the x-ray diffraction, to detect intergrown CaKFe 4As 4, CaFe 2As 2, and KFe 2As 2 within what appearmore » to be single crystals. Guided by the rules of phase equilibria and these data, we adjusted growth parameters to suppress formation of the impurity phases. The resulting optimized procedure yielded phase-pure single crystals of CaKFe 4As 4. In conclusion, this optimization process offers insight into the growth of quaternary compounds and a glimpse of the four-component phase diagram in the pseudoternary FeAs–CaFe 2As 2–KFe 2As 2 system.« less

Nucleation barrier reconstruction via the seeding method in a lattice model with competing nucleation pathways.

PubMed

Lifanov, Yuri; Vorselaars, Bart; Quigley, David

2016-12-07

We study a three-species analogue of the Potts lattice gas model of nucleation from solution in a regime where partially disordered solute is a viable thermodynamic phase. Using a multicanonical sampling protocol, we compute phase diagrams for the system, from which we determine a parameter regime where the partially disordered phase is metastable almost everywhere in the temperature-fugacity plane. The resulting model shows non-trivial nucleation and growth behaviour, which we examine via multidimensional free energy calculations. We consider the applicability of the model in capturing the multi-stage nucleation mechanisms of polymorphic biominerals (e.g., CaCO 3 ). We then quantitatively explore the kinetics of nucleation in our model using the increasingly popular "seeding" method. We compare the resulting free energy barrier heights to those obtained via explicit free energy calculations over a wide range of temperatures and fugacities, carefully considering the propagation of statistical error. We find that the ability of the "seeding" method to reproduce accurate free energy barriers is dependent on the degree of supersaturation, and severely limited by the use of a nucleation driving force Δμ computed for bulk phases. We discuss possible reasons for this in terms of underlying kinetic assumptions, and those of classical nucleation theory.

Effect of temperature on the reaction pathway of calcium carbonate formation via precursor phases

NASA Astrophysics Data System (ADS)

Purgstaller, Bettina; Mavromatis, Vasileios; Konrad, Florian; Dietzel, Martin

2016-04-01

It has been earlier postulated that some biogenic and sedimentary calcium carbonate (CaCO3) minerals (e.g. calcite and aragonite) are secondary in origin and have originally formed via a metastable calcium carbonate precursor phase (e.g. amorphous CaCO3, [1-2]). Such formation pathways are likely affected by various physicochemical parameters including aqueous Mg and temperature. In an effort to improve our understanding on the formation mechanism of CaCO3 minerals, precipitation experiments were carried out by the addition of a 0.6 M (Ca,Mg)Cl2 solution at distinct Mg/Ca ratios (1/4 and 1/8) into a 1 M NaHCO3 solution under constant pH conditions(8.3 ±0.1). The formation of CaCO3 was systematically examined as a function of temperature (6, 12, 18 and 25 ±0.3° C). During the experimental runs mineral precipitation was monitored by in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. The results revealed two pathways of CaCO3 formation depending on the initial Mg/Ca ratio and temperature: (i) In experiments with a Mg/Ca ratio of 1/4 at ≤ 12° C as well as in experiments with a Mg/Ca ratio of 1/8 at ≤ 18° C, ikaite (CaCO3 6H2O) acts as a precursor phase for aragonite formation. (ii) In contrast higher temperatures induced the formation of Mg-rich amorphous CaCO3 (Mg-ACC) which was subsequently transformed to Mg-rich calcite. In situ Raman spectra showed that the transformation of Mg-ACC to Mg-calcite occurs at a higher rate (˜ 8 min) compared to that of ikaite to aragonite (> 2 h). Thus, the formation of aragonite rather than of Mg-calcite occurs due to the slower release of Ca2+and CO32- ions into the Mg-rich reactive solution during retarded ikaite dissolution. This behavior is generally consistent with the observation that calcite precipitation is inhibited at elevated aqueous Mg/Ca ratios. [1] Addadi L., Raz S. and Weiner S. (2003) Advanced Materials 15, 959-970. [2] Rodriguez-Blanco J. D., Shaw S., Bots P., Roncal-Herrero T. and Benning L. G (2014) Geochimica et Cosmochimica Acta 127, 204-220

