Science.gov

Sample records for liquid-phase activity coefficients

  1. Liquid Phase Adsorption of ?-Tocopherol by Activated Carbon

    NASA Astrophysics Data System (ADS)

    Bono, Awang; Ming, Chu Chi; Sundang, Murni

    ?-Tocopherol or commonly called vitamin E can be found in major commercial vegetable oils such as soya oil and palm oil. However the existence in these oil is in low concentration. The recovery of low concentration of ?-tocopherol from palm oils is increasingly popular. Adsorption technique for the recovery of ?-tocopherol from palm oil is believed to be much lower in cost and more effective. As a case study in this work, activated carbon is chosen as the adsorbent and ethanol as the solvent. The adsorption equilibria of ?-tocopherol onto activated carbon was conducted in batch and the concentration of ?-tocopherol was identified by LCMS. Langmuirian monolayer adsorption theory was used for the analysis of the isotherm equilibria. The adsorptivity of ?-tocopherol onto activated carbon was identified. The adsorption equilibria at low concentration found to be linear. The breakthrough curve was then generated using model assuming isothermal, single transition trace component with intraparticle diffusion. Sensitivity test on the curve indicated that the system is very sensitive to changes in diffusitivity and passive to changes on the equilibrium constant.

  2. Liquid-phase adsorption of organic compounds by granular activated carbon and activated carbon fibers

    SciTech Connect

    Lin, S.H.; Hsu, F.M.

    1995-06-01

    Liquid-phase adsorption of organic compounds by granular activated carbon (GAC) and activated carbon fibers (ACFs) is investigated. Acetone, isopropyl alcohol (IPA), phenol, and tetrahydrofuran (THF) were employed as the model compounds for the present study. It is observed from the experimental results that adsorption of organic compounds by GAC and ACF is influenced by the BET (Brunauer-Emmett-Teller) surface area of adsorbent and the molecular weight, polarity, and solubility of the adsorbate. The adsorption characteristics of GAC and ACFs were found to differ rather significantly. In terms of the adsorption capacity of organic compounds, the time to reach equilibrium adsorption, and the time for complete desorption, ACFs have been observed to be considerably better than GAC. For the organic compounds tested here, the GAC adsorptions were shown to be represented well by the Langmuir isotherm while the ACF adsorption could be adequately described by the Langmuir or the Freundlich isotherm. Column adsorption tests indicated that the exhausted ACFs can be effectively regenerated by static in situ thermal desorption at 150 C, but the same regeneration conditions do not do as well for the exhausted GAC.

  3. Liquid phase adsorption behavior of inulin-type fructan onto activated charcoal.

    PubMed

    Li, Kecheng; Liu, Song; Xing, Ronge; Yu, Huahua; Qin, Yukun; Li, Pengcheng

    2015-05-20

    This study describes liquid phase adsorption characteristics of inulin-type fructan onto activated charcoal. Batch mode experiments were conducted to study the effects of pH, contact time, temperature and initial concentration of inulin. Nearly neutral solution (pH 6-8) was favorable to the adsorption and the equilibrium was attained after 40 min with the maximum adsorption Qmax 0.182 g/g (adsorbate/adsorbent) at 298 K. The experimental data analysis indicated that the adsorption process fitted well with the pseudo-second-order kinetic model (R(2) = 1) and Langmuir isotherms model (R(2) > 0.99). Thermodynamic parameters revealed that the adsorption process was spontaneous and exothermic with a physical nature. Inulin desorption could reach 95.9% using 50% ethanol solution and activated charcoal could be reused without significant losses in adsorption capacity. These results are of practical significance for the application of activated charcoal in the production and purification of inulin-type fructan. PMID:25817664

  4. Liquid phase deposition of hemoglobin/SDS/TiO2 hybrid film preserving photoelectrochemical activity.

    PubMed

    Wang, Rui; Zhang, Jingdong; Hu, Yonggang

    2011-04-01

    This work demonstrates that liquid phase deposition (LPD) technique provides a novel approach to the immobilization of hemoglobin (Hb) in TiO(2) film for studying the direct electron transfer of Hb. Using the LPD process, a hybrid film composed of Hb, TiO(2) and sodium dodecylsulfonate (SDS) is successfully prepared on the electrode surface. The surface morphology of as-deposited Hb/SDS/TiO(2) film shows a flower-like structure. The cyclic voltammetric measurement indicates that the LPD hybrid film facilitates the electron transfer of Hb, which yields a pair of redox peaks prior to the characteristic voltammetric peaks of TiO(2). Due to the electrocatalytic activity of Hb towards H(2)O(2), the Hb/SDS/TiO(2) hybrid LPD film can be utilized as an H(2)O(2) sensor, showing a sensitive response linearly proportional to the concentration of H(2)O(2) in the range of 5.010(-7)-4.010(-5) mol/L. At the same time, the Hb/SDS/TiO(2) hybrid film preserves the photoelectrochemical activity of TiO(2). The photovoltaic effect on the electrochemical behavior of Hb/SDS/TiO(2) film is observed after long-time UV irradiation on the film, which could improve the calibration sensitivity for H(2)O(2). PMID:21334986

  5. Correlation of biocatalytic activity in an organic-aqueous two-liquid phase system with solvent concentration in the cell membrane.

    PubMed

    Osborne, S J; Leaver, J; Turner, M K; Dunnill, P

    1990-04-01

    Results presented here show that loss of progesterone 11 alpha-hydroxylase activity in Rhizopus nigricans in aqueous-organic two-liquid phase and cosolvent systems correlates well with the concentration of solvent in the cell membranes. Rhizopus nigricans is shown to retain full 11 alpha-hydroxylase activity at saturating aqueous phase concentrations of hexane and the higher primary alcohols. This reflects their inability to attain a critical concentration in the cell membranes. The relationship between our own findings and the previously described correlation of the logarithm of the partition coefficient with activity retention is explained and design parameters are proposed that may be used to select solvents for future biocatalytic systems. PMID:1366443

  6. Liquid-Phase Adsorption Fundamentals.

    ERIC Educational Resources Information Center

    Cooney, David O.

    1987-01-01

    Describes an experiment developed and used in the unit operations laboratory course at the University of Wyoming. Involves the liquid-phase adsorption of an organic compound from aqueous solution on activated carbon, and is relevant to adsorption processes in general. (TW)

  7. Approach to In- Situ Producing Reinforcing Phase Within an Active-Transient Liquid Phase Bond Seam for Aluminum Matrix Composite

    NASA Astrophysics Data System (ADS)

    Zhang, Guifeng; Liao, Xianjin; Chen, Bo; Zhang, Linjie; Zhang, Jianxun

    2015-06-01

    To optimize the braze composition design route for aluminum matrix composite, the feasibility of in situ producing reinforcing phase within the transient liquid phase bond seam matrix, by adding active melting point increaser (MPI, e.g., Ti) together with general melting point depressant (MPD, e.g., Cu) into the interlayer, was demonstrated. For SiC p /A356 composite, by comparing the wettability, joint microstructure, joint shear strength, and fracture path for the developed Al-19Cu-1Ti, Al-19Cu, Al-33Cu-1Ti, Al-33Cu (wt pct), and commercial Cu foils as interlayer, the feasibility of in situ producing reinforcing phase within the bond seam by adding Ti was demonstrated. Especially for Al-19Cu-1Ti active braze, small and dispersed ternary aluminide of Al-Si-Ti phase was obtained within the bond seam as in situ reinforcement, leading to a favorable fracture path within SiC p /A356, not along the initial interface or within the bond seam. For the formation mechanism of the in situ reinforcing phase of MPI-containing intermetallic compound within the bond seam, a model of repeating concentration-precipitation-termination-engulfment during isothermal solidification is proposed.

  8. Activated carbon catalyzes reactions of phenolics during liquid-phase adsorption

    SciTech Connect

    Cooney, D.O.; Xi, Z. . Chemical Engineering Dept.)

    1994-02-01

    Various phenolic compounds in aqueous buffer solutions were contacted batchwise with powdered activated carbon. Relatively slow, but continual, decreases in the solution phenolic concentrations were measured over a period of several weeks. The decreases were due to oxidative coupling reactions of the phenolics which occurred on the carbon surface subsequent to adsorption. The effects of time, pH, dissolved oxygen, and the molecular nature of the phenolic were determined.

  9. Relationship between surface hydroxyl groups and liquid-phase photocatalytic activity of titanium dioxide.

    PubMed

    Li, Wenjuan; Du, Dandan; Yan, Tingjiang; Kong, Desheng; You, Jinmao; Li, Danzhen

    2015-04-15

    Both theories and experiments show that surface hydroxyl radicals (OH) are the most important intermediate species in the photocatalytic process. As a source of OH, surface hydroxyl (OH) groups play an important role in its generation. In this paper, the OH groups were divided into surface acidic hydroxyl (OH(a)) and surface basic hydroxyl (OH(b)) groups. From the detection by a method of surface acid-base, ion-exchange reactions, the total surface density of OH groups was about 9.5810(-5) mol m(-2). The results measured by Fourier transform infrared spectroscopy, (1)H magnetic-angle spinning NMR and electron spin resonance techniques demonstrated that the role of OH(a) groups was greater than that of OH(b) groups on the generation of OH radicals. By degradation of methyl orange, rhodamine B and p-chlorophenol, the photocatalytic activities of the catalysts were directly influenced by the amount of OH groups. PMID:25585286

  10. Kinetic studies of the liquid-phase adsorption of a reactive dye onto activated lignite

    SciTech Connect

    Petrolekas, P.D.; Maggenakis, G.

    2007-02-14

    The kinetics of batch adsorption of a commercial reactive dye onto activated lignite has been investigated at temperatures of 26, 40, and 55{sup o}C, using aqueous solutions with initial dye concentrations in the range of 15-60 mg/L. An empirical single parameter relationship of the adsorbent loading versus the square root of contact time was proposed, which was determined to provide a very good description of the batch adsorption transients up to equilibrium. The data were also examined by means of the Elovich equation. The effect of the temperature and the initial dye concentration on the adsorption kinetics was analyzed, and the results were discussed by considering that intraparticle diffusion is the dominant mechanism.

  11. In-situ activation of CuO/ZnO/Al.sub.2 O.sub.3 catalysts in the liquid phase

    DOEpatents

    Brown, Dennis M. (Allentown, PA); Hsiung, Thomas H. (Emmaus, PA); Rao, Pradip (Allentown, PA); Roberts, George W. (Emmaus, PA)

    1989-01-01

    The present invention relates to a method of activation of a CuO/ZnO/Al.sub.2 O.sub.3 catalyst slurried in a chemically inert liquid. Successful activation of the catalyst requires the use of a process in which the temperature of the system at any time is not allowed to exceed a certain critical value, which is a function of the specific hydrogen uptake of the catalyst at that same time. This process is especially critical for activating highly concentrated catalyst slurries, typically 25 to 50 wt %. Activation of slurries of CuO/ZnO/Al.sub.2 O.sub.3 catalyst is useful in carrying out the liquid phase methanol or the liquid phase shift reactions.

  12. Liquid-phase chlorination of perchloroethylene

    SciTech Connect

    Levanova, S.V.; Evstigneev, O.V.; Rodova, R.M.; Berlin, E.R.; Ul'yanov, A.A.

    1988-06-01

    The relationships in the liquid-phase chlorination of perchloroethylene to hexachlorethane in a thermal process and in the presence of an initiator have been studied. The rate constants and the activation parameters of the process have been determined.

  13. CATALYST ACTIVITY MAINTENANCE FOR THE LIQUID PHASE SYNTHESIS GAS-TO-DIMETHYL ETHER PROCESS PART II: DEVELOPMENT OF ALUMINUM PHOSPHATE AS THE DEHYDRATION CATALYST FOR THE SINGLE-STEP LIQUID PHASE SYNGAS-TO-DME PROCESS

    SciTech Connect

    Xiang-Dong Peng

    2002-05-01

    At the heart of the single-step liquid phase syngas-to-DME process (LPDME{trademark}) is a catalyst system that can be active as well as stable. In the Alternative Fuels I program, a dual-catalyst system containing a Cu-based commercial methanol synthesis catalyst (BASF S3-86) and a commercial dehydration material ({gamma}-alumina) was demonstrated. It provided the productivity and selectivity expected from the LPDME process. However, the catalyst system deactivated too rapidly to warrant a viable commercial process [1]. The mechanistic investigation in the early part of the DOE's Alternative Fuels II program revealed that the accelerated catalyst deactivation under LPDME conditions is due to detrimental interaction between the methanol synthesis catalyst and methanol dehydration catalyst [2,3]. The interaction was attributed to migration of Cu- and/or Zn-containing species from the synthesis catalyst to the dehydration catalyst. Identification of a dehydration catalyst that did not lead to this detrimental interaction while retaining adequate dehydration activity was elusive. Twenty-nine different dehydration materials were tested, but none showed the desired performance [2]. The search came to a turning point when aluminum phosphate was tested. This amorphous material is prepared by precipitating a solution containing Al(NO{sub 3}){sub 3} and H{sub 3}PO{sub 4} with NH{sub 4}OH, followed by washing, drying and calcination. The aluminum phosphate catalyst has adequate dehydration activity and good stability. It can co-exist with the Cu-based methanol synthesis catalyst without negatively affecting the latter catalyst's stability. This report documents the details of the development of this catalyst. These include initial leads, efforts in improving activity and stability, investigation and development of the best preparation parameters and procedures, mechanistic understanding and resulting preparation guidelines, and the accomplishments of this work.

  14. Hydrogenation of nitriles on a well-characterized nickel surface: From surface science studies to liquid phase catalytic activity measurements

    SciTech Connect

    Gardin, D.E.

    1993-12-01

    Nitrile hydrogenation is the most commonly used method for preparing diverse amines. This thesis is aimed at the mechanism and factors affecting the performance of Ni-based catalysts in nitrile hydrogenations. Surface science techniques are used to study bonding of nitriles and amines to a Ni(111) surface and to identify surface intermediates. Liquid-phase hydrogenations of cyclohexene and 1-hexene on a Pt foil were carried out successfully. Finally, knowledge about the surface structure, surface chemical bond, dynamics of surface atoms (diffusion, growth), and reactivity of metal surfaces from solid-gas interface studies, is discussed.

  15. Development of an automatic multiple dynamic hollow fibre liquid-phase microextraction procedure for specific migration analysis of new active food packagings containing essential oils.

    PubMed

    Pezo, Davinson; Salafranca, Jess; Nern, Cristina

    2007-12-01

    A two-phase based hollow fibre liquid-phase microextraction (HFLPME) with a high automatization degree and able to process up to six samples simultaneously by means of a multiple channel syringe pump has been successfully developed. The experimental set-up allows to carry out dynamic extractions with a considerable reduction of sample handling. The system has been applied for the first time to the determination in aqueous food simulant of migrants from prototypes of active packagings to assess their safety before marketing, showing detection limits in the ng g(-1) range, relative standard deviations below 13% and concentration factors ranging from 83 to 338. PMID:17765253

  16. The influence of reduction methods and conditions on the activity of alumina-supported platinum catalysts for the liquid phase hydrogenation of benzaldehyde in ethanol

    SciTech Connect

    Arai, M.; Obata, A.; Nishiyama, Y.

    1997-02-01

    The activities of supported metal catalysts depend on various preparation variables, including the method of reduction. A variety of reduction procedures can be applied to the preparation of supported metal catalysts. Previously, the authors used a solid-liquid reduction by sodium tetrahydroborate solution for preparing supported platinum catalysts. In this reduction, platinum precursors adsorbed on supports were brought into contact with the reducing solution. The alumina-supported platinum catalysts prepared in this way were found to display interesting activities in the liquid-phase hydrogenation of {alpha},{beta}-unsaturated aldehydes; they were highly selective to the formation of unsaturated alcohols. The selective hydrogenation of C=O bonds of {alpha},{beta}-unsaturated aldehydes is difficult to achieve with platinum catalysts without using some additives like tin and iron. The maximum temperature that the supported platinum catalysts went through was 110{degrees}C, required for the removal of water. This thermal history is a possible reason for the catalytic activity observed. Following those observations, in the present work, the authors have further examined the influence of reduction procedures by using hydrazine as well as sodium tetrahydroborate and different temperatures common during gas-phase reduction with hydrogen. The catalytic activity has been tested by the liquid-phase hydrogenation of benzaldehyde (BAL) in ethanol under mild conditions. 12 refs., 3 figs.

  17. Microstructural evolution in the partial transient liquid phase diffusion bonding of Zircaloy-4 to stainless steel 321 using active titanium filler metal

    NASA Astrophysics Data System (ADS)

    Atabaki, M. Mazar

    2010-11-01

    Microstructural evolution of the partial transient liquid phase diffusion bonded Zircaloy-4 and stainless steel 321 using an active Ti-base interlayer were studied at different temperatures. Additionally, simple analytical models were developed to predict the evolution of the interlayer and intermetallics during the bonding operation. Bonds were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. Precision measurement of the interlayer width was made as a function of the bonding temperature. The liquid film migration occurred as a result of chemical solubility differences between the stable and metastable phases. The formation and growth model of the intermetallic compounds at the interfaces of Zircaloy-4/Ti-base interlayer and stainless steel 321/Ti-base interlayer for controlling the bonding process was studied considering the diffusion kinetics and the thermodynamics. The evolution of the interlayer thickness indicated a good agreement between the calculation and experimental measurement. It was also demonstrated that the low isothermal solidification kinetic was not only due to the enrichment of the liquid phase with the base alloying elements such as Ti and Zr, but also the reduction of solid solubility limit of Cu in the base alloys contributed to the reduction of isothermal solidification kinetic.

  18. Liquid Phase Sintering

    NASA Technical Reports Server (NTRS)

    2004-01-01

    Industry spends billions of dollars each year on machine tools to manufacture products out of metal. This includes tools for cutting every kind of metal part from engine blocks to Shuttle main engine components. Cutting tool tips often break because of weak spots or defects in their composition. Based on a new concept called defect trapping, space offers a novel environment to study defect formation in molten metal materials as they solidify. After the return of these materials from space, researchers can evaluate the source of the defect and seek ways to eliminate them in products prepared on Earth. A widely used process for cutting tip manufacturing is liquid phase sintering. Compared to Earth-sintered samples which slump due to buoyancy induced by gravity, space samples are uniformly shaped and defects remain where they are formed. By studying metals sintered in space the US tool industry can potentially enhance its worldwide competitiveness. The Consortium for Materials Development in Space along with Wyle Labs, Teledyne Advanced Materials, and McDornell Douglas have conducted experiments in space.

  19. Liquid-phase electroepitaxy - Dopant segregation

    NASA Technical Reports Server (NTRS)

    Lagowski, J.; Jastrzebski, L.; Gatos, H. C.

    1980-01-01

    A theoretical model is presented which accounts for the dopant segregation in liquid-phase electroepitaxy in terms of dopant transport in the liquid phase (by electromigration and diffusion), the growth velocity, and the Peltier effect at the substrate-solution interface. The contribution of dopant electromigration to the magnitude of the effective segregation coefficient is dominant in the absence of convection; the contribution of the Peltier effect becomes significant only in the presence of pronounced convection. Quantitative expressions which relate the segregation coefficient to the growth parameters also permit the determination of the diffusion constant and electromigration mobility of the dopant in the liquid phase. The model was found to be in good agreement with the measured segregation characteristics of Sn in the electroepitaxial growth of GaAs from Ga-As solutions. For Sn in Ga-As solution at 900 C the diffusion constant was found to be 4 x 10 to the -5 sq cm/s and the electromigration velocity (toward the substrate with a positive polarity 2 x 10 to the -5 cm/s current density of 10 A/sq cm.

  20. An activity coefficient model for proteins.

    PubMed

    Agena, S M; Bogle, I D; Pessoa, F L

    1997-07-01

    Modeling of the properties of biochemical components is gaining increasing interest due to its potential for further application within the area of biochemical process development. Generally protein solution properties such as protein solubility are expressed through component activity coefficients which are studied here. The original UNIQUAC model is chosen for the representation of protein activity coefficients and, to the best of our knowledge, this is the first time it has been directly applied to protein solutions. Ten different protein-salt-water systems with four different proteins, serum albumin, alphacymotrypsin, beta-lactoglobulin and ovalbumin, are investigated. A root-mean-squared deviation of 0.54% is obtained for the model by comparing calculated protein activity coefficients and protein activity coefficients deduced from osmotic measurements through virial expansion. Model predictions are used to analyze the effect of salt concentrations, pH, salt types, and temperature on protein activity coefficients and also on protein solubility and demonstrate consistency with results from other references. PMID:18636445

  1. Liquid-phase growth of platinum nanoparticles on molybdenum trioxide nanosheets: an enhanced catalyst with intrinsic peroxidase-like catalytic activity

    NASA Astrophysics Data System (ADS)

    Wang, Yixian; Zhang, Xiao; Luo, Zhimin; Huang, Xiao; Tan, Chaoliang; Li, Hai; Zheng, Bing; Li, Bing; Huang, Ying; Yang, Jian; Zong, Yun; Ying, Yibin; Zhang, Hua

    2014-10-01

    A facile method for the synthesis of metal nanostructure-decorated two-dimensional (2D) semiconductor nanosheets was developed. The solution-processable molybdenum trioxide (MoO3) nanosheet was used as a template for direct liquid-phase growth of platinum nanoparticles (Pt NPs) under ambient conditions. Results show that the Pt NPs with sizes of 1-3 nm were uniformly grown on the MoO3 surface. Importantly, the Pt-MoO3 hybrid nanomaterial exhibits an enhanced peroxidase-like catalytic activity compared to the MoO3 nanosheet, Pt NPs, and their physical mixture under the same conditions. As a proof-of-concept application, the Pt-MoO3 hybrid nanomaterial was used as a high-efficiency peroxidase-mimic for ultrasensitive colorimetric detection of glucose in serum samples. This work provides a promising strategy for design and development of biomimetic catalysts by smart assembly of different dimensional nanomaterials.A facile method for the synthesis of metal nanostructure-decorated two-dimensional (2D) semiconductor nanosheets was developed. The solution-processable molybdenum trioxide (MoO3) nanosheet was used as a template for direct liquid-phase growth of platinum nanoparticles (Pt NPs) under ambient conditions. Results show that the Pt NPs with sizes of 1-3 nm were uniformly grown on the MoO3 surface. Importantly, the Pt-MoO3 hybrid nanomaterial exhibits an enhanced peroxidase-like catalytic activity compared to the MoO3 nanosheet, Pt NPs, and their physical mixture under the same conditions. As a proof-of-concept application, the Pt-MoO3 hybrid nanomaterial was used as a high-efficiency peroxidase-mimic for ultrasensitive colorimetric detection of glucose in serum samples. This work provides a promising strategy for design and development of biomimetic catalysts by smart assembly of different dimensional nanomaterials. Electronic supplementary information (ESI) available: Experimental details, Fig. S1-S9, and Tables S1 and S2 as mentioned in the text. See DOI: 10.1039/c4nr04115a

  2. Kinetic modeling of liquid-phase adsorption of Congo red dye using guava leaf-based activated carbon

    NASA Astrophysics Data System (ADS)

    Ojedokun, Adedamola Titi; Bello, Olugbenga Solomon

    2016-02-01

    Guava leaf, a waste material, was treated and activated to prepare adsorbent. The adsorbent was characterized using Scanning Electron Microscopy (SEM), Fourier Transform Infra Red (FTIR) and Energy-Dispersive X-ray (EDX) techniques. The carbonaceous adsorbent prepared from guava leaf had appreciable carbon content (86.84 %). The adsorption of Congo red dye onto guava leaf-based activated carbon (GLAC) was studied in this research. Experimental data were analyzed by four different model equations: Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherms and it was found to fit Freundlich equation most. Adsorption rate constants were determined using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion model equations. The results clearly showed that the adsorption of CR dye onto GLAC followed pseudo-second-order kinetic model. Intraparticle diffusion was involved in the adsorption process. The mean energy of adsorption calculated from D-R isotherm confirmed the involvement of physical adsorption. Thermodynamic parameters were obtained and it was found that the adsorption of CR dye onto GLAC was an exothermic and spontaneous process at the temperatures under investigation. The maximum adsorption of CR dye by GLAC was found to be 47.62 mg/g. The study shows that GLAC is an effective adsorbent for the adsorption of CR dye from aqueous solution.

  3. Effect of Polarity of Activated Carbon Surface, Solvent and Adsorbate on Adsorption of Aromatic Compounds from Liquid Phase.

    PubMed

    Goto, Tatsuru; Amano, Yoshimasa; Machida, Motoi; Imazeki, Fumio

    2015-01-01

    In this study, introduction of acidic functional groups onto a carbon surface and their removal were carried out through two oxidation methods and outgassing to investigate the adsorption mechanism of aromatic compounds which have different polarity (benzene and nitrobenzene). Adsorption experiments for these aromatics in aqueous solution and n-hexane solution were conducted in order to obtain the adsorption isotherms for commercial activated carbon (BAC) as a starting material, its two types of oxidized BAC samples (OXs), and their outgassed samples at 900 °C (OGs). Adsorption and desorption kinetics of nitrobenzene for the BAC, OXs and OGs in aqueous solution were also examined. The results showed that the adsorption of benzene molecules was significantly hindered by abundant acidic functional groups in aqueous solution, whereas the adsorbed amount of nitrobenzene on OXs gradually increased as the solution concentration increased, indicating that nitrobenzene can adsorb favourably on a hydrophilic surface due to its high dipole moment, in contrast to benzene. In n-hexane solution, it was difficult for benzene to adsorb on any sample owing to the high affinity between benzene and n-hexane solvent. On the other hand, adsorbed amounts of nitrobenzene on OXs were larger than those of OGs in n-hexane solution, implying that nitrobenzene can adsorb two adsorption sites, graphene layers and surface acidic functional groups. The observed adsorption and desorption rate constants of nitrobenzene on the OXs were lower than those on the BAC due to disturbance of diffusion by the acidic functional groups. PMID:26329866

  4. Improved liquid phase deposition of anatase TiO2 hollow microspheres with exposed {0 0 1} facets and their photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Lei, Cai-Xia; Jiang, Xiao-Long; Huang, Xu; Liu, Xiang; Zeng, De-Qian; Ma, Ya-Ting; Wang, Lai-Sen; Peng, Dong-Liang

    2015-12-01

    An improved liquid phase deposition (LPD) method was developed to prepare the TiO2 microspheres with enhanced crystallinity in this study. The as-prepared samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), nitrogen adsorption and desorption instrument, as well as the UV-Vis absorption spectroscopy. The results showed that the samples prepared at various precursor concentrations were identified as the well-crystalline anatase TiO2 exposed with reactive {0 0 1} facets, which was caused by the introduction of fluorine during the hydrolysis process of (NH4)2TiF6 precursor solution. Moreover, with increased concentration of precursor solution, the dissolution of {0 0 1} facets occurred and the typical hollow spherical structure was also found. The photocatalytic experiments revealed that the as-prepared anatase TiO2 microspheres exhibited an effective photocatalytic activity during the process of Rhodamine B (RhB) degradation.

  5. Depositing spacing layers on magnetic film with liquid phase epitaxy

    NASA Technical Reports Server (NTRS)

    Moody, J. W.; Shaw, R. W.; Sanfort, R. M.

    1975-01-01

    Liquid phase epitaxy spacing layer is compatible with systems which are hard-bubble proofed by use of second magnetic garnet film as capping layer. Composite is superior in that: circuit fabrication time is reduced; adherence is superior; visibility is better; and, good match of thermal expansion coefficients is provided.

  6. Liquid phase sintered superconducting cermet

    SciTech Connect

    Ray, S.P.

    1990-01-09

    This patent describes a method of making a superconducting cermet having superconducting properties with improved bulk density, low porosity and in situ stabilization. It comprises: forming a structure of a superconducting ceramic material having the formula RM{sub 2}Cu{sub 3}O{sub (6.5 + x)}wherein R is one or more rare earth elements capable of reacting to form a superconducting ceramic, M is one or more alkaline earth metal elements selected from barium and strontium capable of reacting to form a superconducting ceramic, x is greater than 0 and less than 0.5; and a precious metal compound in solid form selected from the class consisting of oxides, sulfides and halides of silver; and liquid phase sintering the mixture at a temperature wherein the precious metal of the precious metal compound is molten and below the melting point of the ceramic material. The liquid phase sintering is carried out for a time less than 36 hours but sufficient to improve the bulk density of the cermet.

  7. New equipment and new technique for measuring activity coefficients and Henry's constants at infinite dilution

    NASA Astrophysics Data System (ADS)

    Richon, Dominique

    2011-02-01

    New equipment is presented along with various experimental procedures and setups to cover a large range of applications. It represents a considerable improvement in terms of speed, accuracy, and simplicity with respect to classical gas stripping methods known as "dilutor techniques." Furthermore, range of conditions of its use is larger in terms of: temperatures (from 90 to 600 K), corrosive power, and toxicity of handled compounds. Solutes that could adsorb inside sampling valves or on the walls of transfer lines between sampling valve and GC detector are now studied easily; thanks to new design and procedure. Activity coefficients of one solute into one solvent at five temperatures, several repeatability tests included, are obtained in worst cases in less than 3 h. One accurate activity coefficient measurement (toluene in water) at one temperature can be realized in less than 2 min, after loading of the dilutor cell, instead of more than half an hour for unreliable results with previous equipment. It must be pointed out that the slope determination (slope of the logarithm of the exponential decay of solute composition in vapor phase which is in equilibrium with liquid phase) is the highest source of errors (flow rate, temperature, number of moles of solute are known with high accuracy with respect to slopes); they are now determined within few instead of up to tens of % in the most difficult cases leading to higher accuracies of measured activity coefficients, Henry's constants at infinite dilutions or solubility data. Successful comparisons with literature data and reproducibility tests are presented herein.

  8. Modeling Secondary Organic Aerosols over Europe: Impact of Activity Coefficients and Viscosity

    NASA Astrophysics Data System (ADS)

    Kim, Y.; Sartelet, K.; Couvidat, F.

    2014-12-01

    Semi-volatile organic species (SVOC) can condense on suspended particulate materials (PM) in the atmosphere. The modeling of condensation/evaporation of SVOC often assumes that gas-phase and particle-phase concentrations are at equilibrium. However, recent studies show that secondary organic aerosols (SOA) may not be accurately represented by an equilibrium approach between the gas and particle phases, because organic aerosols in the particle phase may be very viscous. The condensation in the viscous liquid phase is limited by the diffusion from the surface of PM to its core. Using a surrogate approach to represent SVOC, depending on the user's choice, the secondary organic aerosol processor (SOAP) may assume equilibrium or model dynamically the condensation/evaporation between the gas and particle phases to take into account the viscosity of organic aerosols. The model is implemented in the three-dimensional chemistry-transport model of POLYPHEMUS. In SOAP, activity coefficients for organic mixtures can be computed using UNIFAC for short-range interactions between molecules and AIOMFAC to also take into account the effect of inorganic species on activity coefficients. Simulations over Europe are performed and POLYPHEMUS/SOAP is compared to POLYPHEMUS/H2O, which was previously used to model SOA using the equilibrium approach with activity coefficients from UNIFAC. Impacts of the dynamic approach on modeling SOA over Europe are evaluated. The concentrations of SOA using the dynamic approach are compared with those using the equilibrium approach. The increase of computational cost is also evaluated.

  9. Effect of additions of sodium hydroxide on the catalytic activity of partially deactivated skeletal nickel in reactions of the liquid-phase hydrogenation of sodium maleate in aqueous-organic media

    NASA Astrophysics Data System (ADS)

    Lukin, M. V.; Afineevskii, A. V.

    2015-07-01

    The effect the concentration of sodium hydroxide has on the catalytic activity of skeletal nickel in reactions of the liquid-phase hydrogenation of sodium maleate in ternary methanol-water-sodium hydroxide solutions with a methanol content of 0.11 mole fractions and different concentrations of sodium hydroxide is studied. The key role of the solvent during changes in the activity of skeletal nickel in the hydrogenation reaction of sodium maleate is assumed, based on data on the redistribution of individual forms of adsorbed hydrogen.

  10. COMPARISON OF THE OCTANOL-AIR PARTITION COEFFICIENT AND LIQUID-PHASE VAPOR PRESSURE AS DESCRIPTORS FOR PARTICLE/GAS PARTITIONING USING LABORATORY AND FIELD DATA FOR PCBS AND PCNS

    EPA Science Inventory

    The conventional Junge-Pankow adsorption model uses the sub-cooled liquid vapor pressure (pLo) as a correlation parameter for gas/particle interactions. An alternative is the octanol-air partition coefficient (Koa) absorption model. Log-log plots of the particle-gas partition c...

  11. Liquid-phase combinatorial synthesis.

    PubMed Central

    Han, H; Wolfe, M M; Brenner, S; Janda, K D

    1995-01-01

    A concept termed liquid-phase combinatorial synthesis (LPCS) is described. The central feature of this methodology is that it combines the advantages that classic organic synthesis in solution offers with those that solid-phase synthesis can provide, through the application of a linear homogeneous polymer. To validate this concept two libraries were prepared, one of peptide and the second of nonpeptide origin. The peptide-based library was synthesized by a recursive deconvolution strategy [Erb, E., Janda, K. D. & Brenner, S. (1994) Proc. Natl. Acad. Sci. USA 91, 11422-11426] and several ligands were found within this library to bind a monoclonal antibody elicited against beta-endorphin. The non-peptide molecules synthesized were arylsulfonamides, a class of compounds of known clinical bactericidal efficacy. The results indicate that the reaction scope of LPCS should be general, and its value to multiple, high-throughput screening assays could be of particular merit, since multimilligram quantities of each library member can readily be attained. PMID:7541541

  12. Liquid-phase chromatography detector

    DOEpatents

    Voigtman, Edward G.; Winefordner, James D.; Jurgensen, Arthur R.

    1983-01-01

    A liquid-phase chromatography detector comprising a flow cell having an inlet tubular conduit for receiving a liquid chromatographic effluent and discharging it as a flowing columnar stream onto a vertically adjustable receiving surface spaced apart from and located vertically below and in close proximity to the discharge end of the tubular conduit; a receiver adapted to receive liquid overflowing from the receiving surface; an exit conduit for continuously removing liquid from the receiver; a light source for focussing fluorescence-producing light pulses on the flowing columnar stream as it passes from the outlet of the conduit to the receiving surface and a fluorescence detector to detect the produced fluorescence; a source of light pulse for producing acoustic waves in the columnar stream as it passes from the conduit outlet to the receiving surface; and a piezoelectric transducer adapted to detect those waves; and a source of bias voltage applied to the inlet tubular conduit and adapted to produce ionization of the liquid flowing through the flow cell so as to produce photocurrents therein and an electrical system to detect and record the photocurrents. This system is useful in separating and detecting individual chemical compounds from mixtures thereof.

  13. Liquid-phase chromatography detector

    DOEpatents

    Voigtman, E.G.; Winefordner, J.D.; Jurgensen, A.R.

    1983-11-08

    A liquid-phase chromatography detector comprises a flow cell having an inlet tubular conduit for receiving a liquid chromatographic effluent and discharging it as a flowing columnar stream onto a vertically adjustable receiving surface spaced apart from and located vertically below and in close proximity to the discharge end of the tubular conduit; a receiver adapted to receive liquid overflowing from the receiving surface; an exit conduit for continuously removing liquid from the receiver; a light source for focusing fluorescence-producing light pulses on the flowing columnar stream as it passes from the outlet of the conduit to the receiving surface and a fluorescence detector to detect the produced fluorescence; a source of light pulse for producing acoustic waves in the columnar stream as it passes from the conduit outlet to the receiving surface; and a piezoelectric transducer adapted to detect those waves; and a source of bias voltage applied to the inlet tubular conduit and adapted to produce ionization of the liquid flowing through the flow cell so as to produce photocurrents therein and an electrical system to detect and record the photocurrents. This system is useful in separating and detecting individual chemical compounds from mixtures thereof. 5 figs.

  14. Transient liquid phase ceramic bonding

    DOEpatents

    Glaeser, Andreas M. (Berkeley, CA)

    1994-01-01

    Ceramics are joined to themselves or to metals using a transient liquid phase method employing three layers, one of which is a refractory metal, ceramic or alloy. The refractory layer is placed between two metal layers, each of which has a lower melting point than the refractory layer. The three layers are pressed between the two articles to be bonded to form an assembly. The assembly is heated to a bonding temperature at which the refractory layer remains solid, but the two metal layers melt to form a liquid. The refractory layer reacts with the surrounding liquid and a single solid bonding layer is eventually formed. The layers may be designed to react completely with each other and form refractory intermetallic bonding layers. Impurities incorporated into the refractory metal may react with the metal layers to form refractory compounds. Another method for joining ceramic articles employs a ceramic interlayer sandwiched between two metal layers. In alternative embodiments, the metal layers may include sublayers. A method is also provided for joining two ceramic articles using a single interlayer. An alternate bonding method provides a refractory-metal oxide interlayer placed adjacent to a strong oxide former. Aluminum or aluminum alloys are joined together using metal interlayers.

  15. Preparation and Characterization of Low Molecular Weight Heparin by Liquid Phase Plasma Method.

    PubMed

    Lee, Do-Jin; Kim, Hangun; Kim, Byung Hoon; Park, Young-Kwon; Lee, Heon; Park, Sung Hoon; Jung, Sang-Chul

    2015-08-01

    An liquid phase plasma process system was applied to the production of low molecular weight heparin. The molecular weight of produed heparin decreased with increasing liquid phase plasma treatment time. The abscission of the chemical bonds between the constituents of heparin by liquid phase plasma reaction did not alter the characteristics of heparin. Formation of any by-products due to side reaction was not observed. It is suggested that heparin was depolymerized by active oxygen radicals produced during the liquid phase plasma reaction. PMID:26369227

  16. Activity coefficients in the surface phase of liquid mixtures.

    PubMed

    Santos, M Soledade C S; Reis, Joo Carlos R

    2015-02-01

    A novel equation for evaluating surface activity coefficients is obtained from a recent thermodynamic formalism describing the surface phase of liquid mixtures. The input quantities are the surface tension, bulk activity coefficients and pure constituent thermophysical properties. It is demonstrated thermodynamically that the order of magnitude of each component surface and bulk activity coefficients must be the same. This order is intrinsically associated with the sign of excess surface tension. Reliable activity coefficients of ethanol and water in the surface phase of their mixtures are computed and reported for the first time, by using literature data for the required input quantities. It is shown that the so-called transferring method for estimating surface activity coefficients is severely flawed, because it leads to contradictory values of predicted excess surface tensions depending on which component this prediction is based. PMID:25404471

  17. Liquid phase sintering of silicon carbide

    DOEpatents

    Cutler, Raymond A.; Virkar, Anil V.; Hurford, Andrew C.

    1989-01-01

    Liquid phase sintering is used to densify silicon carbide based ceramics using a compound comprising a rare earth oxide and aluminum oxide to form liquids at temperatures in excess of 1600.degree. C. The resulting sintered ceramic body has a density greater than 95% of its theoretical density and hardness in excess of 23 GPa. Boron and carbon are not needed to promote densification and silicon carbide powder with an average particle size of greater than one micron can be densified via the liquid phase process. The sintered ceramic bodies made by the present invention are fine grained and have secondary phases resulting from the liquid phase.

  18. Liquid phase sintering of silicon carbide

    DOEpatents

    Cutler, R.A.; Virkar, A.V.; Hurford, A.C.

    1989-05-09

    Liquid phase sintering is used to densify silicon carbide based ceramics using a compound comprising a rare earth oxide and aluminum oxide to form liquids at temperatures in excess of 1,600 C. The resulting sintered ceramic body has a density greater than 95% of its theoretical density and hardness in excess of 23 GPa. Boron and carbon are not needed to promote densification and silicon carbide powder with an average particle size of greater than one micron can be densified via the liquid phase process. The sintered ceramic bodies made by the present invention are fine grained and have secondary phases resulting from the liquid phase. 4 figs.

  19. Active-Transient Liquid Phase (A-TLP) Bonding of Pure Aluminum Matrix Composite Reinforced with Short Alumina Fiber Using Al-12Si-xTi Foils as Active Interlayer

    NASA Astrophysics Data System (ADS)

    Zhang, Guifeng; Su, Wei; Suzumura, Akio

    2016-02-01

    To optimize both the interlayer composition design route and pressure for joining aluminum matrix composite reinforced with short alumina fiber (as-cast 30 vol pct Al2O3sf/Al), traditional transient liquid phase (TLP) bonding using Al-12Si and Cu interlayer and active-TLP (A-TLP) bonding using an active Ti-containing interlayer (Al-12Si-xTi, x = 0.1, 0.5, and 1 wt pct) under the same condition [883 K (610 °C) × 30 minutes × 1 or 0.015 MPa in flowing argon] were compared in terms of interfacial wettability, bond seam microstructure, shear strength, and fracture path. It was found that not only the Ti content but also the pressure are critical factors affecting interfacial wettability and bond seam microstructure. The improvement in wettability by adding Ti as an active element were confirmed by reduction of expulsion of liquid interlayer, elimination of interfacial gap, higher shear strength and favorable fracture path (partially through bond seam and the composite). Because of the incubation period for wetting, reducing the pressure after melting of the interlayer could further increase joint shear strength by thickening the remaining bond seam of solid-solution matrix and decreasing fraction of the in situ newly formed Al-Si-Ti IMC phase (short bar shape) within the bond seam. The maximum shear strength of 88.6 MPa (99 pct of the as-cast composite) was obtained by adding trace Ti content (0.5 Ti wt pct) addition and using low pressure (0.015 MPa). The results showed that suitable combination of Ti content and pressure pattern is required for improving both wettability and bond seam microstructure.

  20. Effect of Liquid-phase Siliconizing Process on Silicon Diffusion Behavior in Mo Matrix

    NASA Astrophysics Data System (ADS)

    Zhang, Ying-Yi; Li, Yun-Gang; Shi, Xue-Feng; Qi, Yuan-Hong

    2014-09-01

    MoSi2 functionally graded coating on Mo substrate is prepared by liquid-phase siliconizing technology. The SEM, GDS and XRD analysis shows that the silicon content in gradient layer appears in three changing regularities. Along the Mo substrate to the surface of the coating, the phase composition of gradient coating changes as follows: Mo ? transition layer Mo (main phase) + Mo3Si + Mo5Si3 ? intermediate layer MoSi2 ? surface layer MoSi2 (main phase) + Si. According to the Si-Mo diffusion couple and Arrhenius equation, the activation energy (Q) was obtained as 430 kJmol-1, and the Arrhenius dependence of D on temperature can be described as D = 4.9 10-3 exp(-430000/RT) m2/s. The diffusion temperature has an important influence on silicon diffusion coefficient. As the diffusion temperature increases, silicon diffusion coefficient is also gradually increasing.

  1. Structure analysis of turbulent liquid phase by POD and LSE techniques

    SciTech Connect

    Munir, S. Muthuvalu, M. S.; Siddiqui, M. I.; Heikal, M. R. Aziz, A. Rashid A.

    2014-10-24

    In this paper, vortical structures and turbulence characteristics of liquid phase in both single liquid phase and two-phase slug flow in pipes were studied. Two dimensional velocity vector fields of liquid phase were obtained by Particle image velocimetry (PIV). Two cases were considered one single phase liquid flow at 80 l/m and second slug flow by introducing gas at 60 l/m while keeping liquid flow rate same. Proper orthogonal decomposition (POD) and Linear stochastic estimation techniques were used for the extraction of coherent structures and analysis of turbulence in liquid phase for both cases. POD has successfully revealed large energy containing structures. The time dependent POD spatial mode coefficients oscillate with high frequency for high mode numbers. The energy distribution of spatial modes was also achieved. LSE has pointed out the coherent structured for both cases and the reconstructed velocity fields are in well agreement with the instantaneous velocity fields.

  2. Improved Boat For Liquid-Phase Epitaxy

    NASA Technical Reports Server (NTRS)

    Connolly, John C.

    1991-01-01

    Liquid-phase epitaxial (LPE) growth boat redesigned. Still fabricated from ultra-high-purity graphite, but modified to permit easy disassembly and cleaning, along with improved wiping action for more complete removal of melt to reduce carry-over of gallium. Larger substrates and more uniform composition obtained.

  3. Binary Solid-Liquid Phase Equilibria

    ERIC Educational Resources Information Center

    Ellison, Herbert R.

    1978-01-01

    Indicates some of the information that may be obtained from a binary solid-liquid phase equilibria experiment and a method to write a computer program that will plot an ideal phase diagram to which the experimental results may be compared. (Author/CP)

  4. A Liquid-Phase Diffusion Experiment.

    ERIC Educational Resources Information Center

    Nemetz, Thomas M.; Ball, David W.

    1995-01-01

    Describes an experiment that measures the diffusion of ions in the liquid phase and shows that the relative distances of diffusion are related qualitatively to the inverse of the mass of the solvated ion. Involves soluble salts on opposite sides of a Petri dish diffusing through a layer of water and meeting to form an insoluble salt. (JRH)

  5. Vapor-liquid phase separator permeability results

    NASA Technical Reports Server (NTRS)

    Yuan, S. W. K.; Frederking, T. H. K.

    1981-01-01

    Continued studies are described in the area of vapor-liquid phase separator work with emphasis on permeabilities of porous sintered plugs (stainless steel, nominal pore size 2 micrometer). The temperature dependence of the permeability has been evaluated in classical fluid using He-4 gas at atmospheric pressure and in He-2 on the basis of a modified, thermosmotic permeability of the normal fluid.

  6. Liquid phase sintered compacts in space

    NASA Technical Reports Server (NTRS)

    Mookherji, T. K.; Mcanelly, W. B.

    1974-01-01

    A model that will explain the effect of gravity on liquid phase sintering was developed. Wetting characteristics and density segregation which are the two important phenomena in liquid phase sintering are considered in the model development. Experiments were conducted on some selected material combinations to study the gravity effects on liquid phase sintering, and to verify the validity of the model. It is concluded that: (1) The surface tension forces acting on solid particles in a one-g environment are not appreciably different from those anticipated in a 0.00001g/g sub 0 (or lower) environment. (2) The capillary forces are dependent on the contact angle, the quantity of the liquid phase, and the distance between solid particles. (3) The pores (i.e., bubbles) do not appear to be driven to the surface by gravity-produced buoyancy forces. (4) The length of time to produce the same degree of settling in a low-gravity environment will be increased significantly. (5) A low gravity environment would appear to offer a unique means of satisfactorily infiltrating a larger and/or complex shaped compact.

  7. Activity coefficients of chlorophenols in water at infinite dilution

    SciTech Connect

    Tabai, S.; Rogalski, M.; Solimando, R.; Malanowski, S.K.

    1997-11-01

    The total pressure of aqueous solutions of chlorophenols was determined by a ebulliometric total pressure method for the aqueous solutions of phenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, and 2,4-dichlorophenol in the temperature range from 40 to 90 C. The activity coefficients at infinite dilution and the Henry constants were derived.

  8. Gravitational Role in Liquid Phase Sintering

    NASA Technical Reports Server (NTRS)

    Upadhyaya, Anish; Iacocca, Ronald G.; German, Randall M.

    1998-01-01

    To comprehensively understand the gravitational effects on the evolution of both the microstructure and the macrostructure during liquid phase sintering, W-Ni-Fe alloys with W content varying from 35 to 98 wt.% were sintered in microgravity. Compositions that slump during ground-based sintering also distort when sintered under microgravity. In ground-based sintering, low solid content alloys distort with a typical elephant-foot profile, while in microgravity, the compacts tend to spheroidize. This study shows that microstructural segregation occurs in both ground-based as well as microgravity sintering. In ground-based experiments, because of the density difference between the solid and the liquid phase, the solid content increases from top to the bottom of the sample. In microgravity, the solid content increases from periphery to the center of the samples. This study also shows that the pores during microgravity sintering act as a stable phase and attain anomalous shapes.

  9. Vapor-liquid phase separator studies

    NASA Technical Reports Server (NTRS)

    Yuan, S. W. K.; Hepler, W. A.; Frederking, T. H. K.

    1985-01-01

    A study of porous plug use for vapor-liquid phase seperation in spaceborne cryogenic systems was conducted. The three main topics addressed were: (1) the usefulness of porous media in designs that call for variable areas and flow rates; (2) the possibility of prediction of main parameters of porous plugs for a given material; and (3) prediction of all parameters of the plug, including secondary parameters.

  10. Isotope effect in homolytic liquid-phase fragmentation of diethoxymethane

    SciTech Connect

    Imashev, U.B.; Kalashnikov, S.M.; Gordeeva, G.N.

    1984-02-01

    Examined are the kinetics of free radical liquid-phase transformation of diethoxymethane, dideuterodiethoxymethane, di(pentadeuteroethoxy)methane, dideuterodi(pentadeuteroethoxy)methane, and di(1,1-dideuteroethoxy)methane initiated by the thermal decomposition of t-butyl peroxide at 130/sup 0/C. Results show conclusively that the fundamental direction of the free radical attack on the acetal molecule is at the carbon-hydrogen bond in the vicinity of the 2 oxygen atoms. The introduction of deuterium into the other fragment of the molecule does not have any significant effect on its subsequent activity. 5 references, 1 table.

  11. The gravitational effects on liquid phase sintering

    NASA Technical Reports Server (NTRS)

    Kipphut, C. M.; German, Randall M.; Bose, A.; Kishi, T.

    1989-01-01

    The liquid-phase sintering of heavy-metal PM alloys containing 78, 83, 88, 93, or 98 wt pct W plus Ni and Fe in a 7:3 ratio is investigated experimentally. The focus is on the potential role of gravity in phenomena such as specimen slumping and distortion, liquid migration, and microstructural coarsening. The results are presented in extensive graphs and micrographs and discussed in detail, and a preliminary grain-growth model is developed which accounts for the effects of contiguity and the volume fraction of solid.

  12. Novel mode of liquid-phase microextraction: A magnetic stirrer as the extractant phase holder.

    PubMed

    Luo, Zhi-Yuan; Liu, Hai-Yan; Shi, Zhi-Guo

    2016-01-01

    In the present study, a novel configuration of liquid-phase microextraction was proposed, in which a magnetic stirrer with a groove was used as the extractant phase holder. It was termed as magnetic stirrer liquid-phase microextraction. In this way, the stability of the organic solvent was much improved under high stirring speed; the extraction efficiency was enhanced due to the enormously enlarged contact area between the organic solvent and aqueous phase. The extraction performance of the magnetic stirrer liquid-phase microextraction was studied using chlorobenzenes as the probe analytes. A wide linearity range (20 pg/mL to 200 ng/mL) with a satisfactory linearity coefficient (r(2) > 0.998) was obtained. Limits of detection ranged from 9.0 to 12.0 pg/mL. Good reproducibility was achieved with intra- and inter-day relative standard deviations <4.8%. The proposed magnetic stirrer liquid-phase microextraction was simple, environmentally friendly and efficient; compared to single-drop microextraction, it had obvious advantages in terms of reproducibility and extraction efficiency. It is a promising miniaturized liquid-phase technology for real applications. PMID:26541502

  13. Pore filling process in liquid phase sintering

    NASA Astrophysics Data System (ADS)

    Park, Hyo-Hoon; Cho, Seong-Jai; Yoon, Duk N.

    1984-06-01

    Models for liquid flow into isolated pores during liquid phase sintering are described qualitatively. The grains are assumed to maintain an equilibrium shape determined by a balance between their tendency to become spherical and a negative capillary pressure in the liquid due to menisci at the specimen surface and the pore. With an increase of grain size, the grain sphering force decreases while the radius of liquid menisci increases to maintain the force equilibrium. When grain growth reaches a critical point, the liquid menisci around a pore become spherical and the driving force for filling the pore rapidly increases as liquid flows into it. The critical grain size required for filling a pore increases linearly with pore size. Experimentally, filling of isolated pores has been investigated in Fe-Cu powder mixture after liquid phase sintering treatment and after dipping into a molten matrix alloy. The observed pore filling behaviors agree with the qualitative predictions based on the models. In Fe-Cu alloy, pore filling is terminated by gas bubbles formed in liquid pockets.

  14. Surfactant mediated liquid phase exfoliation of graphene

    NASA Astrophysics Data System (ADS)

    Narayan, Rekha; Kim, Sang Ouk

    2015-10-01

    Commercialization of graphene based applications inevitably requires cost effective mass production. From the early days of research on graphene, direct liquid phase exfoliation (LPE) of graphite has been considered as the most promising strategy to produce high-quality mono or few-layer graphene sheets in solvent dispersion forms. Substantial success has been achieved thus far in the LPE of graphene employing numerous solvent systems and suitable surfactants. This invited review article principally showcase the recent research progress as well as shortcomings of surfactant assisted LPE of graphene. In particular, a comprehensive assessment of the quality and yield of the graphene sheets produced by different categories of the surfactants are summarized. Future direction of LPE methods is also proposed for the eventual success of commercial applications.

  15. On liquid phases in cometary nuclei

    NASA Astrophysics Data System (ADS)

    Miles, Richard; Faillace, George A.

    2012-06-01

    In this paper we review the relevant literature and investigate conditions likely to lead to melting of H2O ice, methanol (CH3OH) ice, ethane (C2H6) ice and other volatile ices in cometary nuclei. On the basis of a heat balance model which takes account of volatiles loss, we predict the formation of occasional aqueous and hydrocarbon liquid phases in subsurface regions at heliocentric distances, rh of 1-3 AU, and 5-12 AU, respectively. Low triple-point temperatures and low vapour pressures of C2H6, C3H8, and some higher-order alkanes and alkenes, favour liquid phase formation in cometary bodies at high rh. Microporosity and the formation of a stabilization crust occluding the escape of volatiles facilitate liquid-phase formation. Characteristics of the near-surface which favour subsurface melting include; low effective surface emissivity (at low rh), high amorphous carbon content, average pore sizes of 10 ?m or less, presence of solutes (e.g. CH3OH), mixtures of C2-C6 hydrocarbons (for melting at high rh), diurnal thermal cycling, and slow rotation rate. Applying the principles of soil mechanics, capillary forces are shown to initiate pre-melting phenomena and subsequent melting, which is expected to impart considerable strength of 104 Pa in partially saturated layers, reducing porosity and permeability, enhancing thermal conductivity and heat transfer. Diurnal thermal cycling is expected to have a marked effect on the composition and distribution of H2O ice in the near-surface leading to frost heave-type phenomena even where little if any true melting occurs. Where melting does take place, capillary suction in the wetted zone has the potential to enhance heat transfer via capillary wetting in a low-gravity environment, and to modify surface topography creating relatively smooth flat-bottomed features, which have a tendency to be located within small depressions. An important aspect of the "wetted layer" model is the prediction that diurnal melt-freeze cycles alter the mixing ratio vs. depth of solutes present, or of other miscible components, largely through a process of fractional crystallization, but also potentially involving frost heave. Wetted layers are potentially durable and can involve significant mass transport of volatile materials in the near-surface, increasing in extent over many rotations of the nucleus prior to and just after perihelion passage, and causing stratification and trapping of the lowest-melting mixtures at depths of several metres. A possible mechanism for cometary outbursts is proposed involving a heat pulse reaching the liquid phase in the deepest wetted zone, leading to supersaturation and triggering the sudden release under pressure of dissolved gases, in particular CO2, CO, CH4 or N2, contained beneath a consolidated near-surface layer. This study indicates that liquid water can persist for long periods of time in the near-surface of some intermediate-sized bodies (102-103 km radius) within protoplanetary discs.

  16. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH(TM)) Process

    SciTech Connect

    1997-06-30

    The Liquid Phase Methanol (LPMEOHTM) Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership). Air Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. The LPMEOIYM Process Demonstration Unit was built at a site located at the Eastman complex in Kingsport. During this quarter, comments from the DOE on the Topical Report "Economic Analysis - LPMEOHTM Process as an Add-on to IGCC for Coproduction" were received. A recommendation to continue with design verification testing for the coproduction of dimethyl ether (DIME) and methanol was made. DME design verification testing studies show the liquid phase DME (LPDME) process will have a significant economic advantage for the coproduction of DME for local markets. An LPDME catalyst system with reasonable long-term activity and stability is being developed. A recommendation document summarizing catalyst targets, experimental results, and the corresponding economics for a commercially successful LPDME catalyst was issued on 30 June 1997. The off-site, product-use test plan was updated in June of 1997. During this quarter, Acurex Environmental Corporation and Air Products screened proposals for this task by the likelihood of the projects to proceed and the timing for the initial methanol requirement. Eight sites from the list have met these criteria. The formal submission of the eight projects for review and concurrence by the DOE will be made during the next reporting period. The site paving and final painting were completed in May of 1997. Start-up activities were completed during the reporting period, and the initial methanol production from the demonstration unit occurred on 02 April 1997. The first extended stable operation at the nameplate capacity of 80,000 gallons per day (260 tons per day) took place on 06 April 1997. Pressure drop and resistance coefficient across the gas sparger at the bottom of the reactor increased over this initial operating period. The demonstration unit was shut down from 08 May -17 June 1997 as part of a scheduled complex outage for the Kingsport site. During this outage, the gas sparger was removed, cleaned, and reinstalled. After completion of other maintenance activities, the demonstration unit was restarted, and maintained stable operation through the remainder of the reporting period. Again, the gas sparger showed an increase in pressure drop and resistance since the restart, although not as rapidly as during the April-May operation. Fresh oil was introduced online for the first time to a new flush connection on the gas inlet line to the reactov the flush lowered the pressure drop by 1 psi. However, the effects were temporary, and the sparger resistance coefficient continued to increase. Additional flushing with both fresh oil and entrained slurry recovered in the cyclone and secondary oil knock-out drum will be attempted in order to stabilize the sparger resistance coefficient.

  17. Replication Experiments in Microgravity Liquid Phase Sintering

    NASA Astrophysics Data System (ADS)

    German, Randall M.; Johnson, John L.

    2016-02-01

    Although considerable experience exists with sintering on Earth, the behavior under reduced gravity conditions is poorly understood. This study analyzes replica microgravity liquid phase sintering data for seven tungsten alloys (35 to 88 wt pct tungsten) sintered for three hold times (1, 180, or 600 minutes) at 1773 K (1500 °C) using 0.002 pct of standard gravity. Equivalent sintering is performed on Earth using the same heating cycles. Microgravity sintering results in a lower density and more shape distortion. For Earth-based sintering, minimized distortion is associated with low liquid contents to avoid solid settling and slumping. Distortion in microgravity sintering involves viscous spreading of the component at points of contact with the containment crucible. Distortion in microgravity is minimized by short hold times; long hold times allow progressive component reshaping toward a spherical shape. Microgravity sintering also exhibits pore coalescence into large, stable voids that cause component swelling. The microgravity sintering results show good replication in terms of mass change and sintered density. Distortion is scattered but statistically similar between the replica microgravity runs. However, subtle factors, not typically of concern on Earth, emerge to influence microgravity sintering, such that ground experiments do not provide a basis to predict microgravity behavior.

  18. Chemical reactions in liquid-phase microextraction.

    PubMed

    Xu, Li; Basheer, Chanbasha; Lee, Hian Kee

    2009-01-23

    In recent years, liquid-phase microextraction (LPME), a microscale implementation of liquid-liquid extraction, has become a very popular sample pretreatment technique because it combines extraction and enrichment, and is inexpensive, easy to operate and nearly solvent-free. Especially so in hollow fiber-protected LPME, sample cleanup is also effected. Essentially, owing to its high sample-to-extracting solvent volume ratio, LPME can achieve high analyte enrichment. Since its advent, the technique has been widely used, and applied to environmental, pharmaceutical, biological and forensic analyses. This review focuses on developments relating to chemical reactions associated with LPME applications, in contrast to conventional, straightforward extractions in which analytes remain as they are during the extraction process. Chemical reactions brought about during LPME serve to promote the extractability of the analytes (thus expanding the scope of applicability of the technique), facilitate their (analyte) compatibility with the analytical system and/or improve detection sensitivity. The reactions that are usually enabled during LPME include ion-pair extraction (carrier-mediated membrane transport), complexation, chemical (pre-extraction, in situ, and post-extraction) derivatization, phase-transfer catalysis and other "special affinity" reactions. Strategies on chemical reactions in LPME are overviewed in this report. PMID:18951550

  19. Liquid phase methanol LaPorte process development unit: Modification, operation, and support studies

    SciTech Connect

    Not Available

    1991-02-02

    This report consists of Detailed Data Acquisition Sheets for Runs E-6 and E-7 for Task 2.2 of the Modification, Operation, and Support Studies of the Liquid Phase Methanol Laporte Process Development Unit. (Task 2.2: Alternate Catalyst Run E-6 and Catalyst Activity Maintenance Run E-7).

  20. Phase equilibria effects on the enhanced liquid phase sintering of tungsten- copper

    NASA Astrophysics Data System (ADS)

    Johnson, J. L.; German, R. M.

    1993-11-01

    The sintering behavior and mechanical properties of W-Cu are improved by the addition of elements that have solubility for W, e.g., Co, Ni, Fe, and Pd. The degree of enhancement with small concentrations of additive is dependent on specific phase diagram features, and the ranking of effectiveness does not follow the trend observed for the activated solid-state sintering of W. These observations are explained through a combination of liquid phase sintering and activated sintering theories that considers the combined W, Cu, and activator phase equilibria effects. In small concentrations, Ni and Pd have little effect on densification because they go into solution with Cu, resulting in only a slight increase in the solubility of W in the liquid phase. In this case, the sintered density, strength, and hardness increase with increasing additive concentration due to enhanced densification through solution-reprecipitation. Cobalt and Fe are the most ef-fective activators due to their limited solubility in Cu and the formation of a stable intermetallic phase with W at the sintering temperature. This promotes the formation of a high-diffusivity interboundary layer which enhances solid-state sintering of the tungsten grains at temperatures at which a liquid phase is present. With Co and Fe additions, the sintered density, strength, and hardness peak with activator concentrations of 0.35 to 0.5 wt pct. An evaluation of models for activated solid-state sintering and liquid phase sintering indicates a substantial solid-state contribution to densification when a high-diffusivity interboundary layer is present and the sol-ubility of W in the liquid phase is small.

  1. Liquid-phase binding assay of human chorionic gonadotropin using high-performance liquid chromatography.

    PubMed

    Nakamura, K; Satomura, S; Matsuura, S

    1993-03-01

    A new enzyme immunoassay technique (LBA: liquid-phase binding assay) to examine the characteristics of liquid-phase antigen-antibody reactions is described. Antigen (human chorionic gonadotropin: hCG) and peroxidase (POD)-labeled anti-hCG monoclonal antibody (Fab'-POD) solutions were mixed, incubated, and analyzed directly by gel filtration high-performance liquid chromatography with postcolumn enzyme activity measurement. Using the system, bound (hCG-Fab'-POD) and free (Fab'-POD) forms of enzyme-labeled antibody were separated by their molecular mass difference, and the POD activity of the conjugate was determined fluorophotometrically. All analytes became bound upon addition of excess Fab'-POD, because reaction conditions in a liquid phase could be easily altered. Thus, hCG molecule could be measured via the activity of one POD molecule. And the liquid-phase antibody reaction was very fast and quantitative. On the basis of this stoichiometric relationship, equilibrium and rate constants, optimum pH, and temperature effects were easily examined. The method is simple and convenient for examination of the antigen-antibody reaction and is applicable for antigen assays requiring an accurate definition of concentrations. PMID:8452248

  2. Solubilities and liquid phase nonidealities in coal liquids: Final report, July 30, 1984-July 30, 1987

    SciTech Connect

    McLaughlin, E.; Coon, J.E.

    1988-01-01

    The research effort was a three year study of the solubilities of polynuclear aromatic hydrocarbons (PAH's) in organic solvents and the vapor-liquid equilibria of some of these same systems. Solubilities of 102 systems were determined as functions of temperature from ambient temperature to the melting point of the solute. The systems are listed and results are presented. Solubility data were analyzed using four solution models (Regular Solution theory, Extended Regular Solution theory, Wilson's Equation, and UNIQUAC) and binary interaction parameters have been obtained for the liquid phase. Also included are analyses of 35 more systems that have been previously published, for the purpose of composition of the predicted activity coefficients. Vapor pressures were determined for five solvents versus temperature. Also determined were the vapor-liquid equilibria for a test system and for six new systems at three temperatures each. New systems are (tetralin-decalin, tetralin-biphenyl, decalin- biphenyl, tetralin-fluorene, tetralin-fluorene, tetralin- dibenzothiophene, and tetralin-dibenzofuran. Results have been analyzed using four common solution models (Wilson's, UNIQUAC, NRTL, and Van Laar) and the optimum binary parameters determined. We have compared the parameters (for Wilson's and UNIQUAC) for the two methods and discussed the pros and cons of each method as a source for these parameters. Some initial steps have been made towards utilizing statistical mechanical methods for these types of systems. 46 refs., 26 figs., 57 tabs.

  3. A model for the thermal properties of liquid-phase sintered composites

    SciTech Connect

    German, R.M. )

    1993-08-01

    Thermal properties are important to several applications for powder metallurgy products. For example, liquid-phase sintered tungsten-copper composites are used in microelectronic packaging to obtain a high thermal conductivity in a low thermal expansion material. This article addresses modeling the thermal properties for composites fabricated by liquid-phase sintering. A computational cell is constructed with interlinked phases, consisting of a core of low thermal expansion material (tungsten) and a edge network of high thermal conductivity phase (copper). This structure is used to calculate the composition effects on the coefficients of thermal expansion and thermal conductivity. The results are applied to prior reports on W-Cu and used as a basis to identify several candidate high thermal conductivity systems for future development.

  4. Mixed Stationary Liquid Phases for Gas-Liquid Chromatography.

    ERIC Educational Resources Information Center

    Koury, Albert M.; Parcher, Jon F.

    1979-01-01

    Describes a laboratory technique for use in an undergraduate instrumental analysis course that, using the interpretation of window diagrams, prepares a mixed liquid phase column for gas-liquid chromatography. A detailed procedure is provided. (BT)

  5. Measurement of gas/water uptake coefficients for trace gases active in the marine environment

    SciTech Connect

    Davidovits, P. . Dept. of Chemistry); Worsnop, D.W.; Zahniser, M.S.; Kolb, C.E. . Center for Chemical and Environmental Physics)

    1992-02-01

    Ocean produced reduced sulfur compounds including dimethylsulfide (DMS), hydrogen sulfide (H{sub 2}S), carbon disulfide (CS{sub 2}), methyl mercaptan (CH{sub 3}CH) and carbonyl sulfide (OCS) deliver a sulfur burden to the atmosphere which is roughly equal to sulfur oxides produced by fossil fuel combustion. These species and their oxidation products dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO{sub 2}) and methane sulfonic acid (MSA) dominate aerosol and CCN production in clean marine air. Furthermore, oxidation of reduced sulfur species will be strongly influenced by NO{sub x}/O{sub 3} chemistry in marine atmospheres. The multiphase chemical processes for these species must be understood in order to study the evolving role of combustion produced sulfur oxides over the oceans. We have measured the chemical and physical parameters affecting the uptake of reduced sulfur compounds, their oxidation products, ozone, and nitrogen oxides by the ocean's surface, and marine clouds, fogs, and aerosols. These parameters include: gas/surface mass accommodation coefficients; physical and chemically modified (effective) Henry's law constants; and surface and liquid phase reaction constants. These parameters are critical to understanding both the interaction of gaseous trace species with cloud and fog droplets and the deposition of trace gaseous species to dew covered, fresh water and marine surfaces.

  6. Graphene via sonication assisted liquid-phase exfoliation.

    PubMed

    Ciesielski, Artur; Samor, Paolo

    2014-01-01

    Graphene, the 2D form of carbon based material existing as a single layer of atoms arranged in a honeycomb lattice, has set the science and technology sectors alight with interest in the last decade in view of its astounding electrical and thermal properties, combined with its mechanical stiffness, strength and elasticity. Two distinct strategies have been undertaken for graphene production, i.e. the bottom-up and the top-down. The former relies on the generation of graphene from suitably designed molecular building blocks undergoing chemical reaction to form covalently linked 2D networks. The latter occurs via exfoliation of graphite into graphene. Bottom-up techniques, based on the organic syntheses starting from small molecular modules, when performed in liquid media, are both size limited, because macromolecules become more and more insoluble with increasing size, and suffer from the occurrence of side reactions with increasing molecular weight. Because of these reasons such a synthesis has been performed more and more on a solid (ideally catalytically active) surface. Substrate-based growth of single layers can be done also by chemical vapor deposition (CVD) or via reduction of silicon carbide, which unfortunately relies on the ability to follow a narrow thermodynamic path. Top-down approaches can be accomplished under different environmental conditions. Alongside the mechanical cleavage based on the scotch tape approach, liquid-phase exfoliation (LPE) methods are becoming more and more interesting because they are extremely versatile, potentially up-scalable, and can be used to deposit graphene in a variety of environments and on different substrates not available using mechanical cleavage or growth methods. Interestingly, LPE can be applied to produce different layered systems exhibiting different compositions such as BN, MoS2, WS2, NbSe2, and TaS2, thereby enabling the tuning of numerous physico-chemical properties of the material. Furthermore, LPE can be employed to produce graphene-based composites or films, which are key components for many applications, such as thin-film transistors, conductive transparent electrodes for indium tin oxide replacement, e.g. in light-emitting diodes, or photovoltaics. In this review, we highlight the recent progress that has led to successful production of high quality graphene by means of LPE of graphite. In particular, we discuss the mechanisms of exfoliation and methods that are employed for graphene characterization. We then describe a variety of successful liquid-phase exfoliation methods by categorizing them into two major classes, i.e. surfactant-free and surfactant-assisted LPE. Furthermore, exfoliation in aqueous and organic solutions is presented and discussed separately. PMID:24002478

  7. Liquid-Phase Processing of Barium Titanate Thin Films

    NASA Astrophysics Data System (ADS)

    Harris, David Thomas

    Processing of thin films introduces strict limits on the thermal budget due to substrate stability and thermal expansion mismatch stresses. Barium titanate serves as a model system for the difficulty in producing high quality thin films because of sensitivity to stress, scale, and crystal quality. Thermal budget restriction leads to reduced crystal quality, density, and grain growth, depressing ferroelectric and nonlinear dielectric properties. Processing of barium titanate is typically performed at temperatures hundreds of degrees above compatibility with metalized substrates. In particular integration with silicon and other low thermal expansion substrates is desirable for reductions in costs and wider availability of technologies. In bulk metal and ceramic systems, sintering behavior has been encouraged by the addition of a liquid forming second phase, improving kinetics and promoting densification and grain growth at lower temperatures. This approach is also widespread in the multilayer ceramic capacitor industry. However only limited exploration of flux processing with refractory thin films has been performed despite offering improved dielectric properties for barium titanate films at lower temperatures. This dissertation explores physical vapor deposition of barium titanate thin films with addition of liquid forming fluxes. Flux systems studied include BaO-B2O3, Bi2O3-BaB2O 4, BaO-V2O5, CuO-BaO-B2O3, and BaO-B2O3 modified by Al, Si, V, and Li. Additions of BaO-B2O3 leads to densification and an increase in average grain size from 50 nm to over 300 nm after annealing at 900 °C. The ability to tune permittivity of the material improved from 20% to 70%. Development of high quality films enables engineering of ferroelectric phase stability using residual thermal expansion mismatch in polycrystalline films. The observed shifts to TC match thermodynamic calculations, expected strain from the thermal expansion coefficients, as well as x-ray diffract measurements . Our system exhibits flux-film-substrate interactions that can lead to dramatic changes to the microstructure. This effect is especially pronounced onc -sapphire, with Al diffusion from the substrate leading to formation of an epitaxial BaAl2O4 second phase at the substrate-film interface. The formation of this second phase in the presence of a liquid phase seeds {111} twins that drive abnormal grain growth. The orientation of the sapphire substrate determines the BaAl2O 4 morphology, enabling control the abnormal grain growth behavior. CuO additions leads to significant grain growth at 900 °C, with average grain size approaching 500 nm. The orthorhombic-tetragonal phase transition is clearly observable in temperature dependent measurements and both linear and nonlinear dielectric properties are improved. All films containing CuO are susceptible to aging. A number of other systems were investigated for efficacy at temperatures below 900 °C. Pulsed laser deposition was used to study flux + BaTiO 3 targets, layered flux films, and in situ liquids. RF-magnetron sputtering using a dual-gun approach was used to explore integration on flexible foils with Ba1-xSrxTiO3. Many of these systems were based on the BaO-B2O3 system, which has proven effective in thin films, multilayer ceramic capacitors, and bulk ceramics. Modifiers allow tailoring of the microstructure at 900 °C, however no compositions were found, and no reports exist in the open literature, that provide significant grain growth or densification below 900 °C. Liquid phase fluxes offer a promising path forward for low temperature processing of barium titanate, with the ultimate goal of integration with metalized silicon substrates. This work demonstrates significant improvements to dielectric properties and the necessity of understanding interactions in the film-flux-substrate system.

  8. Optical on-line method of ethyl mercaptan detection in liquid phase in motor fuels

    NASA Astrophysics Data System (ADS)

    Kireev, S. V.; Shnyrev, S. L.

    2015-11-01

    The letter reports on the experimental research of the absorption spectra of ethyl mercaptan in liquid phase in various motor fuels (petrol, kerosene, and diesel fuel). The values of ethyl mercaptan absorption sections were obtained in the above-mentioned fuels in the spectral range of 280–475 nm, and the dependences of ethyl mercaptan absorption coefficients on its part in the analyzed mixture with motor fuels were researched. On the basis of the obtained results we propose an optical on-line method of ethyl mercaptan detection in motor fuels. The optimal spectral ranges for the highest sensitivity of ethyl mercaptan detection in various motor fuels were determined.

