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Sample records for adsorption phase behavior

  1. 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.

  2. Ionic strength dependent vesicle adsorption and phase behavior of anionic phospholipids on a gold substrate.

    PubMed

    Pramanik, Sumit Kumar; Seneca, Senne; Ethirajan, Anitha; Neupane, Shova; Renner, Frank Uwe; Losada-Pérez, Patricia

    2016-03-08

    The authors report on the effect of ionic strength on the formation of supported vesicle layers of anionic phospholipids 1,2-dimyristoyl-sn-glycero-3-phospho-rac-glycerol (DMPG) and dimyristoylphosphatidylserine (DMPS) onto gold. Using quartz crystal microbalance with dissipation monitoring the authors show that vesicle adsorption is mainly governed by NaCl concentration, reflecting the importance of electrostatic interactions in anionic lipids, as compared to zwitterionic 1,2-dimyristoyl-sn-glycero-3-phosphocholine. At low ionic strength, low or no adsorption is observed as a result of vesicle-vesicle electrostatic repulsion. At medium ionic strength, the negative charges of DMPG and DMPS are screened resulting in larger adsorption and a highly dissipative intact vesicle layer. In addition, DMPS exhibits a peculiar behavior at high ionic strength that depends on the temperature of the process.

  3. Adsorptive behavior and solid-phase microextraction of bare stainless steel sample loop in high performance liquid chromatography.

    PubMed

    Zhang, Wenpeng; Zhang, Zixin; Meng, Jiawei; Zhou, Wei; Chen, Zilin

    2014-10-24

    In this work, we interestingly happened to observe the adsorption of stainless steel sample loop of HPLC. The adsorptive behaviors of the stainless steel loop toward different kinds of compounds were studied, including polycyclic aromatic hydrocarbons (PAHs), halogeno benzenes, aniline derivatives, benzoic acid derivatives, phenols, benzoic acid ethyl ester, benzaldehyde, 1-phenyl-ethanone and phenethyl alcohol. The adsorptive mechanism was probably related to hydrophobic interaction, electron-rich element-metal interaction and hydrogen bond. Universal adsorption of stainless steels was also testified. Inspired by its strong adsorptive capability, bare stainless steel loop was developed as a modification-free in-tube device for solid-phase microextraction (SPME), which served as both the substrate and sorbent and possessed ultra-high strength and stability. Great extraction efficiency toward PAHs was obtained by stainless steel loop without any modification, with enrichment factors of 651-834. By connecting the stainless steel loop onto a six-port valve, an online SPME-HPLC system was set up and an SPME-HPLC method has been validated for determination of PAHs. The method has exceptionally low limits of detection of 0.2-2pg/mL, which is significantly lower than that of reported methods with different kinds of sorbents. Wide linear range (0.5-500 and 2-1000pg/mL), good linearity (R(2)≥0.9987) and good reproducibility (RSD≤2.9%) were also obtained. The proposed method has been applied to determine PAHs in environmental samples. Good recoveries were obtained, ranging from 88.5% to 93.8%.

  4. pi-Selective stationary phases: (II) Adsorption behavior of substituted aromatic compounds on n-alkyl-phenyl stationary phases

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A; Mayfield, Kirsty; Dennis, Gary; Shalliker, R. Andrew

    2010-01-01

    The frontal analysis method was used to measure the adsorption isotherms of phenol, 4-chlorophenol, p-cresol, 4-methoxyphenol and caffeine on a series of columns packed with home-made alkyl-phenyl bonded silica particles. These ligands consist of a phenyl ring tethered to the silica support via a carbon chain of length ranging from 0 to 4 atoms. The adsorption isotherm models that fit best to the data account for solute-solute interactions that are likely caused by p-p interactions occurring between aromatic compounds and the phenyl group of the ligand. These interactions are the dominant factor responsible for the separation of low molecular weight aromatic compounds on these phenyl-type stationary phases. The saturation capacities depend on whether the spacer of the ligands have an even or an odd number of carbon atoms, with the even alkyl chain lengths having a greater saturation capacity than the odd alkyl chain lengths. The trends in the adsorption equilibrium constant are also significantly different for the even and the odd chain length ligands.