Ab Initio Modeling of the Electronic Absorption Spectrum of Previtamin D in Solution

NASA Astrophysics Data System (ADS)

Zhu, Tianyang

To study the solvent effects of water on the previtamin D absorption spectrum, we use the quantum mechanics (QM)/molecular mechanics (MM) method combined with replica-exchange molecular dynamics (REMD). The QM method is applied for the previtamin D molecule and the MM method is used for the water molecules. To enhance conformational sampling of the flexible previtamin D molecule we apply REMD. Based on the REMD structures, we calculate the macroscopic ensemble of the absorption spectrum in solution by time-dependent density functional theory (TDDFT). Comparison between the calculated spectrum in the gas phase and in the solution reveals minor influences of the solvent on the absorption spectrum. In the conventional molecule dynamics simulation, the previtamin D molecule can be trapped by local minimum and cannot overcome energetics barriers when it is calculated at the room temperature. In addition, the higher temperature calculation for the molecule in REMD allows to overcome energetics barriers and to change the structure to other rotational isomers, then switch to the lower temperature and gives a more complete result in the configuration space for the lower temperature.

The Effects of Thermal History on Nucleation of Tetragonal Lysozyme Crystals, or Hot Protein and Cold Nucleation

NASA Technical Reports Server (NTRS)

Burke, Michael; Judge, Russell; Pusey, Marc

2000-01-01

Chicken egg white lysozyme has a well characterized thermally driven phase transition. Between pH 4.2 and 5.2, the transition temperature, as defined by the point where the tetragonal and orthorhombic solubilities are equal, is a function of the pH, salt (precipitant) type and concentration, and most likely of the buffer concentration as well. This phase transition can be carried out with protein solution alone, prior to addition of precipitant solution. Warming a lysozyme solution above the phase transition point, then cooling it back below this point, has been shown to affect the subsequent nucleation rate, as determined by the numbers and size of crystals formed, but not the growth rate for the tetragonal crystal form . We have now measured the kinetics of this process and investigated its reversibility. The transition effects are progressive with temperature, having a half time of about 1 hour at 37C at pH 4.8. After holding a lysozyme solution at 37C (prior to addition of precipitant) for 16 hours, then cooling it back to 4C no return to the pre-warmed nucleation kinetics are observed after at least 4 weeks. Orthorhombic lysozyme crystals apparently do not undergo the flow-induced growth cessation of tetragonal lysozyme crystals. Putting the protein in the orthorhombic form does not affect the averaged face growth kinetics, only nucleation, for tetragonal crystals. This differential behaviour may be exploited to elucidate how and where flow affects the lysozyme crystal growth process. The presentation will focus on the results of these and ongoing studies in this area.

Influence of Annealing on Microstructure and Mechanical Properties of Refractory CoCrMoNbTi0.4 High-Entropy Alloy

NASA Astrophysics Data System (ADS)

Zhang, Mina; Zhou, Xianglin; Zhu, Wuzhi; Li, Jinghao

2018-04-01

A novel refractory CoCrMoNbTi0.4 high-entropy alloy (HEA) was prepared via vacuum arc melting. After annealing treatment at different temperatures, the microstructure evolution, phase stability, and mechanical properties of the alloy were investigated. The alloy was composed of two primary body-centered cubic structures (BCC1 and BCC2) and a small amount of (Co, Cr)2Nb-type Laves phase under different annealing conditions. The microhardness and compressive strength of the heat-treated alloy was significantly enhanced by the solid-solution strengthening of the BCC phase matrix and newborn Laves phase. Especially, the alloy annealed at 1473 K (1200 °C) achieved the maximum hardness and compressive strength values of 959 ± 2 HV0.5 and 1790 MPa, respectively, owing to the enhanced volume fraction of the dispersed Laves phase. In particular, the HEAs exhibited promising high-temperature mechanical performance, when heated to an elevated temperature of 1473 K (1200 °C), with a compressive fracture strength higher than 580 MPa without fracture at a strain of more than 20 pct. This study suggests that the present refractory HEAs have immense potential for engineering applications as a new class of high-temperature structural materials.