  9. Thermodynamic modeling of activity coefficient and prediction of solubility: Part 1. Predictive models.

    PubMed

    Mirmehrabi, Mahmoud; Rohani, Sohrab; Perry, Luisa

    2006-04-01

    A new activity coefficient model was developed from excess Gibbs free energy in the form G(ex) = cA(a) x(1)(b)...x(n)(b). The constants of the proposed model were considered to be function of solute and solvent dielectric constants, Hildebrand solubility parameters and specific volumes of solute and solvent molecules. The proposed model obeys the Gibbs-Duhem condition for activity coefficient models. To generalize the model and make it as a purely predictive model without any adjustable parameters, its constants were found using the experimental activity coefficient and physical properties of 20 vapor-liquid systems. The predictive capability of the proposed model was tested by calculating the activity coefficients of 41 binary vapor-liquid equilibrium systems and showed good agreement with the experimental data in comparison with two other predictive models, the UNIFAC and Hildebrand models. The only data used for the prediction of activity coefficients, were dielectric constants, Hildebrand solubility parameters, and specific volumes of the solute and solvent molecules. Furthermore, the proposed model was used to predict the activity coefficient of an organic compound, stearic acid, whose physical properties were available in methanol and 2-butanone. The predicted activity coefficient along with the thermal properties of the stearic acid were used to calculate the solubility of stearic acid in these two solvents and resulted in a better agreement with the experimental data compared to the UNIFAC and Hildebrand predictive models. PMID:16493594

  10. Green aspects, developments and perspectives of liquid phase microextraction techniques.

    PubMed

    Spietelun, Agata; Marcinkowski, Łukasz; de la Guardia, Miguel; Namieśnik, Jacek

    2014-02-01

    Determination of analytes at trace levels in complex samples (e.g. biological or contaminated water or soils) are often required for the environmental assessment and monitoring as well as for scientific research in the field of environmental pollution. A limited number of analytical techniques are sensitive enough for the direct determination of trace components in samples and, because of that, a preliminary step of the analyte isolation/enrichment prior to analysis is required in many cases. In this work the newest trends and innovations in liquid phase microextraction, like: single-drop microextraction (SDME), hollow fiber liquid-phase microextraction (HF-LPME), and dispersive liquid-liquid microextraction (DLLME) have been discussed, including their critical evaluation and possible application in analytical practice. The described modifications of extraction techniques deal with system miniaturization and/or automation, the use of ultrasound and physical agitation, and electrochemical methods. Particular attention was given to pro-ecological aspects therefore the possible use of novel, non-toxic extracting agents, inter alia, ionic liquids, coacervates, surfactant solutions and reverse micelles in the liquid phase microextraction techniques has been evaluated in depth. Also, new methodological solutions and the related instruments and devices for the efficient liquid phase micoextraction of analytes, which have found application at the stage of procedure prior to chromatographic determination, are presented. PMID:24401382

  11. In situ monitoring of liquid phase electroepitaxial growth

    NASA Technical Reports Server (NTRS)

    Okamoto, A.; Isozumi, S.; Lagowski, J.; Gatos, H. C.

    1982-01-01

    In situ monitoring of the layer thickness during liquid phase electroepitaxy (LPEE) was achieved with a submicron resolution through precise resistance measurements. The new approach to the study and control of LPEE was applied to growth of undoped and Ge-doped GaAs layers. The in situ determined growth kinetics was found to be in excellent agreement with theory.

  12. The possibility of determining the activity coefficients of individual ions from acid-base titration data

    NASA Astrophysics Data System (ADS)

    Jano, I.; Hardcastle, J. E.

    1998-07-01

    A method is described for obtaining the activity coefficients of individual ions from experimental titration data. For this purpose, a general polyprotic acid-base-titration-curve equation is derived. The equation allows obtaining the dissociation equilibrium constants of the acid and the ratio of the activity coefficient of each ion to the activity coefficient of the undissociated acid directly from the titration data. Results obtained are compared with coefficients calculated using Debye-Hckel equation. A general equation relating the ionic strength to the pH of the titration medium is also established. Une mthode pour l'obtention des coefficients d'activit des ions individuels partir des donnes exprimentales de titrage est tablie. ce but, une quation gnrale est drive pour reprsenter la courbe de titrage d'un acide avec une base. Cette quation permet d'obtenir les constants d'quilibre de dissociation de l'acide et le rapport de coefficient d'activit de chaque ion au coefficient d'activit de l'acide non-dissoci partir des donnes de titrage. Les rsultats ainsi obtenus sont compars avec les coefficients calculs l'aide de l'quation de Debye-Hckel. Une quation liant la force ionique au pH du milieu est tablie aussi.

  13. Liquid-liquid phase separation of freely falling undercooled ternary Fe-Cu-Sn alloy

    NASA Astrophysics Data System (ADS)

    Wang, W. L.; Wu, Y. H.; Li, L. H.; Zhai, W.; Zhang, X. M.; Wei, B.

    2015-11-01

    The active modulation and control of the liquid phase separation for high-temperature metallic systems are still challenging the development of advanced immiscible alloys. Here we present an attempt to manipulate the dynamic process of liquid-liquid phase separation for ternary Fe47.5Cu47.5Sn5 alloy. It was firstly dispersed into numerous droplets with 66?~?810??m diameters and then highly undercooled and rapidly solidified under the containerless microgravity condition inside drop tube. 3-D phase field simulation was performed to explore the kinetic evolution of liquid phase separation. Through regulating the combined effects of undercooling level, phase separation time and Marangoni migration, three types of separation patterns were yielded: monotectic cell, core shell and dispersive structures. The two-layer core-shell morphology proved to be the most stable separation configuration owing to its lowest chemical potential. Whereas the monotectic cell and dispersive microstructures were both thermodynamically metastable transition states because of their highly active energy. The Sn solute partition profiles of Fe-rich core and Cu-rich shell in core-shell structures varied only slightly with cooling rate.

  14. Liquid-liquid phase separation of freely falling undercooled ternary Fe-Cu-Sn alloy

    PubMed Central

    Wang, W .L.; Wu, Y. H.; Li, L. H.; Zhai, W.; Zhang, X. M.; Wei, B.

    2015-01-01

    The active modulation and control of the liquid phase separation for high-temperature metallic systems are still challenging the development of advanced immiscible alloys. Here we present an attempt to manipulate the dynamic process of liquid-liquid phase separation for ternary Fe47.5Cu47.5Sn5 alloy. It was firstly dispersed into numerous droplets with 66 ~ 810 μm diameters and then highly undercooled and rapidly solidified under the containerless microgravity condition inside drop tube. 3-D phase field simulation was performed to explore the kinetic evolution of liquid phase separation. Through regulating the combined effects of undercooling level, phase separation time and Marangoni migration, three types of separation patterns were yielded: monotectic cell, core shell and dispersive structures. The two-layer core-shell morphology proved to be the most stable separation configuration owing to its lowest chemical potential. Whereas the monotectic cell and dispersive microstructures were both thermodynamically metastable transition states because of their highly active energy. The Sn solute partition profiles of Fe-rich core and Cu-rich shell in core-shell structures varied only slightly with cooling rate. PMID:26552711

  15. Liquid-liquid phase separation of freely falling undercooled ternary Fe-Cu-Sn alloy.

    PubMed

    Wang, W L; Wu, Y H; Li, L H; Zhai, W; Zhang, X M; Wei, B

    2015-01-01

    The active modulation and control of the liquid phase separation for high-temperature metallic systems are still challenging the development of advanced immiscible alloys. Here we present an attempt to manipulate the dynamic process of liquid-liquid phase separation for ternary Fe47.5Cu47.5Sn5 alloy. It was firstly dispersed into numerous droplets with 66?~?810??m diameters and then highly undercooled and rapidly solidified under the containerless microgravity condition inside drop tube. 3-D phase field simulation was performed to explore the kinetic evolution of liquid phase separation. Through regulating the combined effects of undercooling level, phase separation time and Marangoni migration, three types of separation patterns were yielded: monotectic cell, core shell and dispersive structures. The two-layer core-shell morphology proved to be the most stable separation configuration owing to its lowest chemical potential. Whereas the monotectic cell and dispersive microstructures were both thermodynamically metastable transition states because of their highly active energy. The Sn solute partition profiles of Fe-rich core and Cu-rich shell in core-shell structures varied only slightly with cooling rate. PMID:26552711

  16. Aqueous solubilities and infinite dilution activity coefficients of several polycyclic aromatic hydrocarbons

    SciTech Connect

    Haines, R.I.S.; Sandler, S.I.

    1995-07-01

    Determining the aqueous solubilities and infinite dilution activity coefficients of polycyclic aromatic hydrocarbons (PAHs) is important for environmental reasons. However, common methods for the measurement of infinite dilution activity coefficients, such as ebulliometry or gas chromatography, cannot be used for solutes that are only very slightly soluble in water and have very low vapor pressures, such as the PAHs. Here the authors report values of the aqueous infinite dilution activity coefficients of four polycyclic aromatic hydrocarbons obtained by measuring their very low aqueous solubilities and their enthalpies of fusion. The values of the infinite dilution activity coefficients they obtain range from 4.2 {times} 10{sup 5} for acenaphthene to 3.7 {times} 10{sup 8} for benzo[a]pyrene, with an average error of {+-}12.5%. The other two PAH used were anthracene and benz[a]anthracene.

  17. Liquid-phase compositions from vapor-phase analyses

    SciTech Connect

    Davis, W. Jr. ); Cochran, H.D. )

    1990-02-01

    Arsenic normally is not considered to be a contaminant. However, because arsenic was found in many cylinders of UF{sub 6}, including in corrosion products, a study was performed of the distribution of the two arsenic fluorides, AsF{sub 3} and AsF{sub 5}, between liquid and vapor phases. The results of the study pertain to condensation or vaporization of liquid UF{sub 6}. This study includes use of various experimental data plus many extrapolations necessitated by the meagerness of the experimental data. The results of this study provide additional support for the vapor-liquid equilibrium model of J.M. Prausnitz and his coworkers as a means of describing the distribution of various impurities between vapor and liquid phases of UF{sub 6}. Thus, it is concluded that AsF{sub 3} will tend to concentrate in the liquid phase but that the concentration of AsF{sub 5} in the vapor phase will exceed its liquid-phase concentration by a factor of about 7.5, which is in agreement with experimental data. Because the weight of the liquid phase in a condensation operation may be in the range of thousands of times that of the vapor phase, most of any AsF{sub 5} will be in the liquid phase in spite of this separation factor of 7.5. It may also be concluded that any arsenic fluorides fed into a uranium isotope separation plant will either travel with other low-molecular-weight gases or react with materials present in the plant. 25 refs., 3 figs., 6 tabs.

  18. New topic of supercritical fluids: Local activity coefficients of supercritical solvent and cosolvent around solute

    NASA Astrophysics Data System (ADS)

    Hou, Minqiang; Zhang, Xiaogang; Han, Buxing; Song, Jiyuan; Liu, Gang; Zhang, Zhaofu; Zhang, Jianling

    2008-03-01

    The study of inhomogeneity in supercritical fluids (SCFs) is of great importance. In this work, we propose the concept of local activity coefficients in supercritical (SC) solutions, which link thermodynamics and inhomogeneity in SC systems. The local activity coefficients of CO2+acetonitrile+phenol blue and CO2+aceticacid+phenol blue systems are investigated at 308.15K in critical region and outside critical region. To do this, the local compositions of CO2+acetonitrile and CO2+acetic acid mixed solvents around phenol blue are first estimated using UV-visible spectroscopy. Then it is considered that there exist bulk phase and local phase around phenol blue in the systems. The activity coefficients of CO2 and the cosolvents (acetonitrile or acetic acid) in bulk phase are calculated using Peng-Robinson equation of state. The local activity coefficients of CO2 and the cosolvents are then calculated on the basis of thermodynamic principles. It is demonstrated that in the critical region the local activity coefficients differ from bulk activity coefficients significantly and are sensitive to pressure. This can explain many unusual phenomena in SC systems in critical region thermodynamically.

  19. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH(TM)) Process

    SciTech Connect

    1996-12-31

    The Liquid Phase Methanol (LPMEOH(TM)) Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership). The LPMEOIWM Process Demonstration Unit is being built at a site located at the Eastman Chemical Company (Eastman) complex in Kingsport. During this quarter, the Cooperative Agreement was modified (Mod AO11) on 8 October 1996, authorizing the transition born Budget Period No. 2 (Design and Construction) to the . final Budget Period (Commissioning, Start-up, and Operation), A draft Topical Report on Process Economics Studies concludes that methanol coproduction with integrated gasification combined cycle (IGCC) electric power utilizing the LPMEOW process technology, will be competitive in serving local market needs. Planning for a proof-of- concept test run of the liquid phase dimethyl ether (DME) process at the LaPorte Alternative Fuels Development Unit (AFDU) was recommended; and a deeision to proceed is pending. Construction (Task 2.2) is 97'Mo complete, asof31 December 1996. Completion of pipe pressure testing has taken longer than expected. This will delay completion of construction by about three weeks. Commissioning activities (Task 2.3) commenced in mid-October of 1996, and the demonstration unit is scheduled to be mechanically complete on 24 January 1997.

  20. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH(TM)) Process

    SciTech Connect

    1997-09-30

    The Liquid Phase Methanol (LPMEOH) Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership). Ak Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. The LPMEOITM Process Demonstration Unit was built at a site located at the Eastman complex in Kingsport. During this reporting period, DOE accepted the recommendation to continue with dimethyl ether (DME) design verification testing (DVT). DME design verification testing studies show the liquid phase DME (LPDME) process will have a significant economic advantage for the coproduction of DME for local markets. An LPDME catalyst system with reasonable long-term activity and stzibility is being developed. Planning for a proof-of-concept test run at the LaPorte Alternative Fuels Development Unit (AFDU) was recommended. DOE issued a letter dated 31 July 1997 accepting the recommendation to continue design verification testing. In order to allow for scale-up of the manufacturing technique for the dehydration catalyst from the pilot plant to the commercial scale, the time required to produce the catalyst to the AFDU has slipped. The new estimated delivery date is 01 June 1998.

  1. Liquid-phase sintering of iron aluminide-bonded ceramics

    SciTech Connect

    Schneibel, J.H.; Carmichael, C.A.

    1995-12-31

    Iron aluminide intermetallics exhibit excellent oxidation and sulfidation resistance and are therefore considered as the matrix in metal matrix composites, or the binder in hard metals or cermets. In this paper the authors discuss the processing and properties of liquid-phase sintered iron aluminide-bonded ceramics. It is found that ceramics such as TiB{sub 2}, ZrB{sub 2}, TiC, and WC may all be liquid phase-sintered. nearly complete densification is achieved for ceramic volume fractions ranging up to 60%. Depending on the composition, room temperature three point-bend strengths and fracture toughnesses reaching 1,500 MPa and 30 MPa m{sup 1/2}, respectively, have been found. Since the processing was carried out in a very simple manner, optimized processing is likely to result in further improvements.

  2. Liquid phase oxidation chemistry in continuous-flow microreactors.

    PubMed

    Gemoets, Hannes P L; Su, Yuanhai; Shang, Minjing; Hessel, Volker; Luque, Rafael; Noël, Timothy

    2015-12-22

    Continuous-flow liquid phase oxidation chemistry in microreactors receives a lot of attention as the reactor provides enhanced heat and mass transfer characteristics, safe use of hazardous oxidants, high interfacial areas, and scale-up potential. In this review, an up-to-date overview of both technological and chemical aspects of liquid phase oxidation chemistry in continuous-flow microreactors is given. A description of mass and heat transfer phenomena is provided and fundamental principles are deduced which can be used to make a judicious choice for a suitable reactor. In addition, the safety aspects of continuous-flow technology are discussed. Next, oxidation chemistry in flow is discussed, including the use of oxygen, hydrogen peroxide, ozone and other oxidants in flow. Finally, the scale-up potential for continuous-flow reactors is described. PMID:26203551

  3. Powder metallurgy: Solid and liquid phase sintering of copper

    NASA Technical Reports Server (NTRS)

    Sheldon, Rex; Weiser, Martin W.

    1993-01-01

    Basic powder metallurgy (P/M) principles and techniques are presented in this laboratory experiment. A copper based system is used since it is relatively easy to work with and is commercially important. In addition to standard solid state sintering, small quantities of low melting metals such as tin, zinc, lead, and aluminum can be added to demonstrate liquid phase sintering and alloy formation. The Taguchi Method of experimental design was used to study the effect of particle size, pressing force, sintering temperature, and sintering time. These parameters can be easily changed to incorporate liquid phase sintering effects and some guidelines for such substitutions are presented. The experiment is typically carried out over a period of three weeks.

  4. Activity Coefficient Derivatives of Ternary Systems Based on Scatchard's Neutral Electrolyte description

    SciTech Connect

    Miller, D G

    2007-05-16

    Activity coefficient derivatives with respect to molality are presented for the Scatchard Neutral Electrolyte description of a ternary common-ion electrolyte system. These quantities are needed for the calculation of 'diffusion Onsager coefficients' and in turn for tests of the Onsager Reciprocal Relations in diffusion. The usually-omitted b{sub 23} term is included. The direct SNE binary approximations and a further approximation are discussed. Binary evaluation strategies other than constant ionic strength are considered.

  5. Containerless Liquid-Phase Processing of Ceramic Materials

    NASA Technical Reports Server (NTRS)

    Weber, J. K. Richard (Principal Investigator); Nordine, Paul C.

    1996-01-01

    The present project builds on the results of research supported under a previous NASA grant to investigate containerless liquid-phase processing of molten ceramic materials. The research used an aero-acoustic levitator in combination with cw CO2 laser beam heating to achieve containerless melting, superheating, undercooling, and solidification of poorly-conducting solids and liquids. Experiments were performed on aluminum oxide, binary aluminum oxide-silicon dioxide materials, and oxide superconductors.

  6. SolidLiquid Phase Change Driven by Internal Heat Generation

    SciTech Connect

    John Crepeau; Ali s. Siahpush

    2012-07-01

    This article presents results of solid-liquid phase change, the Stefan Problem, where melting is driven internal heat generation, in a cylindrical geometry. The comparison between a quasi-static analytical solution for Stefan numbers less than one and numerical solutions shows good agreement. The computational results of phase change with internal heat generation show how convection cells form in the liquid region. A scale analysis of the same problem shows four distinct regions of the melting process.

  7. On Asymmetric Diffusional Solidification During Transient Liquid Phase Bonding

    NASA Astrophysics Data System (ADS)

    Ghobadi Bigvand, A.; Ojo, Olanrewaju A.

    2014-04-01

    The underlying cause of asymmetric diffusion solidification which alters microstructure during transient liquid phase bonding under low temperature gradient was studied. A new solute-conserving asymmetric numerical model coupled with experimental verification showed that a transition from bi-directional to unidirectional solidification, under a constant temperature gradient, is controlled by competition between liquid and solid-state diffusion at one of the two liquid-solid interfaces. This mechanistic understanding would aid a more effective use of the process.

  8. Mean ionic activity coefficients in aqueous NaCl solutions from molecular dynamics simulations

    SciTech Connect

    Mester, Zoltan; Panagiotopoulos, Athanassios Z.

    2015-01-28

    The mean ionic activity coefficients of aqueous NaCl solutions of varying concentrations at 298.15 K and 1 bar have been obtained from molecular dynamics simulations by gradually turning on the interactions of an ion pair inserted into the solution. Several common non-polarizable water and ion models have been used in the simulations. Gibbs-Duhem equation calculations of the thermodynamic activity of water are used to confirm the thermodynamic consistency of the mean ionic activity coefficients. While the majority of model combinations predict the correct trends in mean ionic activity coefficients, they overestimate their values at high salt concentrations. The solubility predictions also suffer from inaccuracies, with all models underpredicting the experimental values, some by large factors. These results point to the need for further ion and water model development.

  9. Oxidation Protection of Uranium Nitride Fuel using Liquid Phase Sintering

    SciTech Connect

    Dr. Paul A. Lessing

    2012-03-01

    Two methods are proposed to increase the oxidation resistance of uranium nitride (UN) nuclear fuel. These paths are: (1) Addition of USi{sub x} (e.g. U3Si2) to UN nitride powder, followed by liquid phase sintering, and (2) 'alloying' UN nitride with various compounds (followed by densification via Spark Plasma Sintering or Liquid Phase Sintering) that will greatly increase oxidation resistance. The advantages (high thermal conductivity, very high melting point, and high density) of nitride fuel have long been recognized. The sodium cooled BR-10 reactor in Russia operated for 18 years on uranium nitride fuel (UN was used as the driver fuel for two core loads). However, the potential advantages (large power up-grade, increased cycle lengths, possible high burn-ups) as a Light Water Reactor (LWR) fuel are offset by uranium nitride's extremely low oxidation resistance (UN powders oxidize in air and UN pellets decompose in hot water). Innovative research is proposed to solve this problem and thereby provide an accident tolerant LWR fuel that would resist water leaks and high temperature steam oxidation/spalling during an accident. It is proposed that we investigate two methods to increase the oxidation resistance of UN: (1) Addition of USi{sub x} (e.g. U{sub 3}Si{sub 2}) to UN nitride powder, followed by liquid phase sintering, and (2) 'alloying' UN nitride with compounds (followed by densification via Spark Plasma Sintering) that will greatly increase oxidation resistance.

  10. Cobalt pivalate complex as a catalyst for liquid phase oxidation of n-hexane

    NASA Astrophysics Data System (ADS)

    Moskovskaya, I. F.; Maerle, A. A.; Shvydkiy, N. V.; Romanovsky, B. V.; Ivanova, I. I.

    2015-09-01

    Catalytic properties of cobalt(II) pivalate complex as both individual and supported on mesoporous molecular sieves Si-KIT-6, Al-KIT-6, and Ce-KIT-6 were investigated in liquid-phase oxidation of n-hexane with molecular oxygen. This complex was shown to be an active and selective catalyst for the oxidation of n-C6H14 into C1-C4 carboxylic acids. The activity of Co(II) pivalate remains practically unchanged on heterogenizing the complex on molecular sieve supports. At the same time, its selectivity and resistance towards an oxidative degradation are slightly increased.

  11. Determination of activity coefficients in calculations of carbonate-calcium equilibrium

    SciTech Connect

    Bril', D.M.; Rashitova, R.A.

    1985-09-01

    Plots have been constructed to show the dependence of CO/sub 2/ solubility in electrolyte (NaCl) solution on the ionic strength I (0.000-5.5000 g-ion/liter) and the temperature (0-50/sup 0/C). Plots were also constructed to show the dependence of activity coefficients of Ca/sup 2 +/ and HCO/sup -//sub 3/ ions and of the average activity coefficient on the ionic strength in a wide range of its values. In conclusion, the authors have shown that the activation coefficient can be determined rightfully by using the Debye-Huckel equation for calculating equilibrium in the systems CaCO/sub 3/-CO/sub 2/-NaCl-H/sub 2/O characterizable by different values of ionic strength and temperature, including those for oil field drainage waters.

  12. Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures

    NASA Astrophysics Data System (ADS)

    Ganbavale, G.; Zuend, A.; Marcolli, C.; Peter, T.

    2014-06-01

    This study presents a new, improved parameterisation of the temperature dependence of activity coefficients in the AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) model applicable for aqueous as well as water-free organic solutions. For electrolyte-free organic and organic-water mixtures the AIOMFAC model uses a group-contribution approach based on UNIFAC (UNIversal quasi-chemical Functional-group Activity Coefficients). This group-contribution approach explicitly accounts for interactions among organic functional groups and between organic functional groups and water. The previous AIOMFAC version uses a simple parameterisation of the temperature dependence of activity coefficients, aimed to be applicable in the temperature range from ~275 to ~400 K. With the goal to improve the description of a wide variety of organic compounds found in atmospheric aerosols, we extend the AIOMFAC parameterisation for the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon to atmospherically relevant low temperatures with the introduction of a new temperature dependence parameterisation. The improved temperature dependence parameterisation is derived from classical thermodynamic theory by describing effects from changes in molar enthalpy and heat capacity of a multicomponent system. Thermodynamic equilibrium data of aqueous organic and water-free organic mixtures from the literature are carefully assessed and complemented with new measurements to establish a comprehensive database, covering a wide temperature range (~190 to ~440 K) for many of the functional group combinations considered. Different experimental data types and their processing for the estimation of AIOMFAC model parameters are discussed. The new AIOMFAC parameterisation for the temperature dependence of activity coefficients from low to high temperatures shows an overall improvement of 25% in comparison to the previous model version. The new parameterisation of AIOMFAC agrees well with a large number of experimental datasets and enables the calculation of activity coefficients of a wide variety of different aqueous/water-free organic solutions down to the low temperatures present in the upper troposphere.

  13. Activity coefficients of microquantities of lanthanides and actinides in nitric acid solutions

    SciTech Connect

    Vlasov, V.S.; Rozen, A.M.

    1988-09-01

    We carried out calculations on the basis of the Zdanovskii-Mikulin rule. The radii of the ions of the actinides americium and curium(III) (0.099 nm) are closest to the radius of the neodymium ion (0.0995 nm), and the radius of the californium ion (0.0976 nm) is closest to the radius of the promethium ion (0.0979 nm). It may accordingly be assumed that the activity coefficients of americium and curium are approximately equal to the activity coefficients of neodymium and that the values for californium are approximately equal to the values for promethium.

  14. Numerical simulation of mass transfer in the liquid phase of the bubble layer of a thermal deaerator

    NASA Astrophysics Data System (ADS)

    Laptev, A. G.; Misbakhov, R. Sh.; Lapteva, E. A.

    2015-12-01

    On the basis of one-dimensional diffusion model of the flow structure and boundary layer theory, a method for calculating the mass transfer of dissolved oxygen in the liquid phase of the bubble layer of a thermal deaerator is developed. Mass transfer with the bulk source of mass has been considered, wherein the basic parameter is mass-transfer coefficient. A model of pseudo laminar boundary layer on the bubble surface is proposed, and the possibility of calculating of mass-transfer coefficient from bubbles in the mass source of diffusion model is shown, taking into account the gas content and external turbulence. A comparison of the calculation results of mass-transfer coefficient is given from the bubbles with known experimental data. It is shown that taking into account gas content results in an increase of the mass-transfer coefficient by 2-4 times. Expressions for calculations of gas content, dynamic speed, and inverse stirring coefficient in the liquid phase of the bubble layer are presented. In the special case, transition from the diffusion model of the flow structure to cell model is made, and comparison of the calculation results on the concentration of oxygen in water at the output of DSA-300 bubbling thermal deaerator with experimental data is performed. The developed mathematical model and calculation algorithm can be used in the design, diagnosis, and modernization of thermal deaerators.

  15. Electrical and optical characterization of Er-doped silicon grown by liquid phase epitaxy

    NASA Astrophysics Data System (ADS)

    Cavallini, A.; Fraboni, B.; Pizzini, S.; Binetti, S.; Sanguinetti, S.; Lazzarini, L.; Salviati, G.

    1999-02-01

    We have carried out deep level transient spectroscopy (DLTS), optical DLTS, and capacitance-voltage measurements on liquid phase epitaxy-grown Er-doped Si to characterize the deep levels present in the material and to identify those related to dislocations and involved in the luminescence activity. The optical properties of the material have been studied by photoluminescence, cathodoluminescence investigations, and two emission lines, labeled A and B, have been found, line A being located at 0.806 eV. We have observed that an actual interaction occurs between dislocations and Er-related emitting centers.

  16. Transient liquid-phase bonding in the Ni-Al-B system

    NASA Astrophysics Data System (ADS)

    Campbell, C. E.; Boettinger, W. J.

    2000-11-01

    Transient liquid-phase (TLP) bonding experiments were performed using a Ni-10.3 at. pct Al alloy and a Ni-10 at. pct B filler material, and the results were compared to simulations performed using the finite-difference diffusion code, DICTRA. For the simulations, a thermodynamic assessment of the Ni-Al-B system was used to define the phase diagram and the thermodynamic factors of the diffusion coefficients. Composition-dependent diffusion mobilities were assessed for the ternary system. Predicted liquid widths as functions of time were in good agreement with the experiments. The calculated and experimental Al composition profiles agree in the matrix but not in the liquid. The simulations qualitatively predicted the observed precipitation and later dissolution of the intermetallic ? phase (Ni20Al3B6) in the base material. This research demonstrated the potential for modeling the formation of spurious phases during TLP bonding of practical superalloy systems.

  17. Temperature Dependent Raman Studies on Liquid Phase Exfoliated MoS2

    NASA Astrophysics Data System (ADS)

    Connolly, Mitchell; Winchester, Andrew; Hale, Peter; Dani, Keshav M.; Talapatra, Saikat; Nanophysics Lab, Department of Physics, Southern Illinois University-Carbondale, USA Team; Femtosecond Spectroscopy Unit, Okinawa Institute of Science; Technology, Japan Team

    2014-03-01

    We investigate on the temperature dependence of in-plane E12g and out-of-plane A1g Raman modes of few-layer MoS2 prepared using the liquid-phase exfoliation method. Structural characterization performed after exfoliation using transmission electron microscopy (TEM) indicate the resultant material contains small, submicron size, few-layer flakes. Raman measurements indicating material thickness of 6 layers or fewer were observed at room temperature using a 532 nm laser line (E12g =381.4 cm-1 and A1g =405.8 cm-1). The Raman peak shifts indicate a linear dependence on temperature within the range 293 K to 77 K. The measured temperature coefficients of E12g and A1g modes will be presented and compared with other similar experimental/theoretical data available.

  18. Extending the Diffuse Layer Model of Surface Acidity Behavior: III. Estimating Bound Site Activity Coefficients

    EPA Science Inventory

    Although detailed thermodynamic analyses of the 2-pK diffuse layer surface complexation model generally specify bound site activity coefficients for the purpose of accounting for those non-ideal excess free energies contributing to bound site electrochemical potentials, in applic...

  19. Modeling infinite dilution activity coefficients of environmental pollutants in water using conformal solution theory

    SciTech Connect

    Moore, R.C.; Cochran, H.D.; Bienkowski, P.R. |

    1995-04-01

    The fate of organic pollutants in the environment and in wastewater treatment processes is commonly modeled using a Henry`s law constant approach. By definition, Henry`s law constant is the product of a compound`s vapor pressure and infinite dilution activity coefficient. For many organic compounds in water solution, the infinite dilution activity coefficients are very large and are not adequately modeled by conventional methods such as UNIFAC. In this work, infinite dilution activity coefficients were determined for phenol, pyridine, aniline, p-toluidine, and o-toluidine in water by differential ebulliometry. An equation rigorously derived from conformal solution theory and van der Waals one-fluid mixing rules was used to model the temperature dependency of the infinite dilution activity coefficients. No corrections other than the introduction of two adjustable parameters were incorporated into the model to account for the strong interactions between molecules. Relationships derived from corresponding states theory were used to relate molecular parameters for size and energy interaction to the critical properties. Arithmetic mean combining rules and geometric mean combining rules were used to calculate size and interaction parameters, respectively.

  20. Activity Coefficients of Acetone-Chloroform Solutions: An Undergraduate Experiment. Undergraduate Experiment.

    ERIC Educational Resources Information Center

    Ozog, J. Z.; Morrison, J. A.

    1983-01-01

    Presents information, laboratory procedures, and results of an undergraduate experiment in which activity coefficients for a two-component liquid-vapor system are determined. Working in pairs, students can perform the experiment with 10 solutions in a given three-hour laboratory period. (Author/JN)

  1. Explaining Activity Coefficients and Standard States in the Undergraduate Physical Chemistry Course.

    ERIC Educational Resources Information Center

    Fanelli, A.

    1986-01-01

    Since activity coefficients are difficult even for good students to understand from the normal presentations in undergraduate physical chemistry, the author has reanalyzed this concept and presents a new way for introducing it. A practice problem (with solution) is included. (JN)

  2. Containerless liquid-phase processing of ceramic materials

    NASA Technical Reports Server (NTRS)

    Weber, J. K. R.; Nordine, P. C.

    1994-01-01

    Containerless melting and solidification provides a powerful tool for investigation and synthesis of ceramic and glass materials. The work described in this article explored and extended the limits of ground-based experimentation by using aero-acoustic and aerodynamic levitation in combination with laser beam heating and melting to investigate ceramic and glass processing. Results of liquid-phase processing experiments on calcia-gallia and calcia-gallia-silica glass-forming mixtures, aluminum oxide, and ceramic superconductors are summarized. The work is discussed in the context of low gravity experimental and materials synthesis requirements and opportunities.

  3. Modeling liquid-liquid phase transitions and quasicrystal formation

    NASA Astrophysics Data System (ADS)

    Skibinsky, Anna

    In this thesis, studies which concern two different subjects related to phase transitions in fluids and crystalline solids are presented. Condensed matter formation, structure, and phase transitions are modeled using molecular dynamics simulations of simple discontinuous potentials with attractive and repulsive interactions. Novel phase diagrams are proposed for quasicrystals, crystals, and liquids. In the first part of the thesis, the formation of a quasicrystal in a two dimensional monodisperse system is investigated using molecular dynamics simulations of hard sphere particles interacting via a two-dimensional square-well potential. It is found that for certain values of the square-well parameters more than one stable crystalline phase can form. By quenching the liquid phase at a very low temperature, an amorphous phase is obtained. When this the amorphous phase is heated, a quasicrystalline structure with five-fold symmetry forms. From estimations of the Helmholtz potentials of the stable crystalline phases and of the quasicrystal, it is concluded that within a specific temperature range, the observed quasicrystal phase can be the stable phase. The second part of the thesis concerns a study of the liquid-liquid phase transition for a single-component system in three dimensions, interacting via an isotropic potential with a repulsive soft-core shoulder at short distance and an attractive well at an intermediate distance. The potential is similar to potentials used to describe such liquid systems as colloids, protein solutions, or liquid metals. It is shown that the phase diagram for such a potential can have two lines of first-order fluid-fluid phase transitions: one separating a gas and a low-density liquid (LDL), and another between the LDL and a high-density liquid (HDL). Both phase transition lines end in a critical point, a gas-LDL critical point and, depending on the potential parameters, either a gas-HDL critical point or a LDL-HDL critical point. A systematic study through varying potential parameters is carried out to determine the influence of attractive and repulsive interactions on the formation and stability of the liquid-liquid phase transitions and the two fluid critical points. No hints of the density anomaly are found, suggesting that the absence of the density anomaly, such as the one found in water, is independent of the choice of the parameters and that the liquid-liquid phase transition and density anomaly are not directly related.

  4. Vapors-liquid phase separator. [infrared telescope heat sink

    NASA Technical Reports Server (NTRS)

    Frederking, T. H. K.; Brown, G. S.; Chuang, C.; Kamioka, Y.; Kim, Y. I.; Lee, J. M.; Yuan, S. W. K.

    1980-01-01

    The use of porous plugs, mostly with in the form of passive devices with constant area were considered as vapor-liquid phase separators for helium 2 storage vessels under reduced gravity. The incorporation of components with variable cross sectional area as a method of flow rate modification was also investigated. A particular device which uses a shutter-type system for area variation was designed and constructed. This system successfully permitted flor rate changes of up to plus or minus 60% from its mean value.

  5. Environmental information volume: Liquid Phase Methanol (LPMEOH{trademark}) project

    SciTech Connect

    1996-05-01

    The purpose of this project is to demonstrate the commercial viability of the Liquid Phase Methanol Process using coal-derived synthesis gas, a mixture of hydrogen and carbon monoxide. This report describes the proposed actions, alternative to the proposed action, the existing environment at the coal gasification plant at Kingsport, Tennessee, environmental impacts, regulatory requirements, offsite fuel testing, and DME addition to methanol production. Appendices include the air permit application, solid waste permits, water permit, existing air permits, agency correspondence, and Eastman and Air Products literature.

  6. Growth of Thick Zinc Magnesium Oxide by Liquid Phase Epitaxy

    NASA Astrophysics Data System (ADS)

    Kobayashi, Jun; Sekiwa, Hideyuki; Miyamoto, Miyuki; Ohashi, Naoki; Sakaguchi, Isao; Wada, Yoshiki; Adachi, Yutaka; Haneda, Hajime

    2008-07-01

    Very thick (about 0.5 mm) single crystals of a (Zn,Mg)O were grown on ZnO substrate by using a liquid phase epitaxy (LPE) technique. The source materials, ZnO and MgO, were dissolved in a PbO-Bi2O3 flux, and the (Zn,Mg)O was crystallized on the c-face of ZnO substrate in contact with the melt. The obtained crystal had high crystallinity similar to that of the ZnO substrate and exhibited n-type conductivity with relatively high Hall mobility.

  7. Liquid phase synthesis of copper indium diselenide nanoparticles

    SciTech Connect

    Jakhmola, Priyanka; Agarwal, Garima; Jha, Prafulla K.; Bhatnagar, S. P.

    2014-04-24

    Nanoparticles of Copper Indium diselenide (CuInSe{sub 2}), belongs to I-III-VI{sub 2} family has been synthesized via liquid phase route using ethylenediamine as a solvent. Characterization of as-grown particles is done by XRD, HRTEM, DLS, optical microscopy and UV-Vis spectroscopy. X-ray diffraction pattern confirmed that the CuInSe2 nanoparticles obtained reveals chalcopyrite structure. Particle size evaluated from dynamic light scattering of as grown particle possessing radius of 90 nm. The bandgap of 1.05eV is obtained from UV-Vis spectrum which will applicable to the solar cell devices.

  8. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived synthesis gas. Final technical report

    SciTech Connect

    Not Available

    1993-02-01

    Through the mid-1980s, Air Products has brought the liquid phase approach to a number of other synthesis gas reactions where effective heat management is a key issue. In 1989, in response to DOE`s PRDA No. DE-RA22-88PC88805, Air Products proposed a research and development program entitled ``Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal Derived Syngas.`` The proposal aimed at extending the LPMEOH experience to convert coal-derived synthesis gas to other useful fuels and chemicals. The work proposed included development of a novel one-step synthesis of dimethyl ether (DME) from syngas, and exploration of other liquid phase synthesis of alternative fuel directly from syngas. The one-step DME process, conceived in 1986 at Air Products as a means of increasing syngas conversion to liquid products, envisioned the concept of converting product methanol in situ to DME in a single reactor. The slurry reactor based liquid phase technology is ideally suited for such an application, since the second reaction (methanol to DME) can be accomplished by adding a second catalyst with dehydration activity to the methanol producing reactor. An area of exploration for other alternative fuels directly from syngas was single-step slurry phase synthesis of hydrocarbons via methanol and DME as intermediates. Other possibilities included the direct synthesis of mixed alcohols and mixed ethers in a slurry reactor.

  9. Chemicals from low temperature liquid-phase cracking of coals

    SciTech Connect

    Sato, Y.; Kodera, Y.; Kamo, T.; Yamaguchi, H.; Tatsumoto, K.

    1999-07-01

    Mild gasification and low temperature pyrolysis are considered to be the most promising process for high-moisture subbituminous and lignite coal to produce upgraded solid fuel with high heating value and low sulfur, and to produce a useful liquid product. However effective technology to prevent spontaneous combustion of solid product and to utilize oxygen-rich liquid product has not yet been reported to enhance commercial feasibility of these process. In this study, liquid-phase cracking of low rank coal at 350--450 C under 2 MPa of initial nitrogen atmosphere has been studied to produce upgraded coal and value added liquid product. Liquid-phase cracking of Wyoming subbituminous Buckskin coal using iron oxide catalyst in the presence of t-decalin at 440C gave 10 wt% of liquid product, 12 wt% of gases and 74 wt% of upgraded coal with small amount of water. Gaseous product consisted of mainly carbon dioxide (62wt%) and methane. Therefore, cracking of carboxylic function took place effectively in these conditions. Liquid product contains BTX, phenols and alkylphenols. Concentrated chemicals of BTX, phenol and cresols from the liquid products by hydrocracking and hydrotreating will be discussed.

  10. Modeling the solid-liquid phase transition in saturated triglycerides

    NASA Astrophysics Data System (ADS)

    Pink, David A.; Hanna, Charles B.; Sandt, Christophe; MacDonald, Adam J.; MacEachern, Ronald; Corkery, Robert; Rousseau, Dérick

    2010-02-01

    We investigated theoretically two competing published scenarios for the melting transition of the triglyceride trilaurin (TL): those of (1) Corkery et al. [Langmuir 23, 7241 (2007)], in which the average state of each TL molecule in the liquid phase is a discotic "Y" conformer whose three chains are dynamically twisted, with an average angle of ˜120° between them, and those of (2) Cebula et al. [J. Am. Oil Chem. Soc. 69, 130 (1992)], in which the liquid-state conformation of the TL molecule in the liquid phase is a nematic h∗-conformer whose three chains are in a modified "chair" conformation. We developed two competing models for the two scenarios, in which TL molecules are in a nematic compact-chair (or "h") conformation, with extended, possibly all-trans, chains at low-temperatures, and in either a Y conformation or an h∗ conformation in the liquid state at temperatures higher than the phase-transition temperature, T∗=319 K. We defined an h-Y model as a realization of the proposal of Corkery et al. [Langmuir 23, 7241 (2007)], and explored its predictions by mapping it onto an Ising model in a temperature-dependent field, performing a mean-field approximation, and calculating the transition enthalpy ΔH. We found that the most plausible realization of the h-Y model, as applied to the solid-liquid phase transition in TL, and likely to all saturated triglycerides, gave a value of ΔH in reasonable agreement with the experiment. We then defined an alternative h-h∗ model as a realization of the proposal of Cebula et al. [J. Am. Oil Chem. Soc. 69, 130 (1992)], in which the liquid phase exhibits an average symmetry breaking similar to an h conformation, but with twisted chains, to see whether it could describe the TL phase transition. The h-h∗ model gave a value of ΔH that was too small by a factor of ˜3-4. We also predicted the temperature dependence of the 1132 cm-1 Raman band for both models, and performed measurements of the ratios of three TL Raman bands in the temperature range of -20 °C≤T ≤90 °C. The experimental results were in accord with the predictions of the h-Y model and support the proposal of Corkery et al. [Langmuir 23, 7241 (2007)] that the liquid state is made up of molecules that are each, on average, in a Y conformation. Finally, we carried out computer simulations of minimal-model TLs in the liquid phase, and concluded that although the individual TL molecules are, on average, Y conformers, long-range discotic order is unlikely to exist.

  11. Modeling the solid-liquid phase transition in saturated triglycerides.

    PubMed

    Pink, David A; Hanna, Charles B; Sandt, Christophe; MacDonald, Adam J; MacEachern, Ronald; Corkery, Robert; Rousseau, Drick

    2010-02-01

    We investigated theoretically two competing published scenarios for the melting transition of the triglyceride trilaurin (TL): those of (1) Corkery et al. [Langmuir 23, 7241 (2007)], in which the average state of each TL molecule in the liquid phase is a discotic "Y" conformer whose three chains are dynamically twisted, with an average angle of approximately 120 degrees between them, and those of (2) Cebula et al. [J. Am. Oil Chem. Soc. 69, 130 (1992)], in which the liquid-state conformation of the TL molecule in the liquid phase is a nematic h*-conformer whose three chains are in a modified "chair" conformation. We developed two competing models for the two scenarios, in which TL molecules are in a nematic compact-chair (or "h") conformation, with extended, possibly all-trans, chains at low-temperatures, and in either a Y conformation or an h* conformation in the liquid state at temperatures higher than the phase-transition temperature, T*=319 K. We defined an h-Y model as a realization of the proposal of Corkery et al. [Langmuir 23, 7241 (2007)], and explored its predictions by mapping it onto an Ising model in a temperature-dependent field, performing a mean-field approximation, and calculating the transition enthalpy DeltaH. We found that the most plausible realization of the h-Y model, as applied to the solid-liquid phase transition in TL, and likely to all saturated triglycerides, gave a value of DeltaH in reasonable agreement with the experiment. We then defined an alternative h-h* model as a realization of the proposal of Cebula et al. [J. Am. Oil Chem. Soc. 69, 130 (1992)], in which the liquid phase exhibits an average symmetry breaking similar to an h conformation, but with twisted chains, to see whether it could describe the TL phase transition. The h-h* model gave a value of DeltaH that was too small by a factor of approximately 3-4. We also predicted the temperature dependence of the 1132 cm(-1) Raman band for both models, and performed measurements of the ratios of three TL Raman bands in the temperature range of -20 degrees C < or = T < or = 90 degrees C. The experimental results were in accord with the predictions of the h-Y model and support the proposal of Corkery et al. [Langmuir 23, 7241 (2007)] that the liquid state is made up of molecules that are each, on average, in a Y conformation. Finally, we carried out computer simulations of minimal-model TLs in the liquid phase, and concluded that although the individual TL molecules are, on average, Y conformers, long-range discotic order is unlikely to exist. PMID:20136317

  12. Molecular radiotherapy: The NUKFIT software for calculating the time-integrated activity coefficient

    SciTech Connect

    Kletting, P.; Schimmel, S.; Luster, M.; Kestler, H. A.; Hänscheid, H.; Fernández, M.; Lassmann, M.; Bröer, J. H.; Nosske, D.; Glatting, G.

    2013-10-15

    Purpose: Calculation of the time-integrated activity coefficient (residence time) is a crucial step in dosimetry for molecular radiotherapy. However, available software is deficient in that it is either not tailored for the use in molecular radiotherapy and/or does not include all required estimation methods. The aim of this work was therefore the development and programming of an algorithm which allows for an objective and reproducible determination of the time-integrated activity coefficient and its standard error.Methods: The algorithm includes the selection of a set of fitting functions from predefined sums of exponentials and the choice of an error model for the used data. To estimate the values of the adjustable parameters an objective function, depending on the data, the parameters of the error model, the fitting function and (if required and available) Bayesian information, is minimized. To increase reproducibility and user-friendliness the starting values are automatically determined using a combination of curve stripping and random search. Visual inspection, the coefficient of determination, the standard error of the fitted parameters, and the correlation matrix are provided to evaluate the quality of the fit. The functions which are most supported by the data are determined using the corrected Akaike information criterion. The time-integrated activity coefficient is estimated by analytically integrating the fitted functions. Its standard error is determined assuming Gaussian error propagation. The software was implemented using MATLAB.Results: To validate the proper implementation of the objective function and the fit functions, the results of NUKFIT and SAAM numerical, a commercially available software tool, were compared. The automatic search for starting values was successfully tested for reproducibility. The quality criteria applied in conjunction with the Akaike information criterion allowed the selection of suitable functions. Function fit parameters and their standard error estimated by using SAAM numerical and NUKFIT showed differences of <1%. The differences for the time-integrated activity coefficients were also <1% (standard error between 0.4% and 3%). In general, the application of the software is user-friendly and the results are mathematically correct and reproducible. An application of NUKFIT is presented for three different clinical examples.Conclusions: The software tool with its underlying methodology can be employed to objectively and reproducibly estimate the time integrated activity coefficient and its standard error for most time activity data in molecular radiotherapy.

  13. A Computationally Efficient Model for Multicomponent Activity Coefficients in Aqueous Solutions

    SciTech Connect

    Zaveri, Rahul A.; Easter, Richard C.; Wexler, Anthony S.

    2004-10-04

    Three-dimensional models of atmospheric inorganic aerosols need an accurate yet computationally efficient parameterization of activity coefficients, which are repeatedly updated in aerosol phase equilibrium and gas-aerosol partitioning calculations. In this paper, we describe the development and evaluation of a new mixing rule for estimating multicomponent activity coefficients of electrolytes typically found in atmospheric aerosol systems containing H(+), NH4(+), Na(+), Ca(2+), SO4(2-), HSO4(-), NO3(-), and Cl(-) ions. The new mixing rule, called MTEM (Multicomponent Taylor Expansion Model), estimates the mean activity coefficient of an electrolyte A in a multicomponent solution from a linear combination of its values in ternary solutions of A-A-H2O, A-B-H2O, A-C-H2O, etc., as the amount of A approaches zero in the mixture at the solution water activity, aw, assuming aw is equal to the ambient relative humidity. Predictions from MTEM are found to be within a factor of 0.8 to 1.25 of the comprehensive Pitzer-Simonson-Clegg (PSC) model over a wide range of water activities, and are shown to be significantly more accurate than the widely used Kusik and Meissner (KM) mixing rule, especially for electrolytes in sulfate-rich aerosol systems and for relatively minor but important aerosol components such as HNO3 and HCl acids. Because the ternary activity coefficient polynomials are parameterized as a function of aw, they have to be computed only once at every grid point at the beginning of every 3-D model time step as opposed to repeated evaluations of the ionic strength dependent binary activity coefficient polynomials in the KM method. Additionally, MTEM also yields a non-iterative solution of the bisulfate ion dissociation in sulfate-rich systems, which is a major computational advantage over other iterative methods as will be shown by a comparison of the CPU time requirements of MTEM for both sulfate-poor and sulfate-rich systems relative to other methods.

  14. Microstructure development and solid state reactions during liquid phase sintering

    SciTech Connect

    Yokoi, Hitoshi; Kingery, W.D.

    1996-12-31

    Microstructure development during heating of alumina powders coated with precursors of various metal oxides has been examined. EM studies revealed that the alumina particle surfaces act as sites for heterogeneous nucleation. The solid solution between alumina and titania after the nucleation of rutile on the surface of alumina resulted in sintering rate enhancement, while the slow self-diffusion characteristics of zirconia resulted in {open_quotes}droplets{close_quotes} on the surface of alumina which impeded the grain boundary migration. The final structure of the alumina simultaneously doped with cupric oxide and titania or bismuth oxide and titania was reached in the presence of a liquid phase but large shrinkage occurred before the liquid formed. It was concluded that when a solid state reaction takes place between a matrix phase and a second phase or between second phases during heating, matter transfer is faster and thereby, the sintering is accelerated.

  15. Liquid-Liquid Phase Transition in Nanoconfined Silicon Carbide.

    PubMed

    Wu, Weikang; Zhang, Leining; Liu, Sida; Ren, Hongru; Zhou, Xuyan; Li, Hui

    2016-03-01

    We report theoretical evidence of a liquid-liquid phase transition (LLPT) in liquid silicon carbide under nanoslit confinement. The LLPT is characterized by layering transitions induced by confinement and pressure, accompanying the rapid change in density. During the layering transition, the proportional distribution of tetracoordinated and pentacoordinated structures exhibits remarkable change. The tricoordinated structures lead to the microphase separation between silicon (with the dominant tricoordinated, tetracoordinated, and pentacoordinated structures) and carbon (with the dominant tricoordinated structures) in the layer close to the walls. A strong layer separation between silicon atoms and carbon atoms is induced by strong wall-liquid forces. Importantly, the pressure confinement phase diagram with negative slopes for LLPT lines indicates that, under high pressure, the LLPT is mainly confinement-induced, but under low pressure, it becomes dominantly pressure-induced. PMID:26859609

  16. Supersolidus Liquid Phase Sintering Modeling of Inconel 718 Superalloy

    NASA Astrophysics Data System (ADS)

    Levasseur, David; Brochu, Mathieu

    2015-11-01

    Powder metallurgy of Inconel 718 superalloy is advantageous as a near-net shape process for complex parts to reduce the buy-to-fly ratio and machining cost. However, sintering Inconel 718 requires the assistance of supersolidus liquid formation to achieve near full density and involves the risk of distortion at high temperatures. The present work is focused on modeling the onset of sintering and distortion as a function of temperature, grain size, and part geometry for Inconel 718. Using experimental sintering results and data available in the literature, the supersolidus liquid phase sintering of Inconel 718 was modeled. The model was used to define a processing window where part distortion would be avoided.

  17. Supersolidus Liquid Phase Sintering Modeling of Inconel 718 Superalloy

    NASA Astrophysics Data System (ADS)

    Levasseur, David; Brochu, Mathieu

    2016-02-01

    Powder metallurgy of Inconel 718 superalloy is advantageous as a near-net shape process for complex parts to reduce the buy-to-fly ratio and machining cost. However, sintering Inconel 718 requires the assistance of supersolidus liquid formation to achieve near full density and involves the risk of distortion at high temperatures. The present work is focused on modeling the onset of sintering and distortion as a function of temperature, grain size, and part geometry for Inconel 718. Using experimental sintering results and data available in the literature, the supersolidus liquid phase sintering of Inconel 718 was modeled. The model was used to define a processing window where part distortion would be avoided.

  18. Numerical Simulation of Transient Liquid Phase Bonding under Temperature Gradient

    NASA Astrophysics Data System (ADS)

    Ghobadi Bigvand, Arian

    Transient Liquid Phase bonding under Temperature Gradient (TG-TLP bonding) is a relatively new process of TLP diffusion bonding family for joining difficult-to-weld aerospace materials. Earlier studies have suggested that in contrast to the conventional TLP bonding process, liquid state diffusion drives joint solidification in TG-TLP bonding process. In the present work, a mass conservative numerical model that considers asymmetry in joint solidification is developed using finite element method to properly study the TG-TLP bonding process. The numerical results, which are experimentally verified, show that unlike what has been previously reported, solid state diffusion plays a major role in controlling the solidification behavior during TG-TLP bonding process. The newly developed model provides a vital tool for further elucidation of the TG-TLP bonding process.

  19. Transient liquid-phase bonding of ODS steels

    NASA Astrophysics Data System (ADS)

    Noto, H.; Ukai, S.; Hayashi, S.

    2011-10-01

    The use of transient liquid-phase bonding of 9CrODS steels using Fe-3B-2Si-0.5C filler was investigated for bonding temperature of 1180 C and hold times of 0.5-4.0 h. The sequential process, consisting of isothermal melting, solidification and homogenization, was confirmed for bonding the 9CrODS steel. The precipitation of chromium boride found in 19CrODS steel is avoided in 9CrODS steel due to the lower Cr content. Silicon tends to be slightly enriched inside the bonding zone. Agglomeration and coarsening of Y 2O 3 particles in 9CrODS steel lead to softening inside the bonding zone formed by incipient melting of the foil bonding alloy, and in a diffusion affected zone (DAZ) adjacent to the bonding zone.

  20. Synthesis and Electrochemical Characterization of Liquid Phase Exfoliated Graphene Flakes

    NASA Astrophysics Data System (ADS)

    Richie, Julianna; Huffstutler, Jacob; Wasala, Milinda; Winchester, Andrew; Ghosh, Sujoy; Kar, Swastik; Talapatra, Saikat

    2014-03-01

    We will present our results on synthesis and characterization of few-layer graphene nanoflakes obtained from bulk graphite in isopropanol alcohol (IPA) using Liquid-phase exfoliation technique. Results of sample characterization using ultraviolet-visible (UV-VIS) spectroscopy, transmission electron microscopy (TEM), cyclic voltammetry (CV), electrical impedance spectroscopy (EIS), and galvanostatic charge-discharge will be presented. Potential use of these materials as electric double-layer capacitor (EDLC) electrodes were investigated using 6M KOH as electrolyte. We found that these devices possess specific capacitance values as high as 23F/g at a 1 mV scan rate. Several other parameters related to the EDLC performances will be presented in detail.

  1. Reaction behaviors of mixed plastics in liquid-phase cracking

    SciTech Connect

    Wann, Jyi-Perng A.; Kamo, Tohru; Sato, Yoshiki

    1996-12-31

    The majority of waste plastics today is either incinerated or buried for landfills. However, incineration of waste plastics can cause damages in furnace and air pollution problems. Shortage of available landfill sites also has become a serious concern. The methods of waste plastic recycling therefore have been paid much attention with the viewpoint of effective environmental protection. Liquefaction of waste plastics is an attractive recycling method in terms of producing fuel oil or chemicals. To date, most of the waste plastic liquefaction investigations have been limited to the areas not involving the use of a solvent. Pilot-scaled plants, such as those in the Fuji Recycle Process in Japan and the VCC Process in Germany, have been operated for some time. Although high conversion of waste plastics can be obtained at a temperature as low as 400{degrees}C, problems such as wide molecular weight distribution in the produced oil and high coking tendency have been encountered. Liquid-phase cracking of waste plastics has the potential of overcoming these problems, yet few research has been reported on the liquefaction behaviors for the liquid-phase cracking. Polyethylene (PE) has been regarded as one of the polymers difficult to liquefy, while the cracking of polystyrene (PS) is considered to proceed in a way different from that of PE. Hence, we investigated the cracking of PS, PE, and their mixtures using solvents of different hydrogen donation capability. Differences in the liquefaction behaviors between PS and PE, influences of the solvent type, synergistic effects for the liquefaction of PS/PE mixtures, and a property in the oil are presented in this paper.

  2. Common non-Fermi liquid phases in quantum impurity physics

    NASA Astrophysics Data System (ADS)

    Logan, David E.; Tucker, Adam P.; Galpin, Martin R.

    2014-08-01

    We study correlated quantum impurity models that undergo a local quantum phase transition (QPT) from a strong coupling, Fermi liquid phase to a non-Fermi liquid phase with a globally doubly degenerate ground state. Our aim is to establish what can be shown exactly about such "local moment" (LM) phases, of which the permanent (zero-field) local magnetization is a hallmark, and an order parameter for the QPT. A description of the zero-field LM phase is shown to require two distinct self-energies, which reflect the broken symmetry nature of the phase and together determine the single self-energy of standard field theory. Distinct Friedel sum rules for each phase are obtained, via a Luttinger theorem embodied in the vanishing of appropriate Luttinger integrals. By contrast, the standard Luttinger integral is nonzero in the LM phase but found to have universal magnitude. A range of spin susceptibilites are also considered, including that corresponding to the local order parameter, whose exact form is shown to be RPA-like, and to diverge as the QPT is approached. Particular attention is given to the pseudogap Anderson model, including the basic physical picture of the transition, the low-energy behavior of single-particle dynamics, the quantum critical point itself, and the rather subtle effect of an applied local field. A two-level impurity model that undergoes a QPT ("singlet-triplet") to an underscreened LM phase is also considered, for which we derive on general grounds some key results for the zero-bias conductance in both phases.

  3. Measurement of gas/water uptake coefficients for trace gases active in the marine environment. [Annual report

    SciTech Connect

    Davidovits, P.; Worsnop, D.W.; Zahniser, M.S.; Kolb, C.E.

    1992-02-01

    Ocean produced reduced sulfur compounds including dimethylsulfide (DMS), hydrogen sulfide (H{sub 2}S), carbon disulfide (CS{sub 2}), methyl mercaptan (CH{sub 3}CH) and carbonyl sulfide (OCS) deliver a sulfur burden to the atmosphere which is roughly equal to sulfur oxides produced by fossil fuel combustion. These species and their oxidation products dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO{sub 2}) and methane sulfonic acid (MSA) dominate aerosol and CCN production in clean marine air. Furthermore, oxidation of reduced sulfur species will be strongly influenced by NO{sub x}/O{sub 3} chemistry in marine atmospheres. The multiphase chemical processes for these species must be understood in order to study the evolving role of combustion produced sulfur oxides over the oceans. We have measured the chemical and physical parameters affecting the uptake of reduced sulfur compounds, their oxidation products, ozone, and nitrogen oxides by the ocean`s surface, and marine clouds, fogs, and aerosols. These parameters include: gas/surface mass accommodation coefficients; physical and chemically modified (effective) Henry`s law constants; and surface and liquid phase reaction constants. These parameters are critical to understanding both the interaction of gaseous trace species with cloud and fog droplets and the deposition of trace gaseous species to dew covered, fresh water and marine surfaces.

  4. Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures

    NASA Astrophysics Data System (ADS)

    Ganbavale, G.; Zuend, A.; Marcolli, C.; Peter, T.

    2015-01-01

    This study presents a new, improved parameterisation of the temperature dependence of activity coefficients in the AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) model applicable for aqueous as well as water-free organic solutions. For electrolyte-free organic and organic-water mixtures the AIOMFAC model uses a group-contribution approach based on UNIFAC (UNIversal quasi-chemical Functional-group Activity Coefficients). This group-contribution approach explicitly accounts for interactions among organic functional groups and between organic functional groups and water. The previous AIOMFAC version uses a simple parameterisation of the temperature dependence of activity coefficients, aimed to be applicable in the temperature range from ~ 275 to ~ 400 K. With the goal to improve the description of a wide variety of organic compounds found in atmospheric aerosols, we extend the AIOMFAC parameterisation for the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon to atmospherically relevant low temperatures. To this end we introduce a new parameterisation for the temperature dependence. The improved temperature dependence parameterisation is derived from classical thermodynamic theory by describing effects from changes in molar enthalpy and heat capacity of a multi-component system. Thermodynamic equilibrium data of aqueous organic and water-free organic mixtures from the literature are carefully assessed and complemented with new measurements to establish a comprehensive database, covering a wide temperature range (~ 190 to ~ 440 K) for many of the functional group combinations considered. Different experimental data types and their processing for the estimation of AIOMFAC model parameters are discussed. The new AIOMFAC parameterisation for the temperature dependence of activity coefficients from low to high temperatures shows an overall improvement of 28% in comparison to the previous model version, when both versions are compared to our database of experimentally determined activity coefficients and related thermodynamic data. When comparing the previous and new AIOMFAC model parameterisations to the subsets of experimental data with all temperatures below 274 K or all temperatures above 322 K (i.e. outside a 25 K margin of the reference temperature of 298 K), applying the new parameterisation leads to 37% improvement in each of the two temperature ranges considered. The new parameterisation of AIOMFAC agrees well with a large number of experimental data sets. Larger model-measurement discrepancies were found particularly for some of the systems containing multi-functional organic compounds. The affected systems were typically also poorly represented at room temperature and further improvements will be necessary to achieve better performance of AIOMFAC in these cases (assuming the experimental data are reliable). The performance of the AIOMFAC parameterisation is typically better for systems containing relatively small organic compounds and larger deviations may occur in mixtures where molecules of high structural complexity such as highly oxygenated compounds or molecules of high molecular mass (e.g. oligomers) prevail. Nevertheless, the new parameterisation enables the calculation of activity coefficients for a wide variety of different aqueous/water-free organic solutions down to the low temperatures present in the upper troposphere.

  5. Research on Transient Liquid Phase Diffusion Bonding of Steel Sandwich Panels Under Small Plastic Deformation

    NASA Astrophysics Data System (ADS)

    Li, H.; Li, Z. X.

    2008-12-01

    Plastic deformation was newly introduced in transient liquid phase (TLP) diffusion bonding of steel sandwich panels. The effect of plastic deformation on bonding strength was investigated through lab experiments. It was assumed that three factors, including newly generated metal surface area, deformation heat, and lattice distortion, contribute to the acceleration of interface atoms diffusion and increase of diffusion coefficients. A numerical model of isothermal solidification time was developed for TLP bonding process under plastic deformation and applied to carbon steel sandwich panels bonding with copper interlayer. A reasonable isothermal solidification time was obtained when an effective diffusion coefficient was used. Based on lab experiments, the effects of plastic deformation on interlayer film thickness and isothermal solidification time were studied through theoretical calculation with the new model. The evolution of interlayer film thickness indicates a good agreement between the calculation and experimental measurement. The results show that the isothermal solidification time is obviously reduced due to the effect of plastic deformation. Furthermore, a new steel sandwich cooling panel for heat exchanger was fabricated by TLP diffusion bonding under 13.1% plastic deformation. The test results suggest that a steel sandwich panel of inequidistant fin structure can provide enhanced heat transfer efficiency.

  6. High temperature creep of SiC densified using a transient liquid phase

    SciTech Connect

    Jou, Z.C.; Virkar, A.V. ); Cutler, R.A. )

    1991-09-01

    Silicon carbide-based ceramics can be rapidly densified above approximately 1850 {degree}C due to a transient liquid phase resulting from the reaction between alumina and aluminum oxycarbides. The resulting ceramics are fine-grained, dense, and exhibit high strength at room temperature. SiC hot pressed at 1875 {degree}C for 10 min in Ar was subjected to creep deformation in bending at elevated temperatures between 1500 and 1650 {degree}C in Ar. Creep was thermally activated with an activation energy of 743 kJ/mol. Creep rates at 1575 {degree}C were between 10{sup {minus}9}/s and 10{sup {minus}7}/s at an applied stress between 38 and 200 MPa, respectively, resulting in a stress exponent of {approx}1.7.

  7. Kinetic and thermodynamic study of the liquid-phase etherification of isoamylenes with methanol

    SciTech Connect

    Piccoli, R.L. ); Lovisi, H.R. )

    1995-02-01

    The kinetics and thermodynamics of liquid-phase etherification of isoamylenes with methanol on ion exchange catalyst (Amberlyst 15) were studied. Thermodynamic properties and rate data were obtained in a batch reactor operating under 1,013 kPa and 323--353 K. The kinetic equation was modeled following the Langmuir-Hinshelwood-Hougen-Watson formalism according to a proposed surface mechanism where the rate-controlling step is the surface reaction. According to the experimental results, methanol adsorbs very strongly on the active sites, covering them completely, and thus the reaction follows an apparent first-order behavior. The isoamylenes, according to the proposed mechanism, adsorb simultaneously on the same single active center already occupied by methanol, migrating through the liquid layer formed by the alcohol around the catalyst to react in the acidic site. From the proposed mechanism a model was suggested and the kinetic and thermodynamic parameters were obtained using nonlinear estimation methods.

  8. Glass and liquid phase diagram of a polyamorphic monatomic system

    NASA Astrophysics Data System (ADS)

    Reisman, Shaina; Giovambattista, Nicolas

    2013-02-01

    We perform out-of-equilibrium molecular dynamics (MD) simulations of a monatomic system with Fermi-Jagla (FJ) pair potential interactions. This model system exhibits polyamorphism both in the liquid and glass state. The two liquids, low-density (LDL) and high-density liquid (HDL), are accessible in equilibrium MD simulations and can form two glasses, low-density (LDA) and high-density amorphous (HDA) solid, upon isobaric cooling. The FJ model exhibits many of the anomalous properties observed in water and other polyamorphic liquids and thus, it is an excellent model system to explore qualitatively the thermodynamic properties of such substances. The liquid phase behavior of the FJ model system has been previously characterized. In this work, we focus on the glass behavior of the FJ system. Specifically, we perform systematic isothermal compression and decompression simulations of LDA and HDA at different temperatures and determine "phase diagrams" for the glass state; these phase diagrams varying with the compression/decompression rate used. We obtain the LDA-to-HDA and HDA-to-LDA transition pressure loci, PLDA-HDA(T) and PHDA-LDA(T), respectively. In addition, the compression-induced amorphization line, at which the low-pressure crystal (LPC) transforms to HDA, PLPC-HDA(T), is determined. As originally proposed by Poole et al. [Phys. Rev. E 48, 4605 (1993)], 10.1103/PhysRevE.48.4605 simulations suggest that the PLDA-HDA(T) and PHDA-LDA(T) loci are extensions of the LDL-to-HDL and HDL-to-LDL spinodal lines into the glass domain. Interestingly, our simulations indicate that the PLPC-HDA(T) locus is an extension, into the glass domain, of the LPC metastability limit relative to the liquid. We discuss the effects of compression/decompression rates on the behavior of the PLDA-HDA(T), PHDA-LDA(T), PLPC-HDA(T) loci. The competition between glass polyamorphism and crystallization is also addressed. At our "fast rate," crystallization can be partially suppressed and the glass phase diagram can be related directly with the liquid phase diagram. However, at our "slow rate," crystallization cannot be prevented at intermediate temperatures, within the glass region. In these cases, multiple crystal-crystal transformations are found upon compression/decompression (polymorphism).

  9. Glass and liquid phase diagram of a polyamorphic monatomic system.

    PubMed

    Reisman, Shaina; Giovambattista, Nicolas

    2013-02-14

    We perform out-of-equilibrium molecular dynamics (MD) simulations of a monatomic system with Fermi-Jagla (FJ) pair potential interactions. This model system exhibits polyamorphism both in the liquid and glass state. The two liquids, low-density (LDL) and high-density liquid (HDL), are accessible in equilibrium MD simulations and can form two glasses, low-density (LDA) and high-density amorphous (HDA) solid, upon isobaric cooling. The FJ model exhibits many of the anomalous properties observed in water and other polyamorphic liquids and thus, it is an excellent model system to explore qualitatively the thermodynamic properties of such substances. The liquid phase behavior of the FJ model system has been previously characterized. In this work, we focus on the glass behavior of the FJ system. Specifically, we perform systematic isothermal compression and decompression simulations of LDA and HDA at different temperatures and determine "phase diagrams" for the glass state; these phase diagrams varying with the compression/decompression rate used. We obtain the LDA-to-HDA and HDA-to-LDA transition pressure loci, P(LDA-HDA)(T) and P(HDA-LDA)(T), respectively. In addition, the compression-induced amorphization line, at which the low-pressure crystal (LPC) transforms to HDA, P(LPC-HDA)(T), is determined. As originally proposed by Poole et al. [Phys. Rev. E 48, 4605 (1993)] simulations suggest that the P(LDA-HDA)(T) and P(HDA-LDA)(T) loci are extensions of the LDL-to-HDL and HDL-to-LDL spinodal lines into the glass domain. Interestingly, our simulations indicate that the P(LPC-HDA)(T) locus is an extension, into the glass domain, of the LPC metastability limit relative to the liquid. We discuss the effects of compression/decompression rates on the behavior of the P(LDA-HDA)(T), P(HDA-LDA)(T), P(LPC-HDA)(T) loci. The competition between glass polyamorphism and crystallization is also addressed. At our "fast rate," crystallization can be partially suppressed and the glass phase diagram can be related directly with the liquid phase diagram. However, at our "slow rate," crystallization cannot be prevented at intermediate temperatures, within the glass region. In these cases, multiple crystal-crystal transformations are found upon compression/decompression (polymorphism). PMID:23425481

  10. Solubility parameter and activity coefficient of HDEHP dimer in select organic diluents by vapor pressure osmometry

    SciTech Connect

    Gray, M.; Nilsson, M.; Zalupski, P.

    2013-07-01

    A thorough understanding of the non-ideal behavior of the chemical components utilized in solvent extraction contributes to the success of any large-scale spent nuclear fuel treatment. To address this, our current work uses vapor pressure osmometry to characterize the non-ideal behavior of the solvent extraction agent di-(2-ethylhexyl) phosphoric acid (HDEHP), a common extractant in proposed separation schemes. Solubility parameters were fit to data on HDEHP at four temperatures using models based on Scatchard Hildebrand regular solution theory with Flory Huggins entropic corrections. The results are comparable but not identical to the activity coefficients from prior slope analysis in the literature. (authors)

  11. Experimental Solubility Approach to Determine PDMS-Water Partition Constants and PDMS Activity Coefficients.

    PubMed

    Grant, Sharon; Schacht, Veronika J; Escher, Beate I; Hawker, Darryl W; Gaus, Caroline

    2016-03-15

    Freely dissolved aqueous concentration and chemical activity are important determinants of contaminant transport, fate, and toxic potential. Both parameters are commonly quantified using Solid Phase Micro-Extraction (SPME) based on a sorptive polymer such as polydimethylsiloxane (PDMS). This method requires the PDMS-water partition constants, KPDMSw, or activity coefficient to be known. For superhydrophobic contaminants (log KOW >6), application of existing methods to measure these parameters is challenging, and independent measures to validate KPDMSw values would be beneficial. We developed a simple, rapid method to directly measure PDMS solubilities of solid contaminants, SPDMS(S), which together with literature thermodynamic properties was then used to estimate KPDMSw and activity coefficients in PDMS. PDMS solubility for the test compounds (log KOW 7.2-8.3) ranged over 3 orders of magnitude (4.1-5700 μM), and was dependent on compound class. For polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins (PCDDs), solubility-derived KPDMSw increased linearly with hydrophobicity, consistent with trends previously reported for less chlorinated congeners. In contrast, subcooled liquid PDMS solubilities, SPDMS(L), were approximately constant within a compound class. SPDMS(S) and KPDMSw can therefore be predicted for a compound class with reasonable robustness based solely on the class-specific SPDMS(L) and a particular congener's entropy of fusion, melting point, and aqueous solubility. PMID:26881312

  12. Relative effectiveness coefficient: a quality characteristic of toothpastes containing active components.

    PubMed

    Borissova, R; Kirova, E

    1996-12-01

    It has been proposed that the parameter of relative effectiveness coefficient (REC) be used for the qualitative assessment of toothpastes containing active ingredients. REC is the ratio between the concentration of the active component in water eluates obtained after three minutes and adequately prolonged (up to the reaching of equilibrium state) dispersion of the toothpaste in distilled water at a 1:4 ratio (condition simulating the use of toothpaste in the oral cavity). The change in REC after storage following its production, as well as testing the toothpaste stability at high and low temperatures, provides an evidence for deviations in its quality. REC was applied for the assessment of toothpastes containing 0.5% zinc citrate as an active ingredient. PMID:8996867

  13. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOTH) Process

    SciTech Connect

    1998-12-21

    The Liquid Phase Methanol (LPMEOW) Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership) to produce methanol from coal-derived synthesis gas (syngas). Air Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. The LPMEOI-P Process Demonstration Unit was built at a site located at the Eastman coal-to-chemicals complex in Kingsport. During this quarter, initial planning and procurement work continued on the seven project sites which have been accepted for participation in the off-site, product-use test program. Approximately 12,000 gallons of fuel-grade methanol (98+ wt% methanol, 4 wt% water) produced during operation on carbon monoxide (CO)-rich syngas at the LPMEOW Demonstration Unit was loaded into trailers and shipped off-site for Mure product-use testing. At one of the projects, three buses have been tested on chemical-grade methanol and on fhel-grade methanol from the LPMEOW Demonstration Project. During the reporting period, planning for a proof-of-concept test run of the Liquid Phase Dimethyl Ether (LPDME~ Process at the Alternative Fuels Development Unit (AFDU) in LaPorte, TX continued. The commercial catalyst manufacturer (Calsicat) has prepared the first batch of dehydration catalyst in large-scale equipment. Air Products will test a sample of this material in the laboratory autoclave. Catalyst activity, as defined by the ratio of the rate constant at any point in time to the rate constant for freshly reduced catalyst (as determined in the laborato~ autoclave), was monitored for the initial extended operation at the lower initial reactor operating temperature of 235oC. At this condition, the decrease in catalyst activity with time from the period 20 December 1997 through 27 January 1998 occurred at a rate of 1.0% per day, which represented a significant improvement over the 3.4Yi per day decline measured during the initial six weeks of operation in April and May of 1997. The deactivation rate also improved from the longer-term rate of 1.6% per day calculated throughout the summer and autumn of 1997.