  5. 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)

  6. Adsorption behavior of alpha -cypermethrin on cork and activated carbon.

    PubMed

    Domingues, Valentina F; Priolo, Giuseppe; Alves, Arminda C; Cabral, Miguel F; Delerue-Matos, Cristina

    2007-08-01

    Studies were undertaken to determine the adsorption behavior of alpha -cypermethrin [R)-alpha -cyano-3-phenoxybenzyl(1S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-alpha-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze alpha -cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time - 24 hours for both cork (1-2 mm and 3-4 mm) and GAC. For the studied alpha -cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1-2 mm have the maximum amount of adsorbed alpha-cypermethrin (q(m)) (303 microg/g); followed by GAC (186 microg/g) and cork 3-4 mm (136 microg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the alpha -cypermethrin adsorption phenomena on GAC, while alpha -cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing alpha -cypermethrin from water.

  7. Adsorption behavior of the three species of the biprotic peptide Phe-Ala onto an end-capped C18-bonded organic/inorganic hybrid stationary phase.

    PubMed

    Gritti, Fabrice; Guiochon, Georges

    2009-12-15

    We recorded the overloaded elution band profiles of the dipeptide phenylalanine-alanine (Phe-Ala) on a column packed with C18-bonded organic (ethyl)/inorganic (silica) hybrid porous particles (BEH), eluted with a series of buffered methanol-water mobile phases (20/80, v/v). The (W)(S)pHs of the mobile phases were successively adjusted with addition of suitable buffers to values of 1.67, 2.44, 3.83, 4.94, 7.41, and 10.71 (where the notation (W)(S)pH means that the pH of the solution is directly measured in the solution (S) after the electrode was calibrated in pure water (W)). The ionic strength of the eluent was kept constant at 20 mM. The injected samples had different sizes and concentrations. The retention of the low-concentration samples was minimum at an intermediate (W)(S)pH (k' approximately 0.5) and maximum for the lowest (k' approximately 1.3) and highest (k' approximately 3.5) (W)(S)pHs showing that the zwitterion (+Phe-Ala-) is less strongly adsorbed than the positively (+Phe-Ala) and negatively (Phe-Ala-) charged species of the dipeptide onto BEH-C18. The elution profiles of the concentrated samples demonstrated that the adsorption isotherm of the zwitterionic species is an anti-Langmuirian Moreau isotherm due to significant adsorbate-adsorbate interactions, whereas the isotherms of the charged species are more conventional Langmuir isotherms. A simple ternary isotherm for the coadsorption of the three dipeptide species is proposed. It accounts well for the complex band profiles observed when large concentrated samples of the peptide are injected under controlled pH conditions. The slight departure between the calculated and the experimental band profiles obtained under uncontrolled pH conditions suggests the possible adsorption of the buffer components onto the packing material and the possible influence of microenvironment effects near the stationary phase surface, which would affect the local pH along the column. Preparative chromatography of

  8. A new theoretical approach to adsorption desorption behavior of Ga on GaAs surfaces

    NASA Astrophysics Data System (ADS)

    Kangawa, Y.; Ito, T.; Taguchi, A.; Shiraishi, K.; Ohachi, T.

    2001-11-01

    We propose a new theoretical approach for studying adsorption-desorption behavior of atoms on semiconductor surfaces. The new theoretical approach based on the ab initio calculations incorporates the free energy of gas phase; therefore we can calculate how adsorption and desorption depends on growth temperature and beam equivalent pressure (BEP). The versatility of the new theoretical approach was confirmed by the calculation of Ga adsorption-desorption transition temperatures and transition BEPs on the GaAs (0 0 1) -(4×2) β2 Ga-rich surface. This new approach is feasible to predict how adsorption and desorption depend on the growth conditions.