Dynamical arrest with zero complexity: The unusual behavior of the spherical Blume-Emery-Griffiths disordered model

NASA Astrophysics Data System (ADS)

Rainone, Corrado; Ferrari, Ulisse; Paoluzzi, Matteo; Leuzzi, Luca

2015-12-01

The short- and long-time dynamics of model systems undergoing a glass transition with apparent inversion of Kauzmann and dynamical arrest glass transition lines is investigated. These models belong to the class of the spherical mean-field approximation of a spin-1 model with p -body quenched disordered interaction, with p >2 , termed spherical Blume-Emery-Griffiths models. Depending on temperature and chemical potential the system is found in a paramagnetic or in a glassy phase and the transition between these phases can be of a different nature. In specific regions of the phase diagram coexistence of low-density and high-density paramagnets can occur, as well as the coexistence of spin-glass and paramagnetic phases. The exact static solution for the glassy phase is known to be obtained by the one-step replica symmetry breaking ansatz. Different scenarios arise for both the dynamic and the thermodynamic transitions. These include: (i) the usual random first-order transition (Kauzmann-like) for mean-field glasses preceded by a dynamic transition, (ii) a thermodynamic first-order transition with phase coexistence and latent heat, and (iii) a regime of apparent inversion of static transition line and dynamic transition lines, the latter defined as a nonzero complexity line. The latter inversion, though, turns out to be preceded by a dynamical arrest line at higher temperature. Crossover between different regimes is analyzed by solving mode-coupling-theory equations near the boundaries of paramagnetic solutions and the relationship with the underlying statics is discussed.

Miscibility, Crystallization, and Rheological Behavior of Solution Casting Poly(3-hydroxybutyrate)/poly(ethylene succinate) Blends Probed by Differential Scanning Calorimetry, Rheology, and Optical Microscope Techniques

NASA Astrophysics Data System (ADS)

Sun, Wei-hua; Qiao, Xiao-ping; Cao, Qi-kun; Liu, Jie-ping

2010-02-01

The miscibility and crystallization of solution casting biodegradable poly(3-hydroxybutyrate)/poly(ethylene succinate) (PHB/PES) blends was investigated by differential scanning calorimetry, rheology, and optical microscopy. The blends showed two glass transition temperatures and a depression of melting temperature of PHB with compositions in phase diagram, which indicated that the blend was partially miscible. The morphology observation supported this result. It was found that the PHB and PES can crystallize simultaneously or upon stepwise depending on the crystallization temperatures and compositions. The spherulite growth rate of PHB increased with increasing of PES content. The influence of compositions on the spherulitic growth rate for the partially miscible polymer blends was discussed.

Study of Maxwell–Wagner (M–W) relaxation behavior and hysteresis observed in bismuth titanate layered structure obtained by solution combustion synthesis using dextrose as fuel

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

Subohi, Oroosa, E-mail: oroosa@gmail.com; Shastri, Lokesh; Kumar, G.S.