  14. Hyperdoping silicon with selenium: solid vs. liquid phase epitaxy.

    PubMed

    Zhou, Shengqiang; Liu, Fang; Prucnal, S; Gao, Kun; Khalid, M; Baehtz, C; Posselt, M; Skorupa, W; Helm, M

    2015-01-01

    Chalcogen-hyperdoped silicon shows potential applications in silicon-based infrared photodetectors and intermediate band solar cells. Due to the low solid solubility limits of chalcogen elements in silicon, these materials were previously realized by femtosecond or nanosecond laser annealing of implanted silicon or bare silicon in certain background gases. The high energy density deposited on the silicon surface leads to a liquid phase and the fast recrystallization velocity allows trapping of chalcogen into the silicon matrix. However, this method encounters the problem of surface segregation. In this paper, we propose a solid phase processing by flash-lamp annealing in the millisecond range, which is in between the conventional rapid thermal annealing and pulsed laser annealing. Flash lamp annealed selenium-implanted silicon shows a substitutional fraction of ~ 70% with an implanted concentration up to 2.3%. The resistivity is lower and the carrier mobility is higher than those of nanosecond pulsed laser annealed samples. Our results show that flash-lamp annealing is superior to laser annealing in preventing surface segregation and in allowing scalability. PMID:25660096

  15. Self-Sputtering of Solid and Liquid Phase Tin

    NASA Astrophysics Data System (ADS)

    Coventry, M. D.; Tomchik, C. A.; Ruzic, D. N.

    2004-11-01

    The absolute self-sputtering yields of solid and liquid-phase Sn have been measured for incident ions with energies of 300 to 1000 eV at 45^o using the Ion-surface InterAction eXperiment (IIAX). A Sn divertor^1 would experience self-bombardment from redepositing Sn ions, and its use may be limited by a temperature-enhanced self-sputtering yield. Thus, an understanding of any temperature dependence is a key to predictive modeling of such a device. IIAX uses a Colutron^2 ion source to produce a velocity-filtered Sn^+ beam for sample irradiation. Experiments were carried out with sample temperatures ranging from room temperature to 380^oC. A quartz-crystal microbalance (QCM) monitors sputtering by direct collection of ejected and reflected material; background noise is removed using a reference crystal. VFTRIM^3, which cannot simulate temperature, was used for comparison to recorded data and for data analysis. Hybrid Molecular-Dynamic/Monte Carlo simulations which include temperature effects^4 were also investigated. [1] Brooks, J.N. Fus. Eng. Des. 60 (2002) 515-526. [2] Menzinger, M. and Wahlin, L. Rev. Sci. Instrum. 40 (1969) 102-105. [3] Ruzic, D.N. Nuc. Instrum. Meth. Phys. Res. 47 (1990) 118-125. [4] Allain, J.P., D.N. Ruzic, submitted to Nuc. Instrum. Meth. B, January 2004

  16. Liquid-Liquid Phase Separation of Oil Bodies from Seeds.

    PubMed

    Nykiforuk, Cory L

    2016-01-01

    Fundamentally, oil bodies are discrete storage organelles found in oilseeds, comprising a hydrophobic triacylglycerol core surrounded by a half-unit phospholipid membrane and an outer shell of specialized proteins known as oleosins. Oil bodies possess a number of attributes that were exploited by SemBioSys Genetics to isolate highly enriched fractions of oil bodies through liquid-liquid phase separation for a number of commercial applications. The current chapter provides a general guide for the isolation of oil bodies from Arabidopsis and/or safflower seed, from which protocols can be refined for different oilseed sources. For SemBioSys Genetic's recombinant technology, therapeutic proteins were covalently attached to oleosins or fused in-frame with ligands which bound oil bodies, facilitating their recovery to high levels of purity during "upstream processing" of transformed seed. Core to this technology was oil body isolation consisting of simple manipulation including homogenization of seeds to free the oil bodies, followed by the removal of insoluble fractions, and phase separation to recover the oil bodies. During oil body enrichment (an increase in oil body content concomitant with removal of impurities), a number of options and tips are provided to aid researchers in the manipulation and monitoring of these robust organelles. PMID:26614290

  17. Impedance Spectroscopy of Liquid-Phase Sintered Silicon Carbide

    SciTech Connect

    McLachlan, D.S.; Sauti, G.; Vorster, A.; Hermann, M.

    2004-02-26

    Liquid-Phase Sintered Silicon Carbide (LPSSiC) materials were produced with different Y2O3: Al2O3 and Y2O3: SiO2 sintering additive ratios. Densification was achieved by hot pressing (HP). The ratio of the polytypes and the amount and crystalline composition of the grain boundary phases was determined using Rietveld analysis. Microstructures of the materials were related to the mechanical properties (hardness, fracture toughness and strength), which are not presented. The impedance Spectroscopy measurements were made at temperatures between 100 deg. C and 400 deg. C and analyzed using Effective Media Theories and the Brick Layer Model. In some cases, in order to correctly fit the results, it was necessary to use or model the frequency dependence of the conductivity or dielectric constant of the SiC grains using various theoretical models. The impedance arcs for the SiC grains in the different samples varied widely, probably more due to the 'semiconductor' doping of the grains or nonstoichiometry, than the SiC polytypes in the grains. The SiC grains all showed an Arrhenius behavior with energy gaps in the range 0.3 to 0.5eV.

  18. Dynamic hollow fiber-supported headspace liquid-phase microextraction.

    PubMed

    Jiang, Xianmin; Basheer, Chanbasha; Zhang, Jie; Lee, Hian Kee

    2005-09-16

    With the increasing concern over deteriorating environmental quality, the analysis of organic pollutants in air, water, and soil has become critically important. The development of simple, efficient, and inexpensive analytical sample pretreatment is crucial for monitoring and evaluating the environment. In this work, a dynamic hollow-fiber supported headspace liquid-phase microextraction (DHF-HS-LPME) approach was developed. In dynamic LPME, the extracting solvent is held within a hollow fiber, affixed to a syringe needle and immersed in the sample solution, and is moved to-and-fro by using a programmable syringe pump. The movement facilitates mass transfer from the sample to the solvent. Here, a similar approach was adopted, except that extraction was from the headspace rather than by direct immersion. Analysis of the extract was carried out by gas chromatography-mass spectrometry. The effect of sampling temperature, water, salt, dwelling time were investigated. Results indicated that this novel headspace microextraction method gave good analyte-enrichment factors, linear range, limits of detection and repeatability, all of which were evaluated by extracting PAHs from soil samples. This technique represents an inexpensive, convenient, fast and simple sample preparation of this class of semi-volatile organic compounds. PMID:16130726

  19. Liquid phase deposition synthesis of hexagonal molybdenum trioxide thin films

    SciTech Connect

    Deki, Shigehito; Beleke, Alexis Bienvenu; Kotani, Yuki; Mizuhata, Minoru

    2009-09-15

    Hexagonal molybdenum trioxide thin films with good crystallinity and high purity have been fabricated by the liquid phase deposition (LPD) technique using molybdic acid (H{sub 2}MoO{sub 4}) dissolved in 2.82% hydrofluoric acid (HF) and H{sub 3}BO{sub 3} as precursors. The crystal was found to belong to a hexagonal hydrate system MoO{sub 3}.nH{sub 2}O (napprox0.56). The unit cell lattice parameters are a=10.651 A, c=3.725 A and V=365.997 A{sup 3}. Scanning electron microscope (SEM) images of the as-deposited samples showed well-shaped hexagonal rods nuclei that grew and where the amount increased with increase in reaction time. X-ray photon electron spectroscopy (XPS) spectra showed a Gaussian shape of the doublet of Mo 3d core level, indicating the presence of Mo{sup 6+} oxidation state in the deposited films. The deposited films exhibited an electrochromic behavior by lithium intercalation and deintercalation, which resulted in coloration and bleaching of the film. Upon dehydration at about 450 deg. C, the hexagonal MoO{sub 3}.nH{sub 2}O was transformed into the thermodynamically stable orthorhombic phase. - Abstract: SEM photograph of typical h-MoO{sub 3}.nH{sub 2}O thin film nuclei obtained after 36 h at 40 deg. C by the LPD method. Display Omitted

  20. Hyperdoping silicon with selenium: solid vs. liquid phase epitaxy

    PubMed Central

    Zhou, Shengqiang; Liu, Fang; Prucnal, S.; Gao, Kun; Khalid, M.; Baehtz, C.; Posselt, M.; Skorupa, W.; Helm, M.

    2015-01-01

    Chalcogen-hyperdoped silicon shows potential applications in silicon-based infrared photodetectors and intermediate band solar cells. Due to the low solid solubility limits of chalcogen elements in silicon, these materials were previously realized by femtosecond or nanosecond laser annealing of implanted silicon or bare silicon in certain background gases. The high energy density deposited on the silicon surface leads to a liquid phase and the fast recrystallization velocity allows trapping of chalcogen into the silicon matrix. However, this method encounters the problem of surface segregation. In this paper, we propose a solid phase processing by flash-lamp annealing in the millisecond range, which is in between the conventional rapid thermal annealing and pulsed laser annealing. Flash lamp annealed selenium-implanted silicon shows a substitutional fraction of ~ 70% with an implanted concentration up to 2.3%. The resistivity is lower and the carrier mobility is higher than those of nanosecond pulsed laser annealed samples. Our results show that flash-lamp annealing is superior to laser annealing in preventing surface segregation and in allowing scalability. PMID:25660096

  1. Effect of dimensionality on vapor-liquid phase transition

    SciTech Connect

    Singh, Sudhir Kumar

    2014-04-24

    Dimensionality play significant role on ‘phase transitions’. Fluids in macroscopic confinement (bulk or 3-Dimensional, 3D) do not show significant changes in their phase transition properties with extent of confinement, since the number of molecules away from the surrounding surfaces is astronomically higher than the number of molecules in close proximity of the confining surfaces. In microscopic confinement (quasi 3D to quasi-2D), however, the number of molecules away from the close proximity of the surface is not as high as is the case with macroscopic (3D) confinement. Hence, under the same thermodynamic conditions ‘phase transition’ properties at microscopic confinement may not remain the same as the macroscopic or 3D values. Phase transitions at extremely small scale become very sensitive to the dimensions as well as the surface characteristics of the system. In this work our investigations reveal the effect of dimensionality on the phase transition from 3D to quasi-2D to 2D behavior. We have used grand canonical transition matrix Monte Carlo simulation to understand the vapor–liquid phase transitions from 3D to quasi-2D behavior. Such studies can be helpful in understanding and controlling the fluid film behaviour confined between solid surfaces of few molecular diameters, for example, in lubrication applications.

  2. Positron annihilation in benzene and cyclohexane: a comparison between gas and liquid phase

    NASA Astrophysics Data System (ADS)

    Fedus, Kamil

    2015-06-01

    A comparative study about positron annihilation in gas and liquid phases of two non-polar ring molecules: benzene (C6H6) and cyclohexane (C6H12) is presented including the most recent experimental and theoretical achievements. In addition the preliminary results of positron annihilation lifetime measurements in a liquid phase at room temperature for these two molecules are reported.

  3. Grain growth kinetics in liquid-phase-sintered zinc oxide-barium oxide ceramics

    NASA Technical Reports Server (NTRS)

    Yang, Sung-Chul; German, Randall M.

    1991-01-01

    Grain growth of ZnO in the presence of a liquid phase of the ZnO-BaO system has been studied for temperatures from 1300 to 1400 C. The specimens were treated in boiling water and the grains were separated by dissolving the matrix phase in an ultrasonic bath. As a consequence 3D grain size measurements were possible. Microstructural examination shows some grain coalescence with a wide range of neck size ratios and corresponding dihedral angles, however, most grains are isolated. Lognormal grain size distributions show similar shapes, indicating that the growth mechanism is invariant over this time and temperature. All regressions between G exp n and time for n = 2 and 3 proved statistically significant. The rate constants calculated with the growth exponent set to n = 3 are on the same order of magnitude as in metallic systems. The apparent activation energy for growth is estimated between 355 and 458 kJ/mol.

  4. Computation of infinite dilute activity coefficients of binary liquid alloys using complex formation model

    NASA Astrophysics Data System (ADS)

    Awe, O. E.; Oshakuade, O. M.

    2016-04-01

    A new method for calculating Infinite Dilute Activity Coefficients (γ∞s) of binary liquid alloys has been developed. This method is basically computing γ∞s from experimental thermodynamic integral free energy of mixing data using Complex formation model. The new method was first used to theoretically compute the γ∞s of 10 binary alloys whose γ∞s have been determined by experiments. The significant agreement between the computed values and the available experimental values served as impetus for applying the new method to 22 selected binary liquid alloys whose γ∞s are either nonexistent or incomplete. In order to verify the reliability of the computed γ∞s of the 22 selected alloys, we recomputed the γ∞s using three other existing methods of computing or estimating γ∞s and then used the γ∞s obtained from each of the four methods (the new method inclusive) to compute thermodynamic activities of components of each of the binary systems. The computed activities were compared with available experimental activities. It is observed that the results from the method being proposed, in most of the selected alloys, showed better agreement with experimental activity data. Thus, the new method is an alternative and in certain instances, more reliable approach of computing γ∞s of binary liquid alloys.

  5. Cold flame on Biofilm - Transport of Plasma Chemistry from Gas to Liquid Phase

    NASA Astrophysics Data System (ADS)

    Kong, Michael

    2014-10-01

    One of the most active and fastest growing fields in low-temperature plasma science today is biological effects of gas plasmas and their translation in many challenges of societal importance such as healthcare, environment, agriculture, and nanoscale fabrication and synthesis. Using medicine as an example, there are already three FDA-approved plasma-based surgical procedures for tissue ablation and blood coagulation and at least five phase-II clinical trials on plasma-assisted wound healing therapies. A key driver for realizing the immense application potential of near room-temperature ambient pressure gas plasmas, commonly known as cold atmospheric plasmas or CAP, is to build a sizeable interdisciplinary knowledge base with which to unravel, optimize, and indeed design how reactive plasma species interact with cells and their key components such as protein and DNA. Whilst a logical objective, it is a formidable challenge not least since existing knowledge of gas discharges is largely in the gas-phase and therefore not directly applicable to cell-containing matters that are covered by or embedded in liquid (e.g. biofluid). Here, we study plasma inactivation of biofilms, a jelly-like structure that bacteria use to protect themselves and a major source of antimicrobial resistance. As 60--90% of biofilm is made of water, we develop a holistic model incorporating physics and chemistry in the upstream CAP-generating region, a plasma-exit region as a buffer for as-phase transport, and a downstream liquid region bordering the gas buffer region. A special model is developed to account for rapid chemical reactions accompanied the transport of gas-phase plasma species through the gas-liquid interface and for liquid-phase chemical reactions. Numerical simulation is used to illustrate how key reactive oxygen species (ROS) are transported into the liquid, and this is supported with experimental data of both biofilm inactivation using plasmas and electron spin spectroscopy (ESR) measurement of liquid-phase ROS.

  6. Design and Fabrication of the First Commercial-Scale Liquid Phase Methanol (LPMEOH) Reactor

    SciTech Connect

    1998-12-21

    The Liquid Phase Methanol (LPMEOHT) process uses a slurry bubble column reactor to convert synthesis gas (syngas), primarily a mixture of carbon monoxide and hydrogen, to methanol. Because of its superior heat management the process can utilize directly the carbon monoxide (CO)-rich syngas characteristic of the gasification of coal, petroleum coke, residual oil, wastes, or other hydrocarbon feedstocks. The LPMEOHM Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P., a partnership between Air Products and Chemicals, Inc. and Eastman Chemical Company, to produce methanol from coal-derived syngas. Construction of the LPMEOH~ Process Demonstration Plant at Eastman's chemicals-from-coal complex in Kingsport was completed in January 1997. Following commissioning and shakedown activities, the fwst production of methanol from the facility occurred on April 2, 1997. Nameplate capacity of 260 short tons per day (TPD) was achieved on April 6, 1997, and production rates have exceeded 300 TPD of methanol at times. This report describes the design, fabrication, and installation of the Kingsport LPMEOEFM reactor, which is the first commercial-scale LPMEOEPM reaetor ever built. The vessel is 7.5 feet in diameter and 70 feet tall with design conditions of 1000 psig at 600 `F. These dimensions represent a significant scale-up from prior experience at the DOE-owned Alternative Fuels Development Unit in LaPorte, Texas, where 18-inch and 22-inch diameter reactors have been tested successfidly over thousands of hours. The biggest obstacles discovered during the scale- up, however, were encountered during fabrication of the vessel. The lessons learned during this process must be considered in tailoring the design for future sites, where the reactor dimensions may grow by yet another factor of two.

  7. Asymmetric Diffusional Solidification during Transient Liquid Phase Bonding of Dissimilar Materials

    NASA Astrophysics Data System (ADS)

    Ghoneim, A.; Ojo, O. A.

    2012-03-01

    A theoretical analysis of diffusional solidification during transient liquid phase (TLP) bonding of dissimilar materials was performed in conjunction with experimental verification. A fully implicit, two-dimensional, finite element numerical simulation model, without the inherent symmetry assumption, was developed and used for the theoretical calculations, and good correlations between the model predictions and experimental results were observed. The study showed that an asymmetric distribution of residual interlayer liquid during a dissimilar joining of polycrystal and single crystal alloys is attributable to a mismatch between their lattice diffusion coefficients or solute solubility, irrespective of enhanced intergranular diffusion as was assumed previously. Also, notwithstanding increased solute diffusivity with temperature, it was found that an increase in bonding temperature can result in the prolongation of processing time t f that is required to prevent the formation of deleterious eutectic during bonding of dissimilar materials. The occurrence of this seemingly anomalous behavior, however, reduces when a material is coupled with another type that exhibits a higher solute solubility or better capability of accommodating diffusing melting point depressant solute from the liquid interlayer.

  8. Synthesis and Characterization of Ferroic and Multiferroic Nanostructures by Liquid Phase Deposition

    NASA Astrophysics Data System (ADS)

    Yourdkhani, Amin

    Magnetoelectric multiferroics have garnered an increasing interest in the past decade due to their unique properties and relevant applications in data storage, sensing and spintronics. A key requirement for the enhancement of the magnetoelectric effect at room temperature is the optimization of the interface between the constituting phases by designing nanocomposites with selectable topologies and variable chemical composition. In this research, the rational design of two-phase spinel-perovskite ceramic nanocomposites with two different geometries: coaxial nanostructures (1-D) and bilayered nanostructures (2-D), by a soft solution chemistry approach will be described. The liquid phase deposition (LPD) method is a simple and versatile route for the deposition of highly uniform spinel ferrite (MFe2O4) and/or titanium-based perovskite (BaTiO3, PbTiO3) by the controlled hydrolysis of metal fluoro-complexes at temperatures as low as 40C. By designing a sequential deposition process, 1-D and 2-D magnetoelectric nanostructures were fabricated by filling perovskite nanotubes with the ferrite phase or depositing a ferrite layer on top of a perovskite thin film, respectively. The compositional and morphological characteristics of these highly uniform metal oxide nanostructures were investigated by X-ray diffraction (XRD), Raman spectroscopy, scanning probe microscopy (SPM) and electron microscopy (FE-SEM and TEM). The direct evidence of the stress mediated magnetoelectric coupling between the spinel and perovskite of the bilayered nanostructures was qualitatively studied by Raman spectroscopy. Additionally, the direct magnetoelectric effect in these 1-D and bilayered multiferroic nanocomposites was evaluated both quantitatively and qualitatively by using a novel magnetic field-assisted piezoelectric force microscopy (M-PFM) technique. The quantitative estimation of the magnetoelectric coupling coefficients was performed by tracking the changes in the phase and -amplitude of the piezoelectric signal signals when a in-plane dc magnetic field was applied parallel to the sample. Their non-resonant values typically range between 100-1200 mV/cm.Oe, thereby indicating a strong coupling between the magnetic and electrostrictive phases which can be used in different sensing and data storage applications. Keywords: Ferroics, Multiferroics, Liquid Phase Deposition, Scanning Probe Microscopy, Magnetic Properties, Electrical Properties

  9. Partial-Transient-Liquid-Phase Bonding of Advanced Ceramics Using Surface-Modified Interlayers

    NASA Astrophysics Data System (ADS)

    Reynolds, Thomas Bither

    Partial-transient-liquid-phase (PTLP) bonding of advanced ceramics employs an A/B/A sandwich-style interlayer that is designed such that the outer cladding, A, forms a transient-liquid phase that disappears at the bonding temperature due to diffusion of A into the core layer, B. The resultant bonds can have re-melt temperatures that are significantly higher than the bonding temperature. The success of PTLP bonding relies on the proper selection of the interlayer components: the transient liquid must be able to flow into and fill strength-limiting interfacial flaws, the adhesion between the interlayer and the bulk ceramic must be sufficiently high to prevent interfacial failure, the formation of strength-reducing brittle phases at the interface should be minimized, and the residual stresses due to coefficient of thermal expansion (CTE) mismatch should be minimized. The composition of the transient liquid predominately determines the interfacial characteristics of the bond, while the core composition determines the residual stresses in the assembly. In recent work, Al 2O3 bonded using Ni/Nb/Ni interlayers produced joints that were of such high strength that all bonded samples failed exclusively in the ceramic and not at the joint during 4-point bend testing. The wetting characteristics of the Ni-Nb transient-liquid and the CTE of Nb are favorable for the fabrication of strong PTLP-bonded Al2O 3. However, for other ceramic systems, using a binary interlayer system such as Ni-Nb may not be desirable. When using binary interlayers it is not possible to control the composition of the transient liquid and the core independently. In order to expand PTLP bonding to other advanced ceramics, this study examined a new interlayer design that employs a surface-modified core, such as Mo-surface-modified Nb, instead of a homogeneous core, such as pure Nb. A surface-modified core is a core layer with an intentionally inhomogeneous composition in order to better control the composition of the transient-liquid and the core layer independently. It was found that Al2O3 PTLP bonded using a Mo-surface-modified V core and a Ni cladding had fracture strengths of 302+/-29 MPa. This is comparable to those using Ni/Nb/Ni interlayers, 341+/-28 MPa. In both assemblies, all of the samples failed in the ceramic bulk. The insights gained from these experiments were used to develop interlayer design guidelines for the PTLP bonding of other advanced ceramics.

  10. Calibration of the neutron activation system on the Frascati tokamak upgrade; Comparison between measured and calculated activation response coefficients

    SciTech Connect

    Angelone, M.; Batistoni, P.; Martone, M.; Pillon, M.; Rapisarda, M.; Rollet, S. )

    1991-05-01

    This paper reports on the Frascati Tokamak Upgrade (FTU) neutron activation system has been calibrated using indium foils and a {sup 252}Cf spontaneous fission neutron source located at several positions within the tokamak. The same experimental arrangements have been simulated with the MCNP Monte Carlo neutron and photon transport code in order to numerically reproduce the activation response coefficients measured experimentally. The main purpose of the comparison is to assess the accuracy of the numerical simulation and of the modeling of the FTU device. This analysis has a more general relevance in view of the use of the activation system as an independent method for the absolute measurement of the neutron yield in next-step fusion devices. An overall agreement at the 22% level between experiment and calculation has been demonstrated.

  11. Magnetic field effects on liquid-phase reactive sintering of MnBi

    NASA Astrophysics Data System (ADS)

    Mitsui, Yoshifuru; Abematsu, Ken-ichi; Umetsu, Rie Y.; Takahashi, Kohki; Koyama, Keiichi

    2016-02-01

    Magnetic fields effects on liquid-phase reaction sintering on MnBi were investigated. The liquid-phase reaction was so fast even in a zero field that the fraction of in-field sintered ferromagnetic MnBi phase was independent of the external magnetic field. However, the ferromagnetic MnBi crystals in the in-field sintered sample were oriented along the external magnetic field direction. The Lotgering factor of the in-field sintered sample was 0.99. This result indicated that almost completely anisotropic MnBi phase could be obtained by in-field liquid phase reactive sintering.

  12. Laser-induced separation of hydrogen isotopes in the liquid phase

    DOEpatents

    Freund, Samuel M.; Maier, II, William B.; Beattie, Willard H.; Holland, Redus F.

    1980-01-01

    Hydrogen isotope separation is achieved by either (a) dissolving a hydrogen-bearing feedstock compound in a liquid solvent, or (b) liquefying a hydrogen-bearing feedstock compound, the liquid phase thus resulting being kept at a temperature at which spectral features of the feedstock relating to a particular hydrogen isotope are resolved, i.e., a clear-cut isotope shift is delineated, irradiating the liquid phase with monochromatic radiation of a wavelength which at least preferentially excites those molecules of the feedstock containing a first hydrogen isotope, inducing photochemical reaction in the excited molecules, and separating the reaction product containing the first isotope from the liquid phase.

  13. Transient liquid phase bonding of ferritic oxide dispersion strengthened alloys

    NASA Astrophysics Data System (ADS)

    Krishnardula, Venu Gopal

    2006-04-01

    Oxide dispersion strengthened (ODS) alloys possess excellent properties including resistance to oxidation, corrosion, creep and thermal fatigue. In addition, ferritic ODS alloys exhibit resistance to void swelling and are of particular interest to the nuclear industry. The present study involves the joining of fuel cans to end caps that will be utilized in the nuclear industry. Mechanically alloyed (MA) ODS alloys possess coarse columnar grain structure strengthened with nanosize yttria dispersoids. In that past, fusion welding techniques resulted in microstructural disruption leading to poor joints. This work investigated joining of two ferritic MA ODS alloys, MA956 and PM2000, using; (a) Transient liquid phase (TLP) bonding and (b) Solid-state diffusion bonding. TLP bonds were prepared with MA956 and PM2000 in the unrecrystallized and recrystallized conditions using electron beam physical vapor deposited (EBPVD) boron thin films as interlayers. The use of thin interlayers reduced the amount of substrate dissolution and minimized the bondline microstructural disruption. Different bond orientations were also investigated. Successful bonds with better microstructural continuity were obtained when substrates were joined in the unrecrystallized condition followed by post bond recrystallization heat treatment with the substrate faying surface aligned along the working (extrusion or rolling) direction than when substrates were aligned perpendicular to the working direction. This was attributed to the number of yttria stringers cut by the bondline, which is less when the substrate faying surface is lying parallel to the working direction than when the substrate faying surface is lying perpendicular to the working direction. Solid-state diffusion bonding was conducted using MA956 and PM2000 in the unrecrystallized and recrystallized conditions. Bonding occurred only when an unrecrystallized substrate was involved. Bonding occurred at unusually low stresses. This may be attributed to the grain boundary diffusion, owing to submicron grain size of the unrecrystallized substrates. Post bond heat treatment was conducted in order to induce recrystallization in the bonds. Room temperature mechanical testing was conducted on the bonds and the bulk. Bond shear strengths and tensile strengths of up to 80% and 110% of bulk, respectively, were obtained. Defects in the bulk material such as porosity and unwanted fine grain formation were observed. Pore formation at the bondline during post bond heat treatment seems to decrease the bond strength. These defects were attributed to prior thermomechanical history of the materials.

  14. Activity coefficients and free energies of nonionic mixed surfactant solutions from vapor-pressure and freezing-point osmometry.

    PubMed

    MacNeil, Jennifer A; Ray, Gargi Basu; Leaist, Derek G

    2011-05-19

    The thermodynamic properties of mixed surfactant solutions are widely investigated, prompted by numerous practical applications of these systems and by interest in molecular association and self-organization. General techniques for measuring thermodynamic activities, such as isopiestic equilibration, are well-established for multicomponent solutions. Surprisingly, these techniques have not yet been applied to mixed surfactant solutions, despite the importance of the free energy for micelle stability. In this study, equations are developed for the osmotic coefficients of solutions of nonionic surfactant A + nonionic surfactant B. A mass-action model is used, with virial equations for the activity coefficients of the micelles and free surfactant monomer species. The equations are fitted to osmotic coefficients of aqueous decylsulfobetaine + dodecylsulfobetaine solutions measured by vapor-pressure and freezing-point osmometry. Equilibrium constants for mixed-micelle formation are calculated from the free monomer concentrations at the critical micelle concentrations. The derived activity coefficients of the micelles and free monomers indicate large departures from ideal solution behavior, even for dilute solutions of the surfactants. Stoichiometric activity coefficients of the total surfactant components are evaluated by Gibbs-Duhem integration of the osmotic coefficients. Relatively simple colligative property measurements hold considerable promise for free energy studies of multicomponent surfactant solutions. PMID:21504169

  15. Use of free silicon in liquid phase sintering of silicon nitrides and sialons

    DOEpatents

    Raj, R.; Baik, S.

    1985-11-12

    This invention relates to the production of improved high density nitrogen based ceramics by liquid-phase densification of silicon nitride or a compound of silicon-nitrogen-oxygen-metal, e.g. a sialon. In the process and compositions of the invention minor amounts of finely divided silicon are employed together with the conventional liquid phase producing additives to enhance the densification of the resultant ceramic. 4 figs.

  16. Use of free silicon in liquid phase sintering of silicon nitrides and sialons

    DOEpatents

    Raj, Rishi; Baik, Sunggi

    1985-11-12

    This invention relates to the production of improved high density nitrogen based ceramics by liquid-phase densification of silicon nitride or a compound of silicon-nitrogen-oxygen-metal, e.g. a sialon. In the process and compositions of the invention minor amounts of finely divided silicon are employed together with the conventional liquid phase producing additives to enhance the densification of the resultant ceramic.

  17. Liquid-phase gallium-indium alloy electronics with microcontact printing.

    PubMed

    Tabatabai, Arya; Fassler, Andrew; Usiak, Claire; Majidi, Carmel

    2013-05-21

    Liquid-phase electronic circuits are patterned on an elastomer substrate with a microcontact printer. The printer head dips into a pool of a liquid-phase gallium-indium alloy, e.g., eutectic gallium-indium (EGaIn) or gallium-indium-tin (Galinstan), and deposits a single drop on a silicone elastomer substrate. After patterned deposition, the liquid-phase circuit is sealed with an additional layer of silicone elastomer. We also demonstrate patterned deposition of the liquid-phase GaIn alloy with a molded polydimethylsiloxane stamp that is manually inked and pressed into an elastomer substrate. As with other liquid-phase electronics produced through needle injection or masked deposition, the circuit is elastically deformable and can be stretched to several times its natural length without losing electronic functionality. In contrast to existing fabrication techniques, microcontact printing and stamp lithography can be used to produce circuits with any planar geometric feature, including electrodes with large planar area, intersecting and closed-loop wires, and combs with multiple terminal electrodes. In air, the surface of the coalesced droplets oxidize to form a thin oxide skin that preserves the shape of the circuit during sealing. This first demonstration of soft-lithography fabrication with liquid-phase GaIn alloy expands the space of allowable circuit geometries and eliminates the need for mold or mask fabrication. PMID:23659455

  18. Dynamic changes of integrated backscatter, attenuation coefficient and bubble activities during high-intensity focused ultrasound (HIFU) treatment.

    PubMed

    Zhang, Siyuan; Wan, Mingxi; Zhong, Hui; Xu, Cheng; Liao, Zhenzhong; Liu, Huanqing; Wang, Supin

    2009-11-01

    This paper simultaneously investigated the transient characteristics of integrated backscatter (IBS), attenuation coefficient and bubble activities as time traces before, during and after HIFU treatment, with different HIFU parameters (acoustic power and duty cycle) in both transparent tissue-mimicking phantoms and freshly excised bovine livers. These dynamic changes of acoustic parameters and bubble activities were correlated with the visualization of lesion development selected from photos, conventional B-mode ultrasound images and differential IBS images over the whole procedure of HIFU treatment. Two-dimensional radiofrequency (RF) data were acquired by a modified diagnostic ultrasound scanner to estimate the changes of mean IBS and attenuation coefficient averaged in the lesion region, and to construct the differential IBS images and B-mode ultrasound images simultaneously. Bubble activities over the whole procedure of HIFU treatment were investigated by the passive cavitation detection (PCD) method and the changes in subharmonic and broadband noise were correlated with the transient characteristics of IBS and attenuation coefficient. When HIFU was switched on, IBS and attenuation coefficient increased with the appearance of bubble clouds in the B-mode and differential IBS image. At the same time, the level of subharmonic and broadband noise rose abruptly. Then, there was an initial decrease in the attenuation coefficient, followed by an increase when at lower HIFU power. As the lesion appeared, IBS and attenuation coefficient both increased rapidly to a value twice that of normal. Then the changes in IBS and attenuation coefficient showed more complex patterns, but still showed a slower trend of increases with lesion development. Violent bubble activities were visible in the gel and were evident as strongly echogenic regions in the differential IBS images and B-mode images simultaneously. This was detected by a dramatic high level of subharmonic and broadband noise at the same time. These bubble activities caused fluctuations in IBS and attenuation coefficient during HIFU treatment. After HIFU, IBS and attenuation coefficient decreased gradually accompanied by the fadeout of bright hyperechoic spot in the B-mode and differential IBS image, but were still higher than normal when they were stable. The increases of IBS and attenuation coefficient were greater when using higher acoustic power or a higher duty cycle of the therapeutic emission. These experiments indicated that the bubble activities had the dominant effects on the transient characteristics of IBS and attenuation. This should be taken into consideration when using the dynamic acoustic-property changes for the potentially real-time monitoring imaging of HIFU treatment. PMID:19716225

  19. Ultrasound promoted catalytic liquid-phase dehydrogenation of isopropanol for Isopropanol-Acetone-Hydrogen chemical heat pump.

    PubMed

    Xu, Min; Xin, Fang; Li, Xunfeng; Huai, Xiulan; Liu, Hui

    2015-03-01

    The apparent kinetic of the ultrasound assisted liquid-phase dehydrogenation of isopropanol over Raney nickel catalyst was determined in the temperature range of 346-353 K. Comparison of the effects of ultrasound and mechanical agitation on the isopropanol dehydrogenation was investigated. The ultrasound assisted dehydrogenation rate was significantly improved when relatively high power density was used. Moreover, the Isopropanol-Acetone-Hydrogen chemical heat pump (IAH-CHP) with ultrasound irradiation, in which the endothermic reaction is exposure to ultrasound, was proposed. A mathematical model was established to evaluate its energy performance in term of the coefficient of performance (COP) and the exergy efficiency, into which the apparent kinetic obtained in this work was incorporated. The operating performances between IAH-CHP with ultrasound and mechanical agitation were compared. The results indicated that the superiority of the IAH-CHP system with ultrasound was present even if more than 50% of the power of the ultrasound equipment was lost. PMID:25246094

  20. Biodegradation of 4-chlorophenol by acclimated and unacclimated activated sludge-Evaluation of biokinetic coefficients

    SciTech Connect

    Sahinkaya, Erkan; Dilek, Filiz B. . E-mail: fdilek@metu.edu.tr

    2005-10-01

    Unacclimated and acclimated activated sludges were examined for their ability to degrade 4-CP (4-chlorophenol) in the presence and absence of a readily growing substrate using aerobic batch reactors. The effects of 4-CP on the {mu} (specific growth rate), COD removal efficiency, Y (yield coefficient), and q (specific substrate utilization rate) were investigated. It was observed that the toxicity of 4-CP on the culture decreased remarkably after acclimation. For example, the IC{sub 50} value on the basis of {mu} was found to increase from 130 to 218mg/L with the acclimation of the culture. Although an increase in 4-CP concentration up to 300mg/L has no adverse effect on the COD removal efficiency of the acclimated culture, a considerable decrease was observed in the case of an unacclimated culture. Although 4-CP removal was not observed with an unacclimated culture, almost complete removal was achieved with the acclimated culture, up to 300mg/L. The Haldane kinetic model adequately predicted the biodegradation of 4-CP and the kinetic constants obtained were q{sub m}=41.17mg/(gMLVSSh), K{sub s}=1.104mg/L, and K{sub i}=194.4mg/L. The degradation of 4-CP led to formation of 5-chloro-2-hydroxymuconic semialdehyde, which was further metabolized, indicating complete degradation of 4-CP via a meta-cleavage pathway.

  1. Lab-scale experimental strategy for determining micropollutant partition coefficient and biodegradation constants in activated sludge.

    PubMed

    Pomis, M; Choubert, J M; Wisniewski, C; Mige, C; Budzinski, H; Coquery, M

    2015-03-01

    The nitrifying/denitrifying activated sludge process removes several micropollutants from wastewater by sorption onto sludge and/or biodegradation. The objective of this paper is to propose and evaluate a lab-scale experimental strategy for the determination of partition coefficient and biodegradation constant for micropollutant with an objective of modelling their removal. Four pharmaceutical compounds (ibuprofen, atenolol, diclofenac and fluoxetine) covering a wide hydrophobicity range (log Kow from 0.16 to 4.51) were chosen. Dissolved and particulate concentrations were monitored for 4days, inside two reactors working under aerobic and anoxic conditions, and under different substrate feed conditions (biodegradable carbon and nitrogen). We determined the mechanisms responsible for the removal of the target compounds: (i) ibuprofen was biodegraded, mainly under aerobic conditions by cometabolism with biodegradable carbon, whereas anoxic conditions suppressed biodegradation; (ii) atenolol was biodegraded under both aerobic and anoxic conditions (with a higher biodegradation rate under aerobic conditions), and cometabolism with biodegradable carbon was the main mechanism; (iii) diclofenac and fluoxetine were removed by sorption only. Finally, the abilities of our strategy were evaluated by testing the suitability of the parameters for simulating effluent concentrations and removal efficiency at a full-scale plant. PMID:25300180

  2. Estimation of the bond dissociation energies from the kinetic characteristics of liquid-phase radical reactions

    NASA Astrophysics Data System (ADS)

    Denisov, Evgenii T.; Tumanov, V. E.

    2005-09-01

    Three methods used in the kinetics of liquid-phase radical reactions for estimating the dissociation energies of individual bonds in polyatomic molecules are described. The first approach is based on the study of the equilibrium in radical abstraction reactions involving stable radicals and measurements of the equilibrium constants. The second method is based on the study of the kinetics of homolytic decomposition of molecules. Measuring the activation energy of these reactions makes it possible to estimate the dissociation energies of the weakest bonds, e.g., the O-O bonds in various peroxides. The essence of the third approach developed in the framework of the model of intersecting parabolas is calculations of the bond dissociation energy from the activation energy of a radical reaction involving the molecules under consideration. This method allowed the dissociation energies of the C-H, N-H, O-H and S-H bonds in a large number of organic compounds to be estimated. The scope and the specific features of application of each method are discussed and the bond dissociation energies determined by these methods are given.

  3. Growth Kinetics of Intracellular RNA/Protein Droplets: Signature of a Liquid-Liquid Phase Transition?

    NASA Astrophysics Data System (ADS)

    Berry, Joel; Weber, Stephanie C.; Vaidya, Nilesh; Zhu, Lian; Haataja, Mikko; Brangwynne, Clifford P.

    2015-03-01

    Nonmembrane-bound organelles are functional, dynamic assemblies of RNA and/or protein that can self-assemble and disassemble within the cytoplasm or nucleoplasm. The possibility that underlying intracellular phase transitions may drive and mediate the morphological evolution of some membrane-less organelles has been supported by several recent studies. In this talk, results from a collaborative experimental-theoretical study of the growth and dissolution kinetics of nucleoli and extranucleolar droplets (ENDs) in C. elegans embryos will be presented. We have employed Flory-Huggins solution theory, reaction-diffusion kinetics, and quantitative statistical dynamic scaling analysis to characterize the specific growth mechanisms at work. Our findings indicate that both in vivo and in vitro droplet scaling and growth kinetics are consistent with those resulting from an equilibrium liquid-liquid phase transition mediated by passive nonequilibrium growth mechanisms - simultaneous Brownian coalescence and Ostwald ripening. This supports a view in which cells can employ phase transitions to drive structural organization, while utilizing active processes, such as local transcriptional activity, to fine tune the kinetics of these phase transitions in response to given conditions.

  4. Liquid phase methanol LaPorte process development unit: Modification, operation, and support studies

    SciTech Connect

    Not Available

    1990-10-23

    The objectives of this program are to implement and test the process improvements identified through the engineering studies of the current program to demonstrate the capability of long-term catalyst activity maintenance, and to perform process and design engineering work that can be applied to a scaled-up Liquid Phase Methanol (LPMEOH) facility. An optional series of PDU runs is offered to extend the testing of the process improvements. A parallel research program will be performed to enhance the LPMEOH technical data base to improve the likelihood of commercialization of the LPMEOH process. Activities this quarter include: Flow sheet development for La Porte PDU modifications continues. A preliminary P ID review was completed and flow sheet modifications were identified and are being incorporated. A preliminary hazards review was completed on 22 May. Some minor flow sheet modifications resulted and a number of action items were identified. The most significant action item is to develop a materials reactivity and compatibility grid for the different alcohols, ethers, and esters which will be produced at the PDU. Heat and material balances were completed for the maximum production case of the mixed DME/MEOH synthesis campaign. An improved rate expression was developed. 1 fig.

  5. Liquid Phase Methanol LaPorte Process Development Unit: Modification, operation, and support studies

    SciTech Connect

    Not Available

    1990-08-31

    A gas phase and a slurry phase radioactive tracer study was performed on the 12 ton/day Liquid Phase Methanol (LPMEOH) Process Development Unit (PDU) in LaPorte, Texas. To study the gas phase mixing characteristics, a radioactive argon tracer was injected into the feed gas and residence time distribution was generated by measuring the response at the reactor outlet. Radioactive manganese oxide powder was independently injected into the reactor to measure the slurry phase mixing characteristics. A tanks-in-series model and an axial dispersion model were applied to the data to characterize the mixing in the reactor. From the axial dispersion model, a translation to the number of CSTR's (continuous stirred tank reactors) was made for comparison purposes with the first analysis. Dispersion correlations currently available in the literature were also compared. The tanks-in-series analysis is a simpler model whose results are easily interpreted. However, it does have a few drawbacks; among them, the lack of a reliable method for scaleup of a reactor and no direct correlation between mixing in the slurry and gas phases. The dispersion model allows the mixing in the gas and slurry phases to be characterized separately while including the effects of phase transfer. This analysis offers a means for combining the gas and slurry phase dispersion models into an effective dispersion coefficient, which, in turn, can be related to an equivalent number of tanks-in-series. The dispersion methods reported are recommended for scaleup of a reactor system. 24 refs., 18 figs., 8 tabs.

  6. Liquid phase microextraction and ultratrace determination of cadmium by modified graphite furnace atomic absorption spectrometry.

    PubMed

    Nazari, Saeid

    2009-06-15

    A powerful microextraction technique was used for determination of cadmium in water samples using liquid phase microextraction (LPME) followed by graphite furnace atomic absorption spectrometry (GF-AAS). In a preconcentration step, cadmium was extracted from a 2 ml of its aqueous sample in the pH 7 as 5,7-dibromoquinoline-8-ol (DBQ) complex into a 4 microl drop of benzyl alcohol. After extraction, the micro drop was retracted and directly transferred into a graphite tube modified by [W.Rh.Pd](c). Some effective parameters on extraction and complex formation, such as type and volume of organic solvent, pH, concentration of chelating agent, extraction time and stirring rate were optimized. Under the optimum conditions, the enrichment factor and recovery were 450% and 90%, respectively. The calibration graph was linear in the range of 0.008-1 microg L(-1) with correlation coefficient of 0.9961 under the optimum conditions of the recommended procedure. The detection limit based on the 3Sb criterion was 0.0035 microg L(-1) and relative standard deviation (RSD) for eight replicate measurement of 0.1 microg L(-1) and 0.4 microg L(-1) cadmium was 5.2% and 4.5%, respectively. The characteristic concentration was 0.0032 microg L(-1) equivalent to a characteristic mass of 12.8 fg. In order to evaluate the accuracy and recovery of the presented method the procedure was applied to the analysis of reference materials and seawater. PMID:19010596

  7. Liquid Phase Sintering of Boron-Containing Powder Metallurgy Steel with Chromium and Carbon

    NASA Astrophysics Data System (ADS)

    Wu, Ming-Wei; Fan, Yu-Chi; Huang, Her-Yueh; Cai, Wen-Zhang

    2015-11-01

    Liquid phase sintering is an effective method to improve the densification of powder metallurgy materials. Boron is an excellent alloying element for liquid phase sintering of Fe-based materials. However, the roles of chromium and carbon, and particularly that of the former, on liquid phase sintering are still undetermined. This study demonstrated the effects of chromium and carbon on the microstructure, elemental distribution, boride structure, liquid formation, and densification of Fe-B-Cr and Fe-B-Cr-C steels during liquid phase sintering. The results showed that steels with 0.5 wt pct C densify faster than those without 0.5 wt pct C. Moreover, although only one liquid phase forms in Fe-B-Cr steel, adding 0.5 wt pct C reduces the formation temperature of the liquid phase by about 50 K (C) and facilitates the formation of an additional liquid, resulting in better densification at 1473 K (1200 C). In both Fe-B-Cr and Fe-B-Cr-C steels, increasing the chromium content from 1.5 to 3 wt pct raises the temperature of liquid formation by about 10 K (C). Thermodynamic simulations and experimental results demonstrated that carbon atoms dissolved in austenite facilitate the eutectic reaction and reduce the formation temperature of the liquid phase. In contrast, both chromium and molybdenum atoms dissolved in austenite delay the eutectic reaction. Furthermore, the 3Cr-0.5Mo additive in the Fe-0.4B steel does not change the typical boride structure of M2B. With the addition of 0.5 wt pct C, the crystal structure is completely transformed from M2B boride to M3(B,C) boro-carbide.

  8. Liquid phase fluid dynamic (methanol) run in the LaPorte alternative fuels development unit

    SciTech Connect

    Bharat L. Bhatt

    1997-05-01

    A fluid dynamic study was successfully completed in a bubble column at DOE's Alternative Fuels Development Unit (AFDU) in LaPorte, Texas. Significant fluid dynamic information was gathered at pilot scale during three weeks of Liquid Phase Methanol (LPMEOJP) operations in June 1995. In addition to the usual nuclear density and temperature measurements, unique differential pressure data were collected using Sandia's high-speed data acquisition system to gain insight on flow regime characteristics and bubble size distribution. Statistical analysis of the fluctuations in the pressure data suggests that the column was being operated in the churn turbulent regime at most of the velocities considered. Dynamic gas disengagement experiments showed a different behavior than seen in low-pressure, cold-flow work. Operation with a superficial gas velocity of 1.2 ft/sec was achieved during this run, with stable fluid dynamics and catalyst performance. Improvements included for catalyst activation in the design of the Clean Coal III LPMEOH{trademark} plant at Kingsport, Tennessee, were also confirmed. In addition, an alternate catalyst was demonstrated for LPMEOH{trademark}.

  9. Partial transient liquid phase diffusion bonding of Zircaloy-4 to stabilized austenitic stainless steel 321

    SciTech Connect

    Atabaki, M. Mazar; Hanzaei, A. Talebi

    2010-10-15

    An innovative method was applied for bonding Zircaloy-4 to stabilized austenitic stainless steel 321 using an active titanium interlayer. Specimens were joined by a partial transient liquid phase diffusion bonding method in a vacuum furnace at different temperatures under 1 MPa dynamic pressure of contact. The influence of different bonding temperatures on the microstructure, microindentation hardness, joint strength and interlayer thickness has been studied. The diffusion of Fe, Cr, Ni and Zr has been investigated by scanning electron microscopy and energy dispersive spectroscopy elemental analyses. Results showed that control of the heating and cooling rate and 20 min soaking at 1223 K produces a perfect joint. However, solid-state diffusion of the melting point depressant elements into the joint metal causes the solid/liquid interface to advance until the joint is solidified. The tensile strength of all the bonded specimens was found around 480-670 MPa. Energy dispersive spectroscopy studies indicated that the melting occurred along the interface of the bonded specimens as a result of the transfer of atoms between the interlayer and the matrix during bonding. This technique provides a reliable method of bonding zirconium alloy to stainless steel.

  10. A novel series of isoreticular metal organic frameworks: realizing metastable structures by liquid phase epitaxy

    PubMed Central

    Liu, Jinxuan; Lukose, Binit; Shekhah, Osama; Arslan, Hasan Kemal; Weidler, Peter; Gliemann, Hartmut; Bräse, Stefan; Grosjean, Sylvain; Godt, Adelheid; Feng, Xinliang; Müllen, Klaus; Magdau, Ioan-Bogdan; Heine, Thomas; Wöll, Christof

    2012-01-01

    A novel class of metal organic frameworks (MOFs) has been synthesized from Cu-acetate and dicarboxylic acids using liquid phase epitaxy. The SURMOF-2 isoreticular series exhibits P4 symmetry, for the longest linker a channel-size of 3 × 3 nm2 is obtained, one of the largest values reported for any MOF so far. High quality, ab-initio electronic structure calculations confirm the stability of a regular packing of (Cu++)2- carboxylate paddle-wheel planes with P4 symmetry and reveal, that the SURMOF-2 structures are in fact metastable, with a fairly large activation barrier for the transition to the bulk MOF-2 structures exhibiting a lower, twofold (P2 or C2) symmetry. The theoretical calculations also allow identifying the mechanism for the low-temperature epitaxial growth process and to explain, why a synthesis of this highly interesting, new class of high-symmetry, metastable MOFs is not possible using the conventional solvothermal process. PMID:23213357

  11. Water Detritiation: Better SCK-CEN Catalysts for Liquid Phase Catalytic Exchange

    SciTech Connect

    Bruggeman, Aime; Braet, Johan; Vanderbiesen, Sven

    2005-07-15

    A technically and economically sound technology for water detritiation is mandatory for the future of fusion. This technology is expected to be based on water electrolysis and Liquid Phase Catalytic Exchange (LPCE). LPCE requires an efficient hydrophobic catalyst. SCK-CEN invented and developed such a catalyst in the past, which is prepared by depositing platinum on an activated charcoal carrier and mixing it with polytetrafluorethylene as a hydrophobic material. In combination with an appropriate wettable packing, different batches of this catalyst performed very well during years of extensive testing, allowing us to develop the ELEX process for water detritiation at inland reprocessing plants. Recently we succeeded in reproducing this catalyst and preparing a slightly different but clearly ameliorated type. By extrapolation these new results would allow us to obtain, at 40 deg. C and under typical but conservative operating conditions, a decontamination factor of 10000 with a column of less than 3 meters long. Such performances would make this catalyst an excellent candidate for application at JET or ITER. To confirm the performances of our improved catalyst for a longer period of time and in a longer column, we are now starting experiments in a newly built installation and we are collaborating with ICSI, Romania.

  12. Liquid phase methanol LaPorte process development unit: Modification operation, and support studies

    SciTech Connect

    Not Available

    1991-01-28

    In April 1987, Air Products started the third and final contract with the US Department of Energy to develop the Liquid Phase Methanol (LPMEOH) process. One of the objectives was to identify alternative commercial catalyst(s) for the process. This objective was strategically important as we want to demonstrate that the LPMEOH process is flexible and not catalyst selection limited. Among three commercially available catalysts evaluated in the lab, the catalyst with a designation of F21/0E75-43 was the most promising candidate. The initial judging criteria included not only the intrinsic catalyst activity but also the ability to be used effectively in a slurry reactor. The catalyst was then advanced for a 40-day life test in a laboratory 300 cc autoclave. The life test result also revealed superior stability when compared with that of a standard catalyst. Consequently, the new catalyst was recommended for demonstration in the Process Development Unit (PDU) at LaPorte, Texas. This report details the methodology of testing and selecting the catalyst.

  13. Characterization of liquid phase epitaxial GaAs forblocked-impurity-band far-infrared detectors

    SciTech Connect

    Cardozo, B.L.; Reichertz, L.A.; Beeman, J.W.; Haller, E.E.

    2004-04-07

    GaAs Blocked-Impurity-Band (BIB) photoconductor detectors have the potential to become the most sensitive, low noise detectors in the far-infrared below 45.5 cm{sup -1} (220 {micro}m). We have studied the characteristics of liquid phase epitaxial GaAs films relevant to BIB production, including impurity band formation and the infrared absorption of the active section of the device. Knowledge of the far-infrared absorption spectrum as a function of donor concentration combined with variable temperature Hall effect and resistivity studies leads us to conclude that the optimal concentration for the absorbing layer of a GaAs BIB detector lies between 1 x 10{sup 15} and 6.7 x 10{sup 15} cm{sup -3}. At these concentrations there is significant wavefunction overlap which in turn leads to absorption beyond the 1s ground to 2p bound excited state transition of 35.5 cm{sup -1} (282 {micro}m). There still remains a gap between the upper edge of the donor band and the bottom of the conduction band, a necessity for proper BIB detector operation.

  14. Images reveal that atmospheric particles can undergo liquidliquid phase separations

    PubMed Central

    You, Yuan; Renbaum-Wolff, Lindsay; Carreras-Sospedra, Marc; Hanna, Sarah J.; Hiranuma, Naruki; Kamal, Saeid; Smith, Mackenzie L.; Zhang, Xiaolu; Weber, Rodney J.; Shilling, John E.; Dabdub, Donald; Martin, Scot T.; Bertram, Allan K.

    2012-01-01

    A large fraction of submicron atmospheric aerosol particles contains both organic material and inorganic salts. As the relative humidity cycles in the atmosphere and the water content of the particles correspondingly changes, these mixed particles can undergo a range of phase transitions, possibly including liquidliquid phase separation. If liquidliquid phase separation occurs, the gas-particle partitioning of atmospheric semivolatile organic compounds, the scattering and absorption of solar radiation, and the reactive uptake of gas species on atmospheric particles may be affected, with important implications for climate predictions. The actual occurrence of liquidliquid phase separation within individual atmospheric particles has been considered uncertain, in large part because of the absence of observations for real-world samples. Here, using optical and fluorescence microscopy, we present images that show the coexistence of two noncrystalline phases for real-world samples collected on multiple days in Atlanta, GA as well as for laboratory-generated samples under simulated atmospheric conditions. These results reveal that atmospheric particles can undergo liquidliquid phase separations. To explore the implications of these findings, we carried out simulations of the Atlanta urban environment and found that liquidliquid phase separation can result in increased concentrations of gas-phase NO3 and N2O5 due to decreased particle uptake of N2O5. PMID:22847443

  15. Activity coefficients of aqueous sodium chloride from 15° to 50°C measured with a glass electrode

    USGS Publications Warehouse

    Truesdell, A.H.

    1968-01-01

    Values of the mean activity coefficient of sodium chloride at 15°, 25°, 38° and 50°C were determined for aqueous NaCl solutions of 0.01 to 1.0 molal from electromotive force measurements on the cell: (sodium-sensitive glass electrode, aqueous sodium chloride, silver chloride-silver).

  16. Interactions between 33 solutes and four cyano-containing stationary phases: gas chromatographic activity coefficients and the solvation parameter model.

    PubMed

    Santiuste, Jos M; Takcs, Jzsef M

    2003-07-01

    Infinite-dilution gas-liquid chromatographic activity coefficients at 393.15 K (with their thermal and athermal components) and derived excess partial molar Gibbs energies, enthalpies, and entropies have been determined for each of 33 solutes of different polarity on four stationary phases with cyano groups, using retention data taken from the literature. The strongest interactions predicted by the solvation model are the dipolarity/polarizability, the acidic solute-basic stationary phase interaction, and nonpolar cavity formation and dispersion. These interactions were compared with those evaluated from the solute activity coefficients; the effect of the solute connectivity index and dipole moment on nonpolar and polar interactions, respectively, is discussed. The dependence of the thermal activity coefficient on nonpolar interactions, and the influence of stationary phase polarity on the four solute-stationary phase interactions, were evaluated. The nonpolar interaction increases with increasing connectivity and with increasing athermal activity coefficient. The dipolarity/polarizability interaction increases with increasing solute dipole moment. Finally, polar interactions increase with increasing stationary phase polarity whereas the nonpolar interaction is independent of stationary phase polarity. PMID:12819849

  17. COMPUTATIONAL CHEMISTRY METHOD FOR PREDICTING VAPOR PRESSURES AND ACTIVITY COEFFICIENTS OF POLAR ORGANIC OXYGENATES IN PM2.5

    EPA Science Inventory

    Parameterizations of interactions of polar multifunctional organic oxygenates in PM2.5 must be included in aerosol chemistry models for evaluating control strategies for reducing ambient concentrations of PM2.5 compounds. Vapor pressures and activity coefficients of these compo...

  18. Solute-solvent interactions from gas chromatographic activity coefficients and the solvation parameter model for nitrogen-containing stationary phases.

    PubMed

    Santiuste, Jos M

    2003-04-01

    Infinite dilution gas-liquid chromatographic activity coefficients (gamma) and excess thermodynamic molar partial magnitudes [Gibbs energy (G(E)), enthalpy (H(E)), and entropy (S(E))] for 37 solutes of varied polarity on four stationary phases with -NH groups are obtained from partition coefficients taken from literature. Relationships between G(E) and S(E) with the 37 solutes' structure in terms of the molecular connectivity index ((1)chi(v)) are investigated. Correlations of solute-solvent interactions calculated in light of the solvation parameter model for selected solutes and stationary phases are tested. The effect of the solute's structure, expressed as the molecular connectivity index, on the nonpolar (cavity formation and dispersion interaction) [c+l. log L(16)] and the effect of the dipole moment and of the activity coefficient on the dipolarity-polarizability interaction (spi(2)(H)) are studied. The correlation between the nonpolar interaction with the athermal activity coefficient on the nonpolymeric stationary phases is also attempted. In addition, the influence of the stationary phase polarity on the solute-stationary phase interactions for a series of solutes is studied. PMID:12803811

  19. Oiling out or molten hydrate-liquid-liquid phase separation in the system vanillin-water.

    PubMed

    Svärd, Michael; Gracin, Sandra; Rasmuson, Ake C

    2007-09-01

    Vanillin crystals in a saturated aqueous solution disappear and a second liquid phase emerges when the temperature is raised above 51 degrees C. The phenomenon has been investigated with crystallization and equilibration experiments, using DSC, TGA, XRD and hot-stage microscopy for analysis. The new liquid solidifies on cooling, appears to melt at 51 degrees C, and has a composition corresponding to a dihydrate. However, no solid hydrate can be detected by XRD, and it is shown that the true explanation is that a liquid-liquid phase separation occurs above 51 degrees C where the vanillin-rich phase has a composition close to a dihydrate. To our knowledge, liquid-liquid phase separation has not previously been reported for the system vanillin-water, even though thousands of tonnes of vanillin are produced globally every year. PMID:17497737

  20. Gravity and configurational energy induced microstructural changes in liquid phase sintering

    NASA Astrophysics Data System (ADS)

    Kipphut, C. M.; Bose, A.; Farooq, S.; German, R. M.

    1988-08-01

    Liquid phase sintered materials consist of interconnected crystalline grains in a homogeneous matrix phase that forms the liquid at high temperatures. The dihedral angle, grain size, and volume fraction of solid determine the energy of the system. Energy minimization is possible by the separation of phases due to density differences. This explains why some materials exhibit settling or distortion due to gravity during liquid phase sintering. Experiments performed with W-Ni-Fe heavy alloys are used to measure the microstructural changes vs position that occur in liquid phase sintering under normal gravity. The experimentally observed segregation is less than the calculated equilibrium seg-regation due to the retarding effect from the rigid solid skeleton formed during sintering. These re-sults improve our understanding of microstructure, mechanical properties, component shape, and dimensional stability benefits that may be realized from low gravity sintering.

  1. Applications of liquid-phase microextraction techniques in natural product analysis: a review.

    PubMed

    Yan, Yunyan; Chen, Xuan; Hu, Shuang; Bai, Xiaohong

    2014-11-14

    Over the last years, liquid-phase microextraction (LPME) as a simple, rapid, practical and effective sample-preparation technique, coupled with various instrumental analytical methods, has been increasingly and widely used to research and determine trace or ultra-micro-levels of both inorganic and organic analytes from different matrix-complex samples. In this review, different kinds of LPMEs such as single drop liquid-phase microextraction, dispersive liquid-liquid microextraction, and hollow fibre liquid-phase microextraction are summarized and recent applications of LPMEs in trace compounds in vivo and in vitro from different natural product matrice analysis such as tea, vegetables, seeds, herbs, and galenical are also discussed. Finally, future developments and applications of LPMEs in complex sample analysis are prospected. PMID:25441339

  2. Dynamic evolution of liquid–liquid phase separation during continuous cooling

    DOE PAGESBeta

    Imhoff, Seth D.; Gibbs, Paul J.; Katz, Martha R.; Ott, Thomas J.; Patterson, Brian M.; Lee, Wah-Keat; Fezzaa, Kamel; Cooley, Jason C.; Clarke, Amy J.

    2015-01-06

    Solidification from a multiphase fluid involves many unknown quantities due to the difficulty of predicting the impact of fluid flow on chemical partitioning. Real-time x-ray radiography was used to observe liquid-liquid phase separation in Al90In10 prior to solidification. Quantitative image analysis was used to measure the motion and population characteristics of the dispersed indium-rich liquid phase during cooling. Here we determine that the droplet growth characteristics resemble well known steady-state coarsening laws with likely enhancement by concurrent growth due to supersaturation. Simplistic views of droplet motion are found to be insufficient until late in the reaction due to a hydrodynamicmore » instability caused by the large density difference between the dispersed and matrix liquid phases.« less

  3. Empty liquid phase of colloidal ellipsoids: the role of shape and interaction anisotropy.

    PubMed

    Varga, Szabolcs; Meneses-Jarez, Efrain; Odriozola, Gerardo

    2014-04-01

    We study the effect of anisotropic excluded volume and attractive interactions on the vapor-liquid phase transition of colloidal ellipsoids. In our model, the hard ellipsoid is embedded into an ellipsoidal well, where both the shape of the hard ellipsoid and that of the added enclosing ellipsoidal well can be varied independently. The bulk properties of these particles are examined by means of a van der Waals type perturbation theory and validated with replica exchange Monte Carlo simulations. It is shown that both the critical volume fraction (?c) and the critical temperature (Tc) of the vapor-liquid phase transition vanish with increasing shape anisotropy for oblate shapes, while ?c ? 0 and Tc ? 0 are obtained for very elongated prolate shapes. These results suggest that the chance to stabilize empty liquids (a liquid phase with vanishing density) is higher in suspensions of rod-like colloidal ellipsoids than in those of plate-like ones. PMID:24712814

  4. Dynamic evolution of liquid–liquid phase separation during continuous cooling

    SciTech Connect

    Imhoff, Seth D.; Gibbs, Paul J.; Katz, Martha R.; Ott, Thomas J.; Patterson, Brian M.; Lee, Wah-Keat; Fezzaa, Kamel; Cooley, Jason C.; Clarke, Amy J.

    2015-01-06

    Solidification from a multiphase fluid involves many unknown quantities due to the difficulty of predicting the impact of fluid flow on chemical partitioning. Real-time x-ray radiography was used to observe liquid-liquid phase separation in Al90In10 prior to solidification. Quantitative image analysis was used to measure the motion and population characteristics of the dispersed indium-rich liquid phase during cooling. Here we determine that the droplet growth characteristics resemble well known steady-state coarsening laws with likely enhancement by concurrent growth due to supersaturation. Simplistic views of droplet motion are found to be insufficient until late in the reaction due to a hydrodynamic instability caused by the large density difference between the dispersed and matrix liquid phases.

  5. Rapid destruction of the rhodamine B using TiO2 photocatalyst in the liquid phase plasma

    PubMed Central

    2013-01-01

    Background Rhodamine B (RhB) is widely used as a colorant in textiles and food stuffs, and is also a well-known water tracer fluorescent. It is harmful to human beings and animals, and causes irritation of the skin, eyes and respiratory tract. The carcinogenicity, reproductive and developmental toxicity, neurotoxicity and chronic toxicity toward humans and animals have been experimentally proven. RhB cannot be effectively removed by biological treatment due to the slow kinetics. Therefore, RhB is chosen as a model pollutant for liquid phase plasma (LPP) treatment in the present investigation. Results This paper presents experimental results for the bleaching of RhB from aqueous solutions in the presence of TiO2 photocatalyst with LPP system. Properties of generated plasma were investigated by optical emission spectroscopy methods. The results of electrical-discharge degradation of RhB showed that the decomposition rate increased with the applied voltage, pulse width, and frequency. The oxygen gas addition to reactant solution increases the degradation rate by active oxygen species. The RhB decomposition rate was shown to increase with the TiO2 particle dosage. Conclusion This work presents the conclusions on the photocatalytic oxidation of RhB, as a function of plasma conditions, oxygen gas bubbling as well as TiO2 particle dosage. We knew that using the liquid phase plasma system with TiO2 photocatalyst at high speed we could remove the organic matter in the water. PMID:24041151

  6. Measurements of liquid phase residence time distributions in a pilot-scale continuous leaching reactor using radiotracer technique.

    PubMed

    Pant, H J; Sharma, V K; Shenoy, K T; Sreenivas, T

    2015-03-01

    An alkaline based continuous leaching process is commonly used for extraction of uranium from uranium ore. The reactor in which the leaching process is carried out is called a continuous leaching reactor (CLR) and is expected to behave as a continuously stirred tank reactor (CSTR) for the liquid phase. A pilot-scale CLR used in a Technology Demonstration Pilot Plant (TDPP) was designed, installed and operated; and thus needed to be tested for its hydrodynamic behavior. A radiotracer investigation was carried out in the CLR for measurement of residence time distribution (RTD) of liquid phase with specific objectives to characterize the flow behavior of the reactor and validate its design. Bromine-82 as ammonium bromide was used as a radiotracer and about 40-60MBq activity was used in each run. The measured RTD curves were treated and mean residence times were determined and simulated using a tanks-in-series model. The result of simulation indicated no flow abnormality and the reactor behaved as an ideal CSTR for the range of the operating conditions used in the investigation. PMID:25528019

  7. Radial distribution modeling of liquid-phase phenol concentration in a liquid-solid fluidized bed photoreactor.

    PubMed

    Dong, Shuangshi; Zhou, Dandan; Bi, Xiaotao

    2012-01-01

    A fluidized bed photoreactor with titanium dioxide-immobilized spherical activated carbon particles was examined. The light intensity profile was modeled using the Lambert-Beer rule for the modeling of the radial distribution of liquid-phase phenol concentration in the fluidized bed photoreactor, when considering the reactor composed of numerous differential annular drums and no mass transfer between drums. The model could be well matched with the experimental data which indicated the liquid flow rate of 13.8 L/min was the optimum in the balance of flow rate-related light penetration and photocatalyst concentration. By integration of liquid-phase phenol concentration along the radius, photocatalytic oxidation performance of the photoreactor was evaluated in comparison with the experimental data and model prediction. The results showed that the errors were less than 30% for most of the predictions. It is suggested that mass transfer and flow rate difference along the radial direction should be considered to obtain more precise prediction. PMID:22377991

  8. Pressureless Reaction Sintering of AlON using Aluminum Orthophosphate as a Transient Liquid Phase

    SciTech Connect

    Michael Bakas; Henry Chu

    2009-01-01

    Use of aluminum oxynitride (AlON) in transparent armor systems has been difficult due to the expense and limitations of the processing methods currently necessary to achieve transparency. Development of a pressureless processing method based on direct reaction sintering of alumina and aluminum nitride powders would reduce costs and provide a more flexible and practical manufacturing method. It may be possible to develop such a processing method using liquid phase sintering; as long as the liquid phase does not remain in the final sample. AlPO4 forms a liquid phase with Al2O3 and AlN at the temperatures required to sinter AlON, and slowly decomposes into P2O5 and alumina. Therefore, it was investigated as a possible transient liquid phase for reaction-sintered AlON. Small compacts of alumina and aluminum nitride with up to of 15wt% AlPO4 additive were pressed and sintered. It was found that AlPO4 formed the requisite transient liquid phase, and it was possible to adjust the process to produce AlON samples with good transmission and densities of 3.66-3.67 g/cc. XRD confirmed the samples formed were AlON, with no trace of any remaining phosphate phases or excess alumina or aluminum nitride. Based on the results, it was concluded that AlPO4 could be utilized as a transient liquid phase to improve the density and transmission of AlON produced by pressureless reaction sintering.

  9. In Situ Microfocus Chemical Computed Tomography of the Composition of a Single Catalyst Particle During Hydrogenation of Nitrobenzene in the Liquid Phase**

    PubMed Central

    Price, Stephen W T; Geraki, Kalotina; Ignatyev, Konstantin; Witte, Peter T; Beale, Andrew M; Mosselmans, J Fred W

    2015-01-01

    Heterogeneous catalysis performed in the liquid phase is an important type of catalytic process which is rarely studied in situ. Using microfocus X-ray fluorescence and X-ray diffraction computed tomography (?-XRF-CT, ?-XRD-CT) in combination with X-ray absorption near-edge spectroscopy (XANES), we have determined the active state of a Mo-promoted Pt/C catalyst (NanoSelect) for the liquid-phase hydrogenation of nitrobenzene under standard operating conditions. First, ?-XRF-CT and ?-XRD-CT reveal the active state of Pt catalyst to be reduced, noncrystalline, and evenly dispersed across the support surface. Second, imaging of the Pt and Mo distribution reveals they are highly stable on the support and not prone to leaching during the reaction. This study demonstrates the ability of chemical computed tomography to image the nature and spatial distribution of catalysts under reaction conditions. PMID:26140613

  10. In Situ Microfocus Chemical Computed Tomography of the Composition of a Single Catalyst Particle During Hydrogenation of Nitrobenzene in the Liquid Phase.

    PubMed

    Price, Stephen W T; Geraki, Kalotina; Ignatyev, Konstantin; Witte, Peter T; Beale, Andrew M; Mosselmans, J Fred W

    2015-08-17

    Heterogeneous catalysis performed in the liquid phase is an important type of catalytic process which is rarely studied in?situ. Using microfocus X-ray fluorescence and X-ray diffraction computed tomography (?-XRF-CT, ?-XRD-CT) in combination with X-ray absorption near-edge spectroscopy (XANES), we have determined the active state of a Mo-promoted Pt/C catalyst (NanoSelect) for the liquid-phase hydrogenation of nitrobenzene under standard operating conditions. First, ?-XRF-CT and ?-XRD-CT reveal the active state of Pt catalyst to be reduced, noncrystalline, and evenly dispersed across the support surface. Second, imaging of the Pt and Mo distribution reveals they are highly stable on the support and not prone to leaching during the reaction. This study demonstrates the ability of chemical computed tomography to image the nature and spatial distribution of catalysts under reaction conditions. PMID:26140613

  11. SANS Study of Liquid-Liquid Phase Transition in Protein Electrolyte Solution

    NASA Astrophysics Data System (ADS)

    Chinchalikar, Akshay J.; Aswal, V. K.; Kohlbrecher, J.; Wagh, A. G.

    2011-07-01

    Small-angle Neutron Scattering (SANS) measurements have been performed on lysozyme protein solution to examine liquid-liquid phase transition with the addition of NaCl. We show that the liquid-liquid phase transition is governed by the increase in the attractive interaction between protein molecules as tuned by the salt concentration. This attractive interaction is modeled by the Baxter's sticky hard sphere potential. It is found that when the attractive potential becomes significantly larger than the thermal energy protein molecules coalesce to form gel.

  12. Chemical studies of elements with Z ≥ 104 in liquid phase

    NASA Astrophysics Data System (ADS)

    Nagame, Yuichiro; Kratz, Jens Volker; Schädel, Matthias

    2015-12-01

    Recent studies of the chemical separation and characterization experiments of the first three transactinide elements, rutherfordium (Rf), dubnium (Db), and seaborgium (Sg), conducted atom-at-a-time in liquid phases, are reviewed. A short description on experimental techniques based on partition methods, specifically automated rapid chemical separation systems, is also given. A newly developed experimental approach to investigate single atoms of the heaviest elements with an electrochemical method is introduced. Perspectives for liquid-phase chemistry experiments on heavier elements are briefly discussed.

  13. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH) Process

    SciTech Connect

    1998-12-21

    he Liquid Phase Methanol (LPMEOW) Demonstration Project at Kingsport Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership) to produce methanol from coal-derived synthesis gas (syngas). Air Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. The LPMEOEP Process Demonstration Unit was built at a site located at the Eastman coal-to-chemicals complex in Kingsport. The LPMEOHW Demonstration Facility completed its first year of operation on 02 April 1998. The LPMEOW Demonstration Facility also completed the longest continuous operating run (65 days) on 21 April 1998. Catalyst activity, as defined by the ratio of the rate constant at any point in time to the rate constant for freshly reduced catalyst (as determined in the laboratory autoclave), was monitored throughout the reporting period. During a six-week test at a reactor temperature of 225oC and Balanced Gas flowrate of 700 KSCFH, the rate of decline in catalyst activity was steady at 0.29-0.36% per day. During a second one-month test at a reactor temperature of 220oC and a Balanced Gas flowrate of 550-600 KSCFH, the rate of decline in catalyst activity was 0.4% per day, which matched the pefiorrnance at 225"C, as well as the 4-month proof-of-concept run at the LaPorte AFDU in 1988/89. Beginning on 08 May 1998, the LPMEOW Reactor temperature was increased to 235oC, which was the operating temperature tier the December 1997 restart with the fresh charge of catalyst (50'Yo of design loading). The flowrate of the primary syngas feed stream (Balanced Gas) was also increased to 700-750 KSCFH. During two stable operating periods between 08 May and 09 June 1998, the average catalyst deactivation rate was 0.8% per day. Due to the scatter of the statistical analysis of the results, this test was extended to better quanti& the catalyst aging behavior. During the reporting perio~ two batches of fresh catalyst were activated and transferred to the reactor (on 02 April and 20 June 1998). The weight of catalyst in the LPMEOW Reactor has reached 80% of the design value. At the end of the reporting period, a step-change in the pressure-drop profile within the LPMEOW Reactor and an increase in the pressure of the steam system which provides cooling to the LPMEOW Reactor were observed. No change in the calculated activity of the catalyst was detected during either of these transients. These parameters will be monitored closely for any additional changes.