  9. Adsorption Behavior of Nonplanar Phthalocyanines: Competition of Different Adsorption Conformations

    PubMed Central

    2016-01-01

    Using density functional theory augmented with state-of-the-art van der Waals corrections, we studied the geometric and electronic properties of nonplanar chlorogallium-phthalocyanine GaClPc molecules adsorbed on Cu(111). Comparing these results with published experimental data for adsorption heights, we found indications for breaking of the metal–halogen bond when the molecule is heated during or after the deposition process. Interestingly, the work-function change induced by this dissociated geometry is the same as that computed for an intact adsorbate layer in the “Cl-down” configuration, with both agreeing well with the experimental photoemission data. This is unexpected, as the chemical natures of the adsorbates and the adsorption distances are markedly different in the two cases. The observation is explained as a consequence of Fermi-level pinning due to fractional charge transfer at the interface. Our results show that rationalizing the adsorption configurations on the basis of electronic interface properties alone can be ambiguous and that additional insight from dispersion-corrected DFT simulations is desirable. PMID:27066160

  10. Sb/Si(111) adsorption: hidden phase transitions behind Langmuir-like isotherms.

    PubMed

    Guesmi, H; Lapena, L; Ranguis, A; Müller, P; Tréglia, G

    2005-02-25

    The experimental study of the thermodynamic and kinetic properties of the Sb/Si(111) interface reveals a surprising behavior: a 2D phase condensates when the Sb coverage increases, indicating strong attractive Sb-Sb interactions, whereas the isotherms present a quasi-Langmuir shape, suggesting that these interactions should be negligible. Ab initio calculations raise this contradiction: while the adsorption site evolves from ternary towards the on-top position with increasing coverage, the character of the Sb-Sb effective interactions changes from repulsive towards attractive, resulting in an almost constant average adsorption energy. A simple (Langmuir) thermodynamic behavior can then be the consequence of a surface phase transition.

  11. Adsorption behavior of heavy metals on biomaterials.

    PubMed

    Minamisawa, Mayumi; Minamisawa, Hiroaki; Yoshida, Shoichiro; Takai, Nobuharu

    2004-09-08

    We have investigated adsorption of Cd(II) and Pb(II) at pH 2-6.7 onto the biomaterials chitosan, coffee, green tea, tea, yuzu, aloe, and Japanese coarse tea, and onto the inorganic adsorbents, activated carbon and zeolite. High adsorptive capabilities were observed for all of the biomaterials at pH 4 and 6.7. In the adsorption of Cd(II), blend coffee, tea, green tea, and coarse tea have comparable loading capacities to activated carbon and zeolite. Although activated carbon, zeolite, and chitosan are utilized in a variety of fields such as wastewater treatment, chemical and metallurgical engineering, and analytical chemistry, these adsorbents are costly. On the other hand, processing of the test biomaterials was inexpensive, and all the biomaterials except for chitosan were able to adsorb large amounts of Pb(II) and Cd(II) ions after a convenient pretreatment of washing with water followed by drying. The high adsorption capability of the biomaterials prepared from plant materials is promising in the development of a novel, low-cost adsorbent. From these results, it is concluded that heavy metal removal using biomaterials would be an effective method for the economic treatment of wastewater. The proposed adsorption method was applied to the determination of amounts of Cd(II) and Pb(II) in water samples.

  12. Phase 2 Methyl Iodide Deep-Bed Adsorption Tests

    SciTech Connect

    Soelberg, Nick; Watson, Tony

    2014-09-01

    Nuclear fission produces fission products (FPs) and activation products, including iodine-129, which could evolve into used fuel reprocessing facility off-gas systems, and could require off-gas control to limit air emissions to levels within acceptable emission limits. Research, demonstrations, and some reprocessing plant experience have indicated that diatomic iodine can be captured with efficiencies high enough to meet regulatory requirements. Research on the capture of organic iodides has also been performed, but to a lesser extent. Several questions remain open regarding the capture of iodine bound in organic compounds. Deep-bed methyl iodide adsorption testing has progressed according to a multi-laboratory methyl iodide adsorption test plan. This report summarizes the second phase of methyl iodide adsorption work performed according to this test plan using the deep-bed iodine adsorption test system at the Idaho National Laboratory (INL), performed during the second half of Fiscal Year (FY) 2014. Test results continue to show that methyl iodide adsorption using AgZ can achieve total iodine decontamination factors (DFs, ratios of uncontrolled and controlled total iodine levels) above 1,000, until breakthrough occurred. However, mass transfer zone depths are deeper for methyl iodide adsorption compared to diatomic iodine (I2) adsorption. Methyl iodide DFs for the Ag Aerogel test adsorption efficiencies were less than 1,000, and the methyl iodide mass transfer zone depth exceeded 8 inches. Additional deep-bed testing and analyses are recommended to (a) expand the data base for methyl iodide adsorption under various conditions specified in the methyl iodide test plan, and (b) provide more data for evaluating organic iodide reactions and reaction byproducts for different potential adsorption conditions.