2014-01-01

Graphical abstract: X-ray diffraction studies show that phase formation and crystallinity was reached only after calcinations at 800 °C. Dielectric constant versus temperature curve shows ferroelectric to paraelectric transition temperature (T{sub c}) to be 650 °C. Complex impedance curves show deviation from Debye behavior. The material shows a thin PE Loop with low remnant polarization due to high conductivity in the as prepared sample. - Highlights: • Bi{sub 4}Ti{sub 3}O{sub 12} is synthesized using solution combustion technique with dextrose as fuel. • Dextrose has high reducing capacity (+24) and generates more no. of moles of gases. • Impedance studies showmore » that the sample follows Maxwell–Wagner relaxation behavior. • Shows lower remnant polarization due to higher c-axis ratio. - Abstract: Structural, dielectric and ferroelectric properties of bismuth titanate (Bi{sub 4}Ti{sub 3}O{sub 12}) obtained by solution combustion technique using dextrose as fuel is studied extensively in this paper. Dextrose is used as fuel as it has high reducing valancy and generates more number of moles of gases during the reaction. X-ray diffraction studies show that phase formation and crystallinity was reached only after calcinations at 800 °C. Dielectric constant versus temperature curve shows ferroelectric to paraelectric transition temperature (T{sub c}) to be 650 °C. The dielectric loss is very less (tan δ < 1) at lower temperatures but increases around T{sub c} due to structural changes in the sample. Complex impedance curves show deviation from Debye behavior. The material shows a thin PE Loop with low remnant polarization due to high conductivity in the as prepared sample.« less

Transformation toughened ceramics for the heavy duty diesel engine technology program

NASA Technical Reports Server (NTRS)

Musikant, S.; Feingold, E.; Rauch, H.; Samanta, S.

1984-01-01

The objective of this program is to develop an advanced high temperature oxide structural ceramic for application to the heavy duty diesel engine. The approach is to employ transformation toughening by additions of ZrO.5HfO.5O2 solid solution to the oxide ceramics, mullite (2Al2O3S2SiO2) and alumina (Al2O3). The study is planned for three phases, each 12 months in duration. This report covers Phase 1. During this period, processing techniques were developed to incorporate the ZrO.5HfO.5O2 solid solution in the matrices while retaining the necessary metastable tetragonal phase. Modulus of rupture and of elasticity, coefficient of thermal expansion, fracture toughness by indent technique and thermal diffusivity of representative specimens were measured. In Phase 2, the process will be improved to provide higher mechanical strength and to define the techniques for scale up to component size. In Phase 3, full scale component prototypes will be fabri-]cated.

Phase Behavior of Three PBX Elastomers in High-Pressure Chlorodifluoromethane

NASA Astrophysics Data System (ADS)

Lee, Byung-Chul

2017-10-01

The phase equilibrium behavior data are presented for three kinds of commercial polymer-bonded explosive (PBX) elastomers in chlorodifluoromethane (HCFC22). Levapren^{{registered }} ethylene- co-vinyl acetate (LP-EVA), HyTemp^{{registered }} alkyl acrylate copolymer (HT-ACM), and Viton^{{registered }} fluoroelastomer (VT-FE) were used as the PBX elastomers. For each elastomer + HCFC22 system, the cloud point (CP) and/or bubble point (BP) pressures were measured while varying the temperature and elastomer composition using a phase equilibrium apparatus fitted with a variable-volume view cell. The elastomers examined in this study indicated a lower critical solution temperature phase behavior in the HCFC22 solvent. LP-EVA showed the CPs at temperatures of 323 K to 343 K and at pressures of 3 MPa to 10 MPa, whereas HT-ACM showed the CPs at conditions between 338 K and 363 K and between 4 MPa and 12 MPa. For the LP-EVA and HT-ACM elastomers, the BP behavior was observed at temperatures below about 323 K. For the VT-FE + HCFC22 system, only the CP behavior was observed at temperatures between 323 K and 353 K and at pressures between 6 MPa and 21 MPa. As the elastomer composition increased, the CP pressure increased, reached a maximum value at a specific elastomer composition, and then remained almost constant.