  14. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH) Process

    SciTech Connect

    1998-12-21

    The Liquid Phase Methanol (LPMEOW) Demonstration Project at Kingsport Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership) to produce methanol from coal-derived synthesis gas (syngas). Air Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. The LPMEOW Process Demonstration Unit was built at a site located at the Eastman complex in Kingsport. During this quarter, initial planning and procurement work began on the seven project sites which have been accepted for participation in the off-site, methanol product-use test plan. Two of the projects have begun pre-testing of equipment and three other projects have commenced with equipment procurement, Methanol produced from carbon monoxide (CO)- rich syngas at the Alternative Fuels Development Unit (AFDU) in LaPorte, TX has been shipped to four of the project sites in anticipation of the start of testing during the first quarter of calendar year 1998. Catalyst activity, as defined by the ratio of the rate constant at any point in time to the rate constant for a freshly reduced catalyst (as determined in the laboratory autoclave), continued to decline more rapidly than expected. In response to concentrations of arsenic and sulfbr detected on catalyst samples from the LPMEOW Reactor, Eastman replaced both the arsine- and sulfiwremoval material in the Eastman guard bed which treats the primary syngas feed stream (&danced Gas) prior to its introduction into both the Eastman fixed-bed methanol plant and the LPMEOWM Demonstration Unit. After restarting the demonstration unit, the catalyst deactivation rate remained essentially unchanged. Parallel testing in the laboratory using arsine-doped, and subsequently arsine- and SuIfi-doped syngas, ako ftiIed to prove that arsine was responsible for the higher-than-expected rate of catalyst deactivation in the demonstration unit. Based on the results of plant operation and catalyst sampling, DOE accepted a recommendation by Air Products and Eastman to drain the initial charge of catalyst from the reactor and replace the charge with fresh catalyst. Prior to this catalyst turnaround, a final test was performed to determine the impact of raising the operating temperature of the LPMEOW Reactor from 250"C to 260oC. carbon. Activation of the new flesh charge of catalyst began on 13 November 1997. Just as in the original start-up in April of 1997, only a partial charge of catalyst (20,700 pounds) was activated to limit the amount of material exposed to poisons at the outset. An attempted restart of the LPMEOW Demonstration Unit on 26 November 1997 was unsuccessfid; settling of the flesh catalyst appeared to have occurred in the LPMEOFP Reactor and gas inlet piping, which resulted in the plugging of the gas sparger at the bottom of the vessel.

  15. Construction of polynomial matrix using block coefficient matrix representation auto-regressive moving average model for actively controlled structures

    NASA Astrophysics Data System (ADS)

    Chunxiang, Li; Dai, Zhou

    2004-12-01

    The polynomial matrix using the block coefficient matrix representation auto-regressive moving average (referred to as the PM-ARMA) model is constructed in this paper for actively controlled multi-degree-of-freedom (MDOF) structures with time-delay through equivalently transforming the preliminary state space realization into the new state space realization. The PM-ARMA model is a more general formulation with respect to the polynomial using the coefficient representation auto-regressive moving average (ARMA) model due to its capability to cope with actively controlled structures with any given structural degrees of freedom and any chosen number of sensors and actuators. (The sensors and actuators are required to maintain the identical number.) under any dimensional stationary stochastic excitation.

  16. Ecotoxicology of heavy metals: Liquid-phase extraction by nanosorbents

    NASA Astrophysics Data System (ADS)

    Burakov, A.; Romantsova, I.; Babkin, A.; Neskoromnaya, E.; Kucherova, A.; Kashevich, Z.

    2015-11-01

    The paper considers the problem of extreme toxicity heavy metal compounds dissolved in wastewater and liquid emissions of industrial enterprises to living organisms and environment as a whole. The possibility of increasing extraction efficiency of heavy metal ions by sorption materials was demonstrated. The porous space of the latter was modified by carbon nanotubes (CNTs) during process of the chemical vapour deposition (CVD) of carbon on metal oxide catalysts. The increasing of the sorption capacity (10-30%) and the sorption rate of nanomodified activated carbons in comparison with standard materials in the example of absorption of Co2+ and Ni2+ ions from aqueous solutions was proven.

  17. Evidence for liquid phase reactions during single bubble acoustic cavitation.

    PubMed

    Troia, A; Madonna Ripa, D; Lago, S; Spagnolo, R

    2004-07-01

    We extended the recent experiment by Lepoint et al. [Sonochemistry and Sonoluminescence, NATO ASI Series, Series C 524, Kluwer Academic Publishers, Dordrecht/Boston/London, 1999, p. 285], involving a so-called single bubble sonochemistry process, to a three-phase system. We have found experimental evidence that a single cavitating bubble can activate the oxidation of I- ions after the injection of a CCl4 liquid drop in the bubble trapping apparatus. The solvent drop (CCl4 is almost water insoluble) is pushed towards the bubble position and forms a thin film on the bubble surface. When the acoustic pressure drive is increased above 100 kPa, the three-phase system gives rise to a dark filament, indicating the complexation reaction between starch (added to the water phase) and I2. I2 species is the product of surface reactions involving bubble-induced decomposition of CCl4. Further increase of the acoustic drive causes the thin CCl4 film to separate from the bubble and stops I2 production. The study of the chemical activity of this three-phase system could give new advances on dynamics of the bubble collapse. PMID:15157862

  18. The effect of concentration- and temperature-dependent dielectric constant on the activity coefficient of NaCl electrolyte solutions

    SciTech Connect

    Valiskó, Mónika; Boda, Dezső

    2014-06-21

    Our implicit-solvent model for the estimation of the excess chemical potential (or, equivalently, the activity coefficient) of electrolytes is based on using a dielectric constant that depends on the thermodynamic state, namely, the temperature and concentration of the electrolyte, ε(c, T). As a consequence, the excess chemical potential is split into two terms corresponding to ion-ion (II) and ion-water (IW) interactions. The II term is obtained from computer simulation using the Primitive Model of electrolytes, while the IW term is estimated from the Born treatment. In our previous work [J. Vincze, M. Valiskó, and D. Boda, “The nonmonotonic concentration dependence of the mean activity coefficient of electrolytes is a result of a balance between solvation and ion-ion correlations,” J. Chem. Phys. 133, 154507 (2010)], we showed that the nonmonotonic concentration dependence of the activity coefficient can be reproduced qualitatively with this II+IW model without using any adjustable parameter. The Pauling radii were used in the calculation of the II term, while experimental solvation free energies were used in the calculation of the IW term. In this work, we analyze the effect of the parameters (dielectric constant, ionic radii, solvation free energy) on the concentration and temperature dependence of the mean activity coefficient of NaCl. We conclude that the II+IW model can explain the experimental behavior using a concentration-dependent dielectric constant and that we do not need the artificial concept of “solvated ionic radius” assumed by earlier studies.

  19. New catalytic liquid-phase ammoxidation approach to the preparation of niacin (vitamin B3).

    PubMed

    Raja, Robert; Adams, Richard D; Blom, Douglas A; Pearl, William C; Gianotti, Enrica; Thomas, John Meurig

    2009-07-01

    New highly dispersed bimetallic nanoscale catalysts based on rhenium combined with antimony or bismuth have been shown to be highly effective for the ammoxidation of 3-picoline to nicotinonitrile (precursor for vitamin B3) under mild conditions in the liquid phase. PMID:19462987

  20. Laser two-photon ionization and autoionization spectroscopy of molecules in the liquid phase

    SciTech Connect

    Siomos, K.; Kourouklis, G.A.; Christophorou, L.G.

    1983-01-01

    The observation of autoionizing states of molecules in the liquid phase together with one- and two-photon ionization threshold measurements obtained using a laser conductivity technique are reported. Coherent versus resonant (stepwise) two-photon excitation in the photoionization process in solutions is discussed.

  1. Liquid-liquid phase transitions in supercooled water studied by computer simulations of various water models

    NASA Astrophysics Data System (ADS)

    Brovchenko, Ivan; Geiger, Alfons; Oleinikova, Alla

    2005-07-01

    Liquid-liquid and liquid-vapor coexistence regions of various water models were determined by Monte Carlo (MC) simulations of isotherms of density fluctuation-restricted systems and by Gibbs ensemble MC simulations. All studied water models show multiple liquid-liquid phase transitions in the supercooled region: we observe two transitions of the TIP4P, TIP5P, and SPCE models and three transitions of the ST2 model. The location of these phase transitions with respect to the liquid-vapor coexistence curve and the glass temperature is highly sensitive to the water model and its implementation. We suggest that the apparent thermodynamic singularity of real liquid water in the supercooled region at about 228 K is caused by an approach to the spinodal of the first (lowest density) liquid-liquid phase transition. The well-known density maximum of liquid water at 277 K is related to the second liquid-liquid phase transition, which is located at positive pressures with a critical point close to the maximum. A possible order parameter and the universality class of liquid-liquid phase transitions in one-component fluids are discussed.

  2. Temporal and spatial characterization of turbulent structures in liquid phase using POD technique

    NASA Astrophysics Data System (ADS)

    Munir, S.; Heikal, M. R.; Aziz, A. Rashid A.; Muthuvalu, M. S.; Siddiqui, M. I.

    2015-05-01

    The temporal and spatial structures of turbulent liquid phase (water) in pipelines were investigated. Two cases were considered one single liquid phase flow at 80 l/m, second slugy part of slug flow by introducing gas (compressed air) at 60 l/m while keeping liquid flow rate same. Particle image velocimetry (PIV) was used for quantitative measurement of two-dimensional instantaneous velocity of liquid phase. The overall effect of coherent structures on the dynamics of flow in liquid phase for both cases were studied by proper orthogonal decomposition (POD). POD technique was able to identify the structures and characterize them. Spatial and temporal modes were achieved for both cases. The dynamics of flow structure were quite changed with the introduction of gas phase for case II. For case I, the first two spatial modes contained 40% of the energy while for case II only first spatial contained the maximum energy. FFT analysis of temporal modes showed that the first temporal mode for case I has frequency 4.617 while for case II the first temporal mode has frequency 4.64Hz.

  3. Surfactant-enhanced carbon regeneration in liquid-phase application

    SciTech Connect

    Bhummasobhana, A.; Osuwan, S.; Shooshat, B.

    1996-03-01

    In surfactant-enhanced carbon regeneration, a concentrated surfactant solution is passed over spent activated carbon to desorb the solutes in an in-situ process. The solutes solubilize into micelles in the regenerant solution. Residual adsorbed surfactant can be removed by a water flush. In this study, phenol is the solute and sodium dodecyl sulfate is the anionic surfactant used. Previous studies have measured the ability of the regenerant to remove the solute from the carbon. This study presents the breakthrough curves for subsequent adsorption cycles following the regeneration. The reduction of the effective carbon adsorption capacity is less if a higher regenerant concentration of surfactant, more pore volumes of regenerant, or more pore volumes of water flush solution are used. Effective adsorption capacities of over 50% of that on virgin carbon were observed on regenerated carbon.

  4. Simultaneous reconstruction of emission activity and attenuation coefficient distribution from TOF data, acquired with external transmission source

    NASA Astrophysics Data System (ADS)

    Panin, V. Y.; Aykac, M.; Casey, M. E.

    2013-06-01

    The simultaneous PET data reconstruction of emission activity and attenuation coefficient distribution is presented, where the attenuation image is constrained by exploiting an external transmission source. Data are acquired in time-of-flight (TOF) mode, allowing in principle for separation of emission and transmission data. Nevertheless, here all data are reconstructed at once, eliminating the need to trace the position of the transmission source in sinogram space. Contamination of emission data by the transmission source and vice versa is naturally modeled. Attenuated emission activity data also provide additional information about object attenuation coefficient values. The algorithm alternates between attenuation and emission activity image updates. We also proposed a method of estimation of spatial scatter distribution from the transmission source by incorporating knowledge about the expected range of attenuation map values. The reconstruction of experimental data from the Siemens mCT scanner suggests that simultaneous reconstruction improves attenuation map image quality, as compared to when data are separated. In the presented example, the attenuation map image noise was reduced and non-uniformity artifacts that occurred due to scatter estimation were suppressed. On the other hand, the use of transmission data stabilizes attenuation coefficient distribution reconstruction from TOF emission data alone. The example of improving emission images by refining a CT-based patient attenuation map is presented, revealing potential benefits of simultaneous CT and PET data reconstruction.

  5. Calculation of the chemical potential and the activity coefficient of two layers of CO2 adsorbed on a graphite surface.

    PubMed

    Trinh, T T; Bedeaux, D; Simon, J-M; Kjelstrup, S

    2015-01-14

    We study the adsorption of carbon dioxide at a graphite surface using the new Small System Method, and find that for the temperature range between 300 K and 550 K most relevant for CO2 separation; adsorption takes place in two distinct thermodynamic layers defined according to Gibbs. We calculate the chemical potential and the activity coefficient of both layers directly from the simulations. Based on thermodynamic relations, the entropy and enthalpy of the CO2 adsorbed layers are also obtained. Their values indicate that there is a trade-off between entropy and enthalpy when a molecule chooses for one of the two layers. The first layer is a densely packed monolayer of relatively constant excess density with relatively large repulsive interactions and negative enthalpy. The second layer has an excess density varying with the temperature, an activity coefficient, which also indicates repulsion, but to a much smaller degree than in the first layer. Results for activity coefficients, entropies and enthalpies can be used to model transport through and along graphitic membranes for carbon dioxide separation purposes. PMID:25418118

  6. Liquid phase epitaxial growth of GaAs

    SciTech Connect

    Wynne, D I

    1997-10-01

    Research into new semiconductor materials for measurement of electromagnetic radiation over a wide range of energies has been an active field for several decades. There is a strong desire to identify and develop new materials which can lead to improved detectors. Such devices are expected to solve problems that cannot be solved using the semiconductor materials and device structures which have been traditionally used for radiation detection. In order for a detector which is subjected to some type of irradiation to respond, the radiation must undergo an interaction with the detector. The net result of the radiation interaction in a broad category of detectors is the generation of mobile electric charge carriers (electrons and/or holes) within the detector active volume. This charge is collected at the detector contacts and it forms the basic electrical signal. Typically, the collection of the charge is accomplished through the imposition of an electric field within the detector which causes the positive and/or negative charges created by the radiation to flow in opposite directions to the contacts. For the material to serve as a good radiation detector, a large fraction (preferably 100%) of all carriers created by the interacting incident radiation must be collected. Charge trapping by deep level impurities and structural defects can seriously degrade detector performance. The focus of this thesis is on far infrared and X-ray detection. In X-ray detector applications of p-I-n diodes, the object is to measure accurately the energy distribution of the incident radiation quanta. One important property of such detectors is their ability to measure the energy of individual incident photons with high energy resolution.

  7. Heterogeneity of the Liquid Phase, and Vapor Separation in Los Azufres (Mexico) Geothermal Reservoir

    SciTech Connect

    Nieva, D.; Quijano, L.; Garfias, A.; Barragan, R.M.; Laredo, F.

    1983-12-15

    Data of chemical and isotopic composition of fluids from Los Azufres geothermal wells is interpreted in order to characterize the composition of the liquid phase, and to define the relation between this phase and fluids from steam-producing wells. Chemical and specific enthalpy data show that most wells considered are fed a mixture of steam and liquid. Thus, flashing occurs in the formation. This poses a problem on the interpretation of isotopic data, because the composition of the feeding mixture need not be representative of the composition of the liquid phase in the reservoir. Two extreme alternatives for the interpretation of isotopic data are considered. In the first alternative the composition of the total discharge is considered to be the same as that of the liquid in the reservoir. In the second alternative the feeding fluid is considered to be a mixture of the liquid phase in the reservoir and the calculated fraction of steam. In addition, this steam is assumed to separate from a much larger mass of that liquid phase at the downhole temperature. The contribution of steam is then subtracted from the total discharge to yield the composition of the liquid phase. Using data for silica concentration in total discharge and separated water, the chloride concentration in the reservoir liquid is calculated. This result is used to calculate the fraction of steam in the feeding mixture of each well. The isotopic data is then corrected as proposed for the second alternative, to yield the composition of the liquid phase. Comparison of the corrected and uncorrected isotopic values shows that the correction has an important effect only when the steam mass fraction in the feeding mixture is large (> 20%). The correction tends to reduce the dispersion of data points in a {delta} D vs {delta}{sup 18}O diagram. Points representing composition of liquid phase show an approximately linear distribution, suggesting a process of mixing of two fluids. Available data appears to rule out the possibility of mixture with local meteoric or shallow ground waters. Some spatial correlations of composition are noted. The composition of fluids produced by two steam wells corresponds to steam separated from a much larger mass of liquid. Temporal variations in the composition of fluid produced by steam well A-6 suggests that this well might be fed with steam from more than one section in the reservoir.

  8. Extraterrestrial material analysis: loss of amino acids during liquid-phase acid hydrolysis

    NASA Astrophysics Data System (ADS)

    Buch, Arnaud; Brault, Amaury; Szopa, Cyril; Freissinet, Caroline

    2015-04-01

    Searching for building blocks of life in extraterrestrial material is a way to learn more about how life could have appeared on Earth. With this aim, liquid-phase acid hydrolysis has been used, since at least 1970 , in order to extract amino acids and other organic molecules from extraterrestrial materials (e.g. meteorites, lunar fines) or Earth analogues (e.g. Atacama desert soil). This procedure involves drastic conditions such as heating samples in 6N HCl for 24 h, either under inert atmosphere/vacuum, or air. Analysis of the hydrolyzed part of the sample should give its total (free plus bound) amino acid content. The present work deals with the influence of the 6N HCl hydrolysis on amino acid degradation. Our experiments have been performed on a standard solution of 17 amino acids. After liquid-phase acid hydrolysis (6N HCl) under argon atmosphere (24 h at 100C), the liquid phase was evaporated and the dry residue was derivatized with N-Methyl-N-(t-butyldimethylsilyl)trifluoroacetamide (MTBSTFA) and dimethylformamide (DMF), followed by gas chromatography-mass spectrometry analysis. After comparison with derivatized amino acids from the standard solution, a significant reduction of the chromatographic peak areas was observed for most of the amino acids after liquid-phase acid hydrolysis. Furthermore, the same loss pattern was observed when the amino acids were exposed to cold 6N HCl for a short amount of time. The least affected amino acid, i.e. glycine, was found to be 73,93% percent less abundant compared to the non-hydrolyzed standard, while the most affected, i.e. histidine, was not found in the chromatograms after hydrolysis. Our experiments thereby indicate that liquid-phase acid hydrolysis, even under inert atmosphere, leads to a partial or total loss of all of the 17 amino acids present in the standard solution, and that a quick cold contact with 6N HCl is sufficient to lead to a loss of amino acids. Therefore, in the literature, the reported increase of the total quantity of amino acids after acid hydrolysis, due to the formation/release of amino acids during the whole water extraction / liquid-phase acid hydrolysis, could have hidden a loss of amino acids. Thus, in extraterrestrial material studies involving liquid-phase acid hydrolysis, the quantities of total amino acids may have been underestimated.

  9. Increasing fluorous partition coefficients by solvent tuning.

    PubMed

    Yu, Marvin S; Curran, Dennis P; Nagashima, Tadamichi

    2005-08-18

    Low partition coefficients of fluorous components have been a persistent problem in liquid-liquid separations using perfluoroalkanes as the fluorous phase. Solvent tuning of both the nonfluorous and the fluorous phase dramatically enhances the partitioning of light or polar fluorous molecules into the fluorous liquid phase, while minimally effecting partition coefficients of nonfluorous molecules. These findings suggest an expanded scope for liquid-based separations in fluorous biphasic catalysis, fluorous-tagged reagents, fluorous-supported oligomer synthesis, and related areas. [reaction: see text] PMID:16092848

  10. Slider Induced Convection In Horizontal Liquid Phase Epitaxy (LPE) System

    NASA Astrophysics Data System (ADS)

    Leung, S. Y.; Schumaker, N. E.

    1982-09-01

    The control of thickness uniformity and compositional homogeneity is extremely important in the growth of high quality heterostructure lasers. This is especially important in the growth of the thin active layer of these devices. Slider induced convection within the growth solution in the horizontal LPE system can affect both of these factors and has been largely neglected in the modeling of layer growth. A Plexiglas boat with water and dyes was used to simulate the fluid motions in the melts of the horizontal LPE system. The simulation shows that there are substantial fluid motions induced by the movement of the slider. The duration of the convective cell thus generated can be comparable to the growth time of thin layers. Therefore, a substantial portion of the growth time for thin layers is under nonsteady state conditions where the solution is not static. Furthermore, convection dominates in the initial period of epitaxial growth. The dependence of the convective cell on melt geometry is discussed. A video tape was made showing the solution dynamics of several boat designs used in the growth of (GaA1)As heterostructure lasers.

  11. Temperature-dependent solubilities and mean ionic activity coefficients of alkali halides in water from molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Mester, Zoltan; Panagiotopoulos, Athanassios Z.

    2015-07-01

    The mean ionic activity coefficients of aqueous KCl, NaF, NaI, and NaCl solutions of varying concentrations have been obtained from molecular dynamics simulations following a recently developed methodology based on gradual insertions of salt molecules [Z. Mester and A. Z. Panagiotopoulos, J. Chem. Phys. 142, 044507 (2015)]. The non-polarizable ion models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)], Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)], Reiser et al. [J. Chem. Phys. 140, 044504 (2014)], and Joung and Cheatham [J. Phys. Chem. B 112, 9020 (2008)] were used along with the extended simple point charge (SPC/E) water model [Berendsen et al., J. Phys. Chem. 91, 6269 (1987)] in the simulations. In addition to the chemical potentials in solution used to obtain the activity coefficients, we also calculated the chemical potentials of salt crystals and used them to obtain the solubility of these alkali halide models in SPC/E water. The models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)] and Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)] provide excellent predictions of the mean ionic activity coefficients at 298.15 K and 1 bar, but significantly underpredict or overpredict the solubilities. The other two models generally predicted the mean ionic activity coefficients only qualitatively. With the exception of NaF for which the solubility is significantly overpredicted, the model of Joung and Cheatham predicts salt solubilities that are approximately 40%-60% of the experimental values. The models of Reiser et al. [J. Chem. Phys. 140, 044504 (2014)] make good predictions for the NaCl and NaI solubilities, but significantly underpredict the solubilities for KCl and NaF. We also tested the transferability of the models to temperatures much higher than were used to parametrize them by performing simulations for NaCl at 373.15 K and 1 bar, and at 473.15 K and 15.5 bar. All models overpredict the drop in the values of mean ionic activity coefficients with increased temperature seen in experiments. The present results, together with earlier calculations for a number of models for NaCl aqueous solutions at 298.15 K, point to the strong need for development of improved intermolecular potential models for classical simulations of electrolyte solutions.

  12. Temperature-dependent solubilities and mean ionic activity coefficients of alkali halides in water from molecular dynamics simulations.

    PubMed

    Mester, Zoltan; Panagiotopoulos, Athanassios Z

    2015-07-28

    The mean ionic activity coefficients of aqueous KCl, NaF, NaI, and NaCl solutions of varying concentrations have been obtained from molecular dynamics simulations following a recently developed methodology based on gradual insertions of salt molecules [Z. Mester and A. Z. Panagiotopoulos, J. Chem. Phys. 142, 044507 (2015)]. The non-polarizable ion models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)], Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)], Reiser et al. [J. Chem. Phys. 140, 044504 (2014)], and Joung and Cheatham [J. Phys. Chem. B 112, 9020 (2008)] were used along with the extended simple point charge (SPC/E) water model [Berendsen et al., J. Phys. Chem. 91, 6269 (1987)] in the simulations. In addition to the chemical potentials in solution used to obtain the activity coefficients, we also calculated the chemical potentials of salt crystals and used them to obtain the solubility of these alkali halide models in SPC/E water. The models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)] and Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)] provide excellent predictions of the mean ionic activity coefficients at 298.15 K and 1 bar, but significantly underpredict or overpredict the solubilities. The other two models generally predicted the mean ionic activity coefficients only qualitatively. With the exception of NaF for which the solubility is significantly overpredicted, the model of Joung and Cheatham predicts salt solubilities that are approximately 40%-60% of the experimental values. The models of Reiser et al. [J. Chem. Phys. 140, 044504 (2014)] make good predictions for the NaCl and NaI solubilities, but significantly underpredict the solubilities for KCl and NaF. We also tested the transferability of the models to temperatures much higher than were used to parametrize them by performing simulations for NaCl at 373.15 K and 1 bar, and at 473.15 K and 15.5 bar. All models overpredict the drop in the values of mean ionic activity coefficients with increased temperature seen in experiments. The present results, together with earlier calculations for a number of models for NaCl aqueous solutions at 298.15 K, point to the strong need for development of improved intermolecular potential models for classical simulations of electrolyte solutions. PMID:26233143

  13. Binary Solid-Liquid Phase Diagram of Phenol and t-Butanol: An Undergraduate Physical Chemistry Experiment

    ERIC Educational Resources Information Center

    Xu, Xinhua; Wang, Xiaogang; Wu, Meifen

    2014-01-01

    The determination of the solid-liquid phase diagram of a binary system is always used as an experiment in the undergraduate physical chemistry laboratory courses. However, most phase diagrams investigated in the lab are simple eutectic ones, despite the fact that complex binary solid-liquid phase diagrams are more common. In this article, the…

  14. Binary Solid-Liquid Phase Diagram of Phenol and t-Butanol: An Undergraduate Physical Chemistry Experiment

    ERIC Educational Resources Information Center

    Xu, Xinhua; Wang, Xiaogang; Wu, Meifen

    2014-01-01

    The determination of the solid-liquid phase diagram of a binary system is always used as an experiment in the undergraduate physical chemistry laboratory courses. However, most phase diagrams investigated in the lab are simple eutectic ones, despite the fact that complex binary solid-liquid phase diagrams are more common. In this article, the

  15. Hybrid biofilm-membrane bioreactor (Bf-MBR) for minimization of bulk liquid-phase organic substances and its positive effect on membrane permeability.

    PubMed

    Sun, F Y; Li, P; Li, J; Li, H J; Ou, Q M; Sun, T T; Dong, Z J

    2015-12-01

    Four biofilm membrane bioreactors (Bf-MBRs) with various fixed carrier volumes (C:M) were operated in parallel to investigate the effect of attached-growth mode biomass involvement to the change of liquid-phase organics characteristics and membrane permeability, by comparing with conventional MBR. The experiments displayed that C:M and co-existence of biofilm with suspended solids in Bf-MBRs resulted in slight difference in pollutants removal effectiveness, and in rather distinct biomass properties and bacterial activities. The membrane permeability and specific resistance of bulk suspension of Bf-MBRs related closely with the liquid-phase organic substance, including soluble microbial products (SMP) and biopolymer cluster (BPC). Compared with conventional MBR, Bf-MBR with proper C:M had a low total biomass content and food-chain, where biofilm formation and its dominance affected liquid-phase organics, especially through reducing their content and minimizing strongly and weakly hydrophobic components with small molecular weight, and thus to mitigate membrane fouling significantly. PMID:26454042

  16. Analysis of stimulus-related activity in rat auditory cortex using complex spectral coefficients.

    PubMed

    Krause, Bryan M; Banks, Matthew I

    2013-08-01

    The neural mechanisms of sensory responses recorded from the scalp or cortical surface remain controversial. Evoked vs. induced response components (i.e., changes in mean vs. variance) are associated with bottom-up vs. top-down processing, but trial-by-trial response variability can confound this interpretation. Phase reset of ongoing oscillations has also been postulated to contribute to sensory responses. In this article, we present evidence that responses under passive listening conditions are dominated by variable evoked response components. We measured the mean, variance, and phase of complex time-frequency coefficients of epidurally recorded responses to acoustic stimuli in rats. During the stimulus, changes in mean, variance, and phase tended to co-occur. After the stimulus, there was a small, low-frequency offset response in the mean and modest, prolonged desynchronization in the alpha band. Simulations showed that trial-by-trial variability in the mean can account for most of the variance and phase changes observed during the stimulus. This variability was state dependent, with smallest variability during periods of greatest arousal. Our data suggest that cortical responses to auditory stimuli reflect variable inputs to the cortical network. These analyses suggest that caution should be exercised when interpreting variance and phase changes in terms of top-down cortical processing. PMID:23657279

  17. Analysis of stimulus-related activity in rat auditory cortex using complex spectral coefficients

    PubMed Central

    Krause, Bryan M.

    2013-01-01

    The neural mechanisms of sensory responses recorded from the scalp or cortical surface remain controversial. Evoked vs. induced response components (i.e., changes in mean vs. variance) are associated with bottom-up vs. top-down processing, but trial-by-trial response variability can confound this interpretation. Phase reset of ongoing oscillations has also been postulated to contribute to sensory responses. In this article, we present evidence that responses under passive listening conditions are dominated by variable evoked response components. We measured the mean, variance, and phase of complex time-frequency coefficients of epidurally recorded responses to acoustic stimuli in rats. During the stimulus, changes in mean, variance, and phase tended to co-occur. After the stimulus, there was a small, low-frequency offset response in the mean and modest, prolonged desynchronization in the alpha band. Simulations showed that trial-by-trial variability in the mean can account for most of the variance and phase changes observed during the stimulus. This variability was state dependent, with smallest variability during periods of greatest arousal. Our data suggest that cortical responses to auditory stimuli reflect variable inputs to the cortical network. These analyses suggest that caution should be exercised when interpreting variance and phase changes in terms of top-down cortical processing. PMID:23657279

  18. Chemical Potentials, Activity Coefficients, and Solubility in Aqueous NaCl Solutions: Prediction by Polarizable Force Fields.

    PubMed

    Mou?ka, Filip; Nezbeda, Ivo; Smith, William R

    2015-04-14

    We describe a computationally efficient molecular simulation methodology for calculating the concentration dependence of the chemical potentials of both solute and solvent in aqueous electrolyte solutions, based on simulations of the salt chemical potential alone. We use our approach to study the predictions for aqueous NaCl solutions at ambient conditions of these properties by the recently developed polarizable force fields (FFs) AH/BK3 of Kiss and Baranyai ( J. Chem. Phys. 2013 , 138 , 204507 ) and AH/SWM4-DP of Lamoureux and Roux ( J. Phys. Chem. B 2006 , 110 , 3308 - 3322 ) and by the nonpolarizable JC FF of Joung and Cheatham tailored to SPC/E water ( J. Phys. Chem. B 2008 , 112 , 9020 - 9041 ). We also consider their predictions of the concentration dependence of the electrolyte activity coefficient, the crystalline solid chemical potential, the electrolyte solubility, and the solution specific volume. We first highlight the disagreement in the literature concerning calculations of solubility by means of molecular simulation in the case of the JC FF and provide strong evidence of the correctness of our methodology based on recent independently obtained results for this important test case. We then compare the predictions of the three FFs with each other and with experiment and draw conclusions concerning their relative merits, with particular emphasis on the salt chemical potential and activity coefficient vs concentration curves and their derivatives. The latter curves have only previously been available from Kirkwood-Buff integrals, which require approximate numerical integrations over system pair correlation functions at each concentration. Unlike the case of the other FFs, the AH/BK3 curves are nearly parallel to the corresponding experimental curves at moderate and higher concentrations. This leads to an excellent prediction of the water chemical potential via the Gibbs-Duhem equation and enables the activity coefficient curve to be brought into excellent agreement with experiment by incorporating an appropriate value of the standard state chemical potential in the Henry Law convention. PMID:26574385

  19. Interplay Between Two Phase Transitions: Crystallization and Liquid-Liquid Phase Separation in a Polyolefin Blend

    NASA Astrophysics Data System (ADS)

    Han, Charles C.; Zhang, Xiaohua

    2006-03-01

    The correlation between liquid-liquid phase separation (LLPS) and crystallization at several compositions in statistical copolymer blends of poly (ethylene-co-hexene) (PEH) and poly (ethylene-co-butene) (PEB) has been examined by optical microscopy (OM), atomic force microscopy (AFM) and differential scanning calorimetry (DSC). The overwhelming change in the crystallization kinetics due to the density fluctuation caused by the spontaneous spinodal LLPS is observed. This coupling mechanism suggests a new mechanism in the nucleation-crystallization process. All evidences are pointing to a cross-over mechanism from the spinodal fluctuations (of liquid-liquid phase separation) to the nucleation and than crystallization. The detailed experimental evidences and a suggested physical model will be presented.

  20. A mathematical model for gravity-induced distortion during liquid-phase sintering

    NASA Astrophysics Data System (ADS)

    Raman, R.; German, Randall M.

    1995-03-01

    Liquid-phase-sintered materials consist of interconnected crystalline grains in a homogeneous matrix phase that forms a liquid during sintering. These composites exhibit viscous flow during sintering that allows densification. Gravitational forces give rise to compact distortion when there is a large amount of liquid at a high temperature. This article treats kinetic aspects of distortion during sintering of tungsten heavy alloys (W-Ni-Fe). The mathematical model predicts distortion and highlights the important variables influencing this phenomenon. The results provide guidelines for minimizing distortion due to gravity. Experiments conducted at several different sintering times show reasonably good agreement with theoretical predictions using the liquid-phase viscosity as a single adjustable parameter. Theoretical predictions of the model are crucial to designing microgravity experiments aimed at understanding dimensional stability.

  1. PHASES model for binary-constituent solid-liquid phase transition. Part 2: Applications

    SciTech Connect

    Naterer, G.F.; Schneider, G.E.

    1995-09-01

    A new solution procedure for binary-constituent solid-liquid phase-transition problems has been applied to several one- and two-dimensional problems. Three one-dimensional applications (a pure material melting problem, a unidirectional Ag-Sn solidification problems, and a Bridgman furnace simulation) illustrate different interface solute redistribution and Ste number sensitivity results. In addition, two-dimensional applications examine Pb-Sn and NH{sub 4}Cl-H{sub 2}O solidification problems within moderate- and low-aspect-ratio enclosures. In these problems, buoyancy-driven and shear-driven recirculation cells in the liquid regions of the cavity, penetration of bulk fluid across the liquidus interface, and energy and species advection are observed. The model`s results agree closely with previous analytical and experimental results, and its performance indicates a cost-effective and physically based approach to solid-liquid phase-transition discrete analysis.

  2. Stable non-Fermi liquid phase of itinerant spin-orbit coupled ferromagnets

    NASA Astrophysics Data System (ADS)

    Bahri, Yasaman; Potter, Andrew

    2015-03-01

    Direct coupling between gapless bosons and a Fermi surface results in the destruction of Landau quasiparticles and a breakdown of Fermi liquid theory. Such a non-Fermi liquid phase arises in spin-orbit coupled ferromagnets with spontaneously broken continuous symmetries due to strong coupling between rotational Goldstone modes and itinerant electrons. These systems provide an experimentally accessible context for studying non-Fermi liquid physics. Possible examples include low-density Rashba coupled electron gases, which have a natural tendency towards spontaneous ferromagnetism, or topological insulator surface states with proximity-induced ferromagnetism. Crucially, unlike the related case of a spontaneous nematic distortion of the Fermi surface, for which the non-Fermi liquid regime is expected to be masked by a superconducting dome, we show that the non-Fermi liquid phase in spin-orbit coupled ferromagnets is stable.

  3. Stable non-Fermi-liquid phase of itinerant spin-orbit coupled ferromagnets

    NASA Astrophysics Data System (ADS)

    Bahri, Yasaman; Potter, Andrew C.

    2015-07-01

    Direct (nongradient) coupling between a gapless bosonic field and a Fermi surface results in the destruction of Landau quasiparticles and a breakdown of Fermi liquid theory. Such a non-Fermi-liquid phase arises in spin-orbit coupled ferromagnets with spontaneously broken continuous symmetries due to strong coupling between rotational Goldstone modes and itinerant electrons. These systems provide an experimentally accessible context for studying non-Fermi-liquid physics. Possible examples include low-density Rashba coupled electron gases, which have a natural tendency towards spontaneous ferromagnetism, or topological insulator surface states with proximity-induced ferromagnetism. Crucially, unlike the related case of a spontaneous nematic distortion of the Fermi surface, for which controlled field theory calculations predict that the non-Fermi-liquid regime will be masked by a superconducting dome, we show that the non-Fermi-liquid phase in spin-orbit coupled ferromagnets is stable.

  4. Stabilization of copper catalysts for liquid-phase reactions by atomic layer deposition.

    PubMed

    O'Neill, Brandon J; Jackson, David H K; Crisci, Anthony J; Farberow, Carrie A; Shi, Fengyuan; Alba-Rubio, Ana C; Lu, Junling; Dietrich, Paul J; Gu, Xiangkui; Marshall, Christopher L; Stair, Peter C; Elam, Jeffrey W; Miller, Jeffrey T; Ribeiro, Fabio H; Voyles, Paul M; Greeley, Jeffrey; Mavrikakis, Manos; Scott, Susannah L; Kuech, Thomas F; Dumesic, James A

    2013-12-16

    Atomic layer deposition (ALD) of an alumina overcoat can stabilize a base metal catalyst (e.g., copper) for liquid-phase catalytic reactions (e.g., hydrogenation of biomass-derived furfural in alcoholic solvents or water), thereby eliminating the deactivation of conventional catalysts by sintering and leaching. This method of catalyst stabilization alleviates the need to employ precious metals (e.g., platinum) in liquid-phase catalytic processing. The alumina overcoat initially covers the catalyst surface completely. By using solid state NMR spectroscopy, X-ray diffraction, and electron microscopy, it was shown that high temperature treatment opens porosity in the overcoat by forming crystallites of ?-Al2 O3 . Infrared spectroscopic measurements and scanning tunneling microscopy studies of trimethylaluminum ALD on copper show that the remarkable stability imparted to the nanoparticles arises from selective armoring of under-coordinated copper atoms on the nanoparticle surface. PMID:24282166

  5. Speed of Sound in the Liquid Phase of the R134a/152a Refrigerant Blend

    NASA Astrophysics Data System (ADS)

    Beliajeva, O. V.; Grebenkov, A. J.; Zajatz, T. A.; Timofejev, B. D.

    1999-11-01

    The speed of sound in the liquid phase of the binary blend of R134a and R152a and its components has been studied. The speed of sound was measured by means of the impulse method at a frequency of 2.1 MHz. The temperature range was 230 to 350 K at pressures up to 16 MPa. The values of speed of sound were measured with a standard error of not more than 0.25%. The results obtained for both components of the blend are represented with expressions based on a physical model. The standard deviation (versus the model) of the measured data is 0.09%, On the basis of the results obtained, the Redlich-Kister correlation has been used over the entire ranges of composition, temperature, and pressure to determine the speed of sound in the liquid phase and at the bubble point of the blend investigated.

  6. Dynamic evolution of liquid-liquid phase separation during continuous cooling

    SciTech Connect

    Imhoff, S. D.; Gibbs, P. J.; Katz, M. R.; Ott, T. J.; Patterson, B. M.; Lee, W. -K.; Fezzaa, K.; Cooley, J. C.; Clarke, A. J.

    2015-03-01

    Solidification from a multiphase fluid involves many unknown quantities due to the difficulty of predicting the impact of fluid flow on chemical partitioning. Real-time x-ray radiography has been used to observe liquideliquid phase separation in Al90In10 prior to solidification. Quantitative image analysis has been used to measure the motion and population characteristics of the dispersed indium-rich liquid phase during cooling. Here we determine that the droplet growth characteristics resemble well known steady-state coarsening laws with likely enhancement by concurrent growth due to supersaturation. Simplistic views of droplet motion are found to be insufficient until late in the reaction due to a hydrodynamic instability caused by the large density difference between the dispersed and matrix liquid phases.

  7. Methods and apparatus for using gas and liquid phase cathodic depolarizers

    NASA Technical Reports Server (NTRS)

    Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)

    1998-01-01

    The invention provides methods for using gas and liquid phase cathodic depolarizers in an electrochemical cell having a cation exchange membrane in intimate contact with the anode and cathode. The electrochemical conversion of cathodic depolarizers at the cathode lowers the cell potential necessary to achieve a desired electrochemical conversion, such as ozone evolution, at the anode. When gaseous cathodic depolarizers, such as oxygen, are used, a gas diffusion cathode having the cation exchange membrane bonded thereto is preferred. When liquid phase cathodic depolarizers are used, the cathode may be a flow-by electrode, flow-through electrode, packed-bed electrode or a fluidized-bed electrode in intimate contact with the cation exchange membrane.

  8. Performance of Liquid Phase Exfoliated Graphene As Electrochemical Double Layer Capacitors Electrodes

    NASA Astrophysics Data System (ADS)

    Huffstutler, Jacob; Wasala, Milinda; Richie, Julianna; Winchester, Andrew; Ghosh, Sujoy; Kar, Swastik; Talapatra, Saikat

    2014-03-01

    We will present the results of our investigations of electrochemical double layer capacitors (EDLCs) or supercapacitors (SC) fabricated using liquid-phase exfoliated graphene. Several electrolytes, such as aqueous potassium hydroxide KOH (6M), ionic 1-Butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], and ionic 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate[BMP][FAP] were used. These EDLC's show good performance compared to other carbon nanomaterials based EDLC's devices. We found that the liquid phase exfoliated graphene based devices possess specific capacitance values as high as 262 F/g, when used with ionic liquid electrolyte[BMP][FAP], with power densities (~ 454 W/kg) and energy densities (~ 0.38Wh/kg). Further, these devices indicated rapid charge transfer response even without the use of any binders or specially prepared current collectors. A detailed electrochemical impedance spectroscopy analysis in order to understand the phenomenon of charge storage in these materials will be presented.

  9. Edge states and topological orders in the spin liquid phases of star lattice

    NASA Astrophysics Data System (ADS)

    Huang, Guang-Yao; Liang, Shi-Dong; Yao, Dao-Xin

    2013-09-01

    The integer quantum Hall effect (IQHE) on star lattice is studied through edge states in the context of spin liquid. We apply the bulk-edge correspondence to the star lattice and analyze the edge states and their topological orders for different spin liquid phases. The band structures and Chern number depend on the local spontaneous magnetic flux and hopping parameters due to the breaking of the time reversal and space inversion symmetries. We give the characteristics of bulk and edge energy structures and their corresponding Chern numbers in the uniform, nematic and chiral spin liquids. In particular, we obtain analytically the phase diagram of the topological orders for the chiral spin liquid states SL[ φ,φ,-2 φ], where φ is the magnetic flux in two triangles and a dodecagon in one unit cell. Moreover, because of the direct connection between Chern number and the conductance of IQHE, we can further distinguish the different spin liquid phases through a Hall measurement.

  10. Three-body interactions and solid-liquid phase equilibria: application of a molecular dynamics algorithm.

    PubMed

    Wang, Liping; Sadus, Richard J

    2006-09-01

    The effect of three-body interactions on the solid-liquid phase boundaries of argon, krypton, and xenon is investigated via a novel technique that combines both nonequilibrium and equilibrium molecular dynamics. The simulations involve the evaluation of two- and three-body forces using accurate two-body and three-body intermolecular potentials. The effect of three-body interactions is to substantially increase the coexistence pressure and to lower the densities of liquid and solid phases. Comparison with experiment indicates that three-body interactions are required to accurately determine the total pressure. In contrast to vapor-liquid phase equilibria, the relative contribution of three-body interactions to the freezing pressure exceeds the contribution of two-body interactions at all temperatures. PMID:17025614

  11. Solid-liquid phase equilibria of the Gaussian core model fluid.

    PubMed

    Mausbach, Peter; Ahmed, Alauddin; Sadus, Richard J

    2009-11-14

    The solid-liquid phase equilibria of the Gaussian core model are determined using the GWTS [J. Ge, G.-W. Wu, B. D. Todd, and R. J. Sadus, J. Chem. Phys. 119, 11017 (2003)] algorithm, which combines equilibrium and nonequilibrium molecular dynamics simulations. This is the first reported use of the GWTS algorithm for a fluid system displaying a reentrant melting scenario. Using the GWTS algorithm, the phase envelope of the Gaussian core model can be calculated more precisely than previously possible. The results for the low-density and the high-density (reentrant melting) sides of the solid state are in good agreement with those obtained by Monte Carlo simulations in conjunction with calculations of the solid free energies. The common point on the Gaussian core envelope, where equal-density solid and liquid phases are in coexistence, could be determined with high precision. PMID:19916612

  12. Solid-liquid phase equilibria of the Gaussian core model fluid

    NASA Astrophysics Data System (ADS)

    Mausbach, Peter; Ahmed, Alauddin; Sadus, Richard J.

    2009-11-01

    The solid-liquid phase equilibria of the Gaussian core model are determined using the GWTS [J. Ge, G.-W. Wu, B. D. Todd, and R. J. Sadus, J. Chem. Phys. 119, 11017 (2003)] algorithm, which combines equilibrium and nonequilibrium molecular dynamics simulations. This is the first reported use of the GWTS algorithm for a fluid system displaying a reentrant melting scenario. Using the GWTS algorithm, the phase envelope of the Gaussian core model can be calculated more precisely than previously possible. The results for the low-density and the high-density (reentrant melting) sides of the solid state are in good agreement with those obtained by Monte Carlo simulations in conjunction with calculations of the solid free energies. The common point on the Gaussian core envelope, where equal-density solid and liquid phases are in coexistence, could be determined with high precision.

  13. Liquid phase epitaxial growth and characterization of germanium far infrared blocked impurity band detectors

    SciTech Connect

    Bandaru, Jordana

    2001-05-12

    Germanium Blocked Impurity Band (BIB) detectors require a high purity blocking layer (< 10{sup 13} cm{sup -3}) approximately 1 mm thick grown on a heavily doped active layer ({approx} 10{sup 16} cm{sup -3}) approximately 20 mm thick. Epilayers were grown using liquid phase epitaxy (LPE) of germanium out of lead solution. The effects of the crystallographic orientation of the germanium substrate on LPE growth modes were explored. Growth was studied on substrates oriented by Laue x-ray diffraction between 0.02{sup o} and 10{sup o} from the {l_brace}111{r_brace} toward the {l_brace}100{r_brace}. Terrace growth was observed, with increasing terrace height for larger misorientation angles. It was found that the purity of the blocking layer was limited by the presence of phosphorus in the lead solvent. Unintentionally doped Ge layers contained {approx}10{sup 15} cm{sup -3} phosphorus as determined by Hall effect measurements and Photothermal Ionization Spectroscopy (PTIS). Lead purification by vacuum distillation and dilution reduced the phosphorus concentration in the layers to {approx} 10{sup 14} cm{sup -3} but further reduction was not observed with successive distillation runs. The graphite distillation and growth components as an additional phosphorus source cannot be ruled out. Antimony ({approx}10{sup 16} cm{sup -3}) was used as a dopant for the active BIB layer. A reduction in the donor binding energy due to impurity banding was observed by variable temperature Hall effect measurements. A BIB detector fabricated from an Sb-doped Ge layer grown on a pure substrate showed a low energy photoconductive onset ({approx}6 meV). Spreading resistance measurements on doped layers revealed a nonuniform dopant distribution with Sb pile-up at the layer surface, which must be removed by chemomechanical polishing. Sb diffusion into the pure substrate was observed by Secondary Ion Mass Spectroscopy (SIMS) for epilayers grown at 650 C. The Sb concentration at the interface dropped by an order of magnitude over {approx} 1.5 {micro}m. Layers grown at 550 C did not show significant Sb diffusion. Sn doped In{sub 2}O{sub 3} (ITO) was studied for use in far infrared transparent low temperature contacts for BIB arrays. It was found that {approx}100 nm of ITO deposited on Ge remains electrically conducting at 4 K and is {approx}90% transparent in the far infrared. ITO should be suitable for passivating contacts to Ge BIB arrays.

  14. [Determination of dichloromethane and trichloromethane residues in ranitidine hydrochloride by headspace liquid phase microextraction coupled with gas chromatography].

    PubMed

    Shen, Shuchang; Yun, Dan; Li, Fei

    2009-11-01

    A method for the determination of residual dichloromethane and trichloromethane in ranitidine hydrochloride by headspace liquid phase microextraction coupled with gas chromatography (GC) was developed. A homemade device was used to protect the organic drop. The effects of the nature of extraction solvent, extraction time, extraction temperature and microdrop volume on the extraction efficiency were investigated separately. The optimal experimental conditions were as follows: 2 microL of n-tridecane as extraction solvent, 30 min of extraction time, 60 degrees C of extraction temperature. The correlation coefficients of linear calibration curve were 0.9733 and 0.9724 within the concentration ranges of dichloromethane (1-10 microg/g) and trichloromethane (1-10 microg/g), respectively. The detection limits of dichlormethane and trichloromethane were 0.0273 microg/g and 0.0410 microg/g, respectively, the relative standard deviations were lower than 4.36% and 5.89%, and the recoveries of the method were 93.6%-102% and 98.1% respectively. The method is simple and reliable. PMID:20352943

  15. In situ derivatization hollow fibre liquid-phase microextraction for the determination of biogenic amines in food samples.

    PubMed

    Saaid, Mardiana; Saad, Bahruddin; Ali, Abdussalam Salhin Mohamed; Saleh, Muhammad Idiris; Basheer, Chanbasha; Lee, Hian Kee

    2009-07-01

    Hollow fibre liquid-phase microextraction with in situ derivatization using dansyl chloride has been successfully developed for the high-performance liquid chromatography-ultraviolet (HPLC-UV) determination of the biogenic amines (tryptamine, putrescine, cadaverine, histamine, tyramine, spermidine) in food samples. Parameters affecting the performance of the in situ derivatization process such as type of extraction solvent, temperature, extraction time, stirring speed and salt addition were studied and optimized. Under the optimized conditions (extraction solvent, dihexyl ether; acceptor phase, 0.1M HCl; extraction time, 30 min; extraction temperature, 26 degrees C; without addition of salt), enrichment factors varying from 47 to 456 were achieved. Good linearity of the analytes was obtained over a concentration range of 0.1-5 microg mL(-1) (with correlation coefficients of 0.9901-0.9974). The limits of detection and quantification based on a signal-to-noise ratio of 3-10, ranged from 0.0075 to 0.030 microg mL(-1) and 0.03 to 0.10 microg mL(-1), respectively. The relative standard deviations based on the peak areas for six replicate analysis of water spiked with 0.5 microg mL(-1) of each biogenic amine were lower than 7.5%. The method was successfully applied to shrimp sauce and tomato ketchup samples, offering an interesting alternative to liquid-liquid extraction and solid phase extraction for the analysis of biogenic amines in food samples. PMID:19481215

  16. On Implicit Active Constraints in Linear Semi-Infinite Programs with Unbounded Coefficients

    SciTech Connect

    Goberna, M. A.; Lancho, G. A.; Todorov, M. I.; Vera de Serio, V. N.

    2011-04-15

    The concept of implicit active constraints at a given point provides useful local information about the solution set of linear semi-infinite systems and about the optimal set in linear semi-infinite programming provided the set of gradient vectors of the constraints is bounded, commonly under the additional assumption that there exists some strong Slater point. This paper shows that the mentioned global boundedness condition can be replaced by a weaker local condition (LUB) based on locally active constraints (active in a ball of small radius whose center is some nominal point), providing geometric information about the solution set and Karush-Kuhn-Tucker type conditions for the optimal solution to be strongly unique. The maintaining of the latter property under sufficiently small perturbations of all the data is also analyzed, giving a characterization of its stability with respect to these perturbations in terms of the strong Slater condition, the so-called Extended-Nuernberger condition, and the LUB condition.

  17. The effect of Mo addition on the liquid-phase sintering of W heavy alloy

    NASA Astrophysics Data System (ADS)

    Park, Hee-Dong; Baik, Woon-Hyung; Kang, Suk-Joong L.; Yoon, Duk-Yong

    1996-10-01

    The morphological and compositional changes of grains have been investigated in the initial stage of liquid-phase sintering of W-Mo-Ni-Fe powder compacts. Both large (5.4- ?m) and small (1.3- ?m) W powders have been used to vary their time of dissolution in the liquid matrix. When 8OW-10M0-7Ni-3Fe (wt pct) compacts of fine (about 1- to 2- ?m) Mo, Ni, and Fe and coarse (5.4- ?m) W powders are liquid-phase sintered at 1500 C, the Mo powder and a fraction of the W powder rapidly dissolve in the Ni-Fe liquid matrix. The W-Mo grains (containing small amounts of Ni and Fe) nucleate in the matrix and grow while the W particles slowly dissolve. In this transient initial stage of the liquid-phase sintering, duplex structures of coarse W-Mo grains and fine W particles are obtained. As the W particles dissolve in the liquid matrix during the sintering, the W content in the precipitated solid phase also increases. The dissolution of the small W particles is assessed to be driven partially by the coherency strain produced by Mo diffusion at the surface. During sintering, the W particles continuously dissolve while the W-Mo grains grow. When the compacts are prepared from a fine (1.3- ?m) W powder, the W grains dissolve more rapidly, in about 1 hour, and only W-Mo grains remain. These observations show that the morphological evolution of grains during liquid-phase sintering can be strongly influenced by the chemical equilibrium process.

  18. The liquid-liquid phase transition in silicon revealed by snapshots of valence electrons.

    PubMed

    Beye, Martin; Sorgenfrei, Florian; Schlotter, William F; Wurth, Wilfried; Fhlisch, Alexander

    2010-09-28

    The basis for the anomalies of water is still mysterious. Quite generally tetrahedrally coordinated systems, also silicon, show similar thermodynamic behavior but lack--like water--a thorough explanation. Proposed models--controversially discussed--explain the anomalies as a remainder of a first-order phase transition between high and low density liquid phases, buried deeply in the "no man's land"--a part of the supercooled liquid region where rapid crystallization prohibits any experimental access. Other explanations doubt the existence of the phase transition and its first-order nature. Here, we provide experimental evidence for the first-order-phase transition in silicon. With ultrashort optical pulses of femtosecond duration we instantaneously heat the electronic system of silicon while the atomic structure as defined by the much heavier nuclear system remains initially unchanged. Only on a picosecond time scale the energy is transferred into the atomic lattice providing the energy to drive the phase transitions. With femtosecond X-ray pulses from FLASH, the free-electron laser at Hamburg, we follow the evolution of the valence electronic structure during this process. As the relevant phases are easily distinguishable in their electronic structure, we track how silicon melts into the low-density-liquid phase while a second phase transition into the high-density-liquid phase only occurs after the latent heat for the first-order phase transition has been transferred to the atomic structure. Proving the existence of the liquid-liquid phase transition in silicon, the hypothesized liquid-liquid scenario for water is strongly supported. PMID:20805512

  19. Laser-induced chemical liquid phase deposition of copper from aqueous solutions without reducing agents

    SciTech Connect

    Kochemirovsky, V A; Tumkin, I I; Logunov, L S; Safonov, S V; Menchikov, Leonid G

    2012-08-31

    Laser-induced chemical liquid phase deposition of copper without a traditional reducing agent has been used for the first time to obtain conductive patterns on a dielectric surface having a reducing ability. It is shown that phenol-formaldehyde binder of the dielectric (glass fibre) can successfully play the role of a reducing agent in this process. The resulting copper sediments have low electrical resistance and good topology. (interaction of laser radiation with matter. laser plasmas)

  20. Deposition of gold nanoparticles on liquid phase epitaxy grown garnet films and Faraday rotation enhancement

    NASA Astrophysics Data System (ADS)

    Lang, G. S.; Bowen, D.; Krafft, C.; Mayergoyz, I. D.

    2013-05-01

    Plasmon resonance induced Faraday rotation enhancement in liquid phase epitaxy grown garnet films with gold nanoparticles on their surfaces is discussed. Experimental results are presented, which reveal stronger Faraday rotation enhancement for gold nanoparticles obtained by the annealing of thicker gold films evaporated on garnet film surfaces. This stronger Faraday rotation enhancement can be attributed to larger dimensions and separations of gold nanoparticles, which increase the extent of penetration of plasmon resonance induced electric fields into garnet films.

  1. Liquid-phase ozonization of concentrates of the petrographic components of isometamorphic coals

    SciTech Connect

    S.A. Semenova; Yu.F. Patrakov

    2008-02-15

    The fractionated ozonization products of the vitrain and fusain lithotypes of isometamorphic coals of the middle stage of metamorphism from the Kuznetsk Basin in glacial acetic acid were characterized using IR spectroscopy, thermogravimetry, and chromatography-mass spectrometry. Fusainized coal components exhibited higher reactivity toward ozone. Water-soluble low-molecular-weight compounds were predominant among the products of the liquid-phase ozonization of the lithotypes. 11 refs., 4 figs., 3 tabs.

  2. Sintered plug flow modulation of a vapor-liquid phase separator for a helium II vessel

    NASA Technical Reports Server (NTRS)

    Frederking, T. H. K.; Chuang, C.; Kamioka, Y.; Lee, J. M.; Yuan, S. W. K.

    1984-01-01

    Presented is a system for modulation of a superfluid (helium II) flow in a vapor-liquid phase separator, for use in cryogenic storage tanks in future space missions. The system consists of a semicircular mechanically operated shutter, downstream of the separator plug, rotated at 0.1 rpm to control the operational surface area of the separator. The mass flow rate was varied from 10 to 22 mg/s. Pressure gradients across the plug are also discussed.

  3. Liquid-phase sintering of BN doped Fe-Cu/TiC composites

    SciTech Connect

    Durlu, N.; Yao, N.; Milius, D.L.; Aksay, I.A.

    1996-12-31

    Fe-Cu composites are commonly produced by liquid phase sintering (above the melting temperature of Cu, 1085{degrees}C). The wear resistance of these Fe-Cu alloys can be enhanced by introducing hard particles, e.g, TiC, into the matrix. In such cases, however, the densification of Fe-Cu/TiC composites by liquid phase sintering becomes difficult mainly due to the high wetting angle (110{degrees} at 1100-1200{degrees}C in argon) of liquid Cu with TiC particles. Especially when the amount of the TiC phase is high enough to form a continuous network of TiC grains, full densification is only achieved through hot pressing. We have recently overcome this problem in an [(Fe-4 wt% Cu) + 30 wt% TiC] composite by the addition of small amounts of BN. Composites with BN additives have been successfully sintered at 1275{degrees}C under vacuum or argon by additions of 1 wt% BN. Electron microscopic characterization of these composites has shown that this success is due to the modification of the liquid phase by the addition of BN, which also promotes the liquid phase sintering of the TiC phase. Thin slices of samples were cut from the composites sintered at 1275{degrees}C either under vacuum or argon for 1 h. Mechanically polished samples were thinned with 6 kV argon ions. During ion-milling, the specimens were cooled with liquid nitrogen. Specimens were then examined using a Philips CM 200 FEG-TEM at 200 kV.

  4. Microgravity Studies of Liquid-Liquid Phase Transitions in Alumina-Yttria Melts

    NASA Technical Reports Server (NTRS)

    Guynes, Buddy (Technical Monitor); Weber, Richard; Nordine, Paul

    2004-01-01

    The scientific objective of this research is to increase the fundamental knowledge base for liquid- phase processing of technologically important oxide materials. The experimental objective is to define conditions and hardware requirements for microgravity flight experiments to test and expand the experimental hypotheses that: 1. Liquid phase transitions can occur in undercooled melts by a diffusionless process. 2. Onset of the liquid phase transition is accompanied by a large change in the temperature dependence of melt viscosity. Experiments on undercooled YAG (Y3A15012)- and rare earth oxide aluminate composition liquids demonstrated a large departure from an Arrhenian temperature dependence of viscosity. Liquid YAG is nearly inviscid at its 2240 K melting point. Glass fibers were pulled from melts undercooled by ca. 600 K indicating that the viscosity is on the order of 100 Pans (1000 Poise) at 1600 K. This value of viscosity is 500 times greater than that obtained by extrapolation of data for temperatures above the melting point of YAG. These results show that the liquids are extremely fragile and that the onset of the highly non-Arrhenian viscosity-temperature relationship occurs at a temperature considerably below the equilibrium melting point of the solid phases. Further results on undercooled alumina-yttria melts containing 23-42 mole % yttrium oxide indicate that a congruent liquid-liquid phase transition occurs in the undercooled liquids. The rates of transition are inconsistent with a diffusion-limited process. This research is directed to investigation of the scientifically interesting phenomena of polyamorphism and fragility in undercooled rare earth oxide aluminum oxide liquids. The results bear on the technologically important problem of producing high value rare earth-based optical materials.

  5. Gravity and configurational energy induced microstructural changes in liquid phase sintering

    NASA Technical Reports Server (NTRS)

    Kipphut, C. M.; Bose, A.; Farooq, S.; German, R. M.

    1988-01-01

    Experiments were performed with W-Ni-Fe heavy alloys in order to measure the microstructural changes vs. position that occur in liquid-phase sintering under normal gravity. The experimentally observed segregation is less than the calculated equilibrium segregation due to the retarding effect from the rigid solid skeleton formed during sintering. These results improve understanding of microstructure, mechanical properties, component shape, and dimensional stability benefits that may be realized from low-gravity sintering.

  6. High dielectric constant nickel-doped titanium oxide films prepared by liquid-phase deposition

    NASA Astrophysics Data System (ADS)

    Lee, Ming-Kwei; Yen, Chih-Feng; Fan, Cho-Han

    2014-09-01

    The electrical characteristics of nickel-doped titanium oxide films prepared by liquid-phase deposition on p-type (100) silicon substrate were investigated. The aqueous solutions of ammonium hexafluorotitanate and boric acid were used as precursors for the growth of titanium oxide films and the dielectric constant is 29. The dielectric constant can be improved to 94 by nickel doping at the thermal annealing at 700 C in nitrous oxide.

  7. Atomic structures of a liquid-phase bonded metal/nitride heterointerface.

    PubMed

    Kumamoto, Akihito; Shibata, Naoya; Nayuki, Kei-Ichiro; Tohei, Tetsuya; Terasaki, Nobuyuki; Nagatomo, Yoshiyuki; Nagase, Toshiyuki; Akiyama, Kazuhiro; Kuromitsu, Yoshirou; Ikuhara, Yuichi

    2016-01-01

    Liquid-phase bonding is a technologically important method to fabricate high-performance metal/ceramic heterostructures used for power electronic devices. However, the atomic-scale mechanisms of how these two dissimilar crystals specifically bond at the interfaces are still not well understood. Here we analyse the atomically-resolved structure of a liquid-phase bonded heterointerface between Al alloy and AlN single crystal using aberration corrected scanning transmission electron microscopy (STEM). In addition, energy-dispersive X-ray microanalysis, using dual silicon drift X-ray detectors in STEM, was performed to analyze the local chemistry of the interface. We find that a monolayer of MgO is spontaneously formed on the AlN substrate surface and that a polarity-inverted monolayer of AlN is grown on top of it. Thus, the Al alloy is bonded with the polarity-inverted AlN monolayer, creating a complex atomic-scale layered structure, facilitating the bonding between the two dissimilar crystals during liquid-phase bonding processes. Density-functional-theory calculations confirm that the bonding stability is strongly dependent on the polarity and stacking of AlN and MgO monolayers. Understanding the spontaneous formation of layered transition structures at the heterointerface will be key in fabricating very stable Al alloy/AlN heterointerface required for high reliability power electronic devices. PMID:26961157

  8. Balance of optical, structural, and electrical properties of textured liquid phase crystallized Si solar cells

    SciTech Connect

    Preidel, V. Amkreutz, D.; Haschke, J.; Wollgarten, M.; Rech, B.; Becker, C.

    2015-06-14

    Liquid phase crystallized Si thin-film solar cells on nanoimprint textured glass substrates exhibiting two characteristic, but distinct different surface structures are presented. The impact of the substrate texture on light absorption, the structural Si material properties, and the resulting solar cell performance is analyzed. A pronounced periodic substrate texture with a vertical feature size of about 1 μm enables excellent light scattering and light trapping. However, it also gives rise to an enhanced Si crystal defect formation deteriorating the solar cell performance. In contrast, a random pattern with a low surface roughness of 45 nm allows for the growth of Si thin films being comparable to Si layers on planar reference substrates. Amorphous Si/crystalline Si heterojunction solar cells fabricated on the low-roughness texture exhibit a maximum open circuit voltage of 616 mV and internal quantum efficiency peak values exceeding 90%, resulting in an efficiency potential of 13.2%. This demonstrates that high quality crystalline Si thin films can be realized on nanoimprint patterned glass substrates by liquid phase crystallization inspiring the implementation of tailor-made nanophotonic light harvesting concepts into future liquid phase crystallized Si thin film solar cells on glass.

  9. Atomic structures of a liquid-phase bonded metal/nitride heterointerface

    PubMed Central

    Kumamoto, Akihito; Shibata, Naoya; Nayuki, Kei-ichiro; Tohei, Tetsuya; Terasaki, Nobuyuki; Nagatomo, Yoshiyuki; Nagase, Toshiyuki; Akiyama, Kazuhiro; Kuromitsu, Yoshirou; Ikuhara, Yuichi

    2016-01-01

    Liquid-phase bonding is a technologically important method to fabricate high-performance metal/ceramic heterostructures used for power electronic devices. However, the atomic-scale mechanisms of how these two dissimilar crystals specifically bond at the interfaces are still not well understood. Here we analyse the atomically-resolved structure of a liquid-phase bonded heterointerface between Al alloy and AlN single crystal using aberration corrected scanning transmission electron microscopy (STEM). In addition, energy-dispersive X-ray microanalysis, using dual silicon drift X-ray detectors in STEM, was performed to analyze the local chemistry of the interface. We find that a monolayer of MgO is spontaneously formed on the AlN substrate surface and that a polarity-inverted monolayer of AlN is grown on top of it. Thus, the Al alloy is bonded with the polarity-inverted AlN monolayer, creating a complex atomic-scale layered structure, facilitating the bonding between the two dissimilar crystals during liquid-phase bonding processes. Density-functional-theory calculations confirm that the bonding stability is strongly dependent on the polarity and stacking of AlN and MgO monolayers. Understanding the spontaneous formation of layered transition structures at the heterointerface will be key in fabricating very stable Al alloy/AlN heterointerface required for high reliability power electronic devices. PMID:26961157

  10. Effects of temporally varying liquid-phase mass diffusivity in multicomponent droplet gasification

    SciTech Connect

    Zhang, Huiqiang; Law, Chung K.

    2008-06-15

    The relative roles of liquid-phase diffusional resistance and volatility differential in multicomponent droplet gasification are revisited, recognizing that liquid-phase mass diffusivities can be substantially increased as the droplet is progressively heated upon initiation of gasification, leading to a corresponding substantial weakening of the diffusional resistance. Calculations performed using realistic and temperature-dependent thermal and mass diffusivities indeed substantiate this influence. In particular, the calculated results agree with the literature experimental data, indicating that the gasification mechanism of multicomponent fuels is intermediate between diffusion and distillation limits. Investigation was also performed on gasification at elevated pressures, recognizing that the liquid boiling point and hence the attainable droplet temperature would increase with increasing pressure, causing further weakening of the liquid-phase diffusional resistance. This possibility was again verified through calculated results, suggesting further departure from diffusion limit toward distillation limit behavior for gasification at high pressures. The study also found that diffusional resistance is stronger for the lighter, gasoline-like fuels as compared to the heavier, diesel-like fuels because the former have overall lower boiling points, lower attainable droplet temperatures, and hence lower mass diffusivities in spite of their lower molecular weights. (author)

  11. Liquid-Phase Deposition of CIS Thin Layers: Final Report, February 2003--July 2005

    SciTech Connect

    Ernst, F.; Pirouz, P.

    2006-02-01

    The goal of this project was to fabricate single-phase CIS (a-Cu-In-Se, stoichiometric composition: CuInSe2) thin films for photovoltaic applications from a liquid phase - a Cu-In-Se melt of appropriate composition. This approach of liquid-phase deposition (LPD) is based on the new phase diagram we have established for Cu-In-Se, the first complete equilibrium phase diagram of this system. The liquidus projection exhibits four composition fields in which the primary solid phase, i.e., the first solid material that forms on cooling down from an entirely liquid state, is a-CuInSe2. Remarkably, none of the four composition fields is anywhere near the stoichiometric composition (CuInSe2) of a-CuInSe2. The results demonstrate that the proposed technique is indeed capable of producing films with a particularly large grain size and a correspondingly low density of grain boundaries. To obtain films sufficiently thin for solar cell applications and with a sufficiently smooth surface, it is advantageous to employ a sliding boat mechanism. Future work on liquid-phase deposition of CIS should focus on the interaction between the melt and the substrate surface, the resulting CIS interfaces, the surface morphology of the LPD-grown films, and, of course, the electronic properties of the material.

  12. Two-liquid phase partitioning biotrickling filters for methane abatement: exploring the potential of hydrophobic methanotrophs.

    PubMed

    Lebrero, Raquel; Hernndez, Laura; Prez, Rebeca; Estrada, Jos M; Muoz, Ral

    2015-03-15

    The potential of two-liquid phase biotrickling filters (BTFs) to overcome mass transfer limitations derived from the poor aqueous solubility of CH4 has been scarcely investigated to date. In this context, the abatement of diluted methane emissions in two-liquid phase BTFs was evaluated using two different inocula: a type II methanotrophs culture in BTF 1 and a hydrophobic microbial consortium capable of growing inside silicone oil in BTF 2. Both BTFs supported stable elimination capacities above 45 g m(-3) h(-1) regardless of the inoculum, whereas no improvement derived from the presence of hydrophobic microorganisms compared to the type II metanotrophs culture was observed. Interestingly, the addition of silicone oil mediated a reduced metabolites concentration in the recycling aqueous phase, thus decreasing the needs for mineral medium renewal. Moreover, a 78% similarity was recorded between the microbial communities enriched in both BTFs at the end of the experimental period in spite of the differences in the initial inoculum structure. The results obtained confirmed the superior performance of two-liquid phase BTFs for CH4 abatement compared with conventional biotrickling filters. PMID:25555135

  13. Evidence of Microporous Carbon Nanosheets Showing Fast Kinetics in both Gas Phase and Liquid Phase Environments.

    PubMed

    Jin, Zhen-Yu; Xu, Yuan-Yuan; Sun, Qiang; Lu, An-Hui

    2015-10-01

    Despite the great advantages of microporous carbons for applications in gas phase separation, liquid phase enrichment, and energy storage devices, direct experiment data and theoretical calculations on the relevance of properties and structures are quite limited. Herein, two model carbon materials are designed and synthesized, i.e., microporous carbon nanosheets (MCN) and microporous carbon spheres (MCS). They both have nearly same composition, surface chemistry, and specific surface area, known morphology, but distinguishable diffusion paths. Based on these two types of materials, a reliable relationship between the morphology with different diffusion paths and adsorption kinetics in both gas phase and liquid phase environments is established. When used for CO2 capture, MCN shows a high saturated CO2 capacity of 8.52 ?mol m(-2) and 18.4 mmol cm(-3) at 273 K and ambient pressure, and its calculated first-order rate constant is ?7.4 times higher than that of MCS. Moreover, MCN shows a quick and high uptake of Cr (VI) and a higher-rate performance for supercapacitors than MCS does. These results strongly confirm that MCN exhibits improved kinetics in gas phase separation, liquid phase enrichment, and energy storage devices due to its shorter diffusion paths and larger exposed geometrical area resulting from the nanosheet structure. PMID:26192395

  14. Processing and microstructural development in liquid phase sintered and pure TiB/sub 2/ ceramics

    SciTech Connect

    Angelini, P.; Becher, P.F.; Bentley, J.; Brynestad, J.; Ferber, M.K.; Finch, C.B.; Sklad, P.S.

    1984-01-01

    The fabrication of TiB/sub 2/ ceramics with high fracture strength and toughness requires that grain growth and the development of secondary phase(s) be controlled. Liquid phase assisted densification with nickel-bearing metallic additives allows one to achieve high densities and final grain sizes that are comparable to the particle size of the starting commercial TiB/sub 2/ powders. To gain further reduction in TiB/sub 2/ grain size studies of hot pressing of submicron TiB/sub 2/ powders, in which Ni was not added, were conducted. The results showed densification to be enhanced by liquid phases introduced by Ni and Fe impurities (less than or equal to .5 wt % total) but retarded by oxygen levels >1 wt %. Carbon additions led to high densities and significantly reduced grain growth. Using observations of the evolution of secondary phases in the TiB/sub 2/-Ni type systems, a model of the densification process is proposed. The model is based on reactions between Ti and B components (resulting from the dissolution of TiB/sub 2/), dissolved oxygen or B/sub 2/O/sub 3/ (present as either impurities or oxide surface layers on the initial TiB/sub 2/ powder), and the metallic species including additives present in the liquid phase. 17 refs., 6 figs., 3 tabs.

  15. Balance of optical, structural, and electrical properties of textured liquid phase crystallized Si solar cells

    NASA Astrophysics Data System (ADS)

    Preidel, V.; Amkreutz, D.; Haschke, J.; Wollgarten, M.; Rech, B.; Becker, C.

    2015-06-01

    Liquid phase crystallized Si thin-film solar cells on nanoimprint textured glass substrates exhibiting two characteristic, but distinct different surface structures are presented. The impact of the substrate texture on light absorption, the structural Si material properties, and the resulting solar cell performance is analyzed. A pronounced periodic substrate texture with a vertical feature size of about 1 ?m enables excellent light scattering and light trapping. However, it also gives rise to an enhanced Si crystal defect formation deteriorating the solar cell performance. In contrast, a random pattern with a low surface roughness of 45 nm allows for the growth of Si thin films being comparable to Si layers on planar reference substrates. Amorphous Si/crystalline Si heterojunction solar cells fabricated on the low-roughness texture exhibit a maximum open circuit voltage of 616 mV and internal quantum efficiency peak values exceeding 90%, resulting in an efficiency potential of 13.2%. This demonstrates that high quality crystalline Si thin films can be realized on nanoimprint patterned glass substrates by liquid phase crystallization inspiring the implementation of tailor-made nanophotonic light harvesting concepts into future liquid phase crystallized Si thin film solar cells on glass.

  16. Air-liquid partition coefficient for a diverse set of organic compounds: Henry's Law Constant in water and hexadecane.

    PubMed

    Hilal, Said H; Ayyampalayam, Saravanaraj N; Carreira, Lionel A

    2008-12-15

    The SPARC vapor pressure and activity coefficient models were coupled to successfully estimate Henry's Law Constant (HLC) in water and in hexadecane for a wide range of organic compounds without modification to, or additional parametrization of, either SPARC model. The vapor pressure model quantifies the solute-solute intermolecular interactions in the pure liquid phase, whereas the activity coefficient model quantifies the solute-solvent and solvent-solvent (in addition to the solute-solute) interactions upon placing solute, i, in solvent, j. These intermolecular interactions are factored into dispersion, induction, dipole-dipole, and H-bonding components upon moving a solute molecule from the gas to the liquid phase. The SPARC HLC calculator so produced was tested and validated on the largest experimental HLC data set to date: 1356 organic solutes, spanning a wide range of functional groups, dipolarities and H-bonding capabilities, such as PAHs, PCBs,VOCs, amides, pesticides, and pharmaceuticals. The rms deviation errors for the calculated versus experimental log HLCs for 1222 compounds in water and 563 in hexadecane were 0.456 and 0.192 log [(mol/L)/(mol/L)] units, respectively, spanning a range of more than 13 and 20 log HLC dimensionless units for the compounds in water and hexadecane, respectively. The SPARC calculator web version is available for public use, free of charge, and can be accessed at http://sparc.chem.uga.edu. PMID:19174897

  17. Two-parameter kinetic model based on a time-dependent activity coefficient accurately describes enzymatic cellulose digestion.