  13. Adsorption behavior of the catechins and caffeine onto polyvinylpolypyrrolidone.

    PubMed

    Dong, Zhan-Bo; Liang, Yue-Rong; Fan, Fang-Yuan; Ye, Jian-Hui; Zheng, Xin-Qiang; Lu, Jian-Liang

    2011-04-27

    Adsorbent is one of the most important factors for separation efficiency in fixed-bed purification techniques. The adsorption behavior of catechins and caffeine onto polyvinylpolypyrrolidone (PVPP) was investigated by static adsorption tests. The results showed that catechins rather than caffeine were preferred to adsorb onto PVPP since the adsorption selectivity coefficient of total catechins vs caffeine was around 22.5, and that adsorption of catechins could be described by the pseudo-second-order model. Adsorption amount of caffeine onto PVPP in green tea extracts solution was much higher than that in purified caffeine solution although the initial concentration of caffeine was similar in the two solutions, indicating the caffeine might be attached with catechins which were adsorbed by PVPP instead of being adsorbed by PVPP directly. The results also showed that the adsorption capacity of catechins and caffeine decreased with an increase in temperature, and that Freundlich and Langmuir models were both suitable for describing the isothermal adsorption of catechins, but not suitable for caffeine. The predicted maximum monolayer adsorption capacity of total catechins by PVPP was 671.77 mg g(-1) at 20 °C, which was significantly higher than that by other reported adsorbents. The thermodynamics analyses indicated that the adsorption of catechins onto PVPP was a spontaneous and exothermic physisorption process, revealing lower temperature was favorable for the adsorption of catechins. Elution tests showed that the desorption rates of catechins and caffeine were higher than 91% and 99% after two elution stages; in detail, almost all of the caffeine could be washed down at the water eluting stage, while catechins could be recovered at the dimethyl sulfoxide/ethanol solution eluting stage. Thus, the PVPP could be used as an excellent alternative adsorbent candidate for separating catechins from crude tea extracts, although some investigations, such as exploring the new

  14. The adsorption behavior of U(VI) on granite.

    PubMed

    Fan, Q H; Hao, L M; Wang, C L; Zheng, Z; Liu, C L; Wu, W S

    2014-03-01

    The effects of pH, counter ions and temperature on the adsorption of U(VI) on Beishan granite (BsG) were investigated in the presence and absence of fulvic acid (FA) and humic acid (HA). The adsorption edge of U(VI) on BsG suggested that U(VI) adsorption was mainly controlled by ion exchange and outer-sphere complexation at low pH, whereas inner-sphere complex was the dominant adsorption species in the pH range of 4.0-9.0. Above pH 9.0, Na2U2O7 might play an important role in the rise of U(VI) adsorption again. Counter ions such as Cl(-), SO4(2-) and PO4(3-) can provoke U(VI) adsorption on BsG to some extent, which was directly correlated to the complexing ability of U(VI)-ligand. More noticeably, the large enhancement of U(VI) adsorption in the presence of phosphate can be attributed to the ternary complex formation (BsG-PO4-UO2), precipitation ((UO2)3(PO4)2(s)) and secondary phase (Na-autunite). Both FA and HA can slightly increase U(VI) adsorption at low pH, whereas they strongly inhibited U(VI) adsorption at high pH range. Artificial synthesized granite (AsG) prepared in the laboratory is impossible to use as an analogue of natural granite because of the large difference in the adsorption and surface properties.