Multiple pathways of crystal nucleation in an extremely supersaturated aqueous potassium dihydrogen phosphate (KDP) solution droplet

PubMed Central

Lee, Sooheyong; Wi, Haeng Sub; Jo, Wonhyuk; Cho, Yong Chan; Lee, Hyun Hwi; Jeong, Se-Young; Kim, Yong-Il; Lee, Geun Woo

2016-01-01

Solution studies have proposed that crystal nucleation can take more complex pathways than previously expected in classical nucleation theory, such as formation of prenucleation clusters or densified amorphous/liquid phases. These findings show that it is possible to separate fluctuations in the different order parameters governing crystal nucleation, that is, density and structure. However, a direct observation of the multipathways from aqueous solutions remains a great challenge because heterogeneous nucleation sites, such as container walls, can prevent these paths. Here, we demonstrate the existence of multiple pathways of nucleation in highly supersaturated aqueous KH2PO4 (KDP) solution using the combination of a containerless device (electrostatic levitation), and in situ micro-Raman and synchrotron X-ray scattering. Specifically, we find that, at an unprecedentedly deep level of supersaturation, a high-concentration KDP solution first transforms into a metastable crystal before reaching stability at room temperature. However, a low-concentration solution, with different local structures, directly transforms into the stable crystal phase. These apparent multiple pathways of crystallization depend on the degree of supersaturation. PMID:27791068

Multiple pathways of crystal nucleation in an extremely supersaturated aqueous potassium dihydrogen phosphate (KDP) solution droplet.

PubMed

Lee, Sooheyong; Wi, Haeng Sub; Jo, Wonhyuk; Cho, Yong Chan; Lee, Hyun Hwi; Jeong, Se-Young; Kim, Yong-Il; Lee, Geun Woo

2016-11-29

Solution studies have proposed that crystal nucleation can take more complex pathways than previously expected in classical nucleation theory, such as formation of prenucleation clusters or densified amorphous/liquid phases. These findings show that it is possible to separate fluctuations in the different order parameters governing crystal nucleation, that is, density and structure. However, a direct observation of the multipathways from aqueous solutions remains a great challenge because heterogeneous nucleation sites, such as container walls, can prevent these paths. Here, we demonstrate the existence of multiple pathways of nucleation in highly supersaturated aqueous KH 2 PO 4 (KDP) solution using the combination of a containerless device (electrostatic levitation), and in situ micro-Raman and synchrotron X-ray scattering. Specifically, we find that, at an unprecedentedly deep level of supersaturation, a high-concentration KDP solution first transforms into a metastable crystal before reaching stability at room temperature. However, a low-concentration solution, with different local structures, directly transforms into the stable crystal phase. These apparent multiple pathways of crystallization depend on the degree of supersaturation.

RETRACTED ARTICLE: Microstructure and strengthening mechanism of Ni3Al intermetallic compound

NASA Astrophysics Data System (ADS)

Oh, Chang-Sup; Han, Chang-Suk

2013-09-01

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

In situ sum-frequency generation spectroscopy of ethylene-glycol and poly-N-isopropylacrylamide films

NASA Astrophysics Data System (ADS)

Kurz, Volker; Koelsch, Patrick

2009-03-01

Ethylene-glycol(EG)-based self-assembled monolayers (SAMs) are often used as a model systems for thin liquid films. Temperature series in heavy water were measured using a unique sample cell developed for in situ sum-frequency generation (SFG) spectroscopy experiments. Results obtained from model EG-SAMs with different lengths and terminating groups in various ionic solutions showed temperature-dependent changes in the molecular order. Films of poly-N-isopropylacrylamide(pNIPAM) were also characterized by in situ SFG spectroscopy in the CH, OH, OD and amide spectral regions under different polarization combinations. These systems have many applications as thermo-responsive polymers due to their ability to change solubility in water at the biologically relevant temperature of 32 C. This so-called lower critical solution temperature (LCST) phase transition was characterized in depth, allowing for the identification of the molecular groups involved in this process.