    PubMed

    Kostylev, Maxim; Wilson, David

    2013-08-20

    Lignocellulosic biomass is a potential source of renewable, low-carbon-footprint liquid fuels. Biomass recalcitrance and enzyme cost are key challenges associated with the large-scale production of cellulosic fuel. Kinetic modeling of enzymatic cellulose digestion has been complicated by the heterogeneous nature of the substrate and by the fact that a true steady state cannot be attained. We present a two-parameter kinetic model based on the Michaelis-Menten scheme ( Michaelis, L., and Menten, M. L. ( 1913 ) Biochem. Z. , 49 , 333 - 369 ) with a time-dependent activity coefficient analogous to fractal-like kinetics formulated by Kopelman ( Kopelman, R. ( 1988 ) Science 241 , 1620 - 1626 ). We provide a mathematical derivation and experimental support to show that one of the parameters is a total activity coefficient and the other is an intrinsic constant that reflects the ability of the cellulases to overcome substrate recalcitrance. The model is applicable to individual cellulases and their mixtures at low-to-medium enzyme loads. Using biomass degrading enzymes from cellulolytic bacterium Thermobifida fusca , we show that the model can be used for mechanistic studies of enzymatic cellulose digestion. We also demonstrate that it applies to the crude supernatant of the widely studied cellulolytic fungus Trichoderma reesei ; thus it can be used to compare cellulases from different organisms. The two parameters may serve a similar role to Vmax, KM, and kcat in classical kinetics. A similar approach may be applicable to other enzymes with heterogeneous substrates and where a steady state is not achievable. PMID:23837567

  18. The mean activity coefficients of 2:2 electrolyte solutions: an integral equation study of the restricted primitive model.

    PubMed

    Chung, Ting-Horng; Lee, Lloyd L

    2009-04-01

    We apply the closure theory ZSEP (self-consistent zero-separation based closures) developed earlier to the restricted primitive model (RPM) of 2:2 electrolytes in order to (i) obtain the activity coefficient information via the direct formula for chemical potentials [L. L. Lee, J. Chem. Phys. 97, 8606 (1992)] and (ii) test the performance of this flexible ZSEP closure at high-coupling strengths (i.e., high valency and low temperatures) for cases of 2:2 electrolytes where other closure schemes have encountered difficulties [e.g., the hypernetted chain (HNC) equation]. In particular, we shall remedy the shortcomings of the HNC theory at low concentrations (from 0.001M to 0.2M). The ZSEP closure is found to perform well at coupling strengths beta(') = absolute value(z(1)z(2))e(2)/(epsilon(m)kTd) approaching approximately 10 where some other closure theories cease to give good results. In addition, by applying the direct chemical potential formula, we demonstrate numerically that, in the RPM cases examined, the logarithm of the mean activity coefficients of electrolytes are closely approximated by the electrostatic internal energy, an easily accessible quantity, a fact that shall afford ready access to the chemical potentials for phase equilibrium and electrochemical calculations on electrolytic systems. PMID:19355757

  19. Effect of Titanium Addition on the Thermal Properties of Diamond/Cu-Ti Composites Fabricated by Pressureless Liquid-Phase Sintering Technique

    PubMed Central

    Chung, Chih-Yu; Chu, Chao-Hung; Lee, Mu-Tse; Lin, Chun-Ming; Lin, Su-Jien

    2014-01-01

    In this study, minor-addition elements such as Si, Co, Cr, W, Mo, and Ti were added to matrix to improve the wettability between the diamonds and Cu matrix. The pressureless liquid-phase sintering technique adopted in this study provides a low-cost method for producing diamond/Cu composites with high potential for industrial mass production. Thermal properties of the diamond/Cu-Ti composites fabricated by pressureless liquid-phase sintering at 1373?K with variation in Ti contents were thoroughly investigated. XRD and TEM analysis show that TiC layer formed in the interface between Cu and diamond. The composites exhibited thermal conductivity as high as 620?W/mK for 50?vol% diamond/Cu-0.6? at % Ti composite with diamond particle size of 300?m. This value comes up to 85% of the thermal conductivity calculated by the Hasselman and Johnson (H-J) theoretical analysis. Under these conditions, a suitable coefficient of thermal expansion of 6.9?ppm/K was obtained. PMID:24715816

  20. Esterification of sodium 4-hydroxybenzoate by ultrasound-assisted solid-liquid phase-transfer catalysis using dual-site phase-transfer catalyst.

    PubMed

    Yang, Hung-Ming; Chu, Wei-Ming

    2014-01-01

    The catalytic esterification of sodium 4-hydroxybenzoate with benzyl bromide by ultrasound-assisted solid-liquid phase-transfer catalysis (U-SLPTC) was investigated using the novel dual-site phase-transfer catalyst 4,4'-bis(tributylammoniomethyl)-1,1'-biphenyl dichloride (BTBAMBC), which was synthesized from the reaction of 4,4'-bis(chloromethyl)-1,1'-biphenyl and tributylamine. Without catalyst and in the absence of water, the product yield at 60 C was only 0.36% in 30 min of reaction even under ultrasound irradiation (28 kHz/300 W) and 250 rpm of stirring speed. When 1cm(3) of water and 0.5 mmol of BTBAMBC were added, the yield increased to 84.3%. The catalytic intermediate 4,4'-bis(tributylammoniomethyl)-1,1'-biphenyl di-4-hydroxybenzoate was also synthesized to verify the intrinsic reaction which was mainly conducted in the quasi-aqueous phase locating between solid and organic phases. Pseudo-first-order kinetic equation was used to correlate the overall reaction, and the apparent rate coefficient with ultrasound (28 kHz/300 W) was 0.1057 min(-1), with 88% higher than that (0.0563 min(-1)) without ultrasound. The esterification under ultrasonic irradiation using BTBAMBC by solid-liquid phase-transfer catalysis was developed. PMID:23972326

  1. Determination of Activity Coefficients of di-(2-ethylhexyl) Phosphoric Acid Dimer in Select Organic Solvents Using Vapor Phase Osmometry

    SciTech Connect

    Michael F. Gray; Peter Zalupski; Mikael Nilsson

    2013-08-01

    Effective models for solvent extraction require accurate characterization of the nonideality effects for each component, including the extractants. In this study, the nonideal behavior of the industrial extractant di(2-ethylhexyl) phosphoric acid has been investigated using vapor pressure osmometry (VPO). From the osmometry data, activity coefficients for the HDEHP dimer were obtained based on a formulation of the regular solution theory of Scatchard and Hildebrand, and the Margules two- and three-suffix equations. The results show similarity with a slope-analysis based relation from previous literature, although important differences are highlighted. The work points towards VPO as a useful technique for this type of study, but care must be taken with the choice of standard and method of analysis.

  2. A microstructure-based model for shape distortion during liquid phase sintering

    NASA Astrophysics Data System (ADS)

    Upadhyaya, Anish

    Tight dimensional control is a major concern in consolidation of alloys via liquid phase sintering. This research demonstrates the role of microstructure in controlling the bulk dimensional changes that occur during liquid phase sintering. The dimensional changes were measured using a coordinate measuring machine and also on a real-time basis using in situ video imaging. To quantify compact distortion, a distortion parameter is formulated which takes into consideration the compact distortion in radial as well as axial directions. The microstructural attributes considered in this study are as follows: solid content, dihedral angle, grain size, grain contiguity and connectivity, and solid-solubility. Sintering experiments were conducted with the W-Ni-Cu, W-Ni-Fe, Mo-Ni-Cu, and Fe-Cu systems. The alloy systems and the compositions were selected to give a range of microstructures during liquid phase sintering. The results show that distortion correlates with the measured microstructural attributes. Systems containing a high solid content, high grain coordination number and contiguity, and large dihedral angle have more structural rigidity. The results show that a minimum two-dimensional grain coordination number of 3.0 is necessary for shape preservation. Based on the experimental observations, a model is derived that relates the critical solid content required for maintaining structural rigidity to the dihedral angle. The critical solid content decreases with an increasing dihedral angle. Consequently, W-Cu alloys, which have a dihedral angle of about 95sp, can be consolidated without gross distortion with as little as 20 vol.% solid. To comprehensively understand the gravitational effects in the evolution of both the microstructure and the macrostructure during liquid phase sintering, W-Ni-Fe alloys with W content varying from 78 to 93 wt.% were sintered in microgravity. Compositions that slump during ground-based sintering also distort when sintered under microgravity. In ground-based sintering, low solid content alloys distort with a typical elephant-foot profile, while in microgravity, the compacts tend to spheroidize. This study shows that microstructural segregation occurs in both ground-based as well as microgravity sintering. In ground-based experiments, because of the density difference between the solid and the liquid phase, the solid content increases from top to the bottom of the sample. In microgravity, the solid content increases from periphery to the center of the samples. A model is derived to show that grain agglomeration and segregation are energetically favored events and will therefore be inherent to the system, even in the absence of gravity. Real time distortion measurement in alloys having appreciable solid-solubility in the liquid phase, such as W-Ni-Fe and Fe-Cu, show that the bulk of distortion occur within the first 5 min of melt formation. Distortion in such systems can be minimized by presaturating the matrix with the solid phase.

  3. Computing excess functions of ionic solutions: the smaller-ion shell model versus the primitive model. 1. Activity coefficients.

    PubMed

    Fraenkel, Dan

    2015-01-13

    The present study compares the Monte Carlo (MC) simulation of the primitive model (PM) ( Abbas, Z. et al. J. Phys. Chem. B 2009 , 113 , 5905 ), by which activity coefficients of many binary ionic solutions have been computed through adjusting ion-size parameters (ISPs) for achieving best fit with experiment, with a parallel fit and ISP adjustment, employing the Smaller-ion Shell (SiS) treatment ( Fraenkel, D. Mol. Phys. 2010 , 108 , 1435 ), a Debye-Hückel type theory ("DH-SiS") considering counterions of unequal size. DH-SiS is analogous to the unrestricted PM (UPM), so the comparison is with the MC simulation of the UPM, "MC-UPM". Among the representative electrolytes NaCl, KCl, NaClO4, CaCl2, Ca(ClO4)2, and LaCl3, in water at 25 °C, the 1-1 electrolytes exhibit a far better fit quality for DH-SiS than for MC-UPM, and the fit extends to higher concentration. Moreover, theoretical single-ion activity coefficients derived from DH-SiS agree with experimental estimation for solutions of NaCl, CaCl2, and other electrolytes ( Fraenkel, D. J. Phys. Chem. B 2012 , 116 , 3603 ), whereas parallel MC-UPM predictions are at odds with experiment. Additional advantages of DH-SiS over MC-UPM are in (a) employing co-ion ISPs that are usually equal to the crystallographic ion diameters and (b) easily applying ISP nonadditivity in adjusting counterion ISPs. PMID:26574216

  4. Microscopic Evidence for a dense liquid phase of calcium carbonate (Invited)

    NASA Astrophysics Data System (ADS)

    Wallace, A. F.; Hedges, L.; Fernandez-Martinez, A.; Raiteri, P.; Gale, J. D.; Waychunas, G.; Whitelam, S.; Banfield, J. F.; De Yoreo, J. J.

    2013-12-01

    In the classical sense, minerals are presumed to nucleate directly from solution by overcoming a size-dependent free energy barrier that scales as the ratio of the macroscopic mineral-water interfacial tension cubed to the square of the thermodynamic supersaturation. However, experimental observations of the early stages of calcium carbonate mineralization demonstrate that under certain conditions formation of the crystalline polymorphs is preceded by the apparently spontaneous appearance of nanoscopic clusters that aggregate to produce metastable amorphous phases. This aggregation-based pathway is seemingly at odds with classical expectations. This research (Wallace et al., in press, Science) uses computational approaches to characterize the thermodynamic and dynamic properties of hydrated calcium carbonate cluster species, which are thus far only loosely constrained by experimental investigations. Replica exchange molecular dynamics simulations are employed to probe the initial formation of the clusters and lattice gas simulations are used to explore the general behavior of clusters at the onset of mineralization. The results suggest the growth of carbonate clusters may indeed proceed in the absence of any significant thermodynamic barrier. Moreover, the dynamical properties of the clusters are consistent with those of a dense liquid phase. Coalescence and dehydration of the nanoscale droplets result in the formation of a phase whose structure is consistent with that of amorphous calcium carbonate. These findings indicate that a spontaneous liquid-liquid phase separation may occur within the range of supersaturations spanned by natural waters. The coexistence of the dense and dilute liquid phases is described by a liquid-liquid binodal that may express a lower critical point near ambient temperature. Though liquid-liquid separation in simulations of the CaCO3-H2O system is an unexpected result, it suggests a means of generating nano- and mesoscopic phases consistent with established phase separation mechanisms and experimental observations.

  5. Extended quantum U(1)-liquid phase in a three-dimensional quantum dimer model

    SciTech Connect

    Sikora, Olga; Shannon, Nic; Pollmann, Frank; Penc, Karlo; Fulde, Peter

    2011-09-15

    Recently, quantum dimer models have attracted a great deal of interest as a paradigm for the study of exotic quantum phases. Much of this excitement has centered on the claim that a certain class of quantum dimer model can support a quantum U(1)-liquid phase with deconfined fractional excitations in three dimensions. These fractional monomer excitations are quantum analogs of the magnetic monopoles found in spin ice. In this paper, we use extensive quantum Monte Carlo simulations to establish the ground-state phase diagram of the quantum dimer model on the three-dimensional diamond lattice as a function of the ratio {mu} of the potential to kinetic-energy terms in the Hamiltonian. We find that, for {mu}{sub c}=0.75{+-}0.02, the model undergoes a first-order quantum phase transition from an ordered ''R state'' into an extended quantum U(1)-liquid phase, which terminates in a quantum critical Rokhsar-Kivelson (RK) point for {mu}=1. This confirms the published field-theoretical scenario. We present detailed evidence for the existence of the U(1)-liquid phase and indirect evidence for the existence of its photon and monopole excitations. Simulations are benchmarked against a variety of exact and perturbative results, and a comparison is made of different variational wave functions. We also explore the ergodicity of the quantum dimer model on a diamond lattice within a given flux sector, identifying a new conserved quantity related to transition graphs of dimer configurations. These results complete and extend the previous analysis of O. Sikora et al.[Phys. Rev. Lett. 103, 247001 (2009)].

  6. Commercial-Scale Demonstration of the Liquid Phase methanol (LPMEOH) Process A DOE Assessment

    SciTech Connect

    National Energy Technology Laboratory

    2003-10-27

    The U.S. Department of Energy (DOE) Clean Coal Technology (CCT) Program seeks to offer the energy marketplace more efficient and environmentally benign coal utilization technology options by demonstrating them in industrial settings. This document is a DOE post-project assessment (PPA) of one of the projects selected in Round III of the CCT Program, the commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) Process, initially described in a Report to Congress by DOE in 1992. Methanol is an important, large-volume chemical with many uses. The desire to demonstrate a new process for the production of methanol from coal, prompted Air Products and Chemicals, Inc. (Air Products) to submit a proposal to DOE. In October 1992, DOE awarded a cooperative agreement to Air Products to conduct this project. In March 1995, this cooperative agreement was transferred to Air Products Liquid Phase Conversion Company, L.P. (the Partnership), a partnership between Air Products and Eastman Chemical Company (Eastman). DOE provided 43 percent of the total project funding of $213.7 million. Operation of the LPMEOH Demonstration Unit, which is sited at Eastman's chemicals-from-coal complex in Kingsport, Tennessee, commenced in April 1997. Although operation of the CCT project was completed in December 2002, Eastman continues to operate the LPMEOH Demonstration Unit for the production of methanol. The independent evaluation contained herein is based primarily on information from Volume 2 of the project's Final Report (Air Products Liquid Phase Conversion Co., L.P. 2003), as well as other references cited.

  7. Observations and implications of liquid-liquid phase separation at high relative humidities in secondary organic material produced by ?-pinene ozonolysis without inorganic salts

    NASA Astrophysics Data System (ADS)

    Renbaum-Wolff, L.; Song, M.; Marcolli, C.; Zhang, Y.; Liu, P. F.; Grayson, J. W.; Geiger, F. M.; Martin, S. T.; Bertram, A. K.

    2015-11-01

    Particles consisting of secondary organic material (SOM) are abundant in the atmosphere. To predict the role of these particles in climate, visibility, and atmospheric chemistry, information on particle phase state (i.e. single liquid, two liquids, solid and so forth) is needed. This paper focuses on the phase state of SOM particles free of inorganic salts produced by the ozonolysis of ?-pinene. Phase transitions were investigated both in the laboratory and with a thermodynamic model over the range of < 0.5 % to 100 % relative humidity (RH) at 290 K. In the laboratory studies, a single phase was observed from 0 to 95 % RH while two liquid phases were observed above 95 % RH. For increasing RH, the mechanism of liquid-liquid phase separation (LLPS) was spinodal decomposition. The RH range at which two liquid phases were observed did not depend on the direction of RH change. In the modelling studies at low RH values, the SOM took up hardly any water and was a single organic-rich phase. At high RH values, the SOM underwent LLPS to form an organic-rich phase and an aqueous phase, consistent with the laboratory studies. The presence of LLPS at high RH-values has consequences for the cloud condensation nuclei (CCN) activity of SOM particles. In the simulated Khler curves for SOM particles, two local maxima are observed. Depending on the composition of the SOM, the first or second maximum can determine the critical supersaturation for activation. The presence of LLPS at high RH-values can explain inconsistencies between measured CCN properties of SOM particles and hygroscopic growth measured below water saturation.

  8. Biopolymer-supported ionic-liquid-phase ruthenium catalysts for olefin metathesis.

    PubMed

    Clousier, Nathalie; Filippi, Alexandra; Borr, Etienne; Guibal, Eric; Crvisy, Christophe; Caijo, Frderic; Mauduit, Marc; Dez, Isabelle; Gaumont, Annie-Claude

    2014-04-01

    Original ruthenium supported ionic liquid phase (SILP) catalysts based on alginates as supports were developed for olefin metathesis reactions. The marine biopolymer, which fulfills most of the requisite properties for a support such as widespread abundance, insolubility in the majority of organic solvents, a high affinity for ionic liquids, high chemical stability, biodegradability, low cost, and easy processing, was impregnated by [bmim][PF6 ] containing an ionically tagged ruthenium catalyst. These biosourced catalysts show promising performances in ring-closing metathesis (RCM) and cross-metathesis (CM) reactions, with a high level of recyclability and reusability combined with a good reactivity. PMID:24616203

  9. Liquid Phase Deposition Of Thin Titanium Dioxide Films For NH3 Detection

    NASA Astrophysics Data System (ADS)

    Georgieva, V.; Stefchev, P.; Stefanov, P.; Spassov, L.; Raicheva, Z.; Ivanova, K.

    2007-04-01

    TiO2 thin films are prepared by a new method called Liquid Phase Deposition (LDP). The layers are obtained by the reaction between the metal fluorocomplex and boric acid in aqueous solution. The morphology of the films and the composition are investigated by scanning electron microscopy (SEM) and x-ray photoelectron spectrometry (XPS). The sorption properties of TiO2 film to NH3 are measured by the Quartz Crystal Microbalance (QCM) method. A correlation between NH3 concentration and the sorption ability of as-deposited and annealed samples is obtained.

  10. Polymorphism in glassy silicon: Inherited from liquid-liquid phase transition in supercooled liquid

    NASA Astrophysics Data System (ADS)

    Zhang, Shiliang; Wang, Li-Min; Zhang, Xinyu; Qi, Li; Zhang, Suhong; Ma, Mingzhen; Liu, Riping

    2015-02-01

    Combining molecular dynamics (MD) simulation and Voronoi polyhedral analyses, we discussed the microstructure evolution in liquid and glassy silicon during cooling by focusing on the fraction of various clusters. Liquid-liquid phase transition (LLPT) is detected in supercooled liquid silicon However, freezing the high-density liquid (HDL) to the glassy state is not achieved as the quenching rate goes up to 1014 K/s. The polyamorphism in glassy silicon is found to be mainly associated with low-density liquid (LDL).

  11. Acid-Triggered Colorimetric Hydrophobic Benzyl Alcohols for Soluble Tag-Assisted Liquid-Phase Synthesis.

    PubMed

    Okada, Yohei; Wakamatsu, Hiroki; Sugai, Masae; Kauppinen, Esko I; Chiba, Kazuhiro

    2015-09-01

    Simple screening of acid-triggered reactions of methoxybenzyl alcohols led to the development of a novel colorimetric hydrophobic benzyl alcohol (HBA) tag. HBA tag-3 (14) retained high solubility in less polar solvents and excellent precipitation properties in polar solvents. Our routine procedure for tag-assisted liquid phase peptide synthesis was applied using HBA tag-3 (14), and an effective synthesis of ?-sheet breaker peptide iA?5 (4) was achieved. The tagged peptides showed a vivid blue color under acidic conditions both on TLC plates and in solution, enabling quantitative assay. PMID:26274781

  12. Pinball liquid phase from Hund's coupling in frustrated transition-metal oxides

    NASA Astrophysics Data System (ADS)

    Ralko, Arnaud; Merino, Jaime; Fratini, Simone

    2015-04-01

    The interplay of nonlocal Coulomb repulsion and Hund's coupling in the d -orbital manifold in frustrated triangular lattices is analyzed by a multiband extended Hubbard model. We find a rich phase diagram with several competing phases, including a robust pinball liquid phase, which is an unconventional metal characterized by threefold charge order, bad metallic behavior, and the emergence of high-spin local moments. Our results naturally explain the anomalous charge-ordered metallic state observed in the triangular layered compound AgNiO2. The potential relevance to other triangular transition-metal oxides is discussed.

  13. Low temperature liquid-phase sintering in the magnesium aluminosilicate glass - alumina system

    NASA Astrophysics Data System (ADS)

    Nakajima, Akira

    This study was carried out to obtain a fundamental understanding of the process conditions and strategies for lowering liquid phase sintering temperatures. Alumina coated with 9 vol% of a ternary eutectic glass in the MgO-Alsb2Osb3-SiOsb2 (MAS) was used as the model system. Homogeneous coating of the glass was ensured by using a sol-gel coating technique. Sintering behavior of the glass coated alumina was investigated over a temperature range of 1400sp°C-1460sp°C. Mullite and spinel or sapphirine crystallized from the MAS liquid during sintering. The formation of spinel was observed at the interface between the liquid and alumina, whereas mullite was found to homogeneously crystallize in the liquid. The rate of glass crystallization was enhanced by finer powder. The time at which crystallization rate became significant corresponded to the onset of the decrease of densification rate at the temperature. Attaining a balance of these two competing phenomena at the sintering temperature is proposed as an additional criteria for successful liquid phase sintering at low temperatures. Additional experiments revealed that this balance is not easy to control in the case of bimodal powder mixture, and that homogeneous distribution of liquid at the initial stage is essential for the control of this balance. Densification kinetics and crystallization behavior of 0.2 mum alumina coated with boron or sodium doped glass in the MAS system were also investigated at 1400sp°C and 1460sp°C. Doping the Alsb2Osb3-MAS glass system is effective for liquid phase sintering of alumina at 1400sp°C. The balance between densification and crystallization for the alumina coated with MAS glass was altered by the addition of boron and sodium. However, the mechanisms by which boron and sodium improve the sintering kinetics are different. From the experimentally obtained result, the ratio of the densification rate to crystallization rate was calculated. Using theoretically determined equations and the analysis of above mentioned ratio, strategies to lower the temperature of liquid phase sintering was proposed.

  14. Shear viscosity in a non-Fermi-liquid phase of a quadratic semimetal

    NASA Astrophysics Data System (ADS)

    Dumitrescu, Philipp T.

    2015-09-01

    We study finite temperature transport in the Luttinger-Abrikosov-Beneslavskii phasean interacting, scale invariant, non-Fermi-liquid phase found in quadratic semimetals. We develop a kinetic equation formalism to describe the dc transport properties, which are dominated by collisions, and compute the shear viscosity ? . The ratio of shear viscosity to entropy density ? /s is a measure of the strength of interaction between the excitations of a quantum fluid. As a consequence of the quantum critical nature of the system, ? /s is a universal number and we find it to be consistent with a bound proposed from gauge-gravity duality.

  15. Organic salt-assisted liquid-phase exfoliation of graphite to produce high-quality graphene

    NASA Astrophysics Data System (ADS)

    Du, Wencheng; Lu, Jie; Sun, Peipei; Zhu, Yinyan; Jiang, Xiaoqing

    2013-05-01

    Certain ordinary organic salts, such as edetate disodium, sodium tartrate, potassium sodium tartrate and sodium citrate were found to have universal and efficient assistant effect for liquid-phase exfoliation of graphite in common organic solvents to produce pristine graphene. Up to 123 times enhanced exfoliation efficiency was observed when sodium citrate was introduced into an exfoliation system consisting of natural graphite powder and dimethyl sulfoxide. TEM, AFM, Raman spectroscopy, EDX, TGA, and FTIR analysis showed graphite was successfully exfoliated into single or few-layer graphene nanosheets which were free of defects and oxides. The method is simple, effective, safe and economical.

  16. Liquid phase methanol reactor staging process for the production of methanol

    DOEpatents

    Bonnell, Leo W. (Macungie, PA); Perka, Alan T. (Macungie, PA); Roberts, George W. (Emmaus, PA)

    1988-01-01

    The present invention is a process for the production of methanol from a syngas feed containing carbon monoxide, carbon dioxide and hydrogen. Basically, the process is the combination of two liquid phase methanol reactors into a staging process, such that each reactor is operated to favor a particular reaction mechanism. In the first reactor, the operation is controlled to favor the hydrogenation of carbon monoxide, and in the second reactor, the operation is controlled so as to favor the hydrogenation of carbon dioxide. This staging process results in substantial increases in methanol yield.

  17. Commercial-Scale Demonstration of the Liquid Phase Methanol (LOMEOH(TM)) Process

    SciTech Connect

    1996-03-31

    The Liquid Phase Methanol (LPMEOEP") Demonstration Project at K.ingsport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L, P. (the Partnership). The LPMEOHY Process Demonstration Unit is being built at a site located at the Eastman Chemical Company (Eastman) complex in Kingsport. On 4 October 1994, Air Products and Chemicals, Inc. (Air Products) and signed the agreements that would form the Partnership, secure the demonstration site, and provide the financial commitment and overall project management for the project. These partnership agreements became effective on 15 March 1995, when DOE authorized the commencement of Budget Period No. 2 (Mod. AO08 to the Cooperative Agreement). The Partnership has subcontracted with Air Products to provide the overall management of the project, and to act as the primary interface with DOE. As subcontractor to the Partnership, Air Products will also provide the engineering design, procurement, construction, and commissioning of the LPMEOHTM Process Demonstration Unit, and will provide the technical and engineering supervision needed to conduct the operational testing program required as part of the project. As subcontractor to Air Products, Eastman will be responsible for operation of the LPMEOHTM Process Demonstration Unit, and for the interconnection and supply of synthesis gas, utilities, product storage, and other needed sewices. The project involves the construction of an 80,000 gallons per day (260 tons-per-day (TPD)) methanol unit utilizing coal-derived synthesis gas fi-om Eastman's integrated coal gasification facility. The new equipment consists of synthesis gas feed preparation and compression facilities, the liquid phase reactor and auxiliaries, product distillation facilities, and utilities. The technology to be demonstrated is the product of a cooperative development effort by Air Products and DOE in a program that started in 1981. Developed to enhance electric power generation using integrated gasification combined cycle (IGCC) technology, the LPMEOHTM process is ideally suited for directly processing gases produced by modern day coal gasifiers. Originally tested at a small 3,200 gallons per day, DOE-owned experimental unit in LaPorte, Texas, the technology provides several improvements essential for the economic coproduction of methanol and electricity directly from gasified coal. This liquid phase process suspends fine catalyst particles in an inert liquid, forming a slurry. The slurry dissipates the heat of the chemical reaction away from the catalyst surface, protecting the catalyst and allowing the methanol synthesis reaction to proceed at higher rates.

  18. The Biological Sensor for Detection of Bacterial Cells in Liquid Phase Based on Plate Acoustic Wave

    NASA Astrophysics Data System (ADS)

    Borodina, Irina; Zaitsev, Boris; Shikhabudinov, Alexander; Guliy, Olga; Ignatov, Oleg; Teplykh, Andrey

    The interactions "bacterial cells - bacteriophages", "bacterial cells - antibodies" and "bacterial cells - mini- antibodies" directly in liquid phase were experimentally investigated with a help of acoustic sensor. The acoustic sensor under study represents two-channel delay line based on the plate of Y-X lithium niobate. One channel of delay line was electrically shorted, the second channel was electrically open. The liquid container was glued on plate surface between transducers of delay line. The dependencies of the change in phase and insertion loss on concentration of bacteriophages, antibodies, and mini- antibodies were obtained for both channels of delay line.

  19. Cu-Sn transient liquid phase wafer bonding for MEMS applications

    NASA Astrophysics Data System (ADS)

    Fltgen, C.; Pawlak, M.; Pabo, E.; van de Wiel, H. J.; Hayes, G. R.; Dragoi, V.

    2013-05-01

    The impact of process parameters on final bonding layer quality was investigated for Transient Liquid Phase (TLP) wafer-level bonding based on the Cu-Sn system. Subjects of this investigation were bonding temperature profile, bonding time and contact pressure as well as the choice of metal deposition method and the ratio of deposited metal layer thicknesses. Typical failure modes in Inter-Metallic Compound (IMC) growth for the mentioned process and design parameters were identified and subjected to qualitative and quantitative analysis. The possibilities to avoid abovementioned failures are indicated based on experimental results.

  20. Mssbauer characterization of joints of steel pieces in transient liquid phase bonding experiences

    NASA Astrophysics Data System (ADS)

    di Luozzo, N.; Martnez Stenger, P. F.; Canal, J. P.; Fontana, M. R.; Arcondo, B.

    2011-11-01

    Joining of seamless, low carbon, steel tubes were performed by means of Transient Liquid Phase Bonding process employing a foil of Fe-Si-B metallic glass as filler material. The influence of the main parameters of the process was evaluated: temperature, holding time, pressure and post weld heat treatment. Powder samples were obtained from the joint of tubes and characterized employing Mssbauer Spectroscopy in transmission geometry. The sampling was performed both in tubes successfully welded and in those which show joint defects. The results obtained are correlated with the obtained microstructure and the diffusion of Si and B during the process.

  1. Transient liquid phase diffusion bonding of Udimet 720 for Stirling power converter applications

    NASA Technical Reports Server (NTRS)

    Mittendorf, Donald L.; Baggenstoss, William G.

    1992-01-01

    Udimet 720 has been selected for use on Stirling power converters for space applications. Because Udimet 720 is generally considered susceptible to strain age cracking if traditional fusion welding is used, other joining methods are being considered. A process for transient liquid phase diffusion bonding of Udimet 720 has been theoretically developed in an effort to eliminate the strain age crack concern. This development has taken into account such variables as final grain size, joint homogenization, joint efficiency related to bonding aid material, bonding aid material application method, and thermal cycle.

  2. Liquid phase epitaxy growth of langasite film for resonators and oscillators

    NASA Astrophysics Data System (ADS)

    Zhang, Hong; Singh, Narsingh B.; Berghmans, Andre; Adam, John D.; Tidrow, Steven; Fazi, Chris

    2002-02-01

    We report the growth of crystalline langasite (LGS) films using the liquid phase epitaxy technique. Utilizing a eutectic PbO : Bi 2O 3 flux system we have demonstrated that epitaxial LGS films can be grown on a spinel substrate. The films were characterized by optical and electron microscopes and X-ray diffraction. Detailed analysis revealed that the crystalline langasite films grow epitaxially along the c-direction (in hexagonal setting) which is parallel to the (1 1 1) orientation of the cubic spinel substrate.

  3. Cathodoluminescence of Al/x/Ga/1-x/As grown by liquid-phase epitaxy

    NASA Technical Reports Server (NTRS)

    Levin, E. R.; Ladany, I.

    1978-01-01

    Small-area contrast fluctuations observed in cathodoluminescence-mode SEM images of thin Al(x)Ga(1-x)As layers grown by liquid-phase epitaxy on GaAs:Cr substrates are attributed to local variations in alloy composition. Quantitative estimates of the composition excursions are obtained from the variations in CL intensity by calibration against compositions known from electron-probe microanalysis. In a typical sample, the CL variations are shown to correspond to peak-to-peak fluctuations of about 1 at. % of Al and occur over irregular regions generally in the range 6-20 microns in diameter.

  4. Investigation on Sized-Regulated Iron Nanoparticles Prepared by Liquid Phase Plasma Reduction Process.

    PubMed

    Heon, Lee; Kim, Hwan-Gi; Kim, Byung Hoon; Yun, Je-Jung; Chung, Minchul; Ahn, Ho-Geun; Lee, Young-Seak; Jung, Sang-Chul

    2015-01-01

    The liquid-phase plasma reduction method has been applied to prepare iron nanoparticles from iron chloride solution using a bipolar pulsed electrical discharge system. The excited states of atomic iron, hydrogen, and oxygen as well as the molecular bands of hydroxyl radicals were detected in the emission spectra. The iron nanoclusters formed at the initial stage convert to dispersion of small iron nanoparticles, which then grows slowly to form anisotropic, tetragonal shape. The cationic surfactant of CTAB was shown to exhibit a large influence on the particle generation procedure. PMID:26328393

  5. Transient-Liquid-Phase and Liquid-Film-Assisted Joining ofCeramics

    SciTech Connect

    Sugar, Joshua D.; McKeown, Joseph T.; Akashi, Takaya; Hong, SungM.; Nakashima, Kunihiko; Glaeser, Andreas M.

    2005-02-09

    Two joining methods, transient-liquid-phase (TLP) joining and liquid-film-assisted joining (LFAJ), have been used to bond alumina ceramics. Both methods rely on multilayer metallic interlayers designed to form thin liquid films at reduced temperatures. The liquid films either disappear by interdiffusion (TLP) or promote ceramic/metal interface formation and concurrent dewetting of the liquid film (LFAJ). Progress on extending the TLP method to lower temperatures by combining low-melting-point (<450 C) liquids and commercial reactive-metal brazes is described. Recent LFAJ work on joining alumina to niobium using copper films is presented.

  6. Communication: Protein dynamical transition vs. liquid-liquid phase transition in protein hydration water

    NASA Astrophysics Data System (ADS)

    Schir, Giorgio; Fomina, Margarita; Cupane, Antonio

    2013-09-01

    In this work, we compare experimental data on myoglobin hydrated powders from elastic neutron scattering, broadband dielectric spectroscopy, and differential scanning calorimetry. Our aim is to obtain new insights on the connection between the protein dynamical transition, a fundamental phenomenon observed in proteins whose physical origin is highly debated, and the liquid-liquid phase transition (LLPT) possibly occurring in protein hydration water and related to the existence of a low temperature critical point in supercooled water. Our results provide a consistent thermodynamic/dynamic description which gives experimental support to the LLPT hypothesis and further reveals how fundamental properties of water and proteins are tightly related.

  7. Joining of Ion Transport Membranes Using a Novel Transient Liquid Phase Process

    SciTech Connect

    Darryl P. Butt

    2006-08-30

    The feasibility of a novel transient liquid phase (TLP) joining method has been demonstrated in joining La{sub 0.9}Ca{sub 0.1}FeO{sub 3} materials. Metal oxide powders were processed to form the TLP compositions which were used in the joining process. The method has been successful in producing joint interfaces that effectively disappear, as they are the same material and have the same properties as the joined parts. The feasibility of the method has been demonstrated for a single system, but many systems where the method can potentially be applied have been identified.

  8. Assessment of odor activity value coefficient and odor contribution based on binary interaction effects in waste disposal plant

    NASA Astrophysics Data System (ADS)

    Wu, Chuandong; Liu, Jiemin; Yan, Luchun; Chen, Haiying; Shao, Huiqi; Meng, Tian

    2015-02-01

    Odor activity value (OAV) has been widely used for the assessment of odor pollution from various sources. However, little attention has been paid to the extreme OAV variation and potential inaccuracies of odor contribution assessment caused by odor interaction effects. The objective of this study is to assess the odor interaction effect for precise assessment of odor contribution. In this paper, samples were collected from a food waste disposal plant, and analyzed by instrumental and olfactory method to conclude odorants' occurrence and OAV. Then odor activity value coefficient (γ) was first proposed to evaluate the type and the level of binary interaction effects based on determination of OAV variation. By multiplying OAV and γ, odor activity factor (OAF) was used to reflect the real OAV. Correlation between the sum of OAF and odor concentration reached 80.0 ± 5.7%, which was 10 times higher than the sum of OAV used before. Results showed that hydrogen sulfide contributed most (annual average 66.4 ± 15.8%) to odor pollution in the waste disposal plant. However, as odor intensity of samples in summer rising, odor contribution of trimethylamine increased to 48.3 ± 3.7% by the strong synergistic interaction effect, while odor contribution of phenol decreased to 0.1 ± 0.02% for the increasing antagonistic interaction effect.

  9. Estimation of excess energies and activity coefficients for the penternary Ni-Cr-Co-Al-Mo system and its subsystems

    NASA Astrophysics Data System (ADS)

    Dogan, A.; Arslan, H.; Dogan, T.

    2015-06-01

    Using different prediction methods, such as the General Solution Model of Kohler and Muggianu, the excess energy and activities of molybdenum for the sections of the phase diagram for the penternary Ni-Cr-Co-Al-Mo system with mole ratios xNi/ xMo = 1, xCr/ xMo = 1, xCo/ xMo = 1, and xAl/ xMo = r = 0.5 and 1, were thermodynamically investigated at a temperature of 2000 K, whereas the excess energy and activities of Bi for the section corresponding to the ternary Bi-Ga-Sb system with mole ratio xGa/ xSb = 1/9 were thermodynamically investigated at a temperature of 1073 K. In the case of r = 0.5 and 1 in the alloys Ni-Cr-Co-Al-Mo, a positive deviation in the activity coefficient was revealed, as molybdenum content increased. Moreover, in the calculations performed in Chou's GSM model, the obtained values for excess Gibbs energies are negative in the whole concentration range of bismuth at 1073 K and exhibit the minimum of about -2.2 kJ/mol at the mole ratio xGa/ xSb = 1/9 in the alloy Bi-Ga-Sb.

  10. Optimization of high-molecular-weight polycyclic aromatic hydrocarbons' degradation in a two-liquid-phase bioreactor.

    PubMed

    Marcoux, J; Dziel, E; Villemur, R; Lpine, F; Bisaillon, J G; Beaudet, R

    2000-04-01

    A microbial consortium degrading the high-molecular-weight polycyclic aromatic hydrocarbons (HMW PAHs) pyrene, chrysene, benzo[a]pyrene and perylene in a two-liquid-phase reactor was studied. The highest PAH-degrading activity was observed with silicone oil as the water-immiscible phase; 2,2,4,4,6,8, 8-heptamethylnonane, paraffin oil, hexadecane and corn oil were much less, or not efficient in improving PAH degradation by the consortium. Addition of surfactants (Triton X-100, Witconol SN70, Brij 35 and rhamnolipids) or Inipol EAP22 did not promote PAH biodegradation. Rhamnolipids had an inhibitory effect. Addition of salicylate, benzoate, 1-hydroxy-2-naphtoic acid or catechol did not increase the PAH-degrading activity of the consortium, but the addition of low-molecular-weight (LMW) PAHs such as naphthalene and phenanthrene did. In these conditions, the degradation rates were 27 mg l-1 d-1 for pyrene, 8.9 mg l-1 d-1 for chrysene, 1.8 mg l-1 d-1 for benzo[a]pyrene and 0.37 mg l-1 d-1 for perylene. Micro-organisms from the interface were slightly more effective in degrading PAHs than those from the aqueous phase. PMID:10792524

  11. Enhanced degradation of bioremediation residues in petroleum-contaminated soil using a two-liquid-phase bioslurry reactor.

    PubMed

    Lu, Mang; Zhang, Zhongzhi; Sun, Shanshan; Wang, Qinfang; Zhong, Weizhang

    2009-09-01

    A study was performed to determine the potential of two-liquid-phase (TLP) bioslurry reactors using silicon oil as solvent for degradation of residual contaminants in petroleum-contaminated soil. The residues were characterized by gas chromatography-mass spectrometry and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. This allowed for the identification of a mixture of residual biomarkers, metabolic byproducts, oxygenated and hetero-polynuclear aromatic hydrocarbons in the contaminated soil. The removal amount of total extractable organics (TEO) was 15900mgkg(-1) soil in the TLP reactor within 12weeks. However, TEO remained intact in the bioslurry reactor without the addition of silicon oil for the duration of the experiment, due to high toxicity of metabolites to the microorganisms. The availability of TEO was calculated using a mild extraction with Triton X-100, and the amount of TEO extracted was in accord with the amount of biodegraded TEO. Significantly reduced toxicity in soil was observed at week 12 through TLP remediation. Dehydrogenase activity in the bioslurry reactor was strongly suppressed. Fluorescein diacetate was significantly hydrolyzed by the composition of bioremediation residues in the contaminated soil. Microbial adhesion to the solvent was revealed by the determination of microbial activity in the water-immiscible-liquid. PMID:19709718

  12. Production of the biopesticide azadirachtin by hairy root cultivation of Azadirachta indica in liquid-phase bioreactors.

    PubMed

    Srivastava, Smita; Srivastava, Ashok K

    2013-11-01

    Batch cultivation of Azadirachta indica hairy roots was carried out in different liquid-phase bioreactor configurations (stirred-tank, bubble column, bubble column with polypropylene basket, and polyurethane foam disc as root supports) to investigate possible scale-up of the A. indica hairy root culture for in vitro production of the biopesticide azadirachtin. The hairy roots failed to grow in the conventional bioreactor designs (stirred tank and bubble column). However, modified bubble column reactor (with polyurethane foam as root support) configuration facilitated high-density culture of A. indica hairy roots with a biomass production of 9.2gl(-1)dry weight and azadirachtin yield of 3.2mgg(-1) leading to a volumetric productivity of azadirachtin as 1.14mgl(-1)day(-1). The antifeedant activity in the hairy roots was also evaluated by no choice feeding tests with known concentrations of the hairy root powder and its solvent extract separately on the desert locust Schistocerca gregaria. The hairy root powder and its solvent extract demonstrated a high level of antifeedant activity (with an antifeedant index of 97% at a concentration of 2% w/v and 83% at a concentration of 0.05% (w/v), respectively, in ethanol). PMID:23955295

  13. Liquid phase microextraction using knitting wool as the extractant phase holder before chromatographic analysis: a new approach for trace analysis.

    PubMed

    Zhang, Yufeng; Lee, Hian Kee

    2013-01-18

    In this paper, a novel liquid phase microextraction (LPME) approach was developed in which a piece of knitting wool was used as the extractant solvent holder. Owing to the absorbability of the wool, the extractant could be easily held within the material. When the wool containing the organic solvent was exposed to the sample solution, analytes could directly diffuse from the sample solution to the solvent. Ultraviolet (UV) filters ([2,4-dihydroxybenzophenone (BP-1), benzophenone (BP) and 2-hydroxy-4-methoxybenzophenone (BP-3)]) were used as model analytes to evaluate the procedure. Parameters that affect the extraction efficiency (selection of organic solvent, volume of the extractant, agitation speed, extraction time, salt concentration and pH) were investigated. The proposed method in combination with liquid chromatography-UV detection, provided good enrichment factors up to 366, with relative standard deviations of between 0.6% and 4.2% on the same piece of wool, and good linearity from 0.1 ng/ml to 100 ng/ml for all the analytes with regression coefficients of between 0.9998 and 0.9999. The limits of quantification of these compounds, calculated at S/N=10, were 0.1 ng/ml, 0.07 ng/ml and 0.1 ng/ml for BP-1, BP, BP-3, respectively. The method was applied to the determination of BP-type UV filters in swimming pool water. This is the first report of an application of knitting wool as a solvent holder for LPME. The procedure is cost-effective, and easy to operate. PMID:23276647

  14. Liquid phase sintering of tungsten composites in space: Results of tests performed in Texus

    NASA Astrophysics Data System (ADS)

    Ekbom, Lars B.; Eliasson, Anders

    Tungsten-nickel-iron composites are commersially fabricated from powders by liquid phase sintering. They consist of almost spherical tungsten particles in a matrix of nickel-iron-tungsten. A way to contribute to the understanding of the sintering mechanism and the mechanical properties is to study composites with a low amount of tungsten particles. Depending on the great difference in density between the particles and the matrix, this can only be done under microgravity. A primary sintering test of the tungsten composite was done in space using the Texus 10 modul. Prealloys were fabricated from metal powder mixtures, which were hot isostatic pressed. Liquid phase sintering of the two tungsten composites under microgravity has shown that the particles are evenly distributed and that no segregation occured due to convection. Despite an uneven distribution of the particles in the preformed specimens and the short melting period the patricle distribution has become even. Compared to short time sintering tests made on four alloys in the laboratory, the growth and separation of the particles was fast.

  15. Global phase diagram of competing ordered and quantum spin-liquid phases on the kagome lattice

    NASA Astrophysics Data System (ADS)

    Gong, Shou-Shu; Zhu, Wei; Balents, Leon; Sheng, D. N.

    2015-02-01

    We study the quantum phase diagram of the spin-1 /2 Heisenberg model on the kagome lattice with first-, second-, and third-neighbor interactions J1,J2, and J3 by means of density matrix renormalization group. For small J2 and J3, this model sustains a time-reversal invariant quantum spin-liquid phase. With increasing J2 and J3, we find in addition a q =(0 ,0 ) Nel phase, a chiral spin-liquid phase, an apparent valence-bond crystal phase, and a complex noncoplanar magnetically ordered state with spins forming the vertices of a cuboctahedron known as a cuboc1 phase. Both the chiral spin liquid and cuboc1 phase break time-reversal symmetry in the sense of spontaneous scalar spin chirality. We show that the chiralities in the chiral spin liquid and cuboc1 are distinct, and that these two states are separated by a strong first-order phase transition. The transitions from the chiral spin liquid to both the q =(0 ,0 ) phase and to time-reversal symmetric spin liquid, however, are consistent with continuous quantum phase transitions.

  16. Investigation of the growth of garnet films by liquid phase epitaxy

    NASA Technical Reports Server (NTRS)

    Moody, J. W.; Shaw, R. W.; Sandfort, R. M.

    1974-01-01

    Liquid phase expitaxy was investigated to determine its applicability to fabricating magnetic rare earth garnet films for spacecraft data recording systems. Two mixed garnet systems were investigated in detail: (1) Gd-Y and (2) Eu-Yb-Y. All films were deposited on Gd3Ga5012 substrates. The uniaxial anisotropy of the Gd-Y garnets is primarily stress-induced. These garnets are characterized by high-domain wall mobility, low coercivity and modest anisotropy. Characteristic length was found to be relatively sensitive to temperature. The Eu-Yb-Y garnets exhibit acceptable mobilities, good temperature stability and reasonable quality factors. The uniaxial anisotropy of these garnets is primarily growth-induced. The system is well suited for compositional "tailoring" to optimize specific desirable properties. Liquid phase epitaxy can be used to deposit Gd3Ga5012 spacing layers on magnetic garnet films and this arrangement possesses certain advantages over more conventional magnetic filmspacing layer combinations. However, it cannot be used if the magnetic film is to be ion implanted.

  17. Liquid-liquid phase transformations and the shape of the melting curve.

    PubMed

    Makov, G; Yahel, E

    2011-05-28

    The phase diagram of elemental liquids has been found to be surprisingly rich, including variations in the melting curve and transitions in the liquid phase. The effect of these transitions in the liquid state on the shape of the melting curve is analyzed. First-order phase transitions intersecting the melting curve imply piecewise continuous melting curves, with solid-solid transitions generating upward kinks or minima and liquid-liquid transitions generating downward kinks or maxima. For liquid-liquid phase transitions proposed for carbon, phosphorous selenium, and possibly nitrogen, we find that the melting curve exhibits a kink. Continuous transitions imply smooth extrema in the melting curve, the curvature of which is described by an exact thermodynamic relation. This expression indicates that a minimum in the melting curve requires the solid compressibility to be greater than that of the liquid, a very unusual situation. This relation is employed to predict the loci of smooth maxima at negative pressures for liquids with anomalous melting curves. The relation between the location of the melting curve maximum and the two-state model of continuous liquid-liquid transitions is discussed and illustrated by the case of tellurium. PMID:21639456

  18. Liquid phase crystallized silicon on glass: Technology, material quality and back contacted heterojunction solar cells

    NASA Astrophysics Data System (ADS)

    Haschke, Jan; Amkreutz, Daniel; Rech, Bernd

    2016-04-01

    Liquid phase crystallization has emerged as a novel approach to grow large grained polycrystalline silicon films on glass with high electronic quality. In recent years a lot of effort was conducted by different groups to determine and optimize suitable interlayer materials, enhance the crystallographic quality or to improve post crystallization treatments. In this paper, we give an overview on liquid phase crystallization and describe the necessary process steps and discuss their influence on the absorber properties. Available line sources are compared and different interlayer configurations are presented. Furthermore, we present one-dimensional numerical simulations of a rear junction device, considering silicon absorber thicknesses between 1 and 500 µm. We vary the front surface recombination velocity as well as doping density and minority carrier lifetime in the absorber. The simulations suggest that a higher absorber doping density is beneficial for layer thicknesses below 20 µm or when the minority carrier lifetime is short. Finally, we discuss possible routes for device optimization and propose a hybride cell structure to circumvent current limitations in device design.

  19. The Effect of Rapid Liquid-Phase Reactions on Injector Design and Combustion in Rocket Motors

    NASA Technical Reports Server (NTRS)

    Elverum, Gerard W., Jr.; Staudhammer, Peter

    1959-01-01

    Data are presented indicating the rates and magnitudes of energy released by the liquid-phase reactions of various propellant combinations. The data show that this energy release can contribute significantly to the rate of vaporization of the incoming propellants and thus aid the combustion process. Nevertheless, very low performances were obtained in rocket motors with conventional impinging-jet injectors when highly reactive systems such as N104-N2H4, were employed. A possible explanation for this low performance is that the initial reactions of such systems are so rapid that liquid-phase mixing is inhibited. Evidence for such an effect is presented in a series of color photographs of open flames using various injector elements. Based on these studies, some requirements are suggested for injector elements using highly reactive propellants. Experimental results are presented of motor tests using injector elements in which some of these requirements are met through the use of a set of concentric tubes. These tests, carried out at thrust levels of 40 to 800 lb per element, demonstrated combustion efficiencies of up to 98% based on equilibrium characteristic velocity values. Results are also presented for tests made with impinging-jet and splash-plate injectors for comparison.

  20. Kinetics modeling and growth of Si layers by Liquid Phase Epitaxy Driven by Solvent Evaporation (LPESE)

    NASA Astrophysics Data System (ADS)

    Giraud, S.; Duffar, T.; Pihan, E.; Fave, A.

    2015-12-01

    Crystalline Si thin films on low-cost substrates are expected to be an alternative to bulk Si for PV applications. Liquid Phase Epitaxy (LPE) is one of the most suitable techniques for the growth of high quality Si layers since LPE is performed under almost equilibrium conditions. We investigated a growth technology which allows growing Si epitaxial thin films in steady temperature conditions through the control of solvent evaporation from a metallic solution saturated with silicon: Liquid Phase Epitaxy by Solvent Evaporation (LPESE). An analytical model aiming to predict solvent evaporation and Si crystallization rate is described and discussed for three solvents (Sn, In and Cu). Growth experiments are implemented in order to check the validity of the model. Experimental set up and growth procedure are presented. Si thin films were grown from Sn-Si and In-Si solution at temperatures between 900 and 1200 C under high vacuum. The predicted solvent evaporation rate and Si growth rate are in agreement with the experimental measurements.

  1. Liquid-Liquid Phase Separation in Supersaturated Lysozyme Solutions and Associated Precipitate Formation/Crystallization

    NASA Technical Reports Server (NTRS)

    Muschol, Martin; Rosenberger, Franz

    1997-01-01

    Using cloud point determinations, the phase boundaries (binodals) for metastable liquid-liquid (L-L) separation in supersaturated hen egg white lysozyme solutions with 3%, 5%, and 7% (wlv) NaCl at pH= 4.5 and protein concentrations c between 40 and 400 mg/ml were determined. The critical temperature for the binodal increased approximately linearly with salt concentration. The coexisting liquid phases both remained supersaturated but differed widely in protein concentration. No salt repartitioning was observed between the initial and the two separated liquid phases. After the L-L separation, due to the presence of the high protein concentration phase, crystallization occurred much more rapidly than in the initial solution. At high initial protein concentrations, a metastable gel phase formed at temperatures above the liquid binodal. Both crystal nucleation and gel formation were accelerated in samples that had been cycled through the binodal. Solutions in the gel and L-L regions yielded various types of precipitates. Based on theoretical considerations, previous observations with other proteins, and our experimental results with lysozyme, a generic phase diagram for globular proteins is put forth. A limited region in the (T,c) plane favorable for the growth of protein single crystals is delineated.

  2. pH Variance in Aerosols Undergoing Liquid-Liquid Phase Separation

    NASA Astrophysics Data System (ADS)

    Eddingsaas, N. C.; Dallemagne, M.; Huang, X.

    2014-12-01

    The water content of aerosols is largely governed by relative humidity (RH). As the relative humidity decreases, and thus the water content of aerosols, a number of processes occur including the shrinking of aerosols, the increase in concentration of components, and potentially the formation of liquid liquid phase separation (llps) due to the salting out of inorganic salts. The most ubiquitous salt in atmospheric aerosols is ammonium sulfate which results in many aerosols to be at least mildly acidic. However, during llps, the pH of the different phases is not necessarily the same. Many reactions that take place within atmospheric aerosols are acid catalyzed so a better understanding of the pH of the individual phases as well as the interface between the phases is important to understanding aerosol processing and aging. Through the use of pH sensitive dyes and confocal microscopy we have directly measured the pH of micron sized model aerosols during high RH where the aerosols are in a single phase, at intermediate while the aerosols are in llps, and low RH where the aerosols consist of one liquid phase and one solid phase. We will discuss the variation in RH during these different phase states in the presence and absence of excess sulfuric acid. We will also discuss how this variation in pH affects aging of aerosols.

  3. Growth of a Large GaN Single Crystal Using the Liquid Phase Epitaxy (LPE) Technique

    NASA Astrophysics Data System (ADS)

    Kawamura, Fumio; Iwahashi, Tomoya; Omae, Kunimichi; Morishita, Masanori; Yoshimura, Masashi; Mori, Yusuke; Sasaki, Takatomo

    2003-01-01

    We grew a 12 5 0.8 mm GaN single crystal using the liquid phase epitaxy (LPE) method with Na flux. This GaN single crystal was grown on a 3 ?m-thick GaN thin film synthesized on sapphire using the metal organic chemical vapor deposition (MOCVD) method. It grew in a polyhedral form larger than the MOCVD-GaN substrate. Results indicate that a MOCVD-GaN thin film on a sapphire substrate functions as a seed crystal in Na flux. The use of mixed nitrogen gas containing 40% ammonia instead of pure N2 gas also enabled the growth of a 10 ?m-thick GaN homo-epitaxial film on an MOCVD-GaN film under 5 atm, the lowest reported pressure for growing GaN in Na flux. In this paper, we describe the liquid phase epitaxy (LPE) technique for growing bulk GaN single crystals, as well as the results of photoluminescence (PL) measurements. We also compare the PL intensity of the bulk GaN obtained in this study and the MOCVD-GaN. PL measurements revealed that the peak intensity of GaN single crystal grown by LPE indicates 40 times larger than MOCVD-GaN film. Also, dislocation density of bulk GaN crystals could be drastically reduced by the LPE growth technique.

  4. Transient-pressure analysis in geothermal steam reservoirs with an immobile vaporizing liquid phase

    USGS Publications Warehouse

    Moench, A.F.; Atkinson, P.G.

    1978-01-01

    A finite-difference model for the radial horizontal flow of steam through a porous medium is used to evaluate transient-pressure behavior in the presence of an immobile vaporizing or condensing liquid phase. Graphs of pressure drawdown and buildup in terms of dimensionless pressure and time are obtained for a well discharging steam at a constant mass flow rate for a specified time. The assumptions are made that the steam is in local thermal equilibrium with the reservoir rocks, that temperature changes are due only to phase change, and that effects of vapor-pressure lowering are negligible. Computations show that when a vaporizing liquid phase is present the pressure drawdown exhibits behavior similar to that observed in noncondensable gas reservoirs, but delayed in time. A theoretical analysis allows for the computation of this delay and demonstrates that it is independent of flow geometry. The response that occurs upon pressure buildup is markedly different from that in a noncondensable gas system. This result may provide a diagnostic tool for establishing the existence of phase-change phenomena within a reservoir. ?? 1979.

  5. Unusual stacking variations in liquid-phase exfoliated transition metal dichalcogenides.

    PubMed

    Shmeliov, Aleksey; Shannon, Mervyn; Wang, Peng; Kim, Judy S; Okunishi, Eiji; Nellist, Peter D; Dolui, Kapildeb; Sanvito, Stefano; Nicolosi, Valeria

    2014-04-22

    Liquid-phase exfoliation of layered materials offers a large-scale approach toward the synthesis of 2D nanostructures. Structural properties of materials can however change during transition from bulk to the 2D state. Any such changes must be examined and understood for successful implementation of 2D nanostructures. In this work, we demonstrate nonbulk stacking sequences in the few-layer MoS2 and WS2 nanoflakes produced by liquid-phase exfoliation. Our analysis shows that nonbulk stacking sequences can be derived from its bulk counterparts by translational shifts of the layers. No structural changes within the layers were observed. Twenty-seven MoS2 and five WS2 nanoflakes were imaged and analyzed. Nine MoS2 and four WS2 nanoflakes displayed nonbulk stacking. Such dominance of the nonbulk stacking suggests high possibility of unusual stacking sequences in other 2D nanostructures. Notably, the electronic structure of some non bulk stacked bilayers presents characteristics which are uncommon to either the bulk phase or the single monolayer, for instance, a spin-split conduction band bottom. Our main characterization technique was annular dark-field scanning transmission electron microscopy, which offers direct and reliable imaging of atomic columns. The stacking characterization approach employed here can be readily applied toward other few-layer transition metal chalcogenides and oxides. PMID:24588696

  6. Liquid Phase Sintered Ceramic Bone Scaffolds by Combined Laser and Furnace

    PubMed Central

    Feng, Pei; Deng, Youwen; Duan, Songlin; Gao, Chengde; Shuai, Cijun; Peng, Shuping

    2014-01-01

    Fabrication of mechanically competent bioactive scaffolds is a great challenge in bone tissue engineering. In this paper, ?-tricalcium phosphate (?-TCP) scaffolds were successfully fabricated by selective laser sintering combined with furnace sintering. Bioglass 45S5 was introduced in the process as liquid phase in order to improve the mechanical and biological properties. The results showed that sintering of ?-TCP with the bioglass revealed some features of liquid phase sintering. The optimum amount of 45S5 was 5 wt %. At this point, the scaffolds were densified without defects. The fracture toughness, compressive strength and stiffness were 1.67 MPam1/2, 21.32 MPa and 264.32 MPa, respectively. Bone like apatite layer was formed and the stimulation for apatite formation was increased with increase in 45S5 content after soaking in simulated body fluid, which indicated that 45S5 could improve the bioactivity. Furthermore, MG-63 cells adhered and spread well, and proliferated with increase in the culture time. PMID:25196598

  7. Liquid phase preparation and fluorescence of flake-liked NdF{sub 3} nanomaterials

    SciTech Connect

    Tian, Li; State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 ; Lian, Peili; Sun, Qiliang; Long, Peng; Xiang, Shaobin; Zhu, Guangshan

    2013-01-15

    Graphical abstract: Room-temperature emission spectra of NdF{sub 3} nanoflakes exhibit a strong luminescence emission peak at 402 nm when irradiated by an excitation wavelength of 250 nm. Display Omitted Highlights: ► NdF{sub 3} nanoflakes have been successfully prepared by a facile and repeatable liquid phase preparation. ► The action of oxalic acid in the reaction process was studied, showing important in the morphology of neodymium fluorides. ► The study on the fluorescent properties of flake-like NdF{sub 3} nanomaterials shows a strong emission peak at 402 nm by the excitation wavelength of 250 nm. -- Abstract: Neodymium fluoride nanoflakes were successfully prepared by a facile liquid phase preparation with Nd(NO{sub 3}){sub 3} and NaF as raw materials. In the process, oxalic acid acting as template agent was found to play important roles in the morphology of neodymium fluorides. The as-synthesized NdF{sub 3} nanoflakes were characterized by various techniques of X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray spectrometer instrument (EDS). The fluorescent properties of neodymium fluoride nanoflakes were investigated, showing a strong luminescence emission peak at 402 nm by the excitation wavelength of 250 nm.

  8. Activity Coefficients at Infinite Dilution of Organic Compounds in Trihexyl(tetradecyl)phophonium Bis(trifluoromethylsulfonyl)imide Using Inverse Gas Chromatography

    SciTech Connect

    Revelli, Anne-Laure; Sprunger, Laura; Gibbs, Jennifer; Acree, William; Baker, Gary A; Mutelet, Fabrice

    2009-01-01

    Activity coefficients at infinite dilution of organic compounds in the ionic liquid (IL) trihexyl(tetradecyl) phosphonium bis(trifluoromethylsulfonyl)imide were determined using inverse gas chromatography at three temperatures, T ) (302.45, 322.35, and 342.45) K. Linear free energy relationship (LFER) correlations have been obtained for describing the gas-to-IL and water-to-IL partition coefficients.

  9. Decreased-activity mutants of phosphoglucose isomerase in the cytosol and chloroplast of Clarkia xantiana. Impact on mass-action ratios and fluxes to sucrose and starch, and estimation of Flux Control Coefficients and Elasticity Coefficients.

    PubMed Central

    Kruckeberg, A L; Neuhaus, H E; Feil, R; Gottlieb, L D; Stitt, M

    1989-01-01

    1. Subcellular-compartment-specific decreased-activity mutants of phosphoglucose isomerase in Clarkia xantiana were used to analyse the control of sucrose and starch synthesis during photosynthesis. Mutants were available in which the plastid phosphoglucose isomerase complement is decreased to 75% or 50% of the wild-type level, and the cytosol complement to 64%, 36% or 18% of the wild-type level. 2. The effects on the [product]/[substrate] ratio and on fluxes to sucrose or starch and the rate of photosynthesis were studied with the use of saturating or limiting light intensity to impose a high or low flux through these pathways. 3. Removal of a small fraction of either phosphoglucose isomerase leads to a significant shift of the [product]/[substrate] ratio away, from equilibrium. We conclude that there is no 'excess' of enzyme over that needed to maintain its reactants reasonably close to equilibrium. 4. Decreased phosphoglucose isomerase activity can also alter the fluxes to starch or sucrose. However, the effect on flux does not correlate with the extent of disequilibrium, and also varies depending on the subcellular compartment and on the conditions. 5. The results were used to estimate Flux Control Coefficients for the chloroplast and cytosolic phosphoglucose isomerases. The chloroplast isoenzyme exerts control on the rate of starch synthesis and on photosynthesis in saturating light intensity and CO2, but not at low light intensity. The cytosolic enzyme only exerts significant control when its complement is decreased 3-5-fold, and differs from the plastid isoenzyme in exerting more control in low light intensity. It has a positive Control Coefficient for sucrose synthesis, and a negative Control Coefficient for starch synthesis. 6. The Elasticity Coefficients in vivo of the cytosolic phosphoglucose isomerase were estimated to lie between 5 and 8 in the wild-type. They decrease in mutants with a lowered complement of cytosolic phosphoglucose isomerase. 7. The implications of these results for regulation and for evolution are discussed. PMID:2775228

  10. Transient liquid phase bonding of titanium-, iron- and nickel-based alloys

    NASA Astrophysics Data System (ADS)

    Rahman, A. H. M. Esfakur

    The operating temperature of land-based gas turbines and jet engines are ever-increasing to increase the efficiency, decrease the emissions and minimize the cost. Within the engines, complex-shaped parts experience extreme temperature, fatigue and corrosion conditions. Ti-based, Ni-based and Fe-based alloys are commonly used in gas turbines and jet engines depending on the temperatures of different sections. Although those alloys have superior mechanical, high temperature and corrosion properties, severe operating conditions cause fast degradation and failure of the components. Repair of these components could reduce lifecycle costs. Unfortunately, conventional fusion welding is not very attractive, because Ti reacts very easily with oxygen and nitrogen at high temperatures, Ni-based superalloys show heat affected zone (HAZ) cracking, and stainless steels show intergranular corrosion and knife-line attack. On the other hand, transient liquid phase (TLP) bonding method has been considered as preferred joining method for those types of alloys. During the initial phase of the current work commercially pure Ti, Fe and Ni were diffusion bonded using commercially available interlayer materials. Commercially pure Ti (Ti-grade 2) has been diffusion bonded using silver and copper interlayers and without any interlayer. With a silver (Ag) interlayer, different intermetallics (AgTi, AgTi2) appeared in the joint centerline microstructure. While with a Cu interlayer eutectic mixtures and Ti-Cu solid solutions appeared in the joint centerline. The maximum tensile strengths achieved were 160 MPa, 502 MPa, and 382 MPa when Ag, Cu and no interlayers were used, respectively. Commercially pure Fe (cp-Fe) was diffusion bonded using Cu (25 m) and Au-12Ge eutectic interlayer (100 microm). Cu diffused predominantly along austenite grain boundaries in all bonding conditions. Residual interlayers appeared at lower bonding temperature and time, however, voids were observed in the joint centerline at higher joining temperature and time. Dispersed Au-rich particles were observed in the base metal near interface. The highest ultimate tensile strengths obtained for the bonded Fe were 291+/-2 MPa using a Cu interlayer at 1030°C for 10 h and 315+/-4 MPa using a Au-12Ge interlayer at 950°C for 15 h. Commercially pure Ni (cp-Ni) was diffusion bonded using a Al, Au-12Ge or Cu interlayer. The formation of intermetallics could not be avoided when Al interlayer was used. Even though no intermetallics were obtained with Au-12Ge or Cu interlayer, appreciable strength of the joint was not found. Next, the simple bonding systems were modeled numerically. It is hoped that the simple models can be extended for higher order alloys. The modeling of TLP joint means to come up with a mathematical model which can predict the concentration profiles of diffusing species. The concentration dependence of diffusivity in a multi-component diffusion system makes it complicated to predict the concentration profiles of diffusing species. The so-called chemical diffusivity can be expressed as a function of thermodynamic and kinetic data. DICTRA software can calculate the concentration profiles using appropriate mobility and thermodynamic data. It can also optimize the diffusivity data using experimental diffusivity data. Then the optimized diffusivity data is stored as mobility data which is a linear function of temperature. In this work, diffusion bonding of commercially pure Ni using Cu interlayers is reported. The mobility parameters of Ni-Cu alloy binary systems were optimized using DICTRA/Thermocalc software from the available self-, tracer and chemical diffusion coefficients. The optimized mobility parameters were used to simulate concentration profiles of Ni-Cu diffusion joints using DICTRA/Thermocalc software. The calculated and experimental concentration profiles agreed well at 1100 °C. This method could not be extended for higher order alloys because of the lack of appropriate thermodynamic and kinetic database. In the third phase industrially important alloys such as SS 321, Inconel 718 and Ti-6Al-4V were diffusion bonded. Diffusion bonded SS 321 with Au-12Ge interlayer provided the best microstructure when bonded in either vacuum or argon at 1050°C for 20 h and cooled in air. The maximum strength obtained of the joint was 387+/-4 MPa bonded in vacuum at 1050°C for 20 h and cooled in air. The microstructure of joint centerline of diffusion bonded Inconel 718 using Au-12Ge interlayer at 1050°C for 15 h and cooled in air consisted of residual interlayer (1.3-2.5 microm). The residual interlayer was disappeared by increasing the bonding time by 5 h, however, pores appeared in the joint centerline. As a result, the strength obtained for bonded Inconel 718 was much lower than that of the base alloy. The joint centerline microstructure of bonded Ti-6Al-4V using Cu interlayer was free of intermetallics and solid solution of Cu and base alloy. The strength of the joint is yet to be determined.

  11. Nickel-Aluminum Layered Double Hydroxide Coating on the Surface of Conductive Substrates by Liquid Phase Deposition.

    PubMed

    Maki, Hideshi; Takigawa, Masashi; Mizuhata, Minoru

    2015-08-12

    The direct synthesis of the adhered Ni-Al LDH thin film onto the surface of electrically conductive substrates by the liquid phase deposition (LPD) reaction is carried out for the development of the positive electrode. The complexation and solution equilibria of the dissolved species in the LPD reaction have been clarified by a theoretical approach, and the LPD reaction conditions for the Ni-Al LDH depositions are shown to be optimized by controlling the fluoride ion concentration and the pH of the LPD reaction solutions. The yields of metal oxides and hydroxides by the LPD method are very sensitive to the supersaturation state of the hydroxide in the reaction solution. The surfaces of conductive substrates are completely covered by the minute mesh-like Ni-Al LDH thin film; furthermore, there is no gap between the surfaces of conductive substrates and the deposited Ni-Al LDH thin film. The active material layer thickness was able to be controlled within the range from 100 nm to 1 μm by the LPD reaction time. The high-crystallinity and the arbitrary-thickness thin films on the conductive substrate surface will be beneficial for the interface control of charge transfer reaction fields and the internal resistance reduction of various secondary batteries. PMID:26189509

  12. Effect of alkaline earth metals on the liquid-phase hydrogenation of hydroquinone over Ru-based catalysts

    NASA Astrophysics Data System (ADS)

    Li, Hongwei; Ji, Dong; Li, Yu; Liang, Yalan; Li, Gui Xian

    2015-12-01

    A series of Ru-based catalysts modified by alkaline earth metals were prepared by the impregnation-precipitation method and characterized using transmission electron microscopy, X-ray diffraction, ICP optical emission spectroscopy, Infrared Spectroscopy of adsorbed pyridine analysis and surface area analysis. The performance of the catalysts was measured via liquid-phase hydroquinone hydrogenation reaction. Results show that the Ru-Sr/NaY catalyst has the best activity and selectivity among those Ru-based catalysts. The conversion of hydroquinone and the selectivity to 1,4-cyclohexanediol reached up to 99.6% and 89.6% at optimum reaction condition (700 r/min, 423 K and 5 MPa pressure of H2 in 3 h). This may be attributed to the fact that the right amount of Strontium is beneficial to the good dispersion of the ruthenium nanoclusters on the surface of NaY and modify the acidic properties of the catalyst. Moreover, IR of adsorbed pyridine analysis suggested the proper ratio of L/B acid of the catalysts played an important role in the performance of the hydroquinone hydrogenation reaction.

  13. Mechanisms of bacterial inactivation in the liquid phase induced by a remote RF cold atmospheric pressure plasma jet

    NASA Astrophysics Data System (ADS)

    van Gils, C. A. J.; Hofmann, S.; Boekema, B. K. H. L.; Brandenburg, R.; Bruggeman, P. J.

    2013-05-01

    A radio-frequency atmospheric pressure argon plasma jet is used for the inactivation of bacteria (Pseudomonas aeruginosa) in solutions. The source is characterized by measurements of power dissipation, gas temperature, absolute UV irradiance as well as mass spectrometry measurements of emitted ions. The plasma-induced liquid chemistry is studied by performing liquid ion chromatography and hydrogen peroxide concentration measurements on treated distilled water samples. Additionally, a quantitative estimation of an extensive liquid chemistry induced by the plasma is made by solution kinetics calculations. The role of the different active components of the plasma is evaluated based on either measurements, as mentioned above, or estimations based on published data of measurements of those components. For the experimental conditions being considered in this work, it is shown that the bactericidal effect can be solely ascribed to plasma-induced liquid chemistry, leading to the production of stable and transient chemical species. It is shown that HNO2, ONOO- and H2O2 are present in the liquid phase in similar quantities to concentrations which are reported in the literature to cause bacterial inactivation. The importance of plasma-induced chemistry at the gas-liquid interface is illustrated and discussed in detail.

  14. Modeling the concentration dependence of the methanol self-diffusivity in faujasite systems: comparison with the liquid phase.

    PubMed

    Plant, D F; Maurin, G; Bell, R G

    2006-08-17

    Molecular dynamics simulations were performed to understand further the concentration dependence of the self-diffusion of methanol in the faujasite zeolite systems. The evolution of the self-diffusivity was investigated as a function of coverage for DAY and NaY systems to study the effect of both the pore confinement and the presence of the extraframework cations within the supercage. It was found that the self-diffusivity decreases with loading for DAY, whereas for NaY it passes through a maximum at intermediate coverage, in agreement with pulse-field gradient NMR and quasi elastic neutron scattering data reported in similar systems. The activation energies of the methanol diffusion corresponding to a combination of both intra- and intercage motions were evaluated as a function of the coverage. The simulated trends are interpreted on the basis of the predominant interactions which take place in both systems. Finally, the preferential arrangement of the adsorbate molecules are provided and compared with those simulated in the liquid phase. For the fully loaded materials, it was seen that the methanol molecules form a one-dimensional hydrogen-bonded chain along the channels in DAY whereas only dimers are present in NaY. PMID:16898746

  15. Quantum Dots obtained by LPE from under-saturated In-As liquid phases on GaAs substrates

    NASA Astrophysics Data System (ADS)

    Ortiz, F. E.; Mishurnyi, V.; Gorbatchev, A.; De Anda, F.; Prutskij, T.

    2011-01-01

    In this work we inform about quantum dots (QD) obtained by Liquid Phase Epitaxy (LPE) on GaAs substrates from under-saturated In-As liquid phases. In our processes, we have prepared saturated In-rich liquid phases by dissolving an InAs wafer at one of the temperatures interval from 450 to 414 C for 60 minutes. The contact between In-As liquid phase and the GaAs substrate was always done at a constant temperature of 444 C for 5 seconds. Thus, the growth temperature for most of the samples was higher than the liquidus temperature. We think that the growth driving force is related to a transient process that occurs when the system is trying to reach equilibrium. Under the atom force microscope (AFM) we have observed nano-islands on the surfaces of the samples obtained from under-saturated liquid phases prepared at 438, 432 and 426 C. The 25 K photoluminescence spectrum shows a peak at a 1.33 eV, in addition to the GaAs related line.

  16. Quantitative Apparent Diffusion Coefficient Measurements Obtained by 3-Tesla MRI Are Correlated with Biomarkers of Bladder Cancer Proliferative Activity

    PubMed Central

    Sevcenco, Sabina; Haitel, Andrea; Ponhold, Lothar; Susani, Martin; Fajkovic, Harun; Shariat, Shahrokh F.; Hiess, Manuela; Spick, Claudio; Szarvas, Tibor; Baltzer, Pascal A. T.

    2014-01-01

    Purpose To investigate the association between Apparent Diffusion Coefficient (ADC) values and cell cycle and proliferative biomarkers (p53, p21, Ki67,) in order to establish its potential role as a noninvasive biomarker for prediction of cell cycle, proliferative activity and biological aggressiveness in bladder cancer. Materials and Methods Patients with bladder cancer who underwent 3,0 Tesla DW-MRI of the bladder before TUR-B or radical cystectomy were eligible for this prospective IRB-approved study. Histological specimen were immunohistochemically stained for the following markers: p53, p21 and ki67. Two board-certified uropathologists reviewed the specimens blinded to DW-MRI results. Histological grade and T-stage were classified according to the WHO 2004 and the 2009 TNM classification, respectively. Nonparametric univariate and multivariate statistics including correlation, logistic regression and ROC analysis were applied. Results Muscle invasive bladder cancer was histologically confirmed in 10 out of 41 patients. All examined tissue biomarkers were significantly correlated with ADC values (p<0.05, respectively). Based on multivariate analysis, p53 and ADC are both independent prognostic factors for muscle invasiveness of bladder cancer (>/?=?T2). (p?=?0.013 and p?=?0.018). Conclusion ADC values are associated with cell cycle and proliferative biomarkers and do thereby reflect invasive and proliferative potential in bladder cancer. ADC and p53 are both independent prognostic factors for muscle invasiveness in bladder cancer. PMID:25202965

  17. Effects of methodological variation on assessment of riboflavin status using the erythrocyte glutathione reductase activation coefficient assay.

    PubMed

    Hill, Marilyn H E; Bradley, Angela; Mushtaq, Sohail; Williams, Elizabeth A; Powers, Hilary J

    2009-07-01

    Riboflavin status is usually measured as the in vitro stimulation with flavin adenine dinucleotide of the erythrocyte enzyme glutathione reductase, and expressed as an erythrocyte glutathione reductase activation coefficient (EGRAC). This method is used for the National Diet and Nutrition Surveys (NDNS) of the UK. In the period between the 1990 and 2003 surveys of UK adults, the estimated prevalence of riboflavin deficiency, expressed as an EGRAC value > or = 1.30, increased from 2 to 46 % in males and from 1 to 34 % in females. We hypothesised that subtle but important differences in the detail of the methodology between the two NDNS accounted for this difference. We carried out an evaluation of the performance of the methods used in the two NDNS and compared against an 'in-house' method, using blood samples collected from a riboflavin intervention study. Results indicated that the method used for the 1990 NDNS gave a significantly lower mean EGRAC value than both the 2003 NDNS method and the 'in-house' method (P < 0.0001). The key differences between the methods relate to the concentration of FAD used in the assay and the duration of the period of incubation of FAD with enzyme. The details of the EGRAC method should be standardised for use in different laboratories and over time. Additionally, it is proposed that consideration be given to re-evaluating the basis of the EGRAC threshold for riboflavin deficiency. PMID:19102813

  18. EFFECTS OF COVAPORS ON ADSORPTION RATE COEFFICIENTS OF ORGANIC VAPORS ADSORBED ONTO ACTIVATED CARBON FROM FLOWING AIR

    SciTech Connect

    G. WOOD

    2000-12-01

    Published breakthrough time, adsorption rate, and capacity data for components of organic vapor mixtures adsorbed from flows through fixed activated carbon beds have been analyzed. Capacities (as stoichiometric centers of constant pattern breakthrough curves) yielded stoichiometric times {tau}, which are useful for determining elution orders of mixture components. We also calculated adsorption rate coefficients k{sub v} of the Wheeler (or, more general Reaction Kinetic) breakthrough curve equation, when not reported, from breakthrough times and {tau}. Ninety-five k{sub v} (in mixture)/ k{sub v} (single vapor) ratios at similar vapor concentrations were calculated and averaged for elution order categories. For 43 first-eluting vapors the average ratio (1.07) was statistically no different (0.21 standard deviation) than unity, so that we recommend using the single-vapor k{sub v} for such. Forty-seven second-eluting vapor ratios averaged 0.85 (0.24 standard deviation), also not significantly different from unity; however, other evidence and considerations lead us recommend using k{sub v} (in mixture) = 0.85 k{sub v} (single vapor). Five third- and fourth-eluting vapors gave an average of 0.56 (0.16 standard deviation) for a recommended k{sub v} (in mixture) = 0.56 k{sub v} (single vapor) for such.

  19. μ-'Diving suit' for liquid-phase high-Q resonant detection.

    PubMed

    Yu, Haitao; Chen, Ying; Xu, Pengcheng; Xu, Tiegang; Bao, Yuyang; Li, Xinxin

    2016-02-23

    A resonant cantilever sensor is, for the first time, dressed in a water-proof 'diving suit' for real-time bio/chemical detection in liquid. The μ-'diving suit' technology can effectively avoid not only unsustainable resonance due to heavy liquid-damping, but also inevitable nonspecific adsorption on the cantilever body. Such a novel technology ensures long-time high-Q resonance of the cantilever in solution environment for real-time trace-concentration bio/chemical detection and analysis. After the formation of the integrated resonant micro-cantilever, a patterned photoresist and hydrophobic parylene thin-film are sequentially formed on top of the cantilever as sacrificial layer and water-proof coat, respectively. After sacrificial-layer release, an air gap is formed between the parylene coat and the cantilever to protect the resonant cantilever from heavy liquid damping effect. Only a small sensing-pool area, located at the cantilever free-end and locally coated with specific sensing-material, is exposed to the liquid analyte for gravimetric detection. The specifically adsorbed analyte mass can be real-time detected by recording the frequency-shift signal. In order to secure vibration movement of the cantilever and, simultaneously, reject liquid leakage from the sensing-pool region, a hydrophobic parylene made narrow slit structure is designed surrounding the sensing-pool. The anti-leakage effect of the narrow slit and damping limited resonance Q-factor are modelled and optimally designed. Integrated with electro-thermal resonance excitation and piezoresistive frequency readout, the cantilever is embedded in a micro-fluidic chip to form a lab-chip micro-system for liquid-phase bio/chemical detection. Experimental results show the Q-factor of 23 in water and longer than 20 hours liquid-phase continuous working time. Loaded with two kinds of sensing-materials at the sensing-pools, two types of sensing chips successfully show real-time liquid-phase detection to ppb-level organophosphorous pesticide of acephate and E.coli DH5α in PBS, respectively. The proposed method fundamentally solves the long-standing problem of being unable to operate a resonant micro-sensor in liquid well. PMID:26829920

  20. COMMERCIAL-SCALE DEMONSTRATION OF THE LIQUID PHASE METHANOL (LPMEOH) PROCESS

    SciTech Connect

    E.C. Heydorn; B.W. Diamond; R.D. Lilly

    2003-06-01

    This project, which was sponsored by the U.S. Department of Energy (DOE) under the Clean Coal Technology Program to demonstrate the production of methanol from coal-derived synthesis gas (syngas), has completed the 69-month operating phase of the program. The purpose of this Final Report for the ''Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) Process'' is to provide the public with details on the performance and economics of the technology. The LPMEOH{trademark} Demonstration Project was a $213.7 million cooperative agreement between the DOE and Air Products Liquid Phase Conversion Company, L.P. (the Partnership). The DOE's cost share was $92,708,370 with the remaining funds coming from the Partnership. The LPMEOH{trademark} demonstration unit is located at the Eastman Chemical Company (Eastman) chemicals-from-coal complex in Kingsport, Tennessee. The technology was the product of a cooperative development effort by Air Products and Chemicals, Inc. (Air Products) and DOE in a program that started in 1981. Developed to enhance electric power generation using integrated gasification combined cycle (IGCC) technology, the LPMEOH{trademark} Process is ideally suited for directly processing gases produced by modern coal gasifiers. Originally tested at the Alternative Fuels Development Unit (AFDU), a small, DOE-owned process development facility in LaPorte, Texas, the technology provides several improvements essential for the economic coproduction of methanol and electricity directly from gasified coal. This liquid phase process suspends fine catalyst particles in an inert liquid, forming a slurry. The slurry dissipates the heat of the chemical reaction away from the catalyst surface, protecting the catalyst, and allowing the methanol synthesis reaction to proceed at higher rates. The LPMEOH{trademark} Demonstration Project accomplished the objectives set out in the Cooperative Agreement with DOE for this Clean Coal Technology project. Overall plant availability (defined as the percentage of time that the LPMEOH{trademark} demonstration unit was able to operate, with the exclusion of scheduled outages) was 97.5%, and the longest operating run without interruption of any kind was 94 days. Over 103.9 million gallons of methanol was produced; Eastman accepted all of the available methanol for use in the production of methyl acetate, and ultimately cellulose acetate and acetic acid.

  1. Interplay between two phase transitions: Crystallization and liquid-liquid phase separation in a polyolefin blend

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaohua; Wang, Zhigang; Dong, Xia; Wang, Dujin; Han, Charles C.

    2006-07-01

    The interplay between liquid-liquid phase separation (LLPS) and crystallization at several compositions in statistical copolymer blends of poly(ethyleneco-hexene) and poly(ethylene-cobutene) has been examined by optical microscopy (OM), atomic force microscopy (AFM), and differential scanning calorimetry (DSC). The phase contrast optical microscopy shows interconnected bicontinuous structures for deeply quenched LLPS, characteristic of spinodal decomposition. After a second quench to a temperature below the melting point, an overwhelming change in crystallization kinetics has been clearly observed, which is caused by the increase of the nucleation rate assisted by concentration fluctuations due to the spontaneous spinodal LLPS. We propose a new mechanism of "fluctuation assisted nucleation" in the crystallization process for such interactive process in a blend system. The experimental results from OM, AFM, and DSC measurements at various conditions are all consistent with the fluctuation assisted nucleation model.

  2. 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.

  3. Nature of the first-order liquid-liquid phase transition in supercooled silicon.

    PubMed

    Zhao, G; Yu, Y J; Tan, X M

    2015-08-01

    The first-order liquid-liquid phase transition in supercooled Si is revisited by long-time first-principle molecular dynamics simulations. As the focus of the present paper, its nature is revealed by analyzing the inherent structures of low-density liquid (LDL) and high-density liquid (HDL). Our results show that it is a transition between a sp(3)-hybridization LDL and a white-tin-like HDL. This uncovers the origin of the semimetal-metal transition accompanying it and also proves that HDL is the metastable extension of high temperature equilibrium liquid into the supercooled regime. The pressure-temperature diagram of supercooled Si thus can be regarded in some respects as shifted reflection of its crystalline phase diagram. PMID:26254662

  4. Smart dielectrics of fluorinated silicon glass prepared by liquid phase deposition method

    NASA Astrophysics Data System (ADS)

    Yeh, Ching-Fa; Chen, Tien-Fu; Lee, Yueh-Chuan; Liu, Chien-Hung; Lin, Shyue-Shyh

    2001-11-01

    Fluorinated silicon glass (FSG) film prepared by using liquid-phase deposition (LPD) is very potential for use as a smart dielectric owing to its high fluorine concentration (8.6 at %), low dielectric constant (3.46), low stress (43 Mpa), low leakage current density (4.6E-9 A/cm2 at 2 MV/cm) and low deposition temperature (room temperature). By affecting the physicochemical properties and the electrical characteristics will be introduced. Furthermore, the LPD FSG has been applied as gate oxide to MOSFET's and polysilicon TFT's. Owing to its novel property of selective deposition, LPD FSG has been also employed to cap the sidewalls for degradation-free damascene trenches, and to fabricate micro contact holes for the N+/p diodes and the Schottky diodes.

  5. Nature of the first-order liquid-liquid phase transition in supercooled silicon

    NASA Astrophysics Data System (ADS)

    Zhao, G.; Yu, Y. J.; Tan, X. M.

    2015-08-01

    The first-order liquid-liquid phase transition in supercooled Si is revisited by long-time first-principle molecular dynamics simulations. As the focus of the present paper, its nature is revealed by analyzing the inherent structures of low-density liquid (LDL) and high-density liquid (HDL). Our results show that it is a transition between a sp3-hybridization LDL and a white-tin-like HDL. This uncovers the origin of the semimetal-metal transition accompanying it and also proves that HDL is the metastable extension of high temperature equilibrium liquid into the supercooled regime. The pressure-temperature diagram of supercooled Si thus can be regarded in some respects as shifted reflection of its crystalline phase diagram.

  6. Supercritical supersaturations and ultrafast cooling of the growth solution in liquid-phase epitaxy of semiconductors

    NASA Astrophysics Data System (ADS)

    Abramov, A. V.; Deryagin, N. G.; Tret'yakov, D. N.

    1996-04-01

    A method for accomplishing ultrafast cooling is proposed which makes possible supercritical supersaturations of the growth solution in liquid-phase epitaxy. Growth boat designs providing cooling rates as high as 0268-1242/11/4/025/img1 are considered. The temperatures of contact, 0268-1242/11/4/025/img2, of a GaAs substrate with a Ga-based solution and of a Si substrate with a Sn-based growth solution, calculated for various substrate 0268-1242/11/4/025/img3 and solution temperatures 0268-1242/11/4/025/img4, are in good agreement with experimental values. The maximum attainable supercooling is markedly increased to as high as 0268-1242/11/4/025/img5 for the Ga - As system, when the growth solution is subjected to ultrafast cooling. The prospects of using the method for fabricating heterostructures with a large lattice mismatch are discussed.

  7. Consistent thermodynamic study of the solid and liquid phases of tungsten

    NASA Astrophysics Data System (ADS)

    Fuks, David; Davidov, Genady; Dorfman, Simon

    1995-07-01

    The nonempirical linear-muffin-tin-orbital-atomic-sphere approximation method is used to obtain the effective interaction potential for tungsten. This potential is applied to calculate the second moment of phonon spectrum ?2. We study the convergency of ?2 in real space and find that the main contribution to ?2 is given by the first coordination shell. The presented first-principle approach allows us to obtain correct spherically symmetric potentials. We show that these nonempirically calculated effective potentials may be successfully applied to the calculations of integral spectral characteristics. The obtained cohesive energy, equilibrium lattice parameter, and bulk modulus are well correlated with the measurements. The Gibbs-Bogoliubov inequality and the variational procedure of Ross are used to calculate the temperature dependence of free energy in liquid tungsten. The obtained thermodynamic functions of solid and liquid phases are employed to determine the melting temperature, which is found to be 3530 K whereas the experimental value is 3680 K.

  8. Distortion and Densification Control during Liquid Phase Sintering of High-Performance Materials

    NASA Astrophysics Data System (ADS)

    German, Randall M.; Chung, Suk Hwan; Blaine, Deborah

    2004-06-01

    Liquid phase sintering is used for net-shape fabrication of high performance materials. This work reviews microstructure evolution models needed to simulate the densification and distortion events observed with the semisolid powder-liquid mixtures during sintering. Critical insight in required from the capillarity, pore collapse, solid-liquid morphology, solid phase connectivity, grain growth, and system rheology. These complications are handled using a modified time-dependent viscous flow model that requires data on grain size, density, and boundary conditions (such as substrate friction) versus time. The rheological response model coupled with finite element analysis has proven most effective in predicting final size and shape of engineering components. A simplified material parameter extraction scheme is used to determine many the material constants, providing hope for a generic model in the future.

  9. Liquid-phase dispersion during injection into vapor-dominated reservoirs

    SciTech Connect

    Pruess, K.

    1994-01-01

    The behavior of water injection plumes in vapor-dominated reservoirs is examined. Stressing the similarity to water infiltration in heterogeneous soils, we suggest that ever-present heterogeneities in individual fractures and fracture networks will cause a lateral broadening of descending injection plumes. The process of lateral spreading of liquid phase is viewed in analogy to transverse dispersion in miscible displacement. To account for the postulated ``phase dispersion`` the conventional two-phase immiscible flow theory is extended by adding a Fickian-type dispersive term. The validity of the proposed phase dispersion model is explored by means of simulations with detailed resolution of small-scale heterogeneity. We also present an illustrative application to injection into a depleted vapor zone. It is concluded that phase dispersion effects will broaden descending injection plumes, with important consequences for pressure support and potential water breakthrough at neighboring production wells.

  10. Surface Specularity as an Indicator of Shock-induced Solid-liquid Phase Transitions in Tin

    SciTech Connect

    G. D. Stevens, S. S. Lutz, B. R. Marshall, W.D. Turley, et al.

    2007-12-01

    When highly polished metal surfaces melt upon release after shock loading, they exhibit features that suggest significant surface changes accompany the phase transition. The reflection of light from such surfaces changes from specular (pre-shock) to diffuse upon melting. Typical of this phenomenon is the loss of signal light in velocity interferometer system for any reflector (VISAR) measurements, which usually occurs at pressures high enough to melt the free surface. Unlike many other potential material phase-sensitive diagnostics (e.g., reflectometry, conductivity), that show relatively small (1%-10%) changes, the specularity of reflection provides a more sensitive and definitive (>10x) indication of the solid-liquid phase transition. Data will be presented that support the hypothesis that specularity changes indicate melt in a way that can be measured easily and unambiguously.

  11. Methods for sulfate removal in liquid-phase catalytic hydrothermal gasification of biomass

    DOEpatents

    Elliott, Douglas C; Oyler, James R

    2014-11-04

    Processing of wet biomass feedstock by liquid-phase catalytic hydrothermal gasification must address catalyst fouling and poisoning. One solution can involve heating the wet biomass with a heating unit to a pre-treatment temperature sufficient for organic constituents in the feedstock to decompose, for precipitates of inorganic wastes to form, for preheating the wet feedstock in preparation for subsequent removal of soluble sulfate contaminants, or combinations thereof. Processing further includes reacting the soluble sulfate contaminants with cations present in the feedstock material to yield a sulfate-containing precipitate and separating the inorganic precipitates and/or the sulfate-containing precipitates out of the wet feedstock. Having removed much of the inorganic wastes and the sulfate contaminants that can cause poisoning and fouling, the wet biomass feedstock can be exposed to the heterogeneous catalyst for gasification.

  12. Harmonic strain-optical response revealed in the isotropic (liquid) phase of liquid crystals

    NASA Astrophysics Data System (ADS)

    Kahl, P.; Baroni, P.; Noirez, L.

    2015-08-01

    A strong optical birefringence is observed when applying a small amplitude oscillatory strain to the liquid phase of a liquid crystal. This unpredicted birefringence is found to oscillate at the same frequency as the driving frequency, with frequencies down to 0.01 Hz. This birefringence is visible up to 15 C above the liquid crystal transition. This opto-dynamic property is interpreted as a result of a coupling of the orientational pretransitional fluctuations existing in the isotropic phase and long range elastic interactions recently identified in liquids. The conversion of the mechanical wave in an optical response is shapeable. Two examples of synchronized periodic signals are shown: the sine and the square waves. The optimization of the signal is analyzed using a Heaviside-step shear test. This optical property is immediately exploitable to design low energy on/off switching materials.

  13. Liquid-phase-deposited siloxane-based capping layers for silicon solar cells

    SciTech Connect

    Veith-Wolf, Boris; Wang, Jianhui; Hannu-Kuure, Milja; Chen, Ning; Hadzic, Admir; Williams, Paul; Leivo, Jarkko; Karkkainen, Ari; Schmidt, Jan

    2015-02-02

    We apply non-vacuum processing to deposit dielectric capping layers on top of ultrathin atomic-layer-deposited aluminum oxide (AlO{sub x}) films, used for the rear surface passivation of high-efficiency crystalline silicon solar cells. We examine various siloxane-based liquid-phase-deposited (LPD) materials. Our optimized AlO{sub x}/LPD stacks show an excellent thermal and chemical stability against aluminum metal paste, as demonstrated by measured surface recombination velocities below 10 cm/s on 1.3 Ωcm p-type silicon wafers after firing in a belt-line furnace with screen-printed aluminum paste on top. Implementation of the optimized LPD layers into an industrial-type screen-printing solar cell process results in energy conversion efficiencies of up to 19.8% on p-type Czochralski silicon.

  14. In situ transmission electron microscopy of solid-liquid phase transition of silica encapsulated bismuth nanoparticles.

    PubMed

    Hu, Jianjun; Hong, Yan; Muratore, Chris; Su, Ming; Voevodin, Andrey A

    2011-09-01

    The solid-liquid phase transition of silica encapsulated bismuth nanoparticles was studied by in situ transmission electron microscopy (TEM). The nanoparticles were prepared by a two-step chemical synthesis process involving thermal decomposition of organometallic precursors for nucleating bismuth and a sol-gel process for growing silica. The microstructural and chemical analyses of the nanoparticles were performed using high-resolution TEM, Z-contrast imaging, focused ion beam milling, and X-ray energy dispersive spectroscopy. Solid-liquid-solid phase transitions of the nanoparticles were directly recorded by electron diffractions and TEM images. The silica encapsulation of the nanoparticles prevented agglomeration and allowed particles to preserve their original volume upon melting, which is desirable for applications of phase change nanoparticles with consistently repeatable thermal properties. PMID:21796304

  15. Quasi-ductile mechanisms in porous liquid-phase sintered alumina induced by Hertzian contact

    NASA Astrophysics Data System (ADS)

    Digiovanni, Anthony Albert

    Hertzian indentation has been effective in evaluating material response and deformation behavior through single and repeated contacts of a hard sphere into a representative bulk sample in laboratory conditions. Using this technique, the macroscopic and microscopic deformation characteristics of a commercial alumina substrate were evaluated. Significant 'quasi-ductile' behavior was observed, not unlike that observed for other advanced ceramic systems with heterogeneous microstructures. In pure dense alumina, quasi-ductility is controlled by twin fault formation where a transition from a fine grained to a coarse grained microstructure corresponds to a change from classical cone-crack behavior to a purely quasi-ductile indentation response. The quasi-ductility in the commercial alumina was unexpected because the average grain size was very small---well below the size where one should expect any contribution from a twin faulting mechanism. Subsequent work focused on reproducing the commercial microstructures and then altering the grain size, porosity, and presence of the glassy (liquid) phase. Macroscopic indentation revealed a quasi-ductile residual impression formed prior to the observation of ring crack formation in the porous liquid phase sintered materials. Furthermore, the glass containing samples produced a deeper residual impression for an equivalent load and porosity level. Fully dense samples with or without a glass phase remained completely brittle. Subsurface images corresponded to the macroscopic observations; porous liquid phase materials with a 5 mum grain size revealed greater microstructural damage with increasing loads over that of the pure material. A 2D theoretical treatment of the problem used finite element modeling and periodic boundary conditions to understand the magnifying effect of multiple pores on the stress around a given pore in a biaxial compressive stress state linked to the Hertzian stress at yield. A periodic pore structure was assumed to simplify the modeling. Peak stress was a function of the pore network orientation. The results were in agreement with previously published analytical work at the same orientations. When the pore network was tilted at 45 to the applied stress directions an increase of the peak stress around a pore was observed with increasing porosity. An attempt to randomize the pore network revealed only small changes in the peak stress. Therefore, a linear stress magnification function determined from the FEM results was incorporated into a previously published stress intensity factor solution for an individual pore/flaw arrangement. The stress concentrating effect of the subsurface pores were related to the macroscopic indentation driving force of the Hertzian indenter. Predictions of the critical mean indentation load to initiate subsurface damage were in reasonable agreement with published results. We conclude that porosity acted as a stress concentrator and was the controlling mechanism for quasi-ductility under Hertzian contact in the liquid phase sintered alumina.

  16. Gas-liquid phase-transfer catalysis; A new continuous-flow method in organic synthesis

    SciTech Connect

    Tundo, P. ); Moraglio, G.; Trotta, F. )

    1989-07-01

    A synthetic method, gas-liquid phase-transfer catalysis (GL-PTC0), is described. GL-PTC is a continuous-flow procedure where gaseous reagents flow through a molten phase-transfer (PT) catalyst supported on a solid; no solvent is used. Reactions may develop through new mechanistic pathways compared with those of classical conditions; moreover, the reactions often occur in very selective ways. Some typical syntheses carried out under GL-PTC conditions are described in detail. They include syntheses of 2-alkylmalonic acid esters from the corresponding malonic acid esters and primary alkyl halides from primary alkyl alcohols and the reactions of dimethyl carbonate, which give N-methylanilines from anilines, anisoles from phenols, and 2-arylpropionitriles from aryl-acetonitriles.

  17. Liquid-phase exfoliation of expanded graphites into graphene nanoplatelets using amphiphilic organic molecules.

    PubMed

    Park, Ji Sun; Yu, Lan; Lee, Churl Seung; Shin, Kwonwoo; Han, Jong Hun

    2014-03-01

    Graphenes with a two-dimensional lattice of carbons have been widely employed in diverse applications owing to their excellent electrical, thermal, mechanical, and gas-barrier properties. However, the frequently-used reduced graphene oxide (rGO), which is synthesized from natural graphites by strong oxidation and subsequent reduction via highly toxic components, exhibits imperfect characteristics because of remaining defect sites on its basal planes. Therefore, in this work, we present a convenient way to prepare graphene nanoplatelets (GNPs) with minimized defect sites on their basal planes employing liquid-phase exfoliation of edge-functionalized expanded graphites (EGs) with amphiphilic organic molecules. Exfoliated GNPs revealed approximately sub-7-nm-thickness and showed stable dispersibility in an organic media during 9 months. Furthermore, spray-coated GNP films presented homogeneously stacked morphologies without noticeable agglomerations. PMID:24407700

  18. Microgravity studies in the liquid phase immiscible system, aluminum-indium

    NASA Technical Reports Server (NTRS)

    Gelles, S. H.; Markworth, A. J.

    1977-01-01

    As part of a study to understand the influence of gravity, cooling rate and composition on the structure of liquid phase immiscible materials, two alloys, Al-40 wt % In and Al-70 wt % In were thermally treated on the SPAR II rocket flight. The treatments involved homogenization at a temperature above the miscibility gap and then rapid cooling through the miscibility gap followed by complete solidification. The last two steps were performed while acceleration levels were less than 4 x 10 to the -5th g. The flight alloys produced unexpected results. Instead of fine uniform structures, the alloys consisted of a macroscopically sized aluminum-rich central region surrounded by indium-rich metal.

  19. Liquid-phase dispersion during injection into vapor-dominated reservoirs

    SciTech Connect

    Pruess, Karsten

    1994-01-20

    The behavior of water injection plumes in vapor-dominated reservoirs is examined. Stressing the similarity to water infiltration in heterogeneous soils, we suggest that everpresent heterogeneities in individual fractures and fracture networks will cause a lateral broadening of descending injection plumes. The process of lateral spreading of liquid phase is viewed in analogy to transverse dispersion in miscible displacement. To account for the postulated phase dispersion the conventional two-phase immiscible flow theory is extended by adding a Fickian-type dispersive term. The validity of the proposed phase dispersion model is explored by means of simulations with detailed resolution of small-scale heterogeneity. We also present an illustrative application to injection into a depleted vapor zone. It is concluded that phase dispersion effects will broaden descending injection plumes, with important consequences for pressure support and potential water breakthrough at neighboring production wells.

  20. Liquid-liquid phase transition and structure inheritance in carbon films

    PubMed Central

    He, Yezeng; Li, Hui; Jiang, Yanyan; Li, Xiongying; Bian, Xiufang

    2014-01-01

    Molecular dynamics simulations are performed to study the cooling process of quasi-2D liquid carbon. Our results show an obvious liquid-liquid phase transition (LLPT) from the twofold coordinated liquid to the threefold coordinated liquid with the decrease of temperature, followed by a liquid-solid phase transition (LSPT). The LLPT can be regarded as the preparation stage of LSPT. During the cooling process, the chain structures firstly self-assemble into some ring structures and then aggregate into some stable islands which can further connect together to form a complete polycrystalline film. The threefold coordinated structures play an important role in the formation of atomic rings. The inheritance of the threefold coordinated structures provides essential condition to form rings and islands. PMID:24407276

  1. Solid-liquid phase coexistence of alkali nitrates from molecular dynamics simulations.

    SciTech Connect

    Jayaraman, Saivenkataraman

    2010-03-01

    Alkali nitrate eutectic mixtures are finding application as industrial heat transfer fluids in concentrated solar power generation systems. An important property for such applications is the melting point, or phase coexistence temperature. We have computed melting points for lithium, sodium and potassium nitrate from molecular dynamics simulations using a recently developed method, which uses thermodynamic integration to compute the free energy difference between the solid and liquid phases. The computed melting point for NaNO3 was within 15K of its experimental value, while for LiNO3 and KNO3, the computed melting points were within 100K of the experimental values [4]. We are currently extending the approach to calculate melting temperatures for binary mixtures of lithium and sodium nitrate.

  2. Synthesis and Photoresponse of Few Layer Liquid Phase Exfoliated Molybdenum Disulphide (MoS2) Flakes

    NASA Astrophysics Data System (ADS)

    Ghosh, Sujoy; Muchharla, Baleeswaraiah; Winchester, Andrew; Feng, Simin; Elias, Ana Laura; Lopez, Nestor Perea; Kar, Swastik; Terrones, Mauricio; Talapatra, Saikat

    2014-03-01

    We report on the temperature dependent photo response of thin films of MoS2 consisting of few layered flakes obtained by liquid phase exfoliation of bulk MoS2 powder. We found that under a constant laser power (wavelength = 658 nm) the photocurrent (Iph) increases with increasing temperature and reaches a maximum value of Iph(max) at T =Tm within the studied temperature range (330K

  3. Spectroscopic-ellipsometric study of native oxide removal by liquid phase HF process

    PubMed Central

    Kurhekar, Anil Sudhakar; Apte, Prakash R

    2014-01-01

    Ex situ spectroscopic ellipsometry (SE) measurements have been employed to investigate the effect of liquid-phase hydrofluoric acid (HF) cleaning on Si<100> surfaces for microelectromechanical systems application. The hydrogen terminated (H-terminated) Si surface was realized as an equivalent dielectric layer, and SE measurements are performed. The SE analyses indicate that after a 20-s 100:5 HF dip with rinse, the Si (100) surface was passivated by the hydrogen termination and remained chemically stable. Roughness of the HF-etched bare Si (100) surface was observed and analyzed by the ex-situ SE. Evidence for desorption of the H-terminated Si surface layer is studied using Fourier transform infrared spectroscopy and ellipsometry, and discussed. This piece of work explains the usage of an ex situ, non-destructive technique capable of showing state of passivation, the H-termination of Si<100> surfaces. PMID:24619506

  4. Spectroscopic-ellipsometric study of native oxide removal by liquid phase HF process

    NASA Astrophysics Data System (ADS)

    Kurhekar, Anil Sudhakar; Apte, Prakash R.

    2013-02-01

    Ex situ spectroscopic ellipsometry (SE) measurements have been employed to investigate the effect of liquid-phase hydrofluoric acid (HF) cleaning on Si<100> surfaces for microelectromechanical systems application. The hydrogen terminated (H-terminated) Si surface was realized as an equivalent dielectric layer, and SE measurements are performed. The SE analyses indicate that after a 20-s 100:5 HF dip with rinse, the Si (100) surface was passivated by the hydrogen termination and remained chemically stable. Roughness of the HF-etched bare Si (100) surface was observed and analyzed by the ex-situ SE. Evidence for desorption of the H-terminated Si surface layer is studied using Fourier transform infrared spectroscopy and ellipsometry, and discussed. This piece of work explains the usage of an ex situ, non-destructive technique capable of showing state of passivation, the H-termination of Si<100> surfaces.

  5. Construction materials for reaction unit in the liquid-phase synthesis of propylene oxide

    SciTech Connect

    Zaritskii, V.I.D.

    1987-09-01

    The main components of the reaction medium in equipment for the synthesis of propylene oxide by liquid-phase oxidation of gaseous propylene with peracetic acid are propylene, peracetic acid, ethyl acetate, acetic acid, propylene oxide, carbon dioxide, oxygen, methane, and propylene glycol acetates. The operating conditions of the equipment and content of the main components of the medium are shown. Results are given for the investigation of the corrosion behavior of 12Kh18N10T, 10Kh17N13M2T, 08Kh22N6T, and 08Kh21N6M2T steels, AD0 and AD1 aluminum, and VT1-0 titanium. VSt3 carbon steel was tested for comparison.

  6. Formation of microporous NiTi by transient liquid phase sintering of elemental powders.

    PubMed

    Ismail, Muhammad Hussain; Goodall, Russell; Davies, Hywel A; Todd, Iain

    2012-08-01

    Porous metallic structures are attractive for biomedical implant applications as their open porosity simultaneously improves the degree of fixation and decreases the mismatch in stiffness between bone and implant, improving bonding and reducing stress-shielding effects respectively. NiTi alloys exhibit both the shape memory effect and pseudoelasticity, and are of particular interest, though they pose substantial problems in their processing. This is because the shape memory and pseudoelastic behaviours are exceptionally sensitive to the presence of oxygen, and other minor changes in alloy chemistry. Thus in processing careful control of composition and contamination is vital. In this communication, we investigate these issues in a novel technique for producing porous NiTi parts via transient liquid phase sintering following metal injection moulding (MIM) of elemental Ni and Ti powders, and report a new mechanism for pore formation in the powder processing of metallic materials from elemental powders. PMID:24364948

  7. On the Extension of Processing Time with Increase in Temperature during Transient-Liquid Phase Bonding

    NASA Astrophysics Data System (ADS)

    Abdelfatah, M. M.; Ojo, O. A.

    2009-02-01

    Transient-liquid phase (TLP) bonding of a nickel-based superalloy, IN 738, was performed. Contrary to conventional TLP bonding analytical models, which assume a parabolic relationship between liquid/solid interface migration and holding time, deviation from this law was observed experimentally and by numerical simulation. The deviation, which is caused by reduction in solute concentration gradient below a critical value, is suggested as an alternate phenomenon responsible for anomalous extension of processing time required to produce an eutectic-free joint with increase in bonding temperature. A decrease in the filler gap size and the use of a melting-point depressant (MPD) solute with higher solubility in the base material could reduce the occurrence of the anomalous behavior during a high-temperature TLP joining process.

  8. Micromechanics of deformation in porous liquid phase sintered alumina under hertzian contact

    SciTech Connect

    DIGIOVANNI,ANTHONY A.; CHAN,HELEN M.; HARMER,MARTIN P.; NIED,HERMAN F.

    2000-05-15

    A series of fine-grained porous alumina samples, with and without a liquid phase, were fabricated in compositions matched closely to commercially available alumina used as a microelectronic substrates. Hertzian indentation on monolithic specimens of the glass-containing samples produced a greater quasi-ductile stress-strain response compared to that observed in the pure alumina. Maximum residual indentation depths, determined from surface profilometry, correlated with the stress-strain results. Moreover, microstructural observations from bonded interface specimens revealed significantly more damage in the form of microcracking and under extreme loading, pore collapse, in the glass-containing specimens. The absence of the typical twin faulting mechanism observed for larger-grained alumina suggests that the damage mechanism for quasi-ductility in these fine-grained porous alumina derived from the pores acting as a stress concentrator and the grain boundary glass phase providing a weak path for short crack propagation.

  9. A liquid-phase blocking ELISA for the detection of antibodies to rabies virus.

    PubMed

    Esterhuysen, J J; Prehaud, C; Thomson, G R

    1995-01-01

    A liquid-phase blocking ELISA was adapted to the detection and titration of antibodies to principally the nucleoprotein of rabies virus. Sera from animals that had either been vaccinated against rabies or inoculated with street rabies viruses, as well as sera from animals that had no recorded contact with rabies, were tested. These included sera from people, cattle, sheep, goats, dogs, laboratory mice, rabbits, yellow mongooses, wild dogs and lions. Where possible, the results were compared with those obtained with a commercial kit incorporating an indirect ELISA that measures antibody to the rabies glycoprotein. There was a high correlation (r = 0.79) between the two tests. The blocking ELISA provides a single test suitable for the rapid detection of antibodies against rabies virus in the sera of any animal species and for that reason is particularly apt for epidemiological investigations in regions where species diversity is important, as in southern Africa. PMID:7730435

  10. Methods for sulfate removal in liquid-phase catalytic hydrothermal gasification of biomass

    DOEpatents

    Elliott, Douglas C; Oyler, James

    2013-12-17

    Processing of wet biomass feedstock by liquid-phase catalytic hydrothermal gasification must address catalyst fouling and poisoning. One solution can involve heating the wet biomass with a heating unit to a pre-treatment temperature sufficient for organic constituents in the feedstock to decompose, for precipitates of inorganic wastes to form, for preheating the wet feedstock in preparation for subsequent removal of soluble sulfate contaminants, or combinations thereof. Processing further includes reacting the soluble sulfate contaminants with cations present in the feedstock material to yield a sulfate-containing precipitate and separating the inorganic precipitates and/or the sulfate-containing precipitates out of the wet feedstock. Having removed much of the inorganic wastes and the sulfate contaminants that can cause poisoning and fouling, the wet biomass feedstock can be exposed to the heterogenous catalyst for gasification.

  11. Crystallization and Phase Changes in Paracetamol from the Amorphous Solid to the Liquid Phase

    PubMed Central

    2014-01-01

    For the case of paracetamol, we show how terahertz time-domain spectroscopy can be used to characterize the solid and liquid phase dynamics. Heating of supercooled amorphous paracetamol from 295 K in a covered sample under vacuum leads to its crystallization at 330 K. First, form III is formed followed by the transformation of form III to form II at 375 K, to form I at 405 K, and finally melting is observed around 455 K. We discuss the difference between the featureless spectra of the supercooled liquid and its liquid melt. Lastly, we studied the onset of crystallization from the supercooled liquid in detail and quantified its kinetics based on the AvramiErofeev model. We determined an effective rate constant of k = 0.056 min1 with a corresponding onset of crystallization at T = 329.5 K for a heating rate of 0.4 K min1. PMID:24579729

  12. Mixturelike Behavior Near a Liquid-Liquid Phase Transition in Simulations of Supercooled Water

    NASA Astrophysics Data System (ADS)

    Cuthbertson, Megan J.; Poole, Peter H.

    2011-03-01

    In simulations of a waterlike model (ST2) that exhibits a liquid-liquid phase transition, we test for the occurrence of a thermodynamic region in which the liquid can be modeled as a two-component mixture. We assign each molecule to one of two species based on the distance to its fifth-nearest neighbor, and evaluate the concentration of each species over a wide range of temperature and density. Our concentration data compare well with mixture-model predictions in a region between the liquid-liquid critical temperature and the temperature of maximum density. Fits of the model to the data in this region yield accurate estimates for the location of the critical point. We also show that the liquid outside the region of density anomalies is poorly modeled as a simple mixture.

  13. Free energy surface of ST2 water near the liquid-liquid phase transition

    NASA Astrophysics Data System (ADS)

    Poole, Peter H.; Bowles, Richard K.; Saika-Voivod, Ivan; Sciortino, Francesco

    2013-01-01

    We carry out umbrella sampling Monte Carlo simulations to evaluate the free energy surface of the ST2 model of water as a function of two order parameters, the density and a bond-orientational order parameter. We approximate the long-range electrostatic interactions of the ST2 model using the reaction-field method. We focus on state points in the vicinity of the liquid-liquid critical point proposed for this model in earlier work. At temperatures below the predicted critical temperature we find two basins in the free energy surface, both of which have liquid-like bond orientational order, but differing in density. The pressure and temperature dependence of the shape of the free energy surface is consistent with the assignment of these two basins to the distinct low density and high density liquid phases previously predicted to occur in ST2 water.

  14. Formation of Si02 film on plastic substrate by liquid-phase-deposition method

    NASA Astrophysics Data System (ADS)

    Kitaoka, Masaki; Honda, Hisao; Yoshida, Harunobu; Takigawa, Akio; Kawahara, Hideo

    1991-11-01

    The silicon dioxide (SiO2) film deposition on a plastic was made by liquid phase deposition (LPD) method. This process involves the deposition and growth of SiO2 layer on the plastic while immersing it in the hexafluorosilicic acid (H2SiF6) solution supersaturated with silica. In this study, it was shown that the specific pretreatment of the plastic surface by silane coupling agent was required for better adhesion of the SiO2 film. And the SiO2 film properties, resistance of organic solvent, water vapor permeability and water absorptivity, were evaluated in order to apply the 'LPD-SiO2' film to the protective layer of the polycarbonate (PC) disk for optical memory. As a result, it was shown that the 'LPD-SiO2' film could improve the properties of the plastic substrate.

  15. Mass transfer model liquid phase catalytic exchange column simulation applicable to any column composition profile

    SciTech Connect

    Busigin, A.

    2015-03-15

    Liquid Phase Catalytic Exchange (LPCE) is a key technology used in water detritiation systems. Rigorous simulation of LPCE is complicated when a column may have both hydrogen and deuterium present in significant concentrations in different sections of the column. This paper presents a general mass transfer model for a homogenous packed bed LPCE column as a set of differential equations describing composition change, and equilibrium equations to define the mass transfer driving force within the column. The model is used to show the effect of deuterium buildup in the bottom of an LPCE column from non-negligible D atom fraction in the bottom feed gas to the column. These types of calculations are important in the design of CECE (Combined Electrolysis and Catalytic Exchange) water detritiation systems.

  16. Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH(TM)) Process

    SciTech Connect

    1997-09-30

    The Liquid Phase Methanol (LPMEOHT") demonstration project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L. P. (the Partnership). Air Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. A demonstration unit producing 80,000 gallons per day (260 tons-per-day) of methanol from coal-derived synthesis gas (syngas) was designed, constructed, and is operating at a site located at the Eastman complex in Kingsport. The Partnership will own and operate the facility for the four-year demonstration period. This project is sponsored under the DOE's Clean Coal Technology Program, and its primary objective is to "demonstrate the production of methanol using the LPMEOWM Process in conjunction with an integrated coal gasification facility." The project will also demonstrate the suitability of the methanol produced for use as a chemical feedstock or as a low-sulfur dioxide, low-nitrogen oxides alternative fiel in stationary and transportation applications. The project may also demonstrate the production of dimethyl ether (DME) as a mixed coproduct with methanol, if laboratory- and pilot-scale research and market verification studies show promising results. If implemented, the DME would be produced during the last six months of the four-year demonstration period. The LPMEOITM process is the product of a cooperative development effort by Air Products and the DOE in a program that started in 1981. It was successfdly piloted at a 10 tons-per- day (TPD) rate in the DOE-owned experimental unit at Air Products' LaPorte, Texas, site. This demonstration project is the culmination of that extensive cooperative development effort.

  17. Crystallization of belitemelilite clinker minerals in the presence of liquid phase

    SciTech Connect

    Kurokawa, Daisuke; Yoshida, Hideto; Fukuda, Koichiro

    2014-06-01

    Crystallization of belitemelilite clinker minerals was studied from the view point of a high temperature equilibrium. Ca{sub 2}SiO{sub 4}Ca{sub 2}Al{sub 2}SiO{sub 7} and Ca{sub 2}SiO{sub 4}Ca{sub 2}AlFeSiO{sub 7} clinkers were synthesized at 1330 C1650 C. The constituent phases were determined by X-ray powder diffractometry and optical microscopy. Chemical compositions of the individual clinker minerals were determined using an electron probe microanalyzer. We established the two types of P{sub 2}O{sub 5}-bearing pseudobinary phase diagrams in the systems Ca{sub 2}SiO{sub 4}Ca{sub 2}Al{sub 2}SiO{sub 7} at 1505 C1650 C and Ca{sub 2}SiO{sub 4}Ca{sub 2}(Al,Fe){sub 2}SiO{sub 7} at 1330 C1550 C. In the latter system, the liquid phase appeared at 1390 C, which is approximately 150 C lower than the temperature of liquid formation in the former system. The melilite phenocrysts larger than 50 ?m were observed not only in the slowly cooled Ca{sub 2}SiO{sub 4}Ca{sub 2}(Al,Fe){sub 2}SiO{sub 7} clinker but also in commercial belitemelilite clinkers. These crystals would be nucleated and grown from a liquid phase which was formed at relatively low temperatures.

  18. Liquid phase deposition of a space-durable, antistatic SnO? coating on Kapton.

    PubMed

    Gotlib-Vainstein, Katya; Gouzman, Irina; Girshevitz, Olga; Bolker, Asaf; Atar, Nurit; Grossman, Eitan; Sukenik, Chaim N

    2015-02-18

    Polyimides are widely used in thermal blankets covering the external surfaces of spacecrafts due to their space durability and their thermo-optical properties. However, they are susceptible to atomic oxygen (AO) erosion, the main hazard of low Earth orbit (LEO), and to electrical charging. This work demonstrates that liquid phase deposition (LPD) of 100 nm of tin oxide creates a protective coating on Kapton polyimide that has good adherence and is effective in preventing AO-induced surface erosion and in reducing electrical charging. The as-deposited tin oxide induces no significant changes in the original thermo-optical properties of the polymer and is effective in preventing electrostatic discharge (ESD). The durability of the oxide coating under AO attack was studied using oxygen RF plasma. The AO exposure did not result in any significant changes in surface morphology, thermo-optical, mechanical, and electrical properties of the tin oxide-coated Kapton. The erosion yield of tin oxide-coated Kapton was negligible after exposure to 6.4 10(20) O atomscm(-2) of LEO equivalent AO fluence, indicating a complete protection of Kapton by the LPD deposited coating. Moreover, the tin oxide coating is flexible enough so that its electrical conductivity stays within the desired range of antistatic materials despite mechanical manipulations. The advantages of liquid phase deposited oxides in terms of their not being line of site limited are well established. We now extend these advantages to coatings that reduce electrostatic discharge while still providing a high level of protection from AO erosion. PMID:25607925

  19. Commercial-Scale Demonstration of the Liquid Phase Methanol (LOMEOH(TM)) Process

    SciTech Connect

    1997-12-31

    The Liquid Phase Methanol (LPMEOH) Demonstration Project at Kingsport, Tennessee, is a $213.7 million effort being conducted under a cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership). Air Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. A demonstration unit producing 80,000 gallons per day (260 tons-per-day (TPD)) of methanol from coal-derived synthesis gas (syngas) was designed, constructed, and began a four-year operational period in April of 1997 at a site located at the Eastman complex in Kingsport. The Partnership will own and operate the facility for the four-year demonstration period. This project is sponsored under the DOE's Clean Coal Technology Program, and its primary objective is to "demonstrate the production of methanol using the LPMEOH?M Process in conjunction with an integrated coal gasification facility." The project will also demonstrate the suitability of the methanol produced for use as a chemical feedstock or as a low-sulfur dioxide, low-nitrogen oxides alternative fiel in stationary and transportation applications. The project may also demonstrate the production of dimethyl ether (DME) as a mixed coproduct with methanol, if laboratory- and pilot-scale research and market verification studies show promising results. If implemented, the DME would be produced during the last six months of the four-year demonstration period. The LPMEOJYM process is the product of a cooperative development effort by Air Products and the DOE in a program that started in 1981. It was successfidly piloted at a 10-TPD rate in the DOE-owned experimental unit at Air Products' LaPorte, Texas, site. This Demonstration Project is the culmination of that extensive cooperative development effort.

  20. Pumice-supported Pd-Pt bimetallic catalysts: Synthesis, structural characterization, and liquid-phase hydrogenation of 1,3-cyclooctadiene

    SciTech Connect

    Deganello, G.; Duca, D.; Liotta, L.F.; Martorana, A.; Venezia, M.; Benedetti, A.; Fagherazz, G.

    1995-01-01

    A series of pumice-supported palladium-platinum bimetallic catalysts were prepared and investigated by X-ray scattering (WAXS and SAXS) and XPS techniques. An alloy Pd-Pt was formed. The less abundant metal was found to segregate to the surface. The catalysts were tested in the liquid-phase hydrogenation of 1,3-cyclooctadiene to cyclooctene, and compared with similarly prepared pumice-supported palladium and platinum catalysts and other supported Pd-Pt catalysts reported in the literature. The addition of platinum reduces the activity and the selectivity of the palladium catalysts. Differences between the activity of these pumice-supported catalysts and the activity of previously described Pd and Pd-Pt catalysts on other supports, are attributed to the presence, in the latter, of diffusional processes. 50 refs., 4 figs. 2 tabs.

  1. Linear solvation energy relationship of the limiting partition coefficient of organic solutes between water and activated carbon

    USGS Publications Warehouse

    Luehrs, Dean C.; Hickey, James P.; Nilsen, Peter E.; Godbole, K.A.; Rogers, Tony N.

    1995-01-01

    A linear solvation energy relationship has been found for 353 values of the limiting adsorption coefficients of diverse chemicals:  log K = −0.37 + 0.0341Vi − 1.07β + D + 0.65P with R = 0.951, s = 0.51, n = 353, and F = 818.0, where Vi is the intrinsic molar volume; β is a measure of the hydrogen bond acceptor strength of the solute; D is an index parameter for the research group which includes the effects of the different types of carbon used, the temperature, and the length of time allowed for the adsorption equilibrium to be established; and P is an index parameter for the flatness of the molecule. P is defined to be unity if there is an aromatic system in the molecule or if there is a double bond or series of conjugated double bonds with no more that one non-hydrogen atom beyond the double bond and zero otherwise. A slightly better fit is obtained if the two-thirds power of Vi is used as a measure of the surface area in place of the volume term:  log K = −1.75 + 0.227V2/3 − 1.10β + D + 0.60P with R = 0.954, s = 0.49, n = 353, and F = 895.39. This is the first quantitative measure of the effect of the shape of the molecule on its tendency to be adsorbed on activated carbon.

  2. Transient Liquid Phase Diffusion Bonding of Magnesium Alloy (Mg-AZ31) to Titanium Alloy (Ti-6Al-4V)

    NASA Astrophysics Data System (ADS)

    Atieh, Anas Mahmoud

    The magnesium alloy Mg-AZ31 and titanium alloy Ti-6Al-4V have physical characteristics and mechanical properties that makes it attractive for a wide range of engineering applications in the aerospace and automotive industries. However, the differences in melting temperature and coefficient of thermal expansion hinder the use of traditional fusion welding techniques. Transient liquid phase (TLP) bonding of magnesium alloy Mg-AZ31 and titanium alloy Ti-6Al- 4V was performed and different interlayer types and configurations were used to facilitate joint formation. The joining of these alloys using Ni foils was successful at a bonding temperature of 515C, bonding pressure 0.2 MPa, for bonding time of 5 minutes. At the Ni/Mg-AZ31 bond interface, the formation of a eutectic liquid between Mg and Ni was observed. The formation of Mg2Ni and Mg3AlNi2 were identified along the bond interface resulting in an isothermally solidified joint. At the Ni/Ti-6Al-4V interface, the solid-state diffusion process results in joint formation. The use of double Ni-Cu sandwich joint resulted in further enhancement in joint formation and this produced joints with greater shear strength values. The configuration of Mg-AZ31/Cu- Ni/Ti-6Al-4V or Mg-AZ31/Ni-Cu/Ti-6Al-4V influence the mechanism of bonding and the type of intermetallics formed within the joint. The application of thin Ni electrodeposited coatings resulted in further enhancements of joint quality due to better surface-to-surface contact and a reduction in the formation of intermetallics at the joint. The effect of Cu nano-particles in the coatings was found to decrease the eutectic zone width and this resulted in an increase the shear strength of the joints. The highest shear strength of 69 MPa was possible with bonds made using coatings containing Cu nano-particle dispersion.

  3. Consequences of metallic fuel-cladding liquid phase attack during over-temperature transient on fuel element lifetime

    SciTech Connect

    Lahm, C.E.; Koenig, J.F.; Seidel, B.R.

    1990-01-01

    Metallic fuel elements irradiated in EBR-II at temperatures significantly higher than design, causing liquid phase attack of the cladding, were subsequently irradiated at normal operating temperatures to first breach. The fuel element lifetime was compared to that for elements not subjected to the over-temperature transient and found to be equivalent. 1 ref., 3 figs.

  4. Liquid-liquid phase transitions and water-like anomalies in liquids

    NASA Astrophysics Data System (ADS)

    Lascaris, Erik

    In this thesis we employ computer simulations and statistical physics to understand the origin of liquid-liquid phase transitions and their relationship with anomalies typical of liquid water. Compared with other liquids, water has many anomalies. For example the density anomaly: when water is cooled below 4 °C the density decreases rather than increases. This and other anomalies have also been found to occur in a few other one-component liquids, sometimes in conjunction with the existence of a liquid-liquid phase transition (LLPT) between a low-density liquid (LDL) and a high-density liquid (HDL). Using simple models we explain how these anomalies arise from the presence of two competing length scales. As a specific example we investigate the cut ramp potential, where we show the importance of "competition" in this context, and how one length scale can sometimes be zero. When there is a clear energetic preference for either LDL or HDL for all pressures and temperatures, then there is insufficient competition between the two liquid structures and no anomalies occur. From the simple models it also follows that anomalies can occur without the presence of a LLPT and vice versa. It remains therefore unclear if water has a LLPT that ends in a liquid-liquid critical point (LLCP), a hypothesis that was first proposed based on simulations of the ST2 water model. We confirm the existence of a LLCP in this model using finite size scaling and the Challa-Landau-Binder parameter, and show that the LLPT is not a liquid-crystal transition, as has recently been suggested. Previous research has indicated the possible existence of a LLCP in liquid silica. We perform a detailed analysis of two different silica models (WAC and BKS) at temperatures much lower than was previously simulated. Within the accessible temperature range we find no LLCP in either model, although in the case of WAC potential it is closely approached. We compare our results with those obtained for other tetrahedral liquids and conclude that insufficient "stiffness" in the Si-O-Si bond angle might be responsible for the absence of a LLCP.

  5. Segregation to interphase boundaries in liquid-phase sintered tungsten alloys

    NASA Astrophysics Data System (ADS)

    Lea, C.; Muddle, B. C.; Edmonds, D. V.

    1983-03-01

    Scanning Auger electron spectroscopy has been used to examine the distribution of impurity elements on the fracture surfaces of liquid-phase sintered W-Ni-Cu and W-Ni-Fe alloys. On the interphase boundaries between the fcc Ni-based matrix phase and the tungsten particles, segregation levels of ~0.4 and ~0.2 monolayers of phosphorus have been observed in as-sintered, furnace-cooled specimens of W-Ni-Cu and W-Ni-Fe, respectively. The phosphorus is homogeneously distributed but at fracture adheres preferentially to the matrix phase. High temperature heat treatment (1350 C) followed by water quenching reduces significantly the phosphorus segregation and improves the degree of cohesion across these boundaries. Segregated sulfur is detected on both sides of the interphase boundaries after fracture. The sulfur is much less uniformly distributed than the phosphorus, and its segregation level increases in the heat treated specimens. Copper also segregates to the interphase boundaries during the heat treatment of W-Ni-Cu specimens, but no equivalent segregation of iron was observed in the W-Ni-Fe system. The boundaries developed between adjacent tungsten particles are free of impurity contamination in both alloy systems but have a segregated layer of nickel.

  6. Effect of grain boundaries on isothermal solidification during transient liquid phase brazing

    NASA Astrophysics Data System (ADS)

    Kokawa, H.; Lee, C. H.; North, T. H.

    1991-07-01

    The influence of liquid penetration at grain boundary regions on the rate of advance of the solid-liquid interface during isothermal solidification of transient liquid phase (TLP) brazed nickel joints has been examined. The test samples used in this study were Ohno-cast nickel with a grain size of >4 mm and a fine-grained nickel with a grain size of around 40 μm. Both Ni-base materials had the same chemical composition. The rate of isothermal solidification was greater when fine-grained nickel was employed during TLP brazing using Ni-11 wt pct P filler metal at 1200 °C. Liquid penetration at grain boundaries accelerates the isothermal solidification process by increasing the effective solid-liquid interfacial area and increasing the rate of solute diffusion into the base material. An analysis of electron channeling patterns has confirmed that random high-angle boundaries have a greater influence on the rate of isothermal solidification than ordered boundaries including small-angle or twin boundaries.

  7. Investigating the solid-liquid phase transition of water nanofilms using the generalized replica exchange method

    SciTech Connect

    Lu, Qing; Kim, Jaegil; Straub, John E.; Farrell, James D.; Wales, David J.

    2014-11-14

    The generalized Replica Exchange Method (gREM) was applied to study a solid-liquid phase transition in a nanoconfined bilayer water system using the monatomic water (mW) model. Exploiting optimally designed non-Boltzmann sampling weights with replica exchanges, gREM enables an effective sampling of configurations that are metastable or unstable in the canonical ensemble via successive unimodal energy distributions across phase transition regions, often characterized by S-loop or backbending in the statistical temperature. Extensive gREM simulations combined with Statistical Temperature Weighted Histogram Analysis Method (ST-WHAM) for nanoconfined mW water at various densities provide a comprehensive characterization of diverse thermodynamic and structural properties intrinsic to phase transitions. Graph representation of minimized structures of bilayer water systems determined by the basin-hopping global optimization revealed heterogeneous ice structures composed of pentagons, hexagons, and heptagons, consistent with an increasingly ordered solid phase with decreasing density. Apparent crossover from a first-order solid-liquid transition to a continuous one in nanoconfined mW water with increasing density of the system was observed in terms of a diminishing S-loop in the statistical temperature, smooth variation of internal energies and heat capacities, and a characteristic variation of lateral radial distribution functions, and transverse density profiles across transition regions.

  8. Microstructural evolution during transient liquid phase bonding of Inconel 738LC using AMS 4777 filler alloy

    SciTech Connect

    Jalilvand, V.; Omidvar, H.; Shakeri, H.R.; Rahimipour, M.R.

    2013-01-15

    IN-738LC nickel-based superalloy was joined by transient liquid phase diffusion bonding using AMS 4777 filler alloy. The bonding process was carried out at 1050 Degree-Sign C under vacuum atmosphere for various hold times. Microstructures of the joints were studied by optical and scanning electron microscopy. Continuous centerline eutectic phases, characterized as nickel-rich boride, chromium-rich boride and nickel-rich silicide were observed at the bonds with incomplete isothermal solidification. In addition to the centerline eutectic products, precipitation of boron-rich particles was observed in the diffusion affected zone. The results showed that, as the bonding time was increased to 75 min, the width of the eutectic zone was completely removed and the joint was isothermally solidified. Homogenization of isothermally solidified joints at 1120 Degree-Sign C for 300 min resulted in the elimination of intermetallic phases formed at the diffusion affected zone and the formation of significant {gamma} Prime precipitates in the joint region. - Highlights: Black-Right-Pointing-Pointer TLP bonding of IN-738LC superalloy was performed using AMS 4777 filler alloy. Black-Right-Pointing-Pointer Insufficient diffusion time resulted in the formation of eutectic product. Black-Right-Pointing-Pointer Precipitation of B-rich particles was observed within the DAZ. Black-Right-Pointing-Pointer The extent of isothermal solidification increased with increasing holding time. Black-Right-Pointing-Pointer Homogenizing of joints resulted in the dissolution of DAZ intermetallics.

  9. Gas-Purged Headspace Liquid Phase Microextraction System for Determination of Volatile and Semivolatile Analytes

    PubMed Central

    Zhang, Meihua; Bi, Jinhu; Yang, Cui; Li, Donghao; Piao, Xiangfan

    2012-01-01

    In order to achieve rapid, automatic, and efficient extraction for trace chemicals from samples, a system of gas-purged headspace liquid phase microextraction (GP-HS-LPME) has been researched and developed based on the original HS-LPME technique. In this system, semiconductor condenser and heater, whose refrigerating and heating temperatures were controlled by microcontroller, were designed to cool the extraction solvent and to heat the sample, respectively. Besides, inert gas, whose gas flow rate was adjusted by mass flow controller, was continuously introduced into and discharged from the system. Under optimized parameters, extraction experiments were performed, respectively, using GP-HS-LPME system and original HS-LPME technique for enriching volatile and semivolatile target compounds from the same kind of sample of 15 PAHs standard mixture. GC-MS analysis results for the two experiments indicated that a higher enrichment factor was obtained from GP-HS-LPME. The enrichment results demonstrate that GP-HS-LPME system is potential in determination of volatile and semivolatile analytes from various kinds of samples. PMID:22448341

  10. Dynamical and structural heterogeneities close to liquid-liquid phase transitions: The case of gallium

    NASA Astrophysics Data System (ADS)

    Antonelli, Alex; Cajahuaringa, Samuel; de Koning, Maurice

    2013-03-01

    Liquid-liquid phase transitions (LLPT) have been proposed in order to explain the thermodynamic anomalies exhibited by some liquids. Recently, it was found, through molecular dynamics simulations, that liquid elemental gallium, described by a modified embedded-atom model, exhibits a LLPT between a high-density liquid (HDL) and a low-density liquid (LDL), about 60 K below the melting temperature. In this work, we studied the dynamics of supercooled liquid gallium close to the LLPT. Our results show a large increase in the plateau of the self-intermediate scattering function (β-relaxation process) and in the non-Gaussian parameter, indicating a pronounced dynamical heterogeneity upon the onset of the LLPT. The dynamical heterogeneity of the LDL is closely correlated to its structural heterogeneity, since the fast diffusing atoms belong to high-density domains of predominantly 9-fold coordinated atoms, whereas the slow diffusing ones are mostly in low-density domains of 8-fold coordinated atoms. The energetics suggests that the reason for the sluggish dynamics of LDL is due to its larger cohesive energy as compared to that of the HDL. Work supported by FAPESP, CNPq, CAPES, and FAEPEX/UNICAMP

  11. Improved quantification of farnesene during microbial production from Saccharomyces cerevisiae in two-liquid-phase fermentations.

    PubMed

    Tippmann, Stefan; Nielsen, Jens; Khoomrung, Sakda

    2016-01-01

    Organic solvents are widely used in microbial fermentations to reduce gas stripping effects and capture hydrophobic or toxic compounds. Reliable quantification of biochemical products in these overlays is highly challenging and practically difficult. Here, we present a significant improvement of identification and quantification methods for farnesene produced by Saccharomyces cerevisiae in two-liquid-phase fermentations using GC-MS and GC-FID. By increasing the polarity of the stationary phase introducing a ZB-50 column (50%-phenyl-50%-dimethylsiloxane) peak intensity could be increased and solvent carryover could be minimized. Direct quantification of farnesene in dodecane was achieved by GC-FID whereas GC-MS demonstrated to be an excellent technique for identification of known and unknown metabolites. The GC-FID is a suitable technique for direct quantification of farnesene in complex matrices as shown by the good calibration curve (R(2)>0.998, N=5) within the tested concentration range of 1-50µg/mL and the reproducibility of the intensity (intraday; <10% RSD at each concentration; N=5). The limit of detection (LOD) and limit of quantification (LOQ) of the method were 0.24 and 0.80µg/mL, respectively. Furthermore, the FID method proved to be highly stable with regard to the intensity of the calibration (N=6) when the measurements were performed across 250 samples that were derived from a dodecane overlay. PMID:26695240

  12. The Utilization of Triton X-100 for Enhanced Two-Dimensional Liquid-Phase Proteomics

    PubMed Central

    Kim, Mina; Lee, Sang-Hee; Min, Jiho; Kobayashi, Fumihisa; Um, Hyun-Ju; Kim, Yang-Hoon

    2011-01-01

    One of the main challenges in proteomics lies in obtaining a high level of reproducible fractionation of the protein samples. Automated two-dimensional liquid phase fractionation (PF2D) system manufactured by Beckman Coulter provides a process well suited for proteome studies. However, the protein recovery efficiency of such system is low when a protocol recommended by the manufacturer is used for metaproteome profiling of environmental sample. In search of an alternative method that can overcome existing limitations, this study replaced manufacturer's buffers with Triton X-100 during the PF2D evaluation of Escherichia coli K12. Three different Triton X-100 concentrations0.1%, 0.15%, and 0.2%were used for the first-dimension protein profiling. As the first-dimension result was at its best in the presence of 0.15% Triton X-100, second-dimension protein fractionation was performed using 0.15% Triton X-100 and the standard buffers. When 0.15% Triton X-100 was used, protein recovery increased as much as tenfold. The elution reliability of 0.15% Triton X-100 determined with ribonuclease A, insulin, ?-lactalbumin, trypsin inhibitor, and cholecystokinin (CCK) affirmed Triton X-100 at 15% can outperform the standard buffers without having adverse effects on samples. This novel use of 0.15% Triton X-100 for PF2D can lead to greater research possibilities in the field of proteomics. PMID:22013380

  13. Microporous hydrophobic hollow fiber modules for gas-liquid phase separation in microgravity

    NASA Astrophysics Data System (ADS)

    Noyes, Gary

    Gas-liquid interphase mass transfer operations, such as gas-liquid phase separation, gas absorption into liquid or dissolved gas separation from liquid, gas humidification and drying via liquid contact, and evaporative cooling are readily accomplished on the Earth with settling/spray chambers, packed towers, or bubble columns. This paper reports on gas-water mass transfer tests performed utilizing microporous hydrophobic Hollow Fiber Modules (HFMs) of the type currently employed as blood oxygenators in heart-lung machines. In these HFMs, gases are transferrred to and from water or other hydrophilic liquids through the microporous fiber walls; liquid water does not enter the pores of the highly hydrophobic wall material. The experiments included air-water phase separation, absorption of oxygen and carbon dioxide into water and separation of these dissolved gases from water, air humidification and drying by contact with temperature-controlled water, and controlled evaporation of water into a vacuum. In each of these experiments, a small, light HFM sucessfully performed the mass tranfer function, with no leakage of liquid water through the porous walls of the hollow fibers, even with high pressure across the fiber wall for extended periods of time. These results demonstrate that gas-liquid mass transfer unit operations on hydrophilic liquids, implemented with microporous hydrophobic HFM technology, are ready for use in microgravity fluid processing systems.

  14. Well-posedness of a two-scale model for liquid phase epitaxy with elasticity

    NASA Astrophysics Data System (ADS)

    Kutter, Michael; Rohde, Christian; Sndig, Anna-Margarete

    2015-08-01

    Epitaxy, a special form of crystal growth, is a technically relevant process for the production of thin films and layers. It can generate microstructures of different morphologies, such as steps, spirals or pyramids. These microstructures are influenced by elastic effects in the epitaxial layer. There are different epitaxial techniques, one being liquid phase epitaxy. Thereby, single particles are deposited out of a supersaturated liquid solution on a substrate where they contribute to the growth process. This article studies a two-scale model including elasticity, introduced in Eck et al. (Eur Phys J Special Topics 177:5-21, 2009) and extended in Eck et al. (2006). It consists of a macroscopic Navier-Stokes system and a macroscopic convection-diffusion equation for the transport of matter in the liquid, and a microscopic problem that combines a phase field approximation of a Burton-Cabrera-Frank model for the evolution of the epitaxial layer, a Stokes system for the fluid flow near the layer and an elasticity system for the elastic deformation of the solid film. Suitable conditions couple the single parts of the model. As the main result, existence and uniqueness of a solution are proven in suitable function spaces. Furthermore, an iterative solving procedure is proposed, which reflects, on the one hand, the strategy of the proof of the main result via fixed point arguments and, on the other hand, can be the basis for a numerical algorithm.

  15. Transient liquid phase metallic bonding of an Inconel 718SPF superalloy

    SciTech Connect

    Yeh, M.S.; Chuang, T.H.

    1997-12-01

    The applicability of the transient liquid phase (TLP) metallic bonding method for joining fine-grained Inconel 718SPF{reg_sign} superalloy sheets by inserting a Ni-P or a Ni-Cr-P amorphous interlayer has been evaluated. The results show that a joint with uniform chemical composition could be obtained for the Inconel 718SPF superalloy with a Ni-P interlayer at 1,100 C for 8 h. When a Ni-Cr-P interlayer was used under the same metallic bonding conditions, the concentrations of nickel, iron and niobium in the bond region and in the base metal had a difference of more than 2 wt-%. This means that longer bonding time was required to homogenize the chemical compositions of bonds with a Ni-Cr-P interlayer. The joints with a Ni-P interlayer showed higher bond strength than did those with a Ni-Cr-P interlayer. Furthermore, many grain boundary precipitates were found.

  16. Switchable water: microfluidic investigation of liquid-liquid phase separation mediated by carbon dioxide.

    PubMed

    Lestari, Gabriella; Abolhasani, Milad; Bennett, Darla; Chase, Preston; Gnther, Axel; Kumacheva, Eugenia

    2014-08-27

    Increase in the ionic strength of water that is mediated by the reaction of carbon dioxide (CO2) with nitrogenous bases is a promising approach toward phase separation in mixtures of water with organic solvents and potentially water purification. Conventional macroscale studies of this complicated process are challenging, due to its occurrence via several consecutive and concurrent steps, mass transfer limitation, and lack of control over gas-liquid interfaces. We report a new microfluidic strategy for fundamental studies of liquid-liquid phase separation mediated by CO2 as well as screening of the efficiency of nitrogenous agents. A single set of microfluidic experiments provided qualitative and quantitative information on the kinetics and completeness of water-tetrahydrofuran phase separation, the minimum amount of CO2 required to complete phase separation, the total CO2 uptake, and the rate of CO2 consumption by the liquid mixture. The efficiency of tertiary diamines with different lengths of alkyl chain was examined in a time- and labor-efficient manner and characterized with the proposed efficiency parameter. A wealth of information obtained using the MF methodology can facilitate the development of new additives for switchable solvents in green chemistry applications. PMID:25079335

  17. Proton beam lithography in negative tone liquid phase PDMS polymer resist

    NASA Astrophysics Data System (ADS)

    Huszank, Robert; Rajta, Istvn; Cserhti, Csaba

    2015-04-01

    In this work we investigated the applicability of liquid PDMS polymer as a negative resist material for direct proton beam writing technique. We irradiated the polymer in liquid phase, spin-coated on different substrate materials creating various microstructures. PDMS pre-polymer was cross-linked just by PBW. As the cross-linking process increases, the irradiated area becomes more solid. The rate of the solidification strongly depends on the deposited ion dose. The effects of fluence, beam current, substrate type and developer solvent was investigated. Furthermore, at the irradiated areas the adhesion, the wettability and Young's modulus also changes due to the chemical change of the PDMS polymer. This effect makes the possibility to form microstructures in PDMS with tunable adhesion and wettability properties. In practical viewpoint, the PDMS resist can also have some advantages compared to other resists such as easy stripping, very fast developing (as the un-cross-linked PDMS is soluble in many organic solvents), not sensitive to light, high current or high fluence.

  18. Coulomb Liquid Phases of Bosonic Cluster Mott Insulators on a Pyrochlore Lattice.

    PubMed

    Lv, Jian-Ping; Chen, Gang; Deng, Youjin; Meng, Zi Yang

    2015-07-17

    Employing large-scale quantum Monte Carlo simulations, we reveal the full phase diagram of the extended Hubbard model of hard-core bosons on the pyrochlore lattice with partial fillings. When the intersite repulsion is dominant, the system is in a cluster Mott insulator phase with an integer number of bosons localized inside the tetrahedral units of the pyrochlore lattice. We show that the full phase diagram contains three cluster Mott insulator phases with 1/4, 1/2, and 3/4 boson fillings, respectively. We further demonstrate that all three cluster Mott insulators are Coulomb liquid phases and its low-energy property is described by the emergent compact U(1) quantum electrodynamics. In addition to measuring the specific heat and entropy of the cluster Mott insulators, we investigate the correlation function of the emergent electric field and verify it is consistent with the compact U(1) quantum electrodynamics description. Our result sheds light on the magnetic properties of various pyrochlore systems, as well as the charge physics of the cluster magnets. PMID:26230823

  19. Modern evaluation of liquisolid systems with varying amounts of liquid phase prepared using two different methods.

    PubMed

    Vraníková, Barbora; Gajdziok, Jan; Vetchý, David

    2015-01-01

    Liquisolid systems are an innovative dosage form used for enhancing dissolution rate and improving in vivo bioavailability of poorly soluble drugs. These formulations require specific evaluation methods for their quality assurance (e.g., evaluation of angle of slide, contact angle, or water absorption ratio). The presented study is focused on the preparation, modern in vitro testing, and evaluation of differences of liquisolid systems containing varying amounts of a drug in liquid state (polyethylene glycol 400 solution of rosuvastatin) in relation to an aluminometasilicate carrier (Neusilin US2). Liquisolid powders used for the formulation of final tablets were prepared using two different methods: simple blending and spraying of drug solution onto a carrier in fluid bed equipment. The obtained results imply that the amount of liquid phase in relation to carrier material had an effect on the hardness, friability, and disintegration of tablets, as well as their height. The use of spraying technique enhanced flow properties of the prepared mixtures, increased hardness values, decreased friability, and improved homogeneity of the final dosage form. PMID:26075249

  20. Advanced far infrared blocked impurity band detectors based on germanium liquid phase epitaxy

    SciTech Connect

    Olsen, C S

    1998-05-01

    This research has shown that epilayers with residual impurity concentrations of 5 x 10{sup 13} cm{sup {minus}3} can be grown by producing the purest Pb available in the world. These epilayers have extremely low minority acceptor concentrations, which is ideal for fabrication of IR absorbing layers. The Pb LPE growth of Ge also has the advantageous property of gettering Cu from the epilayer and the substrate. Epilayers have been grown with intentional Sb doping for IR absorption on lightly doped substrates. This research has proven that properly working Ge BIB detectors can be fabricated from the liquid phase as long as pure enough solvents are available. The detectors have responded at proper wavelengths when reversed biased even though the response did not quite reach minimum wavenumbers. Optimization of the Sb doping concentration should further decrease the photoionization energy of these detectors. Ge BIB detectors have been fabricated that respond to 60 cm{sup {minus}1} with low responsivity. Through reduction of the minority residual impurities, detector performance has reached responsivities of 1 A/W. These detectors have exhibited quantum efficiency and NEP values that rival conventional photoconductors and are expected to provide a much more sensitive tool for new scientific discoveries in a number of fields, including solid state studies, astronomy, and cosmology.

  1. Liquid-phase benzene oxidation to phenol with molecular oxygen catalyzed by Cu-zeolites

    SciTech Connect

    Ohtani, Tsuyoshi; Nishiyama, Satoru; Tsuruya, Shigeru

    1995-08-01

    The oxidation of benzene to form phenol using cuprous chloride as a catalyst has been reported by Sasaki and his co-workers, who used reaction system oxygen molecules as the oxidant. Takehira and his co-workers have studied benzene oxidation with molecular oxygen catalyzed by Cu(II) salts in the presence of ascorbic acid. Cu ion-exchanged zeolites have been reported to be useful as catalysts for the gas-phase oxidation of some organic materials, and copper ions in zeolites have been indicated to have redox properties according to physicochemical measurements. Armed with this knowledge, the authors have tried the liquid-phase oxidation of benzene with molecular oxygen under atmospheric pressure at room temperature using Cu ion-exchanged zeolite catalysts in the presence of ascorbic acid as a reducing reagent for Cu ions. The catalytic behavior of the Cu zeolites for the benzene oxidation was compared with that of nonanchored cupric and cuprous chloride catalysts. Also, some Cu catalysts impregnated on some amorphous oxide supports, in addition to the zeolites, were tested as catalysts for benzene oxidation with molecular oxygen. 13 refs., 5 figs., 3 tabs.

  2. Numerical study of liquid phase diffusion growth of SiGe subjected to accelerated crucible rotation

    NASA Astrophysics Data System (ADS)

    Sekhon, M.; Lent, B.; Dost, S.

    2016-03-01

    The effect of accelerated crucible rotation technique (ACRT) on liquid phase diffusion (LPD) growth of SixGe1-x crystal has been investigated numerically. Transient, axisymmetric simulations have been carried out for triangular and trapezoidal ACRT cycles. Natural convection driven flow in the early growth hours is found to be modified by the ACRT induced Ekman flow. Results also reveal that a substantial mixing in the solution can be induced by the application of ACRT in the later hours of growth which is otherwise a diffusion dominated growth period for LPD growth technique. A comparison is drawn to the cases of stationary crucible and crucible rotating at a constant speed examined previously for this growth system by Sekhon and Dost (J. Cryst. Growth 430 (2015) 63). It is found that a superior interface flattening effect and radial compositional uniformity along the growth interface can be accomplished by employing ACRT at 12 rpm than that which could be achieved by using steady crucible rotation at 25 rpm, owing to the higher time averaged growth velocity achieved in the former case. Furthermore, minor differences are also predicted in the results obtained for trapezoidal and triangular ACRT cycles.

  3. CTU Optical probes for liquid phase detection in the 1000 MW steam turbine

    NASA Astrophysics Data System (ADS)

    Kolovratník, Michal; Bartoš, Ondřej

    2015-05-01

    The aim of this paper is to introduce the measurement capacity of a new generation of CTU's optical probes to determine the liquid phase distribution in steam turbines and other energy systems. At the same time the paper presents the first part of the results concerning output wetness achieved through the use of experimental research performed with the probes in a new low pressure (LP) part of the steam turbine 1000MW in the Temelin nuclear power plant (ETE). Two different probes were used. A small size extinction probe with a diameter of 25mm which was developed for measuring in a wider range of turbines in comparison with the previous generation with a diameter of 50mm. The second probe used was a photogrammetric probe developed to observe the coarse droplets. This probe is still under development and this measurement was focused on verifying the capabilities of the probe. The data processing technique is presented together with yielded examples of the wetness distribution along the last blade of the 1000MW steam turbine. The experimental measurement was done in cooperation with Doosan Škoda Power s.r.o. (DSP).

  4. Liquid-liquid phase separation in aerosol particles: Imaging at the Nanometer Scale

    SciTech Connect

    O'Brien, Rachel; Wang, Bingbing; Kelly, Stephen T.; Lundt, Nils; You, Yuan; Bertram, Allan K.; Leone, Stephen R.; Laskin, Alexander; Gilles, Mary K.

    2015-04-21

    Atmospheric aerosols can undergo phase transitions including liquid-liquid phase separation (LLPS) while responding to changes in the ambient relative humidity (RH). Here, we report results of chemical imaging experiments using environmental scanning electron microscopy (ESEM) and scanning transmission x-ray microscopy (STXM) to investigate the LLPS of micron sized particles undergoing a full hydration-dehydration cycle. Internally mixed particles composed of ammonium sulfate (AS) and either: limonene secondary organic carbon (LSOC), a, 4-dihydroxy-3-methoxybenzeneaceticacid (HMMA), or polyethylene glycol (PEG-400) were studied. Events of LLPS with apparent core-shell particle morphology were observed for all samples with both techniques. Chemical imaging with STXM showed that both LSOC/AS and HMMA/AS particles were never homogeneously mixed for all measured RH’s above the deliquescence point and that the majority of the organic component was located in the shell. The shell composition was estimated as 65:35 organic: inorganic in LSOC/AS and as 50:50 organic: inorganic for HMMA/AS. PEG-400/AS particles showed fully homogeneous mixtures at high RH and phase separated below 89-92% RH with an estimated 50:50% organic to inorganic mix in the shell. These two chemical imaging techniques are well suited for in-situ analysis of the hygroscopic behavior, phase separation, and surface composition of collected ambient aerosol particles.

  5. Joining of NiAl to nickel-base alloys by transient liquid phase bonding

    SciTech Connect

    Abdo, Z.A.M.; Guan, Y.; Gale, W.F.

    1999-07-01

    A transmission and scanning electron microscope investigation is undertaken to study microstructural development during transient liquid phase (TLP) bonding of NiAl to Ni-base substrates. The bonds were produced through a conventional technique employing a Cu foil interlayer or a wide-gap technique using a composite preform containing powders of NiAl and Cu. The time required for completion of isothermal solidification was greatly reduced in wide-gap bonds as compared to conventional bonds. Microstructural features of conventional TLP bonds of polycrystalline-NiAl/Ni were controlled by the ratio of Al: Cu across the joint. The precipitation of the {sigma} phase encountered in polycrystalline-NiAl/Martin Marietta 247 superalloy (MM247) bonds was suppressed in wide-gap bonds of single crystal-NiAl(Hf) and MM247. In general, the extent of second phase precipitation, in the as-bonded condition, was greatly reduced by the use of the wide-gap technique. However, extensive precipitation of HfC and W-rich phases was observed after post-bond heat treatments.

  6. Liquid-phase laser process for simple and area-specific calcium phosphate coating.

    PubMed

    Oyane, Ayako; Sakamaki, Ikuko; Shimizu, Yoshiki; Kawaguchi, Kenji; Koshizaki, Naoto

    2012-10-01

    Simple, mild, and area-specific calcium phosphate (CaP) coating techniques are useful for the production and surface modification of biomaterials. In this study, an area-specific CaP coating technique for polymer substrates was successfully developed using a liquid-phase laser process. In the proposed method, Nd-YAG laser light (355 nm, 30 Hz, and 1-3 W) irradiated an ethylene-vinyl alcohol copolymer (EVOH) substrate immersed in a supersaturated CaP solution for various periods of time (up to 30 min). The CaP-forming ability increased with an increase in the laser power and irradiation period. At the optimal laser power (3 W), a continuous CaP layer formed within 30 min on the laser-irradiated surface of the EVOH substrate. The formation of CaP was attributed to laser absorption by the EVOH substrate, which promoted the surface modification of EVOH and an increase in the temperature of the solution near the surface of the substrate. The resulting CaP coating showed better cell adhesion property than the naked EVOH substrate. The proposed CaP coating technique is simple (quick and single step) and area specific. Furthermore, the present process is carried out under mild conditions, that is, at normal pressures and temperatures in a safe aqueous medium. These are significant advantages of the proposed CaP coating technique. PMID:22528860

  7. Transient Liquid Phase Bonding Single-Crystal Superalloys with Orientation Deviations: Creep Properties

    NASA Astrophysics Data System (ADS)

    Sheng, Naicheng; Liu, Jide; Jin, Tao; Sun, Xiaofeng; Hu, Zhuangqi

    2015-12-01

    Superalloys single crystals with various orientation deviations were bonded using transient liquid phase bonding method, then the creep properties of the bonded specimens were tested at 1033 K (760 °C)/780 MPa. It is found that the creep life of the bonded specimens decreases with the increase of the relative orientation deviations. Despite the fracture of the specimens appears on the bonding region, the deformation mechanism changes from specimens with low angle boundary to high angle boundary. In low angle boundary specimens, cleavage originated from the defects grows perpendicularly to the tensile stress and connects through the different slip planes around the cleavage planes. In this case, the deformation proceeds by the dislocations and stacking faults on multi-planes. With increasing orientation deviation, dislocation and stacking faults moved on single plane. As a result, the dislocations interact with the grain boundary and lead to fracture. Based on the present investigation, the orientation of the bonded superalloys single crystal should be controlled so that the introduced grain boundaries are relatively small and exhibit higher creep strength.

  8. Third-order gas-liquid phase transition and the nature of Andrews critical point

    NASA Astrophysics Data System (ADS)

    Ma, Tian; Wang, Shouhong

    2011-12-01

    The main objective of this article is to study the nature of the Andrews critical point in the gas-liquid transition in a physical-vapor transport (PVT) system. A dynamical model, consistent with the van der Waals equation near the Andrews critical point, is derived. With this model, we deduce two physical parameters, which interact exactly at the Andrews critical point, and which dictate the dynamic transition behavior near the Andrews critical point. In particular, it is shown that 1) the gas-liquid co-existence curve can be extended beyond the Andrews critical point, and 2) the transition is first order before the critical point, second-order at the critical point, and third order beyond the Andrews critical point. This clearly explains why it is hard to observe the gas-liquid phase transition beyond the Andrews critical point. Furthermore, the analysis leads naturally the introduction of a general asymmetry principle of fluctuations and the preferred transition mechanism for a thermodynamic system. The theoretical results derived in this article are in agreement with the experimental results obtained in (K. Nishikawa and T. Morita, Fluid behavior at supercritical states studied by small-angle X-ray scattering, Journal of Supercritical Fluid, 13 (1998), pp. 143-148). Also, the derived second-order transition at the critical point is consistent with the result obtained in (M. Fisher, Specific heat of a gas near the critical point, Physical Review, 136:6A (1964), pp. A1599-A1604).

  9. Rapid heating of a strongly coupled plasma at the solid-liquid phase transition

    NASA Astrophysics Data System (ADS)

    Jensen, M. J.; Hasegawa, T.; Bollinger, J. J.; Dubin, D. H. E.

    2004-11-01

    Between 10^4 and 10^6 ^9Be^+ ions are trapped in a 4.5 Tesla Penning trap and laser-cooled to 1 mK, where the ions form a crystalline plasma with an interparticle spacing of 20 ?m. This system is a realization of a strongly coupled one-component plasma. Using Doppler laser spectroscopy on a single-photon transition, we measured the temperature and heating rate of this plasma when not being laser-cooled. We measured a slow heating rate of ? 100 mK/s due to residual gas collisions for the first 100-200 ms after turning off the cooling laser. This slow heating is followed by a rapid heating to 1-2 K in 100 ms as the plasma undergoes the solid-liquid phase transition at T=10 mK (? 170). We will present evidence that this rapid heating is due to a sudden release of energy from weakly cooled degrees of freedom involving the cyclotron motion of trapped impurity ions. We will also discuss the prospects for observing the latent heat associated with the phase transition.

  10. Redistribution of black carbon in aerosol particles undergoing liquid-liquid phase separation

    NASA Astrophysics Data System (ADS)

    Brunamonti, Simone; Krieger, Ulrich K.; Marcolli, Claudia; Peter, Thomas

    2015-04-01

    Atmospheric black carbon (BC) is a major anthropogenic greenhouse agent, yet substantial uncertainties obstruct understanding its radiative forcing. Particularly debated is the extent of the absorption enhancement by internally compared to externally mixed BC, which critically depends on the interior morphology of the BC-containing particles. Here we suggest that a currently unaccounted morphology, optically very different from the customary core-shell and volume-mixing assumptions, likely occurs in aerosol particles undergoing liquid-liquid phase separation (LLPS). Using Raman spectroscopy on micrometer-sized droplets, we show that LLPS of an organic/inorganic model system drives redistribution of BC into the outer (organic) phase of the host particle. This results in an inverted core-shell structure, in which a transparent aqueous core is surrounded by a BC-containing absorbing shell. Based on Mie theory calculations, we estimate that such a redistribution can reduce the absorption efficiency of internally-mixed BC aerosols by up to 25% compared to the volume-mixing approximation.

  11. Redistribution of black carbon in aerosol particles undergoing liquid-liquid phase separation

    NASA Astrophysics Data System (ADS)

    Brunamonti, S.; Krieger, U. K.; Marcolli, C.; Peter, T.

    2015-04-01

    Atmospheric black carbon (BC) is a major anthropogenic greenhouse agent, yet substantial uncertainties obstruct understanding its radiative forcing. Particularly debated is the extent of the absorption enhancement by internally compared to externally mixed BC, which critically depends on the interior morphology of the BC-containing particles. Here we suggest that a currently unaccounted morphology, optically very different from the customary core-shell and volume-mixing assumptions, likely occurs in aerosol particles undergoing liquid-liquid phase separation (LLPS). Using Raman spectroscopy on micrometer-sized droplets, we show that LLPS of an organic/inorganic model system drives redistribution of BC into the outer (organic) phase of the host particle. This results in an inverted core-shell structure, in which a transparent aqueous core is surrounded by a BC-containing absorbing shell. Based on Mie theory calculations, we estimate that such a redistribution can increase the absorption efficiency of internally mixed BC aerosols by up to 25% compared to the core-shell approximation.

  12. Liquid-liquid phase transition in quasi-two-dimensional supercooled silicon.

    PubMed

    Zhang, K; Li, H; Jiang, Y Y

    2014-09-01

    Anomalies of the local structural order in quasi-two-dimensional liquid silicon upon cooling are investigated. Results show that the appearance of the left subpeak in pair correlation functions is the signature of the liquid-liquid phase transition (LLPT). The structural origin of the LLPT is the formation of a crystal-like ordered structure with a short-range scale, which in turn forms the local well-organized paracrystalline region. Unlike in the bulk liquid silicon, the stages of the LLPT and liquid-solid phase transition (LSPT) in the quasi-two-dimensional liquid silicon do not overlap. The crystal-like ordered structures formed in the LLPT are precursors which are prepared for the subsequent LSPT. Also observed was a strong interconnection between the local well-organized paracrystalline region and the transition from the typical metal to the semimetal in the two-dimensional silicon. This study will aid in better understanding of the essential phase change in two-dimensional liquid silicon. PMID:25050842

  13. Fabrication and Characterization of Liquid-Phase Sensor utilizing GaN-Based Two Terminal Devices

    NASA Astrophysics Data System (ADS)

    Abidin, Mastura Shafinaz Zainal; Jeat, Wang Soo; Hashim, Abdul Manaf; Rahman, Shaharin Fadzli Abd; Sharifabad, Maneea Eizadi; Omar, Nurul Afzan; Qindeel, Rabia

    2011-05-01

    Gallium Nitride (GaN) based materials are highly suitable for liquid-phase sensor applications due to their chemical stability and high internal piezoelectric polarization. The sensitivity of GaN surfaces in aqueous solutions and polar liquids has been investigated. For this purpose, two terminal devices fabricated on bulk Si doped-GaN structures and undoped-AlGaN/GaN heterostructures with unpassivated open area are used to measure the responses to the changes of the H+ concentration in aqueous solutions and the dipole moment in polar liquids. The I-V characteristics show that the devices are able to distinguish the variations of pH. It is observed that the drain current decreases linearly with pH for both device structures. Evaluating the sensitivity in aqueous solutions at VDS = 2V, a quite large current change is obtained for both structures. For the response to polar liquids, it is also found that the drain current decreases with the dipole moments. The results indicate that both devices are capable of distinguishing molecules with different dipole moments.

  14. Synthesis of structurally well-defined and liquid-phase-processable graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Narita, Akimitsu; Feng, Xinliang; Hernandez, Yenny; Jensen, Søren A.; Bonn, Mischa; Yang, Huafeng; Verzhbitskiy, Ivan A.; Casiraghi, Cinzia; Hansen, Michael Ryan; Koch, Amelie H. R.; Fytas, George; Ivasenko, Oleksandr; Li, Bing; Mali, Kunal S.; Balandina, Tatyana; Mahesh, Sankarapillai; de Feyter, Steven; Müllen, Klaus

    2014-02-01

    The properties of graphene nanoribbons (GNRs) make them good candidates for next-generation electronic materials. Whereas ‘top-down’ methods, such as the lithographical patterning of graphene and the unzipping of carbon nanotubes, give mixtures of different GNRs, structurally well-defined GNRs can be made using a ‘bottom-up’ organic synthesis approach through solution-mediated or surface-assisted cyclodehydrogenation reactions. Specifically, non-planar polyphenylene precursors were first ‘built up’ from small molecules, and then ‘graphitized’ and ‘planarized’ to yield GNRs. However, fabrication of processable and longitudinally well-extended GNRs has remained a major challenge. Here we report a bottom-up solution synthesis of long (>200 nm) liquid-phase-processable GNRs with a well-defined structure and a large optical bandgap of 1.88 eV. Self-assembled monolayers of GNRs can be observed by scanning probe microscopy, and non-contact time-resolved terahertz conductivity measurements reveal excellent charge-carrier mobility within individual GNRs. Such structurally well-defined GNRs may prove useful for fundamental studies of graphene nanostructures, as well as the development of GNR-based nanoelectronics.

  15. Storing solar energy with liquid phase Diels-Alder reactions. Final report

    SciTech Connect

    Poling, B.E.

    1983-07-28

    At the beginning of this project, a preliminary study was completed that indicated the Diels-Alder reaction between maleic anhydride and 2 methyl furan had an energy storage capacity greater than water. During the last two years when this grant was in effect, three additional projects have been completed. First, an improved calorimetric techniques was developed for determination of the energy storage capacity of a reversible liquid phase chemical reaction. This technique confirmed the validity of the earlier results for the maleic anhydride-methyl furan reaction. Second, a technique was developed for characterizing solution nonidealities for mixtures in which reversible chemical reactions occur. It was found that for the maleic anhydride-2 methyl furan reaction, these non idealities could affect equilibrium compositions by nearly 40%. Third, drop calorimetry was used as a screening method to examine sixteen reactions for their potential as energy storage candidates. Of the sixteen examined, three (all involving maleic anhydride and substituted furan) showed an increased energy storage capacity due to reaction while the remaining thirteen showed no increase. In the following report, results of these three studies are summarized. Finally, a general summary of the status of energy storage by chemical reactions is presented.

  16. Roaming-mediated ultrafast isomerization of geminal tri-bromides in the gas and liquid phases

    NASA Astrophysics Data System (ADS)

    Mereshchenko, Andrey S.; Butaeva, Evgeniia V.; Borin, Veniamin A.; Eyzips, Anna; Tarnovsky, Alexander N.

    2015-07-01

    Roaming is a new and unusual class of reaction mechanism that has recently been discovered in unimolecular dissociation reactions of isolated molecules in the gas phase. It is characterized by frustrated bond cleavage, after which the two incipient fragments roam on a flat region of the potential energy surface before reacting with one another. Here, we provide evidence that supports roaming in the liquid phase. We are now able to explain previous solution-phase experiments by comparing them with new ultrafast transient absorption data showing the photoisomerization of gas-phase CHBr3. We see that, upon S0-S1 excitation, gas-phase CHBr3 isomerizes within 100?fs into the BrHCBr-Br species, which is identical to what has been observed in solution. Similar sub-100 fs isomerization is now also observed for BBr3 and PBr3 in solution upon S1 excitation. Quantum chemical simulations of XBr3 (X?=?B, P or CH) suggest that photochemical reactivity in all three cases studied is governed by S1/S0 conical intersections and can best be described as occurring through roaming-mediated pathways.

  17. Large magneto-optic enhancement in ultra-thin liquid-phase-epitaxy iron garnet films

    NASA Astrophysics Data System (ADS)

    Levy, Miguel; Chakravarty, A.; Huang, H.-C.; Osgood, R. M.

    2015-07-01

    Significant departures from bulk-like magneto-optic behavior are found in ultra-thin bismuth-substituted iron-garnet films grown by liquid-phase-epitaxy. These changes are due, at least in part, to geometrical factors and not to departures from bulk-composition in the transient layer at the film-substrate interface. A monotonic increase in specific Faraday rotation with reduced thickness is the signature feature of the observed phenomena. These are traced to size-dependent modifications in the diamagnetic transition processes responsible for the Faraday rotation. These processes correspond to the electronic transitions from singlet 6S ground states to spin-orbit split excited states of the Fe3+ ions in the garnet. A measurable reduction in the corresponding ferrimagnetic resonance linewidths is found, thus pointing to an increase in electronic relaxation times and longer lived excitations at reduced thicknesses. These changes together with a shift in vibrational frequency of the Bi-O bonds in the garnet at reduced thicknesses result in greatly enhanced magneto-optical performance. These studies were conducted on epitaxial monocrystalline Bi0.8Gd0.2Lu2Fe5O12 films.

  18. Nanostructure Particle-Reinforced Transient Liquid Phase Diffusion Bonding: a Comparative Study

    NASA Astrophysics Data System (ADS)

    Cooke, Kavian O.; Khan, Tahir I.; Oliver, Gossett D.

    2011-08-01

    Particle-reinforced aluminum-metal matrix composites (Al-MMCs) are used in many engineering applications, because they provide significant advantages when compared to monolithic aluminum alloys. However, there still exists the need to identify a suitable joining process for these materials, which minimizes particulate disruption and retains the strength of the MMC within the joint region. This study presents a comparison between joint qualities achieved when a monolithic interlayer is used vs when a nanoparticle-reinforced composite interlayer is used during transient liquid phase diffusion bonding of Al-6061 alloy containing 15 vol pct of Al2O3 particles. Examination of the joint region using scanning electron microscopy (SEM), wavelength dispersive spectroscopy (WDS), and X-ray diffraction (XRD) showed the formation of eutectic phases such as Al3Ni, Al9FeNi, and Ni3Si within the joint zone. The results indicate that the addition of nanoparticle reinforcements into the interlayer can be used to improve joint strength and minimize particle segregation.

  19. Grain refinement of transient liquid phase bonding zone using ODS insert foil

    NASA Astrophysics Data System (ADS)

    Noto, Hiroyuki; Kasada, Ryuta; Kimura, Akihiko; Ukai, Shigeharu

    2013-11-01

    Joint strengthening of oxide dispersion strengthened (ODS) martensitic steel has been attained by a transient liquid phase (TLP) bonding utilizing a newly developed ODS insert foil. The ODS insert foil (Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.5C-3B-2Si) was fabricated using mechanical alloying and a spark plasma sintering method. Compared to conventional TLP bonding with a non-ODS insert foil (Fe-0.5C-3B-2Si), the microstructure of the melted zone consists of finer grains in the joint with the newly developed ODS insert material, and the grain size is almost one third of that in the conventional insert material. This increases the hardness by ?Hv = 100 in the region of the joints. Oxide particles that are coherent to the ferritic matrix in the ODS insert foil could be responsible for the grain refinement, which is explained in terms of enhanced nucleation of consolidation matrix at the oxide particles.

  20. Room temperature ferromagnetism in liquid-phase pulsed laser ablation synthesized nanoparticles of nonmagnetic oxides

    NASA Astrophysics Data System (ADS)

    Singh, S. C.; Kotnala, R. K.; Gopal, R.

    2015-08-01

    Intrinsic Room Temperature Ferromagnetism (RTF) has been observed in undoped/uncapped zinc oxide and titanium dioxide spherical nanoparticles (NPs) obtained by a purely green approach of liquid phase pulsed laser ablation of corresponding metal targets in pure water. Saturation magnetization values observed for zinc oxide (average size, 9 1.2 nm) and titanium dioxide (average size, 4.4 0.3 nm) NPs are 62.37 and 42.17 memu/g, respectively, which are several orders of magnitude larger than those of previous reports. In contrast to the previous works, no postprocessing treatments or surface modification is required to induce ferromagnetism in the case of present communication. The most important result, related to the field of intrinsic ferromagnetism in nonmagnetic materials, is the observation of size dependent ferromagnetism. Degree of ferromagnetism in titanium dioxide increases with the increase in particle size, while it is reverse for zinc oxide. Surface and volume defects play significant roles for the origin of RTF in zinc oxide and titanium dioxide NPs, respectively. Single ionized oxygen and neutral zinc vacancies in zinc oxide and oxygen and neutral/ionized titanium vacancies in titanium dioxide are considered as predominant defect centres responsible for observed ferromagnetism. It is expected that origin of ferromagnetism is a consequence of exchange interactions between localized electron spin moments resulting from point defects.

  1. Advanced far infrared blocked impurity band detectors based on germanium liquid phase epitaxy

    NASA Technical Reports Server (NTRS)

    Olsen, C. S.

    1998-01-01

    This research has shown that epilayers with residual impurity concentrations of 5 x 10(sup 13) cm(exp -3) can be grown by producing the purest Pb available in the world. These epilayers have extremely low minority acceptor concentrations, which is ideal for fabrication of IR absorbing layers. The Pb LPE growth of Ge also has the advantageous property of gettering Cu from the epilayer and the substrate. Epilayers have been grown with intentional Sb doping for IR absorption on lightly doped substrates. This research has proven that properly working Ge BIB detectors can be fabricated from the liquid phase as long as pure enough solvents are available. The detectors have responded at reach minimum wavenumbers. Optimization of the Sb doping concentration should further decrease the photoionization energy of these detectors. Ge BIB detectors have been fabricated that respond to 60 cm(exp -1) with low responsivity. Through reduction of the minority residual impurities, detector performance has reached responsivities of 1 A/W. These detectors have exhibited quantum efficiency and NEP values that rival conventional photoconductors and are expected to provide a much more sensitive tool for new scientific discoveries in a number of fields, including solid state studies, astronomy, and cosmology.

  2. High-yield production of graphene by liquid-phase exfoliation of graphite.

    PubMed

    Hernandez, Yenny; Nicolosi, Valeria; Lotya, Mustafa; Blighe, Fiona M; Sun, Zhenyu; De, Sukanta; McGovern, I T; Holland, Brendan; Byrne, Michele; Gun'Ko, Yurii K; Boland, John J; Niraj, Peter; Duesberg, Georg; Krishnamurthy, Satheesh; Goodhue, Robbie; Hutchison, John; Scardaci, Vittorio; Ferrari, Andrea C; Coleman, Jonathan N

    2008-09-01

    Fully exploiting the properties of graphene will require a method for the mass production of this remarkable material. Two main routes are possible: large-scale growth or large-scale exfoliation. Here, we demonstrate graphene dispersions with concentrations up to approximately 0.01 mg ml(-1), produced by dispersion and exfoliation of graphite in organic solvents such as N-methyl-pyrrolidone. This is possible because the energy required to exfoliate graphene is balanced by the solvent-graphene interaction for solvents whose surface energies match that of graphene. We confirm the presence of individual graphene sheets by Raman spectroscopy, transmission electron microscopy and electron diffraction. Our method results in a monolayer yield of approximately 1 wt%, which could potentially be improved to 7-12 wt% with further processing. The absence of defects or oxides is confirmed by X-ray photoelectron, infrared and Raman spectroscopies. We are able to produce semi-transparent conducting films and conducting composites. Solution processing of graphene opens up a range of potential large-area applications, from device and sensor fabrication to liquid-phase chemistry. PMID:18772919

  3. Thermal Diffusivity and Thermal Conductivity of Five Different Steel Alloys in the Solid and Liquid Phases

    NASA Astrophysics Data System (ADS)

    Wilthan, B.; Schützenhöfer, W.; Pottlacher, G.

    2015-08-01

    The need for characterization of thermophysical properties of steel and nickel-based alloys was addressed in the FFG-Bridge Project 810999 in cooperation with a partner from industry, Böhler Edelstahl GmbH & Co KG. To optimize numerical simulations of production processes, such as remelting or plastic deformation, additional, and more accurate data were necessary for the alloys under investigation. With a fast ohmic pulse heating circuit system, the temperature-dependent specific electrical resistivity, density, and specific heat capacity for a set of five high alloyed steels were measured. Hence, using the Wiedemann-Franz law with a Lorenz number of , the thermal diffusivity and thermal conductivity could be calculated for the solid and liquid phases up to temperatures of 2500 K. This experimental approach is limited by the following requirements for the specimens: they have to be electrically conducting, the melting point has to be high enough for the implemented pyrometric temperature measurement, and one has to be able to draw wires of the material. The latter restriction is technologically challenging with some of the materials being very brittle. For all samples, electrical and temperature signals are recorded and a fast shadowgraph method is used to measure the volume expansion. For each material under investigation, a set of data including the chemical composition, the density at room temperature, solidus and liquidus temperatures, and the change of enthalpy, resistivity, density, thermal conductivity, and thermal diffusivity as a function of temperature is reported.

  4. Liquid-liquid phase separation in aerosol particles: imaging at the nanometer scale.

    PubMed

    O'Brien, Rachel E; Wang, Bingbing; Kelly, Stephen T; Lundt, Nils; You, Yuan; Bertram, Allan K; Leone, Stephen R; Laskin, Alexander; Gilles, Mary K

    2015-04-21

    Atmospheric aerosols can undergo phase transitions including liquid-liquid phase separation (LLPS) while responding to changes in the ambient relative humidity (RH). Here, we report results of chemical imaging experiments using environmental scanning electron microscopy (ESEM) and scanning transmission X-ray microscopy (STXM) to investigate the LLPS of micrometer-sized particles undergoing a full hydration-dehydration cycle. Internally mixed particles composed of ammonium sulfate (AS) and either: limonene secondary organic carbon (LSOC), ?, 4-dihydroxy-3-methoxybenzeneaceticacid (HMMA), or polyethylene glycol (PEG-400) were studied. Events of LLPS were observed for all samples with both techniques. Chemical imaging with STXM showed that both LSOC/AS and HMMA/AS particles were never homogeneously mixed for all measured RH's above the deliquescence point and that the majority of the organic component was located in the outer phase. The outer phase composition was estimated as 65:35 organic: inorganic in LSOC/AS and as 50:50 organic: inorganic for HMMA/AS. PEG-400/AS particles showed fully homogeneous mixtures at high RH and phase separated below 89-92% RH with an estimated 70:30% organic to inorganic mix in the outer phase. These two chemical imaging techniques are well suited for in situ analysis of the hygroscopic behavior, phase separation, and surface composition of collected ambient aerosol particles. PMID:25850933

  5. Spectroscopic studies of ZnSe grown by liquid phase epitaxy

    NASA Astrophysics Data System (ADS)

    Fitzpatrick, B. J.; McGee, T. F., III; Harnack, P. M.; Herko, S. P.; Bhargava, R. N.; Werkhoven, C. J.; Dean, P. J.

    1981-04-01

    Spectroscopic studies of the sources of contamination and the shallow acceptor behavior of group V-doped specimens of ZnSe grown by liquid phase epitaxy are reported. ZnSe samples were grown from molten metal solutions in a horizontal heat-pipe lined system using a four-melt graphite boat, a vertical dipping system, a horizontal tipping system for use with a sealed ampoule, or a horizontal system with a graphite slider boat, at temperatures generally between 900 and 825 C. Photoluminescence measurements made using argon ion laser irradiation at 363.8 nm in the bound exciton region reveal the presence of Al and In donors and Li acceptors, with occasional Cl and Ga donors and Na acceptors and an unidentified line apparently related to an isoelectronic center. The bound exciton lines also indicate that the total shallow donor concentration is less then 5 x 10 to the 16th/cu cm, with all transitions apparently originating from impurities in undoped material. Donor-acceptor pair region spectra of As-, P- and N-doped specimens provide evidence for the existence of shallow acceptors due to group V elements, however the nature of the acceptors as simple substitutional centers has yet to be confirmed.

  6. Spin liquid phases of large-spin Mott insulating ultracold bosons

    NASA Astrophysics Data System (ADS)

    Rutkowski, Todd C.; Lawler, Michael J.

    2016-03-01

    Mott insulating ultracold gases possess a unique whole-atom exchange interaction which enables large quantum fluctuations between the Zeeman sublevels of each atom. By strengthening this interaction—either through the use of large-spin atoms or by tuning the particle-particle interactions via optical Feshbach resonance—one may enhance fluctuations and facilitate the appearance of the long-sought-after quantum spin liquid phase—all in the highly tunable environment of cold atoms. To illustrate the relationship between the spin magnitude, interaction strength, and resulting magnetic phases, we present and solve a mean-field theory for bosons optically confined to the one-particle-per-site Mott state, using both analytic and numerical methods. We find on square and triangular lattices for bosons of hyperfine spin f >2 that making the repulsive s -wave scattering length through the singlet channel small—relative to the higher-order scattering channels—accesses a short-range resonating valence bond (s-RVB) spin liquid phase.

  7. Liquid-phase epitaxial growth of two-dimensional semiconductor hetero-nanostructures.

    PubMed

    Tan, Chaoliang; Zeng, Zhiyuan; Huang, Xiao; Rui, Xianhong; Wu, Xue-Jun; Li, Bing; Luo, Zhimin; Chen, Junze; Chen, Bo; Yan, Qingyu; Zhang, Hua

    2015-02-01

    Although many two-dimensional (2D) hybrid nanostructures are being prepared, the engineering of epitaxial 2D semiconductor hetero-nanostructures in the liquid phase still remains a challenge. The preparation of 2D semiconductor hetero-nanostructures by epitaxial growth of metal sulfide nanocrystals, including CuS, ZnS and Ni3S2, is achieved on ultrathin TiS2 nanosheets by a simple electrochemical approach by using the TiS2 crystal and metal foils. Ultrathin CuS nanoplates that are 50-120 nm in size and have a triangular/hexagonal shape are epitaxially grown on TiS2 nanosheets with perfect epitaxial alignment. ZnS and Ni3S2 nanoplates can be also epitaxially grown on TiS2 nanosheets. As a proof-of-concept application, the obtained 2D CuS-TiS2 composite is used as the anode in a lithium ion battery, which exhibits a high capacity and excellent cycling stability. PMID:25530025

  8. Gas-purged headspace liquid phase microextraction system for determination of volatile and semivolatile analytes.

    PubMed

    Zhang, Meihua; Bi, Jinhu; Yang, Cui; Li, Donghao; Piao, Xiangfan

    2012-01-01

    In order to achieve rapid, automatic, and efficient extraction for trace chemicals from samples, a system of gas-purged headspace liquid phase microextraction (GP-HS-LPME) has been researched and developed based on the original HS-LPME technique. In this system, semiconductor condenser and heater, whose refrigerating and heating temperatures were controlled by microcontroller, were designed to cool the extraction solvent and to heat the sample, respectively. Besides, inert gas, whose gas flow rate was adjusted by mass flow controller, was continuously introduced into and discharged from the system. Under optimized parameters, extraction experiments were performed, respectively, using GP-HS-LPME system and original HS-LPME technique for enriching volatile and semivolatile target compounds from the same kind of sample of 15 PAHs standard mixture. GC-MS analysis results for the two experiments indicated that a higher enrichment factor was obtained from GP-HS-LPME. The enrichment results demonstrate that GP-HS-LPME system is potential in determination of volatile and semivolatile analytes from various kinds of samples. PMID:22448341

  9. Modern Evaluation of Liquisolid Systems with Varying Amounts of Liquid Phase Prepared Using Two Different Methods

    PubMed Central

    Vetchý, David

    2015-01-01

    Liquisolid systems are an innovative dosage form used for enhancing dissolution rate and improving in vivo bioavailability of poorly soluble drugs. These formulations require specific evaluation methods for their quality assurance (e.g., evaluation of angle of slide, contact angle, or water absorption ratio). The presented study is focused on the preparation, modern in vitro testing, and evaluation of differences of liquisolid systems containing varying amounts of a drug in liquid state (polyethylene glycol 400 solution of rosuvastatin) in relation to an aluminometasilicate carrier (Neusilin US2). Liquisolid powders used for the formulation of final tablets were prepared using two different methods: simple blending and spraying of drug solution onto a carrier in fluid bed equipment. The obtained results imply that the amount of liquid phase in relation to carrier material had an effect on the hardness, friability, and disintegration of tablets, as well as their height. The use of spraying technique enhanced flow properties of the prepared mixtures, increased hardness values, decreased friability, and improved homogeneity of the final dosage form. PMID:26075249

  10. Visual investigation of solid-liquid phase equilibria for nonflammable mixed refrigerant

    NASA Astrophysics Data System (ADS)

    Lee, C.; Yoo, J.; Park, I.; Park, J.; Cha, J.; Jeong, S.

    2015-12-01

    Non-flammable mixed refrigerant (NF-MR) Joule Thomson (J-T) refrigerators have desirable characteristics and wide cooling temperature range compared to those of pure J-T refrigerators. However, the operating challenge due to freezing is a critical issue to construct this refrigerator. In this paper, the solid-liquid phase equilibria (i.e. freezing point) of the NF-MR which is composed of Argon, R14 (CF4), and R218 (C3F8), has been experimentally investigated by a visualized apparatus. Argon, R14 and R218 mixtures are selected to be effectively capable of reaching 100 K in the MR J-T refrigerator system. Freezing points of the mixtures have been measured with the molar compositions from 0.1 to 0.8 for each component. Each test result is simultaneously acquired by a camcorder for visual inspection and temperature measurement during a warming process. Experimental results show that the certain mole fraction of Argon, R14, and R218 mixture can achieve remarkably low freezing temperature even below 77 K. This unusual freezing point depression characteristic of the MR can be a useful information for designing a cryogenic MR J-T refrigerator to reach further down to 77 K.

  11. Liquid phase exfoliation of 2D layered materials and their application

    NASA Astrophysics Data System (ADS)

    Winchester, Andrew J.

    In this work, several materials possessing a layered structure were investigated using a technique of exfoliation in liquid phase to produce few- to mono-layers of the material. Materials exfoliated in such a way included graphite, boron nitride, molybdenum disulfide and tungsten disulfide. Subsequent transmission electron microscopy and accompanying electron diffraction patterns revealed that few and mono layer forms of these materials have been realized through this exfoliation method. Ultraviolet-visible spectroscopy confirmed the shifting of the band gaps in molybdenum and tungsten disulfides that is predicted in reducing the number of layers of these materials and was also used to confirm the band gap of the boron nitride. As a potential application, exfoliated molybdenum disulfide was used in the construction of electrodes for electrical charge storage in an electrochemical double layer capacitor, or supercapacitor, style device. Cyclic voltammetry, galvanostatic charge discharge, and electrochemical impedance spectroscopy measurements were performed using three different electrolytes, which showed good capacitive behavior for these devices. Using the data from electrochemical impedance spectroscopy, equivalent circuit models were generated to represent the systems in different electrolytes. From this, it was determined that the capacitive behavior of these systems was partially diffusion limited.

  12. Vector chiral spin liquid phase in quasi-one-dimensional incommensurate helimagnets

    SciTech Connect

    Cinti, Fabio; Cuccoli, Alessandro; Rettori, Angelo

    2011-05-01

    Making use of detailed classical Monte Carlo simulations, we study the critical properties of a two-dimensional planar spin model on a square lattice composed by weakly interacting helimagnetic chains. We find a large temperature window where the vector chirality order parameter, <{kappa}{sub jk}> = , the key quantity in multiferroic systems, takes nonzero value in the absence of long-range order or quasi-long-range order. The phase diagram we obtain for different strengths of the interchain coupling clearly shows that the weakness of the interchain interaction plays an essential role in order to observe the vector chiral spin liquid phase in a temperature range of up to now unattained width ({approx_equal}7%, to be compared with {approx_equal}1% or less previously reported for fully frustrated models, the only well-investigated systems unambiguously displaying spin-chirality decoupling). The relevance of our results for three-dimensional models is also discussed.

  13. Liquid-phase reactions induced by atmospheric pressure glow discharge with liquid electrode

    NASA Astrophysics Data System (ADS)

    Tochikubo, Fumiyoshi; Shirai, Naoki; Uchida, Satoshi

    2014-12-01

    We experimentally investigated some of the initial reactions in a liquid induced by electron or positive-ion irradiation from an atmospheric-pressure dc glow discharge in contact with the liquid. We used an H-shaped glass reactor to observe the effects of electron irradiation and positive-ion irradiation on the liquid-phase reaction separately and simultaneously. Aqueous solutions of NaCl, AgNO3, HAuCl4, and FeCl2 are used as the electrolyte. Solutions of AgNO3 and HAuCl4 are used for the generation of Ag and Au nanoparticles, respectively. Solution of FeCl2 is used for the generation of ferromagnetic particles. Experimental results showed that electron irradiation of the liquid surface generates OH- in water and that positive-ion irradiation of the liquid surface generates H+ in water even without the dissolution of gas-phase nitrogen oxide. A possible reaction process is qualitatively discussed. We also showed that the control of reductive and oxidative environment in the liquid is possible not only by the gas composition for the plasma generation but also by the liquid composition.

  14. Enhanced microbial degradation of humin-bound phenanthrene in a two-liquid-phase system.

    PubMed

    Zhang, Yinping; Wang, Fang; Wang, Congying; Hong, Qing; Kengara, Fredrick Orori; Wang, Tao; Song, Yang; Jiang, Xin

    2011-02-28

    Humin, the main component of soil organic matter, greatly influences the nonlinear sorption and desorption hysteresis of polycyclic aromatic hydrocarbons (PAHs) in soil. However, little is known about the bioavailability of PAHs bound to humin. In the present study, a phenanthrene (PHE)-degrading bacterial strain--PHE9--was isolated and identified as the genus Micrococcus. It was used to investigate the degradation of humin-bound PHE and PHE not bound to humin (non-humin PHE) in liquid mineral medium (MM) and in a two-liquid-phase system (TLPs). The results showed that in MM, about 66.84% of humin-bound PHE was degraded after 49 days, whereas almost all the non-humin PHE was degraded after 27 days. Compared to MM, the TLPs showed a much better efficacy in the removal of PHE, especially for humin-bound PHE: more than 97.28% of non-humin PHE was degraded in 11 days and over 85.62% of humin-bound PHE was degraded in 32 days. It could be concluded that most of humin-bound PHE could be degraded in the MM although humin decreased the bioavailability of PHE, whereas the application of TLPs could enhance the biodegradation of humin-bound PHE. PMID:21232850

  15. Preparation and Optical Properties of Spherical Inverse Opals by Liquid Phase Deposition Using Spherical Colloidal Crystals

    NASA Astrophysics Data System (ADS)

    Aoi, Y.; Tominaga, T.

    2013-03-01

    Titanium dioxide (TiO2) inverse opals in spherical shape were prepared by liquid phase deposition (LPD) using spherical colloidal crystals as templates. Spherical colloidal crystals were produced by ink-jet drying technique. Aqueous emulsion droplets that contain polystyrene latex particles were ejected into air and dried. Closely packed colloidal crystals with spherical shape were obtained. The obtained spherical colloidal crystals were used as templates for the LPD. The templates were dispersed in the deposition solution of the LPD, i.e. a mixed solution of ammonium hexafluorotitanate and boric acid and reacted for 4 h at 30 C. After the LPD process, the interstitial spaces of the spherical colloidal crystals were completely filled with titanium oxide. Subsequent heat treatment resulted in removal of templates and spherical titanium dioxide inverse opals. The spherical shape of the template was retained. SEM observations indicated that the periodic ordered voids were surrounded by titanium dioxide. The optical reflectance spectra indicated that the optical properties of the spherical titanium dioxide inverse opals were due to Bragg diffractions from the ordered structure. Filling in the voids of the inverse opals with different solvents caused remarkable changes in the reflectance peak.

  16. SOLID-LIQUID PHASE TRANSFER CATALYZED SYNTHESIS OF CINNAMYL ACETATE-KINETICS AND ANALYSIS OF FACTORS AFFECTING THE REACTION IN A BATCH REACTOR

    EPA Science Inventory

    The use of solid-liquid phase transfer catalysis has an advantage of carrying out reaction between two immiscible substrates, one in solid phase and the other in liquid phase, with high selectivity and at relatively low temperatures. In this study we investigated the synthesis ci...

  17. Gas-particle partitioning of semi-volatile organics on organic aerosols using a predictive activity coefficient model: analysis of the effects of parameter choices on model performance

    NASA Astrophysics Data System (ADS)

    Chandramouli, Bharadwaj; Jang, Myoseon; Kamens, Richard M.

    The partitioning of a diverse set of semivolatile organic compounds (SOCs) on a variety of organic aerosols was studied using smog chamber experimental data. Existing data on the partitioning of SOCs on aerosols from wood combustion, diesel combustion, and the α-pinene-O 3 reaction was augmented by carrying out smog chamber partitioning experiments on aerosols from meat cooking, and catalyzed and uncatalyzed gasoline engine exhaust. Model compositions for aerosols from meat cooking and gasoline combustion emissions were used to calculate activity coefficients for the SOCs in the organic aerosols and the Pankow absorptive gas/particle partitioning model was used to calculate the partitioning coefficient Kp and quantitate the predictive improvements of using the activity coefficient. The slope of the log K p vs. log p L0 correlation for partitioning on aerosols from meat cooking improved from -0.81 to -0.94 after incorporation of activity coefficients iγ om. A stepwise regression analysis of the partitioning model revealed that for the data set used in this study, partitioning predictions on α-pinene-O 3 secondary aerosol and wood combustion aerosol showed statistically significant improvement after incorporation of iγ om, which can be attributed to their overall polarity. The partitioning model was sensitive to changes in aerosol composition when updated compositions for α-pinene-O 3 aerosol and wood combustion aerosol were used. The octanol-air partitioning coefficient's ( KOA) effectiveness as a partitioning correlator over a variety of aerosol types was evaluated. The slope of the log K p- log K OA correlation was not constant over the aerosol types and SOCs used in the study and the use of KOA for partitioning correlations can potentially lead to significant deviations, especially for polar aerosols.

  18. Vapor-Liquid Phase Equilibria in the Multicomponent Systems Formed by Normal Alcohols and Esters of Ethanoic Acid

    NASA Astrophysics Data System (ADS)

    Suntsov, Yu. K.

    2008-02-01

    Boiling points of some multicomponent systems formed by aliphatic alcohols and esters of ethanoic acid were measured ebulliometrically at various pressures. The activity coefficients of solution components were calculated using the Wilson and Non-Random Two-Liquid equations. The computational results were verified experimentally.

  19. Activity coefficients and thermodynamic parameters for RbCl/CsCl + amide (acetamide, propanamide, and n-butanamide) + water system at 298.15 K.

    PubMed

    Jiang, Yucheng; Hu, Mancheng; Fan, Peng; Wang, Jianji; Zhuo, Kelei

    2005-10-22

    Electromotive force (emf) of the chemical cell without liquid-junction K-ISE | RbCl/CsCl ( m(E)) | ISE-Cl and K-ISE | RbCl/CsCl (m(E)), amide (m(N)) | ISE-Cl, have been measured at 298.15 K, where m(E)=(0.005 to 0.5) mol kg(-1) and m(N)= (0.05 to 3.0) mol kg(-1). The activity coefficients of RbCl/CsCl in amide (acetamide, propanamide, and n-butanamide) + water mixture can be obtained from these electromotive force data and in the mean time the Gibbs free energy interaction parameters of RbCl/CsCl + amide pair in water, g(EN), as well as the salt constant, k(S), can be evaluated. The results show that both g(EN)>0, k(S)>0 at 298.15 K, and all the activity coefficients of electrolyte in amide + water mixture increase with increasing the m(N), but it is a little complicated for the dependence of activity coefficients on m(E). These thermodynamic parameters were discussed in terms of a model of the structural interaction and electrostatic interaction and the dependence of them on the number of carbon atoms in amide as well as the radius of metal ions were interpreted by the group additivity principle. PMID:16039039

  20. On-Chip Pressure Generation for Driving Liquid Phase Separations in Nanochannels.

    PubMed

    Xia, Ling; Choi, Chiwoong; Kothekar, Shrinivas C; Dutta, Debashis

    2016-01-01

    In this Article, we describe the generation of pressure gradients on-chip for driving liquid phase separations in submicrometer deep channels. The reported pressure-generation capability was realized by applying an electrical voltage across the interface of two glass channel segments with different depths. A mismatch in the electroosmotic flow rate at this junction led to the generation of pressure-driven flow in our device, a fraction of which was then directed to an analysis channel to carry out the desired separation. Experiments showed the reported strategy to be particularly conducive for miniaturization of pressure-driven separations yielding flow velocities in the separation channel that were nearly unaffected upon scaling down the depth of the entire fluidic network. Moreover, the small dead volume in our system allowed for high dynamic control over this pressure gradient, which otherwise was challenging to accomplish during the sample injection process using external pumps. Pressure-driven velocities up to 3.1 mm/s were realized in separation ducts as shallow as 300 nm using our current design for a maximum applied voltage of 3 kV. The functionality of this integrated device was demonstrated by implementing a pressure-driven ion chromatographic analysis that relied on analyte interaction with the nanochannel surface charges to yield a nonuniform solute concentration across the channel depth. Upon coupling such analyte distribution to the parabolic pressure-driven flow profile in the separation duct, a mixture of amino acids could be resolved. The reported assay yielded a higher separation resolution compared to its electrically driven counterpart in which sample migration was realized using electroosmosis/electrophoresis. PMID:26636608

  1. Determination of bile acids by hollow fibre liquid-phase microextraction coupled with gas chromatography.

    PubMed

    Ghaffarzadegan, T; Nyman, M; Jnsson, J ; Sandahl, M

    2014-01-01

    A method based on hollow-fibre liquid phase microextraction combined with gas chromatography was developed for determination of specific bile acids in caecal materials of rats. Nine unconjugated bile acids, including the primary bile acids (cholic acid, chenodeoxycholic acid and ?-muricholic acid) and the secondary bile acids (lithocholic acid, deoxycholic acid, ursodeoxycholic acid, hyodeoxycholic acid, ?-muricholic acid and ?-muricholic acid) were quantified. Extraction conditions were evaluated, including: sample pH, type of organic solvent and amount of caecal material to be extracted. To compensate for sample matrix effects during extraction the method of standard addition was applied. The satisfactory linearity (r(2)>0.9840), high recovery (84.2-108.7%) and good intra-assay (6.3-10.6%) and inter-assay (6.9-11.1%) precision illustrated the good performance of the present method. The method is rapid, simple and capable of detecting and determining bile acids with limit of detection (LOD) ranged from 0.002 to 0.067?g/mL and limits of quantification (LOQ) varied from 0.006 to 0.224?g/mL. The results indicated that the concentration of some secondary bile acids, which usually are associated with health problems, were lower in rats fed with fermentable dietary fibre compared with a fibre free control diet, while the concentration of primary bile acids, usually connected with positive health effects, were higher in rats fed with diets containing dietary fibre. Of the dietary fibres, guar gum and to some extent the mixture of pectin+guar gum had the most positive effects. Thus, it was concluded that the composition of bile acids can be affected by the type of diet. PMID:24295906

  2. Liquid-Phase Exfoliation of Phosphorene: Design Rules from Molecular Dynamics Simulations.

    PubMed

    Sresht, Vishnu; Pádua, Agílio A H; Blankschtein, Daniel

    2015-08-25

    The liquid-phase exfoliation of phosphorene, the two-dimensional derivative of black phosphorus, in the solvents dimethyl sulfoxide (DMSO), dimethylformamide (DMF), isopropyl alcohol, N-methyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone is investigated using three molecular-scale "computer experiments". We modeled solvent-phosphorene interactions using an atomistic force field, based on ab initio calculations and lattice dynamics, that accurately reproduces experimental mechanical properties. We probed solvent molecule ordering at phosphorene/solvent interfaces and discovered that planar molecules such as N-methyl-2-pyrrolidone preferentially orient parallel to the interface. We subsequently measured the energy required to peel a single phosphorene monolayer from a stack of black phosphorus and analyzed the role of "wedges" of solvent molecules intercalating between phosphorene sheets in initiating exfoliation. The exfoliation efficacy of a solvent is enhanced when either molecular planarity "sharpens" this molecular wedge or strong phosphorene-solvent adhesion stabilizes the newly exposed phosphorene surfaces. Finally, we examined the colloidal stability of exfoliated flakes by simulating their aggregation and showed that dispersion is favored when the cohesive energy between the molecules in the solvent monolayer confined between the phosphorene sheets is high (as with DMSO) and is hindered when the adhesion between these molecules and phosphorene is strong; the molecular planarity in solvents like DMF enhances the cohesive energy. Our results are consistent with, and provide a molecular context for, experimental exfoliation studies of phosphorene and other layered solids, and our molecular insights into the significant role of solvent molecular geometry and ordering should complement prevalent solubility-parameter-based approaches in establishing design rules for effective nanomaterial exfoliation media. PMID:26192620

  3. Liquid-phase processing of fast pyrolysis bio-oil using platinum/HZSM-5 catalyst

    NASA Astrophysics Data System (ADS)

    Santos, Bjorn Sanchez

    Recent developments in converting biomass to bio-chemicals and liquid fuels provide a promising sight to an emerging biofuels industry. Biomass can be converted to energy via thermochemical and biochemical pathways. Thermal degradation processes include liquefaction, gasification, and pyrolysis. Among these biomass technologies, pyrolysis (i.e. a thermochemical conversion process of any organic material in the absence of oxygen) has gained more attention because of its simplicity in design, construction and operation. This research study focuses on comparative assessment of two types of pyrolysis processes and catalytic upgrading of bio-oil for production of transportation fuel intermediates. Slow and fast pyrolysis processes were compared for their respective product yields and properties. Slow pyrolysis bio-oil displayed fossil fuel-like properties, although low yields limit the process making it uneconomically feasible. Fast pyrolysis, on the other hand, show high yields but produces relatively less quality bio-oil. Catalytic transformation of the high-boiling fraction (HBF) of the crude bio-oil from fast pyrolysis was therefore evaluated by performing liquid-phase reactions at moderate temperatures using Pt/HZSM-5 catalyst. High yields of upgraded bio-oils along with improved heating values and reduced oxygen contents were obtained at a reaction temperature of 200°C and ethanol/HBF ratio of 3:1. Better quality, however, was observed at 240 °C even though reaction temperature has no significant effect on coke deposition. The addition of ethanol in the feed has greatly attenuated coke deposition in the catalyst. Major reactions observed are esterification, catalytic cracking, and reforming. Overall mass and energy balances in the conversion of energy sorghum biomass to produce a liquid fuel intermediate obtained sixteen percent (16 wt.%) of the biomass ending up as liquid fuel intermediate, while containing 26% of its initial energy.

  4. Microstructural study of transient liquid phase bonded DD98 and K465 superalloys at high temperature

    SciTech Connect

    Liu Jide Jin Tao; Zhao Nairen; Wang Zhihui; Sun Xiaofeng; Guan Hengrong; Hu Zhuangqi

    2011-05-15

    Microstructure of a transient liquid phase (TLP) bonded joint between single crystal DD98 and polycrystalline K465 superalloys was investigated by scanning electron microscopy, transmission electron microscopy and X-ray diffraction techniques. After bonding at 1190 deg. C for 2 h, many phases formed in the centerline of the bonding zone due to an incompletely solidified liquid interlayer. There are script-like, tree-like and blocky compounds besides solid solution {gamma} phase in this region. The script-like phase is CrB boride that is rich in Cr, the tree-like compound rich in Ni is M{sub 23}B{sub 6} with FCC structure, and the blocky phase enriched in Ti, Ta, and Nb, is MC carbide that resulted from the interdiffusion of C atoms between dissimilar base metals. After TLP bonding, many blocky and fine M{sub 6}C particles rich in Cr and W appeared in the diffusion zone of the K465 side. A number of blocky and platelet M{sub 3}B{sub 2} borides rich in W, Cr and Mo precipitated in the diffusion zone of the DD98 side. - Research Highlights: {yields} DD98 and K465 alloy was TLP bonded. {yields} The microstructure changes of different parts were studied. {yields} CrB, M{sub 23}B{sub 6} and MC formed in the bonding zone. {yields} M{sub 6}C appeared in diffusion zone of K465 side and M{sub 3}B{sub 2} existed in diffusion zone of DD98 side.

  5. Transient-liquid-phase (TLP) bonding of aluminum trioxide using niobium-based multilayer interlayers

    NASA Astrophysics Data System (ADS)

    Hong, Sung Moo

    Transient-liquid-phase (TLP) bonding was used to join high-strength, high-purity Al2O3 ceramic. This method uses a multilayer interlayer (B/A/B sandwich structure), which forms thin transient-liquid layers between the Al2O3 and the refractory core layer (A), then isothermally solidifies through a diffusive mechanism. The presence of thin liquid layers allow interfacial gaps and voids to be filled, while allowing bonding times comparable to those used for conventional brazing. It was shown that TLP bonding produces high-strength joints with re-melt temperatures that are significantly higher than the bonding temperatures used. This study explores the interrelationships between the processing conditions, fracture strengths of the joints, wetting behavior of the TLP, and the diffusion/isothermal solidification kinetics. In particular, when Ni/Nb/Ni interlayers were utilized, four-point bend tests revealed that the fracture strengths of the joints matched those of the monolithic Al2O3, even after a 5-min holding time at 1400C, the bonding temperature. The resulting interlayer consists of >99% Nb, which has a melting point >2000C. Sessile-drop wetting experiments revealed that the Ni-Nb liquid alloy formed during bonding exhibits relatively low contact angles (?90) on Al2O3, which enables the formation of nearly flaw-free interfaces. An analytical diffusion calculation model was also used to describe the isothermal-solidification and homogenization kinetics, and will be used in future studies to aid new interlayer designs.

  6. Three-Dimensional Graphene-Based Microbarriers for Controlling Release and Reactivity in Colloidal Liquid Phases.

    PubMed

    Creighton, Megan A; Zhu, Wenpeng; van Krieken, Finn; Petteruti, Robert A; Gao, Huajian; Hurt, Robert H

    2016-02-23

    Two-dimensional materials are of great interest as high-performance molecular barriers. Graphene in particular is atomically thin, is impermeable to all molecules, and in some forms can be easily deposited over large areas into planar multilayer films that have been shown to suppress molecular transport. Graphene and graphene oxide sheets are also known to spontaneously self-assemble at liquid-liquid interfaces on the surfaces of dispersed droplets, but much less is known about the barrier properties of these ultrathin films in 3D curved microgeometries. This article demonstrates that 3D films self-assembled from graphene oxide or reduced graphene oxide sheets can be exploited to control the release of small molecules from dispersed liquid phase droplets by evaporation. The release rate and containment time can be tuned by addition of multivalent cations that recruit additional sheets from the bulk liquid to the interface, which is shown by molecular dynamics to occur by an electrostatic bridging mechanism. 3D graphene-based films on droplet surfaces can also be used to control the release and transport of soluble molecules from the droplet to surrounding bulk solvent phases. In some cases, the release can be effectively stopped to produce unique kinetically trapped emulsion phases consisting of two fully miscible but segregated liquids. Finally, interfacial graphene-based films are also shown to control interfacial chemical reaction processes by serving as transport barriers between the phases or by intercepting reactive cross-phase molecular collisions. This reaction control is demonstrated by using 3D graphene-based microbarriers to protect oxidation-sensitive oils from attack by aqueous-phase reactive oxygen species, which is an undesirable pathway implicated in many chemical product degradation and spoilage processes. PMID:26775824

  7. Interplay of the Glass Transition and the Liquid-Liquid Phase Transition in Water

    NASA Astrophysics Data System (ADS)

    Giovambattista, Nicolas

    2013-03-01

    Most liquids can form a single glass or amorphous state when cooled sufficiently fast (in order to prevent crystallization). However, there are a few substances that are relevant to scientific and technological applications which can exist in at least two different amorphous states, a property known as polyamorphism. Examples include silicon, silica, and in particular, water. In the case of water, experiments show the existence of a low-density (LDA) and high-density (HDA) amorphous ice that are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation evolves into a first-order liquid-liquid phase transition (LLPT) at temperatures above the glass transition temperature Tg. However, obtaining direct experimental evidence of the LLPT has been challenging since the LLPT occurs at conditions where water rapidly crystallizes. In this talk, I will (i) discuss the general phenomenology of polyamorphism in water and its implications, and (ii) explore the effects of a LLPT on the pressure dependence of Tg(P) for LDA and HDA. Our study is based on computer simulations of two water models - one with a LLPT (ST2 model), and one without (SPC/E model). In the absence of a LLPT, Tg(P) for all glasses nearly coincide. Instead, when there is a LLPT, different glasses exhibit dramatically different Tg(P) loci which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario that includes a LLPT (ST2 model) and hence, our results support the view that a LLPT may exist for the case of water.

  8. Thermophysical Properties of a Chromium Nickel Molybdenum Steel in the Solid and Liquid Phases

    NASA Astrophysics Data System (ADS)

    Wilthan, B.; Reschab, H.; Tanzer, R.; Schützenhöfer, W.; Pottlacher, Gernot

    2008-02-01

    Numerical simulation of vacuum arc re-melting, pressurized or protective electro-slag re-melting, and ingot casting have become quite important in the metal industry. However, a major drawback of these simulation techniques is the lack of accurate thermophysical properties for temperatures above 1,500 K. Heat capacity, heat of fusion, density, and thermal conductivity are important input parameters for the heat transfer equation. Since, direct measurements of thermal conductivity of alloys in the liquid state are almost impossible, its estimation from electrical conductivity using the Wiedemann Franz law is very useful. The afore-mentioned thermophysical properties of several steels are investigated within the context of an ongoing project. Here, we present a full set of thermophysical data for the chromium nickel molybdenum steel meeting the standard DIN 1.4435 (X2CrNiMo18-14-3); these values will be used by our partner to simulate various re-melting and solidification processes. Wire-shaped samples of the steel are resistively volume-heated, as part of a fast capacitor discharge circuit. Time-resolved measurements with sub-μs resolution of current through the specimen are performed with a Pearson probe. The voltage drop across the specimen is measured with knife-edge contacts and ohmic voltage dividers, the temperature of the sample with a pyrometer, and the volumetric expansion of the wire with a fast acting CCD camera. These measurements enable the heat of fusion, the heat capacity, and the electrical resistivity to be determined as a function of temperature in the solid and liquid phases. The thermal conductivity and thermal diffusivity are estimated via the Wiedemann Franz law.

  9. High purity liquid phase epitaxial GaAs for radiation detectors

    SciTech Connect

    Wynne, D.I.; Haller, E.E.; Rossington Tull, C.S.

    1998-12-31

    The authors report on the growth of high purity n-GaAs using Liquid Phase Epitaxy (LPE) and the fabrication of room temperature p-i-n radiation detectors. The epilayers are grown from a Ga solvent in a graphite boat in a pure hydrogen atmosphere. Growth is started at a temperature of approximately 800 C. The best epilayers show a net-residual-donor concentration of 2 {times} 10{sup 13} cm{sup {minus}3}, confirmed by Hall effect measurements. The residual donors have been analyzed by far infrared spectroscopy and found to be sulfur and silicon. Epilayers with thicknesses of up to 120 {micro}m have been deposited on 650 {micro}m thick semi-insulating GaAs substrates and on 500 {micro}m thick n{sup +}-type GaAs substrates. The authors report the results obtained with Schottky barrier diodes fabricated from these high purity n-type GaAs epilayers and operated as X-ray detectors. The Schottky barrier contacts consisted of evaporated circular gold contacts on epilayers on n{sup +} substrates. The ohmic contacts were formed by evaporated and alloyed Ni-Ge-Au films on the back of the substrate. Several of the diodes exhibit currents of the order of 1 to 10 nA at reverse biases depleting approximately 50 {micro}m of the epilayer. This very encouraging result, demonstrating the possibility for fabricating GaAs p-i-n diodes with depletion layers in high purity GaAs instead of semi-insulating GaAs, is supported by similar results obtained by several other groups. The consequences of using high purity instead of semi-insulating GaAs will be much reduced charge carrier trapping. Diode electrical characteristics and detector performance results using {sup 55}Fe and {sup 241}Am radiation will be discussed.

  10. Novel Approach to Space-survivable Polyimides: Liquid Phase Deposition of Titania Coating on Kapton

    NASA Astrophysics Data System (ADS)

    Gouzman, Irina; Gershevitz, Olga; Grossman, Eitan; Eliaz, Noam; Sukenik, Chaim N.

    2009-01-01

    Polyimides are widely used as spacecraft external surfaces materials. They are exposed to atomic oxygen (AO), which is the main constituent of a residual atmosphere at low Earth orbit (LEO) and should be protected from the space harsh environment. This work presents an innovative approach to applying a protective coating on Kapton polyimide using liquid-phase deposition (LPD) and shows its effectiveness in reduction of AO-induced surface erosion. Titania coatings, 100 nm thick, were deposited on Kapton films by LPD using an aqueous solution of a metal-fluoride complex and boric acid at near ambient conditions. Adherent, crack-free, coatings have been obtained by optimization of the deposition conditions, the substrate surface pre-treatment procedure and post-deposition drying. Characterization of the oxide coating included Atomic Force Microscopy (AFM) in tapping and nano-indentation modes, Environmental Scanning Electron Microscopy (ESEM), and X-ray Photoelectron Spectroscopy (XPS). The durability of the titania coating under AO attack was studied using a RF plasma based facility. Surface erosion was measured both gravimetrically and by in situ Quartz Crystal Microbalance (QCM) measurements of mass loss. A dramatic reduction in the erosion of titania-coated Kapton relative to uncoated Kapton was observed: the erosion yield was as low as 2% of that of uncoated Kapton after exposure to 41020 O-atoms?cm-2 of LEO equivalent AO fluence. In addition, the surface hardness of coated Kapton was improved both in the as-deposited titania coatings and in the AO-exposed titania films.

  11. Unusual liquid-liquid phase transition in aqueous mixtures of a well-known dendrimer.

    PubMed

    da Costa, Viviana C P; Annunziata, Onofrio

    2015-11-21

    Liquid-liquid phase separation (LLPS) has been extensively investigated for polymer and protein solutions due to its importance in mixture thermodynamics, separation science and self-assembly processes. However, to date, no experimental studies have been reported on LLPS of dendrimer solutions. Here, it is shown that LLPS of aqueous solutions containing a hydroxyl-functionalized poly(amido amine) dendrimer of fourth generation is induced in the presence of sodium sulfate. Both the LLPS temperature and salt-dendrimer partitioning between the two coexisting phases at constant temperature were measured. Interestingly, our experiments show that LLPS switches from being induced by cooling to being induced by heating as the salt concentration increases. The two coexisting phases also show opposite temperature response. Thus, this phase transition exhibits a simultaneous lower and upper critical solution temperature-type behavior. Dynamic light-scattering and dye-binding experiments indicate that no appreciable conformational change occurs as the salt concentration increases. To explain the observed phase behavior, a thermodynamic model based on two parameters was developed. The first parameter, which describes dendrimer-dendrimer interaction energy, was determined by isothermal titration calorimetry. The second parameter describes the salt salting-out strength. By varying the salting-out parameter, it is shown that the model achieves agreement not only with the location of the experimental binodal at 25 °C but also with the slope of this curve around the critical point. The proposed model also predicts that the unusual temperature behavior of this phase transition can be described as the net result of two thermodynamic factors with opposite temperature responses: salt thermodynamic non-ideality and salting-out strength. PMID:26451401

  12. Measurement of residence time distribution of liquid phase in an industrial-scale continuous pulp digester using radiotracer technique.

    PubMed

    Sheoran, Meenakshi; Goswami, Sunil; Pant, Harish J; Biswal, Jayashree; Sharma, Vijay K; Chandra, Avinash; Bhunia, Haripada; Bajpai, Pramod K; Rao, S Madhukar; Dash, A

    2016-05-01

    A series of radiotracer experiments was carried out to measure residence time distribution (RTD) of liquid phase (alkali) in an industrial-scale continuous pulp digester in a paper industry in India. Bromine-82 as ammonium bromide was used as a radiotracer. Experiments were carried out at different biomass and white liquor flow rates. The measured RTD data were treated and mean residence times in individual digester tubes as well in the whole digester were determined. The RTD was also analyzed to identify flow abnormalities and investigate flow dynamics of the liquid phase in the pulp digester. Flow channeling was observed in the first section (tube 1) of the digester. Both axial dispersion and tanks-in-series with backmixing models preceded with a plug flow component were used to simulate the measured RTD and quantify the degree of axial mixing. Based on the study, optimum conditions for operating the digester were proposed. PMID:26896681

  13. Phosphate removal ability of biochar/MgAl-LDH ultra-fine composites prepared by liquid-phase deposition.

    PubMed

    Zhang, Ming; Gao, Bin; Yao, Ying; Inyang, Mandu

    2013-08-01

    Morphological structures and adsorption properties of biochar/MgAl-LDH ultra-fine composites prepared by liquid-phase deposition have been determined in laboratory. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDS), and Fourier transform infrared (FTIR) were used to characterize the biochar based ultra-composites. The XRD and FTIR data indicated that the biochar/MgAl-LDHs ultra-fine composites can successfully be obtained by liquid-phase deposition. The SEM images showed the dispersion of colloidal and nanosized LDH flakes on the carbon surfaces within the biochar matrix. The thickness and size of single LDH platelet are 20-40 nm and 100-300 nm. Batch sorption experiments were also conducted and the results indicated that the biochar/MgAl-LDHs ultra-fine composites is an effective sorbent for the removal of phosphate from aqueous solutions. PMID:23545188

  14. Elastic constants and ultrasound attenuation in the spin-liquid phase of Cs2CuCl4

    NASA Astrophysics Data System (ADS)

    Streib, S.; Kopietz, P.; Cong, P. T.; Wolf, B.; Lang, M.; van Well, N.; Ritter, F.; Assmus, W.

    2015-01-01

    The spin excitations in the spin-liquid phase of the anisotropic triangular lattice quantum antiferromagnet Cs2CuCl4 have been shown to propagate dominantly along the crystallographic b axis. To test this dimensional reduction scenario, we have performed ultrasound experiments in the spin-liquid phase of Cs2CuCl4 probing the elastic constant c22 and the sound attenuation along the b axis as a function of an external magnetic field along the a axis. We show that our data can be quantitatively explained within the framework of a nearest-neighbor spin-1 /2 Heisenberg chain, where fermions are introduced via the Jordan-Wigner transformation and the spin-phonon interaction arises from the usual exchange-striction mechanism.

  15. Ground-state and finite-temperature properties of spin liquid phase in the J1-J2 honeycomb model

    NASA Astrophysics Data System (ADS)

    Yu, Xiang-Long; Liu, Da-Yong; Li, Peng; Zou, Liang-Jian

    2014-05-01

    In this paper we analyze the groundstate and finite-temperature properties of a frustrated Heisenberg J1-J2 model on a honeycomb lattice by employing the Schwinger boson technique. The phase diagram and spin gap as functions of J2/J1 are presented, showing that the exotic spin liquid phase lies in 0.21liquid phase for further experiments.

  16. Double multiple-relaxation-time lattice Boltzmann model for solid-liquid phase change with natural convection in porous media

    NASA Astrophysics Data System (ADS)

    Liu, Qing; He, Ya-Ling

    2015-11-01

    In this paper, a double multiple-relaxation-time lattice Boltzmann model is developed for simulating transient solid-liquid phase change problems in porous media at the representative elementary volume scale. The model uses two different multiple-relaxation-time lattice Boltzmann equations, one for the flow field and the other for the temperature field with nonlinear latent heat source term. The model is based on the generalized non-Darcy formulation, and the solid-liquid interface is traced through the liquid fraction which is determined by the enthalpy-based method. The present model is validated by numerical simulations of conduction melting in a semi-infinite space, solidification in a semi-infinite corner, and convection melting in a square cavity filled with porous media. The numerical results demonstrate the efficiency and accuracy of the present model for simulating transient solid-liquid phase change problems in porous media.

  17. Magnetic Properties of Liquid-Phase Sintered CoFe2O4 for Application in Magnetoelastic and Magnetoelectric Transducers

    PubMed Central

    de Brito, Vera Lcia Othro; Cunha, Stphanie Al; Lemos, Leonardo Violim; Nunes, Cristina Bormio

    2012-01-01

    Cobalt ferrite is a ferrimagnetic magnetostrictive ceramic that has potential application in magnetoelastic and magnetoelectric transducers. In this work, CoFe2O4 was obtained using a conventional ceramic method and Bi2O3 was used as additive in order to obtain liquid-phase sintered samples. Bi2O3 was added to the ferrite in amounts ranging from 0.25 mol% to 0.45 mol% and samples were sintered at 900 C and 950 C. It was observed the presence of Bi-containing particles in the microstructure of the sintered samples and the magnetostriction results indicated microstructural anisotropy. It was verified that it is possible to get dense cobalt ferrites, liquid-phase sintered, with relative densities higher than 90% and with magnetostriction values very close to samples sintered without additives. PMID:23112589

  18. Elastic constants and ultrasound attenuation in the spin-liquid phase of Cs2CuCl4

    NASA Astrophysics Data System (ADS)

    Streib, Simon; Kopietz, Peter; Cong, Pham Thanh; Wolf, Bernd; Lang, Michael; van Well, Natalija; Ritter, Franz; Assmus, Wolf

    2015-03-01

    The spin excitations in the spin-liquid phase of the anisotropic triangular lattice quantum antiferromagnet Cs2CuCl4 have been shown to propagate dominantly along the crystallographic b-axis. To test this dimensional reduction scenario, we have performed ultrasound experiments in the spin-liquid phase of Cs2CuCl4 probing the elastic constant c22 and the sound attenuation along the b-axis as a function of an external magnetic field along the a-axis. We show that our data can be quantitatively explained within the framework of a nearest neighbor spin- 1 / 2 Heisenberg chain, where fermions are introduced via the Jordan-Wigner transformation and the spin-phonon interaction arises from the usual exchange-striction mechanism. Financial support by the DFG via SFB/TRR49 is gratefully acknowledged.

  19. Liquid phase epitaxy of binary III–V nanocrystals in thin Si layers triggered by ion implantation and flash lamp annealing

    SciTech Connect

    Wutzler, Rene Rebohle, Lars; Prucnal, Slawomir; Bregolin, Felipe L.; Hübner, Rene; Voelskow, Matthias; Helm, Manfred; Skorupa, Wolfgang

    2015-05-07

    The integration of III–V compound semiconductors in Si is a crucial step towards faster and smaller devices in future technologies. In this work, we investigate the formation process of III–V compound semiconductor nanocrystals, namely, GaAs, GaSb, and InP, by ion implantation and sub-second flash lamp annealing in a SiO{sub 2}/Si/SiO{sub 2} layer stack on Si grown by plasma-enhanced chemical vapor deposition. Raman spectroscopy, Rutherford Backscattering spectrometry, and transmission electron microscopy were performed to identify the structural and optical properties of these structures. Raman spectra of the nanocomposites show typical phonon modes of the compound semiconductors. The formation process of the III–V compounds is found to be based on liquid phase epitaxy, and the model is extended to the case of an amorphous matrix without an epitaxial template from a Si substrate. It is shown that the particular segregation and diffusion coefficients of the implanted group-III and group-V ions in molten Si significantly determine the final appearance of the nanostructure and thus their suitability for potential applications.

  20. Determination of lewisite constituents in aqueous samples using hollow-fibre liquid-phase microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    Cheh, M Y; Chua, H C; Hopkins, F B; Riches, J R; Timperley, C M; Lee, H S Nancy

    2014-08-01

    The applicability of hollow-fibre liquid-phase microextraction for extracting 2-chlorovinyldichloroarsine (lewisite 1), bis(2-chlorovinyl)chloroarsine (lewisite 2), tris(2-chlorovinyl)arsine (lewisite 3) and arsenic trichloride from aqueous samples is reported. Parameters affecting the extraction efficiency of these chemicals were optimised. These parameters included the type of derivatising agent, extraction solvent, derivatisation method, pH, ionic strength, stirring speed and extraction time. A linear range between 0.002 and 0.2 ?g/mL was established for the lewisites with good square regression coefficients (0.9955-0.9992). Good reproducibility with relative standard deviations (RSDs) from 8 to 10% was achieved. The limit of detection was 0.002 ?g/mL for the lewisites and 0.005 ?g/mL for arsenic trichloride (3:1 signal-to-noise ratio). The extraction method was validated with a proficiency test sample issued by the Organisation for the Prohibition of Chemical Weapons (OPCW). The rapidity and precision of the new method should help deter against the employment of lewisite as a chemical warfare agent: its use could be confirmed easily from analysis of aqueous samples. PMID:24633588

  1. Quantification of tetramethyl-terephthalic acid in rat liver, spleen and urine matrices by liquid-liquid phase extraction and HPLC-photodiode array detection.

    PubMed

    Baati, Tarek; Horcajada, Patricia; David, Olivier; Gref, Ruxandra; Couvreur, Patrick; Serre, Christian

    2012-01-01

    Tetramethyl-terephthalate (TMT) is the constitutive linker of the flexible porous iron(III) carboxylate Metal Organic Framework (MOF) MIL-88B_4CH? based drug nanocarrier (MIL stands for Material from Institut Lavoisier). A method for the determination of the concentration of tetramethyl-terephthalic acid has been developed in different biological rat matrices (liver, spleen and urine) using a liquid-liquid phase extraction and high-performance liquid chromatography (HPLC) coupled to photodiode array detection with 4-aminosalicylic acid as internal standard. The extraction conditions of TMT have been varied from urine to tissue depending on the complexity of the biological matrices. The chromatographic separation was performed with a gradient elution. In all matrices, the limits of detection and quantification of TMT was 0.01 and 0.05 ?g ml?, respectively. The recovery of the TMT reached 86, 89 and 97% for urine, spleen and liver tissues, respectively. The linearity of the calibration curves in urine and tissues was satisfactory in all cases as evidenced by correlation coefficients >0.990. The within-day and between-day precisions were <15% (n=6) and the accuracy ranged in all cases between 86 and 103%. This method has finally allowed the quantification of TMT in rat urine and in tissue samples of rats administered intravenously with iron(III) tetramethyltherepthalate MIL-88B_4CH? nanoparticles. PMID:22608098

  2. Liquid phase epitaxy of binary III-V nanocrystals in thin Si layers triggered by ion implantation and flash lamp annealing

    NASA Astrophysics Data System (ADS)

    Wutzler, Rene; Rebohle, Lars; Prucnal, Slawomir; Bregolin, Felipe L.; Hbner, Rene; Voelskow, Matthias; Helm, Manfred; Skorupa, Wolfgang

    2015-05-01

    The integration of III-V compound semiconductors in Si is a crucial step towards faster and smaller devices in future technologies. In this work, we investigate the formation process of III-V compound semiconductor nanocrystals, namely, GaAs, GaSb, and InP, by ion implantation and sub-second flash lamp annealing in a SiO2/Si/SiO2 layer stack on Si grown by plasma-enhanced chemical vapor deposition. Raman spectroscopy, Rutherford Backscattering spectrometry, and transmission electron microscopy were performed to identify the structural and optical properties of these structures. Raman spectra of the nanocomposites show typical phonon modes of the compound semiconductors. The formation process of the III-V compounds is found to be based on liquid phase epitaxy, and the model is extended to the case of an amorphous matrix without an epitaxial template from a Si substrate. It is shown that the particular segregation and diffusion coefficients of the implanted group-III and group-V ions in molten Si significantly determine the final appearance of the nanostructure and thus their suitability for potential applications.

  3. Effect of the particle size of a heterogeneous catalyst on the kinetics of liquid-phase oxidation of tetralin

    SciTech Connect

    Artemov, A.V.; Vainshtein, E.F.

    1988-01-10

    The dependence of the initial rate of oxidation of tetralin on the particle size of the Co/sup 2 +//SiO/sub 2/ catalyst is shown. The method proposed permitted explanation of the dependence of the kinetics of liquid-phase processes in the absence of extra- and intradiffusion hindrances on the particle size of a heterogeneous catalyst and estimation of the values of the kinetic constants from this dependence.

  4. Model of the primary rearrangement processes at liquid phase sintering and selective laser sintering due to biparticle interactions

    NASA Astrophysics Data System (ADS)

    Anestiev, L. A.; Froyen, L.

    1999-10-01

    A theoretical description of the rearrangement processes at selective laser sintering (SLS) and liquid phase sintering (LPS) is made. A general solution, based on the dimensional analysis and rigorous analytical solution of the equations governing the rearrangement process is obtained. The influence of the process parameters and the physicochemical properties of the sintered materials on the rearrangement processes at SLS and LPS is studied with the model developed. The obtained results are in good agreement with the available experimental data.

  5. Oxidative Dissolution of Transition Metals in a Liquid Phase. Role of Oxygen and of the Surface Oxide Layer

    NASA Astrophysics Data System (ADS)

    Lavrent'ev, I. P.; Khidekel', M. L.

    1983-04-01

    The results of recent studies of the oxidative dissolution of transition metals in a liquid phase are generalised, and an analysis of the role of molecular oxygen and of the oxide film on the metal surface in oxidation processes in donor-acceptor organic media is proposed. The prospects of oxidative dissolution as a direct (single-stage) method of preparation of transition metal complexes are examined. 115 references.

  6. Soot and liquid-phase fuel distributions in a newly designed optically accessible D.I. diesel engine

    SciTech Connect

    Dec, J.E.; Espey, C.

    1993-10-01

    Two-dimensional (2-D) laser-sheet imaging has been used to examine the soot and liquid-phase fuel distributions in a newly designed, optically accessible, direct-injection Diesel engine of the heavy-duty size class. The design of this engine preserves the intake port geometry and basic dimensions of a Cummins N-series production engine. It also includes several unique features to provide considerable optical access. Liquid-phase fuel and soot distribution studies were conducted at a medium speed (1,200 rpm) using a Cummins closed-nozzle fuel injector. The scattering was used to obtain planar images of the liquid-phase fuel distribution. These images show that the leading edge of the liquid-phase portion of the fuel jet reaches a maximum length of 24 mm, which is about half the combustion bowl radius for this engine. Beyond this point virtually all the fuel has vaporized. Soot distribution measurements were made at a high load condition using three imaging diagnostics: natural flame luminosity, 2-D laser-induced incandescence, and 2-D elastic scattering. This investigation showed that the soot distribution in the combusting fuel jet develops through three stages. First, just after the onset of luminous combustion, soot particles are small and nearly uniformly distributed throughout the luminous region of the fuel jet. Second, after about 2 crank angle degrees a pattern develops of a higher soot concentration of larger sized particles in the head vortex region of the jet and a lower soot concentration of smaller sized particles upstream toward the injector. Third, after fuel injection ends, both the soot concentration and soot particle size increase rapidly in the upstream portion of the fuel jet.

  7. A rotor unbalance response based approach to the identification of the closed-loop stiffness and damping coefficients of active magnetic bearings

    NASA Astrophysics Data System (ADS)

    Zhou, Jin; Di, Long; Cheng, Changli; Xu, Yuanping; Lin, Zongli

    2016-01-01

    The stiffness and damping coefficients of active magnetic bearings (AMBs) have direct influence on the dynamic response of a rotor bearing system, including the bending critical speeds, modes of vibrations and stability. Rotor unbalance response is informative in the identification of these bearing support parameters. In this paper, we propose a method for identifying closed-loop AMB stiffness and damping coefficients based on the rotor unbalance response. We will use a flexible rotor-AMB test rig to help describe the proposed method as well as to validate the identification results. First, based on a rigid body model of the rotor, a formula is derived that computes the nominal values of the bearing stiffness and damping coefficients at a given rotating speed from the experimentally measured rotor unbalance response at the given speed. Then, based on a finite element model of the rotor, an error response surface is constructed for each parameter to estimate the identification errors induced by the rotor flexibility. The final identified values of the stiffness and damping coefficients equal the sums of the nominal values initially computed from the unbalance response and the identification errors determined by the error response surfaces. The proposed identification method is carried out on the rotor-AMB test rig. In order to validate the identification results, the identified values of the closed-loop AMB stiffness and damping coefficients are combined with the finite element model of the rotor to form a full model of the rotor-AMB test rig, from which the model unbalance responses at various rotating speeds are determined through simulation and compared with the experimental measurements. The close agreements between the simulation results and the measurements validate the proposed identification method.

  8. Interaction potentials of anisotropic nanocrystals from the trajectory sampling of particle motion using in situ liquid phase transmission electron microscopy

    DOE PAGESBeta

    Chen, Qian; Cho, Hoduk; Manthiram, Karthish; Yoshida, Mark; Ye, Xingchen; Alivisatos, A. Paul

    2015-03-23

    We demonstrate a generalizable strategy to use the relative trajectories of pairs and groups of nanocrystals, and potentially other nanoscale objects, moving in solution which can now be obtained by in situ liquid phase transmission electron microscopy (TEM) to determine the interaction potentials between nanocrystals. Such nanoscale interactions are crucial for collective behaviors and applications of synthetic nanocrystals and natural biomolecules, but have been very challenging to measure in situ at nanometer or sub-nanometer resolution. Here we use liquid phase TEM to extract the mathematical form of interaction potential between nanocrystals from their sampled trajectories. We show the power ofmore » this approach to reveal unanticipated features of nanocrystal–nanocrystal interactions by examining the anisotropic interaction potential between charged rod-shaped Au nanocrystals (Au nanorods); these Au nanorods assemble, in a tip-to-tip fashion in the liquid phase, in contrast to the well-known side-by-side arrangements commonly observed for drying-mediated assembly. These observations can be explained by a long-range and highly anisotropic electrostatic repulsion that leads to the tip-selective attachment. As a result, Au nanorods stay unassembled at a lower ionic strength, as the electrostatic repulsion is even longer-ranged. Our study not only provides a mechanistic understanding of the process by which metallic nanocrystals assemble but also demonstrates a method that can potentially quantify and elucidate a broad range of nanoscale interactions relevant to nanotechnology and biophysics.« less

  9. Investigations of a new field in gas chromatography: capillary columns with a super-thick layer of stationary liquid phase.

    PubMed

    Berezkin, V G; Lapin, A B; Lipsky, J B

    2005-08-19

    Basic characteristics (efficiency, selectivity, non-equilibrium) of capillary columns with a super-thick layer of stationary liquid phase are investigated. In contrast to traditionally used capillary columns with standard stationary phase thickness of 0.1-0.5 um, some new variables are now established. Firstly, the values of relative retention depend on carrier gas linear velocity. Secondly, the asymmetry of chromatographic peaks increased in accordance with the increase in carrier gas velocity. Thirdly, it was theoretically and experimentally shown that dependence of the height equivalent to a theoretical plate (HETP) on carrier gas velocity is linear. The above noted variables are evidences that the new type of GC is realized under these conditions. The use of capillary columns with super-thick layer of stationary liquid phase is practical when the following problems have to be solved: (1) Separation of highly volatile substances; (2) Preliminary concentration of trace compounds from strong diluted samples; (3) Improvements in measurement and accuracy due to the advantages of splitless injection into wide bore columns with super-thick films. Solutions to some analytical tasks while using super-thick stationary liquid phase are shown: (1) Large volume injection into capillary column with sample transfer speed up to 100 microL min(-1); (2) Isothermal splitless injection; (3) Separation of low boiling compounds; (4) Separation of polar substances (alcohols). PMID:16114231

  10. Entrapment of Ba-Cu-O liquid phase during growth of a Y 1Ba 2Cu 3O 7- y domain

    NASA Astrophysics Data System (ADS)

    Kim, Chan-Joong; Kim, Ki-Baik; Won, Dong-Yeon; Hong, Gye-Won

    1994-07-01

    Entrapment of Ba-Cu-O liquid phase during the growth of a 123 domain was investigated in the melt-textured Y-Ba-Cu-O oxide. From the microstructural examination of the growth front of the 123 domain, it is found that liquid phase is entrapped in the channels between adjacent 123 platelets formed ahead of the 123 domain, owing to the anisotropic growth of the 123 platelet, the difference between the growth rate of the 123 platelet and the dissolution rate of 211 in the liquid phase, and the inhomogeneous distribution of 211 particles at the peritectic reaction front. Dissolution of 211 particles in the reaction region, which supplies an yttrium source to the liquid channels, allows the entrapped liquid phase to solidify to 123 phase. After the peritectic reaction, the liquid channels turn into plate boundaries containing residual liquid phase as evidence of the entrapment. Isolation of the entrapped liquid phase from the yttrium source (211 particles) by the solidified 123 phase appears to be responsible for the presence of the residual liquid phase.

  11. Effect of micro-gravity on the microstructural evolution during liquid phase sintering

    NASA Astrophysics Data System (ADS)

    Tewari, Asim

    The effect of gravity on the evolution of microstructure during liquid phase sintering was studied using Ni-Fe tungsten heavy alloy, for varying sintering times, compositions, and gravity conditions (microgravity and normal gravity). A serial sectioning of the samples was carried out and the three dimensional microstructure was reconstructed. The microstructure was quantified using volume-probe techniques developed in the course of this research. Computer codes were written to extract descriptors of spatial arrangement of grains from the image data. It was seen that the microstructure in gravity evolves as just a scale factor change with sintering time whereas it is not so in microgravity. The scale factor change in gravity was seen in the evolution of grain size distribution function, radial distribution function and 1st, 2nd and 3rd nearest neighbor distribution functions. In specimens processed in both gravity and microgravity environment there are practically no isolated grains suspended in the matrix. This was expected in gravity where the grains have to contact each other to provide normal force to balance gravity, but it was surprising to see this in microgravity. At a given sintering time, the coordination number in microgravity was significantly lower than that in gravity. In microgravity, the coordination number remains constant whereas in gravity, it increases with time. This increase is attributed to grain shape accommodation. A strong correlation was found between the coordination number and the mean surface area of grains forming that coordination which was expressed by a linear equation. Inspite of significant differences between the volume fractions of gravity and microgravity samples, the 1st and 2nd 3D nearest neighbor distances are only a scale change, with the scale factor being the mean grain size. In the initial stages of sintering, the kinetics of grain growth is slower in microgravity than in gravity environment resulting in a significant difference in the grain sizes. However, the difference in grain size after 120 minutes of sintering becomes insignificant. The observed difference in rates of grain growth at lower times (upto 1 minute) is attributed to the effect of coalescence. It was observed that there is no densification with time in microgravity though this effect is seen in gravity.

  12. Determination of Atmospheric Hydroxyl Radical by Liquid Phase Scrubbing and High Performance Liquid Chromatography.

    NASA Astrophysics Data System (ADS)

    Chen, Xiaohui

    A new in situ method for determining atmospheric hydroxyl radical (OH) was developed. This method is based on liquid phase scrubbing technique and high performance liquid chromatography (LPS-HPLC). The sampling system employs glass bubblers to trap atmospheric OH into a buffered solution containing the chemical probe, salicylic acid (o-hydroxybenzoic acid, OHBA). The reaction of OHBA with OH produces a stable fluorescent product, 2,5-dihydroxybenzoic acid (2,5-DHBA), which is determined by reverse phase HPLC and fluorescence detection. The atmospheric OH concentration ( (OH)) is inferred from the resulting 2,5-DHBA amount in the aqueous scrubbing solution, fraction of 2,5-DHBA in the products, air sampling flow rate, sampling time, local pressure and temperature, etc. HPLC separation efficiency and fluorescence detection sensitivity for 2,5-DHBA have been studied. The results indicate that: the reagent blank can be controlled by suitable recrystallization; pH affects both separation and detection processes; the fluorometer should be adjusted to reach its highest signal-to-noise ratio by light source selection, flow cell size selection, wavelength selection, etc. Preliminary column switch experiments reveal the possibility to automate the whole sampling and detection system to enhance the temporal resolution. During an intercomparison of tropospheric OH measurement techniques at the Caribou site, CO (relatively unpolluted air) in Fall 1993, overlapping data were obtained with long path absorption and ion-assisted coupled with MS methods. LPS -HPLC day-time (OH) s, which range from {< }10^6 to 6times10 ^6 radicals/cm^3, agree well with those derived from the other two methods, especially the latter. LPS-HPLC (OH) depends linearly on the combined effects of solar flux, ozone and water vapor, however, it has a nonlinear dependence on NO _{x} and hydrocarbons. These results are consistent with that predicted from photochemical models. Experimental results and model calculations indicate that there is negligible or only slight interference from atmospheric species, including HO_2, ozone, NO_{rm x} and hydrocarbons.

  13. Liquid phase sintered composite solders for next generation thermal interface applications

    NASA Astrophysics Data System (ADS)

    Liu, Jia

    It is undeniable that electronics are becoming increasingly powerful and that there is continual effort towards miniaturization of these devices and thus increasing heat generation requires a new paradigm in thermal interface materials (TIM) design. This work was aimed at optimizing the processing parameters and characterizing the performance of Cu-In composite solders produced by liquid phase sintering (LPS). These composites comprise a high-melting phase (HMP) such as Cu embedded in a matrix of a low-melting phase (LMP) such as In. Copper contributes to high thermal and electrical conductivity of composites, whereas the soft In matrix helps maintain high shear compliance. This combination of high electrical/thermal conductivities and high shear compliance makes these solders suitable for a range of next-generation thermal interface material (TIM) and interconnect (IC) applications. After considering a range of compositions, a solder with 60 volume percent In was found to possess the requisite combination of high compliance and high conductivity. During the study, interfacial engineering was introduced to slow down the reaction between Cu and In, and hence further improve the performance of composite solders. A dual interfacial layer consisting of Al 2O3 and Au was used to mitigate the reaction between Cu and In. A 1 nm Al2O3 layer was used as a diffusion barrier to prohibit the inter-diffusion between Cu and In, while a 20 nm Au layer was coated on top of the ceramic Al2O3 for wetting enhancement. The dual layer increased the thermal conductivity of the solder by a factor of ˜2 while reducing the yield strength to make the solder more compliant. The effects of particle size, shape and volume fraction was also studied, and a simple model was utilized to explain the trends in the mechanical and the thermal properties. The optimized Cu-In composite solders were further used to study the performance of solder joints. Mechanical properties under shear and joint thermal resistance were measured as a function of joint thickness, thermal excursion history, and different inter-layers between solder and Cu. Minimizing interfacial contact-resistance is desired, especially when the joint thickness becomes sub-millimeter, and hence role of inter-layer on the contact-resistance was studied.

  14. Hollow fiber-liquid-phase microextraction of fungicides from orange juices.

    PubMed

    Barahona, Francisco; Gjelstad, Astrid; Pedersen-Bjergaard, Stig; Rasmussen, Knut Einar

    2010-03-26

    Liquid-phase microextraction (LPME) based on polypropylene hollow fibers was evaluated for the extraction of the post-harvest fungicides thiabendazole (TBZ), carbendazim (CBZ) and imazalil (IMZ) from orange juices. Direct LPME was performed without any sample pretreatment prior to the extraction, using a simple home-built equipment. A volume of 500 microL of 840 mM NaOH was added to 3 mL of orange juice in order to compensate the acidity of the samples and to adjust pH into the alkaline region. Analytes were extracted in their neutral state through a supported liquid membrane (SLM) of 2-octanone into 20 microL of a stagnant aqueous solution of 10 mM HCl inside the lumen of the hollow fiber. Subsequently, the acceptor solution was directly subjected to analysis. Capillary electrophoresis (CE) was used during the optimization of the extraction procedure. Working under the optimized extraction conditions, LPME effectively extracted the analytes from different orange juices, regardless of different pH or solid material (pulp) present in the sample, with recoveries that ranged between 17.0 and 33.7%. The analytical performance of the method was evaluated by liquid chromatography coupled with mass spectrometry (LC/MS). This technique provided better sensitivity than CE and permitted the detection below the microg L(-1) level. The relative standard deviations of the recoveries (RSDs) ranged between 3.4 and 10.6%, which are acceptable values for a manual microextraction technique without any previous sample treatment, using a home-built equipment and working under non-equilibrium conditions (30 min extraction). Linearity was obtained in the range 0.1-10.0 microg L(-1), with r=0.999 and 0.998 for TBZ and IMZ, respectively. Limits of detection were below 0.1 microg L(-1) and are consistent with the maximum residue levels permitted for pesticides in drinking water, which is the most restrictive regulation applicable for these kinds of samples. It has been demonstrated the suitability of three-phase LPME for the extraction of pesticides from citrus juices, suppressing any pretreatment step such as filtration or removal of the solid material from the sample, that may potentially involve a loss of analyte. PMID:20181342

  15. Kinetic aspects of hollow fiber liquid-phase microextraction and electromembrane extraction.

    PubMed

    Gjelstad, Astrid; Jensen, Henrik; Rasmussen, Knut Einar; Pedersen-Bjergaard, Stig

    2012-09-12

    In this paper, extraction kinetics was investigated experimentally and theoretically in hollow fiber liquid-phase microextraction (HF-LPME) and electromembrane extraction (EME) with the basic drugs droperidol, haloperidol, nortriptyline, clomipramine, and clemastine as model analytes. In HF-LPME, the analytes were extracted by passive diffusion from an alkaline sample, through a (organic) supported liquid membrane (SLM) and into an acidic acceptor solution. In EME, the analytes were extracted by electrokinetic migration from an acidic sample, through the SLM, and into an acidic acceptor solution by application of an electrical potential across the SLM. In both HF-LPME and EME, the sample (donor solution) was found to be rapidly depleted for analyte. In HF-LPME, the mass transfer across the SLM was slow, and this was found to be the rate limiting step of HF-LPME. This finding is in contrast to earlier discussions in the literature suggesting that mass transfer across the boundary layer at the donor-SLM interface is the rate limiting step of HF-LPME. In EME, mass transfer across the SLM was much more rapid due to electrokinetic migration. Nevertheless, mass transfer across the SLM was rate limiting even in EME. Theoretical models were developed to describe the kinetics in HF-LPME, in agreement with the experimental findings. In HF-LPME, the extraction efficiency was found to be maintained even if pH in the donor solution was lowered from 10 to 7-8, which was below the pK(a)-value for several of the analytes. Similarly, in EME, the extraction efficiency was found to be maintained even if pH in the donor solution increased from 4 to 11, which was above the pK(a)-value for several of the analytes. The two latter experiments suggested that both techniques may be used to effectively extract analytes from samples in a broader pH range as compared to the pH range recommended in the literature. PMID:22884201

  16. Numerical simulation and experimental study of transient liquid phase bonding of single crystal superalloys

    NASA Astrophysics Data System (ADS)

    Ghoneim, Adam

    The primary goals of the research in this dissertation are to perform a systematic study to identify and understand the fundamental cause of prolonged processing time during transient liquid phase bonding of difficult-to-bond single crystal Ni-base materials, and use the acquired knowledge to develop an effective way to reduce the isothermal solidification time without sacrificing the single crystalline nature of the base materials. To achieve these objectives, a multi-scale numerical modeling approach, that involves the use of a 2-D fully implicit moving-mesh Finite Element method and a Cellular Automata method, was developed to theoretically investigate the cause of long isothermal solidification times and determine a viable way to minimize the problem. Subsequently, the predictions of the theoretical models are experimentally validated. Contrary to previous suggestions, numerical calculations and experimental verifications have shown that enhanced intergranular diffusivity has a negligible effect on solidification time in cast superalloys and that another important factor must be responsible. In addition, it was found that the concept of competition between solute diffusivity and solubility as predicted by standard analytical TLP bonding models and reported in the literature as a possible cause of long solidification times is not suitable to explain salient experimental observations. In contrast, however, this study shows that the problem of long solidification times, which anomalously increase with temperature is fundamentally caused by departure from diffusion controlled parabolic migration of the liquid-solid interface with holding time during bonding due to a significant reduction in the solute concentration gradient in the base material. Theoretical analyses showed it is possible to minimize the solidification time and prevent formation of stray-grains in joints between single crystal substrates by using a composite powder mixture of brazing alloy and base alloy as the interlayer material, which prior to the present work has been reported to be unsuitable. This was experimentally verified and the use of the composite powder mixture as interlayer material to reduce the solidification time and avoid stray-grain formation during TLP bonding of single crystal superalloys has been reported for the first time in this research.

  17. Growth of bulk single crystals under applied magnetic field by liquid phase electroepitaxy

    NASA Astrophysics Data System (ADS)

    Sheibani, H.; Dost, S.; Sakai, S.; Lent, B.

    2003-11-01

    Binary (GaAs) and ternary (InGaAs) bulk single crystals have been grown by the growth process of liquid phase electroepitaxy (LPEE with and without the application of an external static magnetic field. Two significant achievements were made: first is the development of a new, improved LPEE system to grow, flat, thick and uniform single crystals of In 0.04Ga 0.96As, and the second is the significant improvement of the LPEE growth rate by the application of an external static magnetic field. Experiments performed under no magnetic field have shown that LPEE can grow large (thick) and flat single crystals of In 0.04Ga 0.96As with uniform composition. Experiments have also proved the reproducibility of LPEE growth of such single crystals in terms of crystal thickness, flatness, and compositional uniformity. It was possible to use higher electric current density levels (up to 7 A/cm 2) in spite of the achievement of large crystal thicknesses. Experiments conducted under various magnetic field levels have shown that the LPEE growth process at the 4.5 kG and lower magnetic field levels yields satisfactory growth. However, the growth experiments at higher magnetic field and electric current density levels were unsatisfactory and unstable. Although the crystals were still grown, large holes and unstable interfaces were observed in the grown crystals. However, lower magnetic field and electric current levels had very beneficial effects, namely flat growth interfaces and prolonged growth due to weak convection in the liquid zone, and a substantial increase in the growth rate (about up to 20 times higher at 4.5 kG and 7 A/cm 2 levels). Such a significant increase in the growth rate under a static magnetic field can be attributed to the positive effect of applied magnetic field on the mechanism of "electromigration". The performed electron probe micro analysis (EPMA) and the energy dispersive X-ray spectroscopy (EDS) measurements have shown that the indium composition distribution in grown crystals was uniform in both the radial and growth directions. Advances made through this work may be considered as a significant initial step towards the commercialization of the LPEE technique for growth of high-quality, bulk single crystals.

  18. On inferring liquid-liquid phase boundaries and tie lines from ternary mixture light scattering.

    PubMed

    Wahle, Chris W; Ross, David S; Thurston, George M

    2012-07-21

    We investigate the possibility of using light scattering data in the single-phase regions of a ternary liquid mixture phase diagram to infer ternary mixture coexistence curves, and to infer tie lines joining the compositions of isotropic liquid phases in thermodynamic equilibrium. Previous analyses of a nonlinear light scattering partial differential equation (LSPDE) show that it provides for reconstruction of ternary [D. Ross, G. Thurston, and C. Lutzer, J. Chem. Phys. 129, 064106 (2008); C. Wahle, D. Ross, and G. Thurston, J. Chem. Phys. 137, 034201 (2012)] and quaternary [C. Wahle, D. Ross, and G. Thurston, J. Chem. Phys. 137, 034202 (2012)] mixing free energies from light scattering data, and that if the coexistence curves are already known, it can also yield ternary tie lines and triangles [D. Ross, G. Thurston, and C. Lutzer, J. Chem. Phys. 129, 064106 (2008)]. Here, we show that the LSPDE can be used more generally, to infer phase boundaries and tie lines from light scattering data in the single-phase region, without prior knowledge of the coexistence curve, if the single-phase region is connected. The method extends the fact that the reciprocal light scattering intensity approaches zero at the thermodynamic spinodal. Expressing the free energy as the sum of ideal and excess parts leads to a natural family of Padé approximants for the reciprocal Rayleigh ratio. To test the method, we evaluate the single-phase reciprocal Rayleigh ratio resulting from the mean-field, regular solution model on a fine grid. We then use a low-order approximant to extrapolate the reciprocal Rayleigh ratio into metastable and unstable regions. In the metastable zone, the extrapolation estimates light scattering prior to nucleation and growth of a new phase. In the unstable zone, the extrapolation produces a negative function that in the present context is a computational convenience. The original and extrapolated reciprocal light scattering are jointly used as input to solving the LSPDE to deduce the mixing free energy and its convex hull. When projected onto the composition triangle, the boundary of the convexified part of the free energy is the phase boundary, and lines on the convexified region along which the second directional derivative is zero are the tie lines. We find that the tie lines and phase boundaries so deduced agree well with their exact values. This work is a step toward developing methods for inferring phase boundaries from real light scattering intensities measured with noise, from mixtures having compositions on a coarser grid. PMID:22830695

  19. Active Control of Fan Noise: Feasibility Study. Volume 5; Numerical Computation of Acoustic Mode Reflection Coefficients for an Unflanged Cylindrical Duct

    NASA Technical Reports Server (NTRS)

    Kraft, R. E.

    1996-01-01

    A computational method to predict modal reflection coefficients in cylindrical ducts has been developed based on the work of Homicz, Lordi, and Rehm, which uses the Wiener-Hopf method to account for the boundary conditions at the termination of a thin cylindrical pipe. The purpose of this study is to develop a computational routine to predict the reflection coefficients of higher order acoustic modes impinging on the unflanged termination of a cylindrical duct. This effort was conducted wider Task Order 5 of the NASA Lewis LET Program, Active Noise Control of aircraft Engines: Feasibility Study, and will be used as part of the development of an integrated source noise, acoustic propagation, ANC actuator coupling, and control system algorithm simulation. The reflection coefficient prediction will be incorporated into an existing cylindrical duct modal analysis to account for the reflection of modes from the duct termination. This will provide a more accurate, rapid computation design tool for evaluating the effect of reflected waves on active noise control systems mounted in the duct, as well as providing a tool for the design of acoustic treatment in inlet ducts. As an active noise control system design tool, the method can be used preliminary to more accurate but more numerically intensive acoustic propagation models such as finite element methods. The resulting computer program has been shown to give reasonable results, some examples of which are presented. Reliable data to use for comparison is scarce, so complete checkout is difficult, and further checkout is needed over a wider range of system parameters. In future efforts the method will be adapted as a subroutine to the GEAE segmented cylindrical duct modal analysis program.

  20. Relationship between transfer activity coefficients, S1?S2, of cryptate 2.2.2 complexes and their stability constant in various solvents

    PubMed Central

    Kolthoff, Izaak M.; Chantooni, Miran K.

    1980-01-01

    Between dipolar aprotic solvents S1 and S2, the transfer activity coefficients, S1?S2, of complexed sodium, potassium, thallium(I), and silver ions with cryptand 2.2.2 have been found to be equal to that of the cryptand. With reference to methanol (S1), this equality does not hold, the cryptates being more or less solvated by hydrogen bonding in this solvent. In water as a solvent, the cryptates are on a considerably higher level of free energy than in the organic solvents. This is attributed to hydrophobic hydration of the cryptates. PMID:16592871

  1. High-efficient synthesis and biological activities of allosamidins.

    PubMed

    Huang, Gangliang; Peng, Daquan; Mei, Xinya; Chen, Xin; Xiao, Feng; Tang, Qilin

    2015-12-01

    The pseudo-trisaccharide allosamidin 1 is a potent inhibitor of all family-18 chitinases, and it is confirmed to have insecticidal and antifungal activities. But the synthesis of allosamidins is very difficult, and it is a challengeable subject. Allosamidins were synthesized in solid-liquid phase, total solid-phase and total liquid-phase, respectively. Solid-liquid phase method realizes the partial solid-phase synthesis of allosamidins. Total solid-phase method greatly simplifies the purification process. Total liquid-phase method shortens the synthetic steps of allosamidins. The insecticidal and antifungal activities of allosamidins were also reported herein. PMID:25486024

  2. ERRORS IN APPLYING LOW ION-STRENGTH ACTIVITY COEFFICIENT ALGORITHMS TO HIGHER IONIC-STRENGTH AQUATIC MEDIA

    EPA Science Inventory

    The toxicological and regulatory communities are currently exploring the use of free-ion-activity- models as a means of reducing uncertainties in current methods for assessing metals bioavailabi- lity from contaminated aquatic media. While most practitioners would support the des...

  3. ERRORS IN APPLYING LOW IONIC-STRENGTH ACTIVITY COEFFICIENT ALGORITHMS TO HIGHER IONIC-STRENGTH AQUATIC MEDIA

    EPA Science Inventory

    The toxicological and regulatory communities are currently exploring the use of the free-ion-activity (FIA) model both alone and in conjunction with the biotic ligand model (BLM) as a means of reducing uncertainties in current methods for assessing metals bioavailability from aqu...

  4. Determination of perfluorinated compounds (PFCs) in solid and liquid phase river water samples in Chao Phraya River, Thailand.

    PubMed

    Kunacheva, Chinagarn; Tanaka, Shuhei; Fujii, Shigeo; Boontanon, Suwanna Kitpati; Musirat, Chanatip; Wongwattana, Thana

    2011-01-01

    Perfluorinated compounds (PFCs), especially perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are fully fluorinated organic compounds, which have been used in many industrial applications. These chemicals have contaminated surface water all over the world even in developing countries like Thailand. The previous study showed the contamination in Chao Phraya River in 2006 and 2007. The purposes of this field study were to determine the solid and liquid phase of PFCs contamination in Chao Phraya River and to compare the changes of PFC concentration in 2008. Surveys were conducted in the lower reach of Chao Phraya River in the industrialized area. A solid phase extraction (SPE) coupled with HPLC-ESI-MS/MS were used for the analysis for ten PFCs. Ten PFCs were analyzed to identify the contamination in both solid and liquid phases. PFCs were detected in both the solid and liquid phase in every sample. PFOA was the most dominant PFC while PFPA and PFOS were also highly detected in most samples. The average loadings of PFPA, PFOA and PFOS in Chao Phraya River were 94.3, 284.6 and 93.4 g/d, respectively. PFOS concentrations did not show differences between 2006 and 2008. However, PFOA concentrations were higher in 2008/5/26, while comparing other samplings. The ratio of solid:liquid PFPA (2.1:1.0) [(ng/g)/(ng/L)] was lower than PFOA (13.9:1.0) [(ng/g)/(ng/L)] and PFOS (17.6:1.0) [(ng/g)/(ng/L)]. The shorter chain (more hydrophilic) PFC was better to dissolve in water rather than adsorb onto suspended solids. PFOS also showed more potential to attach in the suspended solids than PFOA. PMID:22097048

  5. The electrochemical potential and ionic activity coefficients. A possible correction for Debye-Hckel and Maxwell-Boltzmann equations for dilute electrolyte equilibria.

    PubMed

    van der Weg, P B

    2009-11-15

    When the electrical contribution in the electrochemical potential of ionic species is reduced with a factor two from its traditional value, the ionic activity coefficients are closer to unity and need to account only for the short-range interactions at high concentrations. Such a change is needed to remove inconsistencies in the models and to comply with basic electrostatic principles. This will have serious implications, in many applications. For example, it will cause changes in many of the fundamental models that are used to explain measured data in the dilute range for the various disciplines that embrace classical electrochemistry. Examples are Debye-Hckel and Gouy-Chapman theories; Maxwell-Boltzmann distribution; Nernst theory; Donnan equilibrium, etc. These theories impact a wide range of observable phenomena such as activity coefficients of electrolytes, diffuse double layer capacitance, electrode potentials, membrane potentials, streaming potentials, electro-osmosis, flotation, sedimentation, corrosion, charged micellar behaviour, space-charge semiconductor behaviour, and electrical phenomena in biological tissue, e.g. membranes; cells; and nerves, etcetera. PMID:19656523

  6. The importance of hard core repulsion in models of activity coefficients in aqueous electrolyte solutions: Illustration in the case of hydration theory

    SciTech Connect

    Wolery, T.J.; Jackson, K.J.

    1992-07-01

    Activity coefficients in aqueous electrolyte solutions are primarily affected by two kinds of phenomena. The standard Debye-Huckel equation represents only one of these, the long range electrical interactions. Of nearly equal importance is hard core (HC) repulsion, which is not electrical in nature. To a first-order approximation, HC repulsive effects are independent of the ionic strength, depending instead on the sum of the solute molalities ({Sigma}m). Adding a term for HC repulsion to the standard Debye-Huckel model produces what we call a hybrid two-term model In a previous work (Wolery and Jackson 1990) we proposed a new method for making hydration corrections to the standard Debye-Huckel model. In the present work, we examine the effect of extending this model to include hard core repulsion. Although the activity coefficients of 1:1 electrolytes can be fit quite well by the model without a HC term the inclusion of such a term is critical to success in fitting the data for 2:1 and other higher-order electrolytes.

  7. The importance of hard core repulsion in models of activity coefficients in aqueous electrolyte solutions: Illustration in the case of hydration theory

    SciTech Connect

    Wolery, T.J.; Jackson, K.J.

    1992-07-01

    Activity coefficients in aqueous electrolyte solutions are primarily affected by two kinds of phenomena. The standard Debye-Huckel equation represents only one of these, the long range electrical interactions. Of nearly equal importance is hard core (HC) repulsion, which is not electrical in nature. To a first-order approximation, HC repulsive effects are independent of the ionic strength, depending instead on the sum of the solute molalities ([Sigma]m). Adding a term for HC repulsion to the standard Debye-Huckel model produces what we call a hybrid two-term model In a previous work (Wolery and Jackson 1990) we proposed a new method for making hydration corrections to the standard Debye-Huckel model. In the present work, we examine the effect of extending this model to include hard core repulsion. Although the activity coefficients of 1:1 electrolytes can be fit quite well by the model without a HC term the inclusion of such a term is critical to success in fitting the data for 2:1 and other higher-order electrolytes.

  8. Buoyant thermocapillary flow with nonuniform supra-heating. I - Liquid-phase behavior. II - Two-phase behavior

    NASA Technical Reports Server (NTRS)

    Schiller, David N.; Sirignano, William A.

    1992-01-01

    The present computational study of transient heat transfer and fluid flow in a circular pool of n-decane which is undergoing central radiative heating from above gives attention to the volumetric absorption of the radiation incident on the pool surface. The first part of this study notes that buoyancy influences the number and recirculation rates of the subsurface vortices by stabilizing hot subsurface fluid above the colder core fluid; this affects the liquid surface temperature profile and in turn governs the velocity profile that is due to thermocapillarity. In the second part, the effects of gas-liquid phase coupling, variable density and thermophysical properties, and vaporization are considered.

  9. Liquid-phase plasma synthesis of silicon quantum dots embedded in carbon matrix for lithium battery anodes

    SciTech Connect

    Wei, Ying; Yu, Hang; Li, Haitao; Ming, Hai; Pan, Keming; Huang, Hui; Liu, Yang; Kang, Zhenhui

    2013-10-15

    Graphical abstract: - Highlights: • Silicon quantum dots embedded in carbon matrix (SiQDs/C) were fabricated. • SiQDs/C exhibits excellent battery performance as anode materials with high specific capacity. • The good performance was attributed to the marriage of small sized SiQDs and carbon. - Abstract: Silicon quantum dots embedded in carbon matrix (SiQDs/C) nanocomposites were prepared by a novel liquid-phase plasma assisted synthetic process. The SiQDs/C nanocomposites were demonstrated to show high specific capacity, good cycling life and high coulmbic efficiency as anode materials for lithium-ion battery.

  10. Boride Zone Formation in Transient Liquid Phase Bonding of Pairings of Parent Superalloy Materials with Different Compositions and Grain Structures

    NASA Astrophysics Data System (ADS)

    Steuer, S.; Singer, R. F.

    2013-05-01

    Two nickel-base superalloys are joined via transient liquid phase (TLP) bonding with boron as the MPD. Boride formation is observed in the parent materials at some distance from the solid/liquid interface. The boron concentration profile over the joint is measured with glow discharge optical emission spectroscopy (GDOES). Boron concentration peaks are observed corresponding to the boride formation. Boron distribution is discussed on the basis of theoretical predictions in the literature. It is concluded that diffusion of another element is necessary to explain the results with the second element influencing the solubility of boron.

  11. Liquid-phase immunoassay utilizing binding reactions between magnetic markers and targets in the presence of a magnetic field

    NASA Astrophysics Data System (ADS)

    Enpuku, Keiji; Ueoka, Yuta; Sakakibara, Tatsuto; Ura, Masakazu; Yoshida, Takashi; Mizoguchi, Takako; Kandori, Akihiko

    2014-09-01

    We developed a new and improved method for the liquid-phase detection of biological targets using magnetic markers. Unlike conventional studies, we performed a binding reaction between markers and targets in the presence of a magnetic field. This field acts to prevent the Brownian rotation of markers during the reaction. In this case, markers are bound to the targets with their magnetic moments (ms) aligned, which is in contrast to the conventional case where ms are randomly oriented after the reaction. As a result, we could obtain much larger signals from the bound markers without increasing the blank signal from the free markers.

  12. Solid-liquid phase transitions in 3D systems with the inverse-power and Yukawa potentials

    NASA Astrophysics Data System (ADS)

    Vaulina, O. S.; Koss, X. G.

    2016-03-01

    The melting of face-centered cubic (fcc) and body-centered cubic (bcc) crystal lattices was studied analytically and numerically for the systems of particles interacting via the inverse-power-law and Yukawa potentials. New approach is proposed for determination of the solid-liquid phase transitions in these systems. The suggested approach takes into account a nonlinearity (anharmonicity) of pair interaction forces and allows to correctly predict the conditions of melting of the systems with various isotropic pair interaction potentials. The obtained results are compared with the existing theoretical and numerical data.

  13. Characterization of transparent conducting p-type nickel oxide films grown by liquid phase deposition on glass

    NASA Astrophysics Data System (ADS)

    Lee, Ming-Kwei; Lai, Yen-Ting

    2013-02-01

    Transparent conducting nickel oxide (NiO) films were prepared by liquid phase deposition on glass. Saturated NiF2 and boric acid solutions were used as precursors. There was a growth delay time of 5 h and the growth rate was 34.3 nm per hour in the growth region. After annealing at 400 C in air, the resistivity was improved from 4.85 103 ? cm to 7.5 10-1 ? cm, and the transmittance decreased from 91.85% to 66.49% at a wavelength of 550 nm, respectively.

  14. Novel one-step headspace dynamic in-syringe liquid phase derivatization-extraction technique for the determination of aqueous aliphatic amines by liquid chromatography with fluorescence detection.

    PubMed

    Muniraj, Sarangapani; Shih, Hou-Kung; Chen, Ying-Fang; Hsiech, Chunming; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

    2013-06-28

    A novel one-step headspace (HS) dynamic in-syringe (DIS) based liquid-phase derivatization-extraction (LPDE) technique has been developed for the selective determination of two short-chain aliphatic amines (SCAAs) in aqueous samples using high performance liquid chromatography (HPLC) with fluorescence detection (FLD). Methylamine (MA) and dimethylamine (DMA) were selected as model compounds of SCAAs. In this method, a micro-syringe pre-filled with derivatizing reagent solution (9-fluorenylmethyl chloroformate) in the barrel was applied to achieve the simultaneous derivatization and extraction of two methylamines evolved from alkalized aqueous samples through the automated reciprocated movements of syringe plunger. After the derivatization-extraction process, the derivatized phase was directly injected into HPLC-FLD for analysis. Parameters influencing the evolution of methylamines and the HS-DIS-LPDE efficiency, including sample pH and temperature, sampling time, as well as the composition of derivatization reagent, reaction temperature, and frequency of reciprocated plunger movements, were thoroughly examined and optimized. Under optimal conditions, detections were linear in the range of 25-500?gL(-1) for MA and DMA with correlation coefficients all above 0.995. The limits of detection (based on S/N=3) were 5 and 19ngmL(-1) for MA and DMA, respectively. The applicability of the developed method was demonstrated for the determination of MA and DMA in real water samples without any prior cleanup of the sample. The present method provides a simple, selective, automated, low cost and eco-friendly procedure to determine aliphatic amines in aqueous samples. PMID:23591526

  15. Immunoassay of paralytic shellfish toxins by moving magnetic particles in a stationary liquid-phase lab-on-a-chip.

    PubMed

    Kim, Myoung-Ho; Choi, Suk-Jung

    2015-04-15

    In this study, we devised a stationary liquid-phase lab-on-a-chip (SLP LOC), which was operated by moving solid-phase magnetic particles in the stationary liquid phase. The SLP LOC consisted of a sample chamber to which a sample and reactants were added, a detection chamber containing enzyme substrate solution, and a narrow channel connecting the two chambers and filled with buffer. As a model system, competitive immunoassays of saxitoxin (STX), a paralytic shellfish toxin, were conducted in the SLP LOC using protein G-coupled magnetic particles (G-MPs) as the solid phase. Anti-STX antibodies, STX-horseradish peroxidase conjugate, G-MPs, and a STX sample were added to the sample chamber and reacted by shaking. While liquids were in the stationary state, G-MPs were transported from the sample chamber to the detection chamber by moving a magnet below the LOC. After incubation to allow the enzymatic reaction to occur, the absorbance of the detection chamber solution was found to be reciprocally related to the STX concentration of the sample. Thus, the SLP LOC may represent a novel, simple format for point-of-care testing applications of enzyme-linked immunosorbent assays by eliminating complicated liquid handling steps. PMID:25460894

  16. Migration of carbon nanotubes from liquid phase to vapor phase in the refrigerant-based nanofluid pool boiling.

    PubMed

    Peng, Hao; Ding, Guoliang; Hu, Haitao

    2011-01-01

    The migration characteristics of carbon nanotubes from liquid phase to vapor phase in the refrigerant-based nanofluid pool boiling were investigated experimentally. Four types of carbon nanotubes with the outside diameters from 15 to 80 nm and the lengths from 1.5 to 10 ?m were used in the experiments. The refrigerants include R113, R141b and n-pentane. The oil concentration is from 0 to 10 wt.%, the heat flux is from 10 to 100 kWm-2, and the initial liquid-level height is from 1.3 to 3.4 cm. The experimental results indicate that the migration ratio of carbon nanotube increases with the increase of the outside diameter or the length of carbon nanotube. For the fixed type of carbon nanotube, the migration ratio decreases with the increase of the oil concentration or the heat flux, and increases with the increase of the initial liquid-level height. The migration ratio of carbon nanotube increases with the decrease of dynamic viscosity of refrigerant or the increase of liquid phase density of refrigerant. A model for predicting the migration ratio of carbon nanotubes in the refrigerant-based nanofluid pool boiling is proposed, and the predictions agree with 92% of the experimental data within a deviation of 20%. PMID:21711730

  17. Evidence of liquid phase during laser-induced periodic surface structures formation induced by accumulative ultraviolet picosecond laser beam

    NASA Astrophysics Data System (ADS)

    Huynh, T. T. D.; Vayer, M.; Sauldubois, A.; Petit, A.; Semmar, N.

    2015-11-01

    Laser-induced periodic surface structures (LIPSS) were formed on Cu/Si or Cu/glass thin films using Nd:YAG laser beam (40 ps, 10 Hz, and 30 mJ/cm2). The study of ablation threshold is always achieved over melting when the variation of the number of pulses increases from 1 to 1000. But the incubation effect is leading to reduce the threshold of melting as increasing the number of laser pulse. Also, real time reflectivity signals exhibit typical behavior to stress the formation of a liquid phase during the laser-processing regime and helps to determine the threshold of soft ablation. Atomic Force Microscopy (AFM) analyses have shown the topology of the micro-crater containing regular spikes with different height. Transmission Electron Microscopy (TEM) allows finally to show three distinguished zones in the close region of isolated protrusions. The central zone is a typical crystallized area of few nanometers surrounded by a mixed poly-crystalline and amorphous area. Finally, in the region far from the protrusion zone, Cu film shows an amorphous structure. The real time reflectivity, AFM, and HR-TEM analyses evidence the formation of a liquid phase during the LIPSS formation in the picosecond regime.

  18. 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

  19. A numerical study of aerosol influence on mixed-phase stratiform clouds through modulation of the liquid phase

    NASA Astrophysics Data System (ADS)

    de Boer, G.; Hashino, T.; Tripoli, G. J.; Eloranta, E. W.

    2013-02-01

    Numerical simulations were carried out in a high-resolution two-dimensional framework to increase our understanding of aerosol indirect effects in mixed-phase stratiform clouds. Aerosol characteristics explored include insoluble particle type, soluble mass fraction, influence of aerosol-induced freezing point depression and influence of aerosol number concentration. Simulations were analyzed with a focus on the processes related to liquid phase microphysics, and ice formation was limited to droplet freezing. Of the aerosol properties investigated, aerosol insoluble mass type and its associated freezing efficiency was found to be most relevant to cloud lifetime. Secondary effects from aerosol soluble mass fraction and number concentration also alter cloud characteristics and lifetime. These alterations occur via various mechanisms, including changes to the amount of nucleated ice, influence on liquid phase precipitation and ice riming rates, and changes to liquid droplet nucleation and growth rates. Alteration of the aerosol properties in simulations with identical initial and boundary conditions results in large variability in simulated cloud thickness and lifetime, ranging from rapid and complete glaciation of liquid to the production of long-lived, thick stratiform mixed-phase cloud.

  20. A numerical study of aerosol influence on mixed-phase stratiform clouds through modulation of the liquid phase

    NASA Astrophysics Data System (ADS)

    de Boer, G.; Hashino, T.; Tripoli, G. J.; Eloranta, E. W.

    2012-08-01

    Numerical simulations were carried out in a high-resolution two dimensional framework to increase our understanding of aerosol indirect effects in mixed-phase stratiform clouds. Aerosol characteristics explored include insoluble particle type, soluble mass fraction, the influence of aerosol-induced freezing point depression and the influence of aerosol number concentration. These experiments were completed with an emphasis on the liquid phase, with droplet freezing the mechanism for ice production. Of the aerosol properties investigated, aerosol insoluble mass type and its associated freezing efficiency was found to be most relevant to cloud lifetime. Secondary effects from aerosol soluble mass fraction and number concentration also alter cloud characteristics and lifetime. These alterations occur via various mechanisms, including changes to the amount of nucleated ice, influence on liquid phase precipitation and ice riming rates, and changes to liquid droplet growth rates. Simulation of the same environment leads to large variability of cloud thickness and lifetime, ranging from rapid and complete glaciation of the cloud to the production of a long-lived, thick stratiform mixed-phase cloud. In the end, these processes are summarized into a diagram that includes internal feedback loops that act within the cloud system.

  1. Surfactant free fabrication of polymeric nanoparticles by combined liquid-liquid phase separation and solvent/nonsolvent mixing technology.

    PubMed

    Xiong, J Y; Liu, X Y; Sawant, P D; Chen, S B; Chung, T S; Pramoda, K P

    2004-12-22

    It is generally agreed that, in most cases, surfactants are required to obtain stable polymeric nanoparticle dispersions. Here, we report a method which can be used to produce surfactant free yet stable polymeric nanoparticle dispersions. This method is based on explored mechanism of selective solvation of nanoparticles and EPD (electron pair donor)/EPA (electron pair acceptor) complexes formed among solvent and nonsolvent molecules. Using polyimide P84 (copolyimide 3,3(') 4,4(')-benzophenone tetracarboxylic dianhydride and 80% methylphenylene diamine+20% methylene dianiline) as the model polymer, this mechanism was realized through a combined liquid-liquid phase separation and solvent/nonsolvent mixing technology. Surfactant-free polyimide nanoparticles (<100 nm) were produced. Experimental details and principles of this technology were given based on the ternary diffusion, the liquid-liquid phase separation and the advanced nucleation and growth theory. Two types of methods [denoted as the forward titration method and the backward titration (BT) method] were examined. It was found that the BT method is extremely helpful to prepare polyimide nanoparticles (<100 nm). As another important aspect, explored stabilization mechanism of the resultant nanoparticle dispersions was supported by the comparative experiments, implying that selective solvation of nanoparticles and EPD/EPA complexes may play key roles in stabilization. PMID:15606287

  2. 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. PMID:26574523

  3. Manganese oxide nanosheets and a 2D hybrid of graphene-manganese oxide nanosheets synthesized by liquid-phase exfoliation

    NASA Astrophysics Data System (ADS)

    Coelho, João; Mendoza-Sánchez, Beatriz; Pettersson, Henrik; Pokle, Anuj; McGuire, Eva K.; Long, Edmund; McKeon, Lorcan; Bell, Alan P.; Nicolosi, Valeria

    2015-06-01

    Manganese oxide nanosheets were synthesized using liquid-phase exfoliation that achieved suspensions in isopropanol (IPA) with concentrations of up to 0.45 mg ml-1. A study of solubility parameters showed that the exfoliation was optimum in N,N-dimethylformamide followed by IPA and diethylene glycol. IPA was the solvent of choice due to its environmentally friendly nature and ease of use for further processing. For the first time, a hybrid of graphene and manganese oxide nanosheets was synthesized using a single-step co-exfoliation process. The two-dimensional (2D) hybrid was synthesized in IPA suspensions with concentrations of up to 0.5 mg ml-1 and demonstrated stability against re-aggregation for up to six months. The co-exfoliation was found to be a energetically favorable process in which both solutes, graphene and manganese oxide nanosheets, exfoliate with an improved yield as compared to the single-solute exfoliation procedure. This work demonstrates the remarkable versatility of liquid-phase exfoliation with respect to the synthesis of hybrids with tailored properties, and it provides proof-of-concept ground work for further future investigation and exploitation of hybrids made of two or more 2D nanomaterials that have key complementary properties for various technological applications.

  4. Migration of carbon nanotubes from liquid phase to vapor phase in the refrigerant-based nanofluid pool boiling

    PubMed Central

    2011-01-01

    The migration characteristics of carbon nanotubes from liquid phase to vapor phase in the refrigerant-based nanofluid pool boiling were investigated experimentally. Four types of carbon nanotubes with the outside diameters from 15 to 80 nm and the lengths from 1.5 to 10 μm were used in the experiments. The refrigerants include R113, R141b and n-pentane. The oil concentration is from 0 to 10 wt.%, the heat flux is from 10 to 100 kW·m-2, and the initial liquid-level height is from 1.3 to 3.4 cm. The experimental results indicate that the migration ratio of carbon nanotube increases with the increase of the outside diameter or the length of carbon nanotube. For the fixed type of carbon nanotube, the migration ratio decreases with the increase of the oil concentration or the heat flux, and increases with the increase of the initial liquid-level height. The migration ratio of carbon nanotube increases with the decrease of dynamic viscosity of refrigerant or the increase of liquid phase density of refrigerant. A model for predicting the migration ratio of carbon nanotubes in the refrigerant-based nanofluid pool boiling is proposed, and the predictions agree with 92% of the experimental data within a deviation of ±20%. PMID:21711730

  5. Factor Scores, Structure Coefficients, and Communality Coefficients

    ERIC Educational Resources Information Center

    Goodwyn, Fara

    2012-01-01

    This paper presents heuristic explanations of factor scores, structure coefficients, and communality coefficients. Common misconceptions regarding these topics are clarified. In addition, (a) the regression (b) Bartlett, (c) Anderson-Rubin, and (d) Thompson methods for calculating factor scores are reviewed. Syntax necessary to execute all four

  6. A group contribution activity coefficient model for enhanced oil recovery process involving electrolyte solutions: Part II-Solutions in the presence of partial molecular association

    SciTech Connect

    Chien, M.C.H.; Lee, S.T.

    1984-04-01

    Earlier in this series, a group contribution activity coefficient model for electrolyte solutions was developed based on Debye-Huckel theory, solvation theory and local composition theory. It was demonstrated that the model can satisfactorily correlate the complex thermodynamic properties of electrolyte solutions in the absence of partial molecular association. In this work, the above described model is extended to electrolyte solutions which exhibit partial molecular association. This model includes the chemical equilibrium theory to represent chemical association between molecular species in the solution. The equilibrium thermodynamic properties are then solved by invoking a recently developed simultaneous phase and chemical equilibrium calculation scheme. Studies show that the model is capable of modelling micellization and the complex phase transition of oil-water mixture containing an amphilphile, and that it can be incorporated in a simulator to study the mechanisms of recovery processes involving electrolyte solutions or to design such processes.

  7. Activity coefficients for NaCl-monosaccharide (D-glucose, D-galactose, D-xylose, D-arabinose)-water systems at 298.15 K.

    PubMed

    Zhuo, K; Wang, J; Wang, H

    2000-03-24

    Electrochemical cells with a sodium ion selectivity electrode (Na-ISE) versus a chloride ion selectivity electrode (Cl-ISE) as a reference electrode were used to determine the activity coefficients for NaCl-monosaccharide (D-glucose, D-galactose, D-xylose, and D-arabinose) systems in water at 298.15 K. A comparison of the results thus obtained was made with those determined by another electromotive force (emf) method. It is shown that agreement is excellent. The Gibbs free energy parameters of the interactions between these sugars and NaCl in water were evaluated together with the parameter C1(CHOH, exo), indicating the interaction of the exocyclic CHOH group of saccharide molecules and NaCl. The results suggested that the interactions of these monosaccharides with NaCl are controlled mostly by the dominant conformer of their molecules in water. PMID:10741826

  8. Effect of Silicon on Activity Coefficients of Siderophile Elements (P, Au, Pd, As, Ge, Sb, and In) in Liquid Fe, with Application to Core Formation

    NASA Technical Reports Server (NTRS)

    Righter, K.; Pando, K.; Danielson, L. R.; Humayun, M.; Righter, M.; Lapen, T.; Boujibar, A.

    2016-01-01

    Earth's core contains approximately 10 percent light elements that are likely a combination of S, C, Si, and O, with Si possibly being the most abundant. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE) in Fe liquids, and thus the partitioning behavior of those elements between core and mantle. The effect of Si can be small such as for Ni and Co, or large such as for Mo, Ge, Sb, As. The effect of Si on many siderophile elements is unknown yet could be an important, and as yet unquantified, influence on the core-mantle partitioning of SE. Here we report new experiments designed to quantify the effect of Si on the partitioning of P, Au, Pd, and many other SE between metal and silicate melt. The results will be applied to Earth, for which we have excellent constraints on the mantle siderophile element concentrations.

  9. Modeling solubility, acid-base properties and activity coefficients of amoxicillin, ampicillin and (+)6-aminopenicillanic acid, in NaCl(aq) at different ionic strengths and temperatures.

    PubMed

    Crea, Francesco; Cucinotta, Daniela; De Stefano, Concetta; Milea, Demetrio; Sammartano, Silvio; Vianelli, Giuseppina

    2012-11-20

    The total solubility of three penicillin derivatives was determined, in pure water and NaCl aqueous solutions at different salt concentrations (from ?0.15 to 1.0 mol L(-1) for ampicillin and amoxicillin, and from ?0.05 to 2.0 mol L(-1) for (+)6-aminopenicillanic acid), using the shake-flask method for generating the saturated solutions, followed by potentiometric analysis. The knowledge of the pH of solubilization and of the protonation constants determined in the same experimental conditions, allowed us to calculate, by means of the mass balance equations, the solubility of the neutral species at different ionic strength values, to model its dependence on the salt concentration and to determine the corresponding values at infinite dilution. The salting parameter and the activity coefficients of the neutral species were calculated by the Setschenow equation. The protonation constants of ampicillin and amoxicillin, determined at different temperatures (from T=288.15 to 318.15K), from potentiometric and spectrophotometric measurements, were used to calculate, by means of the Van't Hoff equation, the temperature coefficients at different ionic strength values and the corresponding protonation entropies. The protonation enthalpies of the (+)6-aminopenicillanic acid were determined by isoperibol calorimetric titrations at T=298.15K and up to I=2.0 mol L(-1). The dependence of the protonation constants on ionic strength was modeled by means of the Debye-Hckel and SIT (Specific ion Interaction Theory) approaches, and the specific interaction parameters of the ionic species were determined. The hydrolysis of the ?-lactam ring was studied by spectrophotometric and H NMR investigations as a function of pH, ionic strength and time. Potentiometric measurements carried out on the hydrolyzed (+)6-aminopenicillanic acid allowed us to highlight that the opened and the closed ?-lactam forms of the (+)6-aminopenicillanic acid have quite different acid-base properties. An analysis of literature solubility, protonation constants, enthalpies and activity coefficients is reported too. PMID:22903046

  10. In Situ Activation of Microcapsules

    NASA Technical Reports Server (NTRS)

    Morrison, Dennis R. (Inventor); Mosier, Benjamin (Inventor)

    2000-01-01

    Disclosed are microcapsules comprising a polymer shell enclosing two or more immiscible liquid phases in which a drug, or a prodrug and a drug activator are partitioned into separate phases. or prevented from diffusing out of the microcapsule by a liquid phase in which the drug is poorly soluble. Also disclosed are methods of using the microcapsules for in situ activation of drugs where upon exposure to an appropriate energy source the internal phases mix and the drug is activated in situ.

  11. Solidification of floating organic drop liquid-phase microextraction cell fishing with gas chromatography-mass spectrometry for screening bioactive components from Amomum villosum Lour.

    PubMed

    Xue, Xue; Yang, Depo; Wang, Dongmei; Xu, Xinjun; Zhu, Longping; Zhao, Zhimin

    2015-04-01

    In this study, a novel solidification of floating organic drop liquid-phase microextraction cell fishing with gas chromatography-mass spectrometry (SFOD-LPME-CF-GC-MS) method was established and used to screen, isolate and analyze bioactive components from Amomum villosum Lour. extract. Through comparision of its effect on the models of normal cell and inflammatory cells, anti-inflammatory active components of essential oil from A. villosum Lour. were readily screened, and the components obtained are in agreement with related pharmacological articles. SFOD-LPME-CF-GC-MS was used to analyze the interaction of A. villosum Lour. extracts with normal and lipopolysaccharide-stimulated RAW264.7 macrophage cells. The effect of A. villosum Lour. essential oil extracts in the LPS-stimulated RAW264.7 model were also assessed in terms of cytotoxicity and nitric oxide production as an indication of bioactivity. Three potentially bioactive components were identified, demonstrating that SFOD-LPME-CF-GC-MS can be used successfully in the drug-screening process. This approach avoids the requirement for protein precipitation, but more importantly, generates a high concentration ratio, allowing analysis of trace components in traditional Chinese medicines. SFOD-LPME-CF-GC-MS is a simple, fast, effective and reliable method for the screening and analysis of bioactive components, and it can be extended to screen other bioactive components from TCMs. PMID:25251881

  12. Liquid phase methanol LaPorte process development unit: Modification operation, and support studies. Task 3.6/3.7: Alternative catalyst/life run

    SciTech Connect

    Not Available

    1991-01-28

    In April 1987, Air Products started the third and final contract with the US Department of Energy to develop the Liquid Phase Methanol (LPMEOH) process. One of the objectives was to identify alternative commercial catalyst(s) for the process. This objective was strategically important as we want to demonstrate that the LPMEOH process is flexible and not catalyst selection limited. Among three commercially available catalysts evaluated in the lab, the catalyst with a designation of F21/0E75-43 was the most promising candidate. The initial judging criteria included not only the intrinsic catalyst activity but also the ability to be used effectively in a slurry reactor. The catalyst was then advanced for a 40-day life test in a laboratory 300 cc autoclave. The life test result also revealed superior stability when compared with that of a standard catalyst. Consequently, the new catalyst was recommended for demonstration in the Process Development Unit (PDU) at LaPorte, Texas. This report details the methodology of testing and selecting the catalyst.

  13. Ultrafast Intrinsic Photoresponse and Direct Evidence of Sub-gap States in Liquid Phase Exfoliated MoS2Thin Films

    PubMed Central

    Ghosh, Sujoy; Winchester, Andrew; Muchharla, Baleeswaraiah; Wasala, Milinda; Feng, Simin; Elias, Ana Laura; Krishna, M. Bala Murali; Harada, Takaaki; Chin, Catherine; Dani, Keshav; Kar, Swastik; Terrones, Mauricio; Talapatra, Saikat

    2015-01-01

    2-Dimensional structures with swift optical response have several technological advantages, for example they could be used as components of ultrafast light modulators, photo-detectors, and optical switches. Here we report on the fast photo switching behavior of thin films of liquid phase exfoliated MoS2, when excited with a continuous laser of λ = 658 nm (E = 1.88 eV), over a broad range of laser power. Transient photo-conductivity measurements, using an optical pump and THz probe (OPTP), reveal that photo carrier decay follows a bi-exponential time dependence, with decay times of the order of picoseconds, indicating that the photo carrier recombination occurs via trap states. The nature of variation of photocurrent with temperature confirms that the trap states are continuously distributed within the mobility gap in these thin film of MoS2, and play a vital role in influencing the overall photo response. Our findings provide a fundamental understanding of the photo-physics associated with optically active 2D materials and are crucial for developing advanced optoelectronic devices. PMID:26175112

  14. Modeling, design, packing and experimental analysis of liquid-phase shear-horizontal surface acoustic wave sensors

    NASA Astrophysics Data System (ADS)

    Pollard, Thomas B

    Recent advances in microbiology, computational capabilities, and microelectromechanical-system fabrication techniques permit modeling, design, and fabrication of low-cost, miniature, sensitive and selective liquid-phase sensors and lab-on-a-chip systems. Such devices are expected to replace expensive, time-consuming, and bulky laboratory-based testing equipment. Potential applications for devices include: fluid characterization for material science and industry; chemical analysis in medicine and pharmacology; study of biological processes; food analysis; chemical kinetics analysis; and environmental monitoring. When combined with liquid-phase packaging, sensors based on surface-acoustic-wave (SAW) technology are considered strong candidates. For this reason such devices are focused on in this work; emphasis placed on device modeling and packaging for liquid-phase operation. Regarding modeling, topics considered include mode excitation efficiency of transducers; mode sensitivity based on guiding structure materials/geometries; and use of new piezoelectric materials. On packaging, topics considered include package interfacing with SAW devices, and minimization of packaging effects on device performance. In this work novel numerical models are theoretically developed and implemented to study propagation and transduction characteristics of sensor designs using wave/constitutive equations, Green's functions, and boundary/finite element methods. Using developed simulation tools that consider finite-thickness of all device electrodes, transduction efficiency for SAW transducers with neighboring uniform or periodic guiding electrodes is reported for the first time. Results indicate finite electrode thickness strongly affects efficiency. Using dense electrodes, efficiency is shown to approach 92% and 100% for uniform and periodic electrode guiding, respectively; yielding improved sensor detection limits. A numerical sensitivity analysis is presented targeting viscosity using uniform-electrode and shear-horizontal mode configurations on potassium-niobate, langasite, and quartz substrates. Optimum configurations are determined yielding maximum sensitivity. Results show mode propagation-loss and sensitivity to viscosity are correlated by a factor independent of substrate material. The analysis is useful for designing devices meeting sensitivity and signal level requirements. A novel, rapid and precise microfluidic chamber alignment/bonding method was developed for SAW platforms. The package is shown to have little effect on device performance and permits simple macrofluidic interfacing. Lastly, prototypes were designed, fabricated, and tested for viscosity and biosensor applications; results show ability to detect as low as 1% glycerol in water and surface-bound DNA crosslinking.

  15. Condensation coefficient of methanol vapor near vapor-liquid equilibrium states

    NASA Astrophysics Data System (ADS)

    Fujikawa, S.; Yano, T.; Ichijo, M.; Iwanami, K.

    This paper is concerned with the nonequilibrium condensation from a vapor to a liquid phase on the plate endwall of a shock tube behind a reflected shock wave. The growth of a liquid film on the endwall is measured by an optical interferometer using a laser beam. The experiment is carefully conducted on the precisely designed apparatus, and thereby the condensation coefficient of methanol vapor is determined in a wide range of vapor-liquid conditions from near to far from equilibrium states. The result shows that the condensation coefficient increases with the increase of the ratio of number densities of vapor and saturated vapor at the interface.

  16. Ultrasound-assisted liquid-phase microextraction based on a nanostructured supramolecular solvent.

    PubMed

    Moradi, Morteza; Yamini, Yadollah; Tayyebi, Moslem; Asiabi, Hamid

    2013-05-01

    Novel ultrasonically enhanced supramolecular solvent microextraction (USESSM) then high-performance liquid chromatography with ultraviolet detection have been used for extraction and determination of phthalates in water and cosmetics. Coacervates consisting of decanoic acid-based nano-structured aggregates, specifically reverse micelles, have been used the first time as solvents for ultrasound-assisted emulsification microextraction (USAEME). Sonication accelerated mass transfer of the target analytes into the nano-structured solvent from the aqueous sample, thus reducing extraction time. Several conditions affecting extraction efficiency, for example the concentrations of major components of the supramolecular solvent (tetrahydrofuran and decanoic acid), sample solution pH, salt addition, and ultrasonication time, were investigated and optimized. Under the optimum conditions, preconcentration of the analytes ranged from 176 to 412-fold and the linear range was 0.5-100 ?g L(-1), with correlation coefficients (R(2)) ? 0.9984. The detection sensitivity of the method was excellent, with limits of detection (LOD, S/N = 3) in the range 0.10-0.70 ?g L(-1) and precision in the range 4.1-11.7 % (RSD, n = 5). This method was successfully used for analysis of phthalates in water and cosmetics, with good recovery of spiked phthalates (91.0-108.5 %). PMID:23417551

  17. Free-surface optical scattering as an indicator of the shock-induced solid-liquid phase transition in tin

    NASA Astrophysics Data System (ADS)

    Stevens, G. D.; Lutz, S. S.; Marshall, B. R.; Turley, W. D.; Veeser, L. R.; Furlanetto, M. R.; Hixson, R. S.; Holtkamp, D. B.; Jensen, B. J.; Rigg, P. A.; Wilke, M. D.

    2008-07-01

    When highly polished metal surfaces melt upon release after shock loading, they exhibit features that suggest that significant surface changes accompany the phase transition. The reflection of light from such surfaces changes from specular (preshock) to diffuse upon melting. A familiar manifestation of this phenomenon is the loss of signal light observed with a velocity interferometer system for any reflector, which occurs at pressures high enough to melt the free surface. Unlike many other potential material phase-sensitive diagnostics (e.g., reflectometry and conductivity) that show relatively small changes, the specularity of reflection provides a more sensitive and definitive indication of the solid-liquid phase transition. Data are presented that support the hypothesis that specularity changes indicate melt in a way that can be measured easily and unambiguously.

  18. Microstructure and Mechanical Properties of Al2024/Ti-6Al-4V Transient Liquid Phase Bonded Joint

    NASA Astrophysics Data System (ADS)

    Samavatian, M.; Halvaee, A.; Amadeh, A.; Zakipour, S.

    2015-06-01

    Transient liquid phase bonding mechanism of two dissimilar alloys Al2024 and Ti-6Al-4V using Sn-Ag-Cu-Ni interlayer with different thicknesses (40, 80, 120 µm) was studied at 510 °C under 10-4 mBar. The results showed that with an increase in bonding time, the interlayer elements diffused into the parent metals and formed various intermetallic compounds in the joint zone. While diffusion mechanism led to isothermal solidification and process completion at 60 min bonding time, remaining interlayer was observed in the bond made with 120-μm-thick interlayer. With an increase in bonding time growth, the hardness of the joints at the interface rose to 139 VHN. Although the shear strength was proportional to the bonding time, the interlayer thickness showed a critical value at which the maximum shear strength was attained.

  19. The Boson peak in confined water: An experimental investigation of the liquid-liquid phase transition hypothesis

    NASA Astrophysics Data System (ADS)

    Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Wang, Zhe; Chen, Sow-Hsin

    2015-10-01

    The Boson peak (BP) of deeply cooled confined water is studied by using inelastic neutron scattering (INS) in a large interval of the ( P, T) phase plane. By taking into account the different behavior of such a collective vibrational mode in both strong and fragile glasses as well as in glass-forming materials, we were able to determine the Widom line that characterizes supercooled bulk water within the frame of the liquid-liquid phase transition (LLPT) hypothesis. The peak frequency and width of the BP correlated with the water polymorphism of the LLPT scenario, allowing us to distinguish the "low-density liquid" (LDL) and "high-density liquid" (HDL) phases in deeply cooled bulk water.Moreover, the BP properties afford a further confirmation of theWidom line temperature T W as the ( P, T) locus in which the local structure of water transforms from a predominately LDL form to a predominately HDL form.

  20. Dynamic liquid-phase microextraction of three phthalate esters from water samples and determination by gas chromatography.

    PubMed

    Xu, Jing; Liang, Pei; Zhang, Taozhi

    2007-07-30

    A fast and simple method, which involves dynamic liquid-phase microextraction followed by gas chromatography with flame ionization detection, has been developed to facilitate the identification and quantification of three phthalate esters (dimethyl phthalate (DMP), diethyl phthalate (DEP), and di-n-butyl phthalate (DnBP)) in water samples. Experimental parameters affecting the extraction efficiency, such as extraction solvent, solvent volume, dwell time and extraction frequency were investigated. Under the optimal conditions, the method yields a linear calibration curve over three orders of magnitude for the target analytes. The limits of detection of DMP, DEP and DnBP were 4.30, 0.66 and 0.43 ng mL(-1), respectively, and relative standard deviations at the 100 ng mL(-1) level were 6.4%, 5.4% and 5.2%, respectively (n=6). Lake water, tap water and bottled mineral water samples were successfully analyzed using the proposed method. PMID:17658305