  15. Molecular simulation of excess isotherm and excess enthalpy change in gas-phase adsorption.

    PubMed

    Do, D D; Do, H D; Nicholson, D

    2009-01-29

    We present a new approach to calculating excess isotherm and differential enthalpy of adsorption on surfaces or in confined spaces by the Monte Carlo molecular simulation method. The approach is very general and, most importantly, is unambiguous in its application to any configuration of solid structure (crystalline, graphite layer or disordered porous glass), to any type of fluid (simple or complex molecule), and to any operating conditions (subcritical or supercritical). The behavior of the adsorbed phase is studied using the partial molar energy of the simulation box. However, to characterize adsorption for comparison with experimental data, the isotherm is best described by the excess amount, and the enthalpy of adsorption is defined as the change in the total enthalpy of the simulation box with the change in the excess amount, keeping the total number (gas + adsorbed phases) constant. The excess quantities (capacity and energy) require a choice of a reference gaseous phase, which is defined as the adsorptive gas phase occupying the accessible volume and having a density equal to the bulk gas density. The accessible volume is defined as the mean volume space accessible to the center of mass of the adsorbate under consideration. With this choice, the excess isotherm passes through a maximum but always remains positive. This is in stark contrast to the literature where helium void volume is used (which is always greater than the accessible volume) and the resulting excess can be negative. Our definition of enthalpy change is equivalent to the difference between the partial molar enthalpy of the gas phase and the partial molar enthalpy of the adsorbed phase. There is no need to assume ideal gas or negligible molar volume of the adsorbed phase as is traditionally done in the literature. We illustrate this new approach with adsorption of argon, nitrogen, and carbon dioxide under subcritical and supercritical conditions.

  16. Carbon Dioxide Adsorption Behavior of Modified HKUST-1

    NASA Astrophysics Data System (ADS)

    Ma, Lan; Tang, Huamin; Zhou, Chaohua; Zhang, Hongpeng; Yan, Chunxiao; Hu, Xiaochun; Yang, Yang; Yang, Weiwei; Li, Yuming; He, Dehua

    2014-12-01

    A kind of typical metal-organic frameworks (MOFs) material, HKUST-1 was prepared by hydrothermal method and characterized by XRD and SEM. The results of characterizations manifested that HKUST-1 showed a regular octahedral crystal structure. The as-prepared HKUST-1 was modified by several kinds of organic base materials and the CO2 adsorption behaviors of modified HKUST-1 materials were evaluated. The CO2 adsorption capacities of different base modified HKUST-1 varied with the base intensity of modified organic base materials.

  17. The Influence of Adsorption on PVT Measurements in the Gaseous Phase

    NASA Astrophysics Data System (ADS)

    Chernyak, Y.; Zhelezny, V. P.; Yokozeki, A.

    1999-11-01

    PVT measurements of 1,1,1,2-tetrafluoroethane (C2H2F4, HFC-134a) and its blend with octofluoropropane (C3F8, FC-218) have been performed in the gas phase near the dew curve. The experimental data were obtained by variable-volume and vibrating tube methods. Discrepancies in the behavior of isotherms from their classical behavior were experimentally observed. It was found that the phase transition does not go to completion at a single point of the thermodynamic surface but extends over a limited range of conditions. Obtained results are in accordance with a concept of adsorption of the vapor sample on the surface of the experimental cell. An increase in adsorption under the conditions close to condensation is caused by capillary condensation of the sample at the walls of the cell that initiates an early phase transition. The ranges of diffuse phase transitions were determined for 1,1,1,2-tetrafluoroethane as well as for its mixture with octofluoropropane at different thermodynamic parameters. The influence of selective adsorption on the change in the conditions of phase transition of the 1,1,1,2-tetrafluoroethane/octofluoropropane mixture was also experimentally studied.

  18. Effects of heat treatment of calcium hydroxyapatite particles on the protein adsorption behavior.

    PubMed

    Kandori, Kazuhiko; Mizumoto, Saki; Toshima, Satoko; Fukusumi, Masao; Morisada, Yoshiaki

    2009-08-06

    The effects of heat treatment of calcium hydroxyapatite (Hap) on the protein adsorption behavior were examined using typical proteins of bovine serum albumin (BSA: isoelectric point (iep) = 4.7, molecular mass (Ms) = 67,200 Da, acidic protein), myoglobin (MGB: iep = 7.0, Ms = 17,800 Da, neutral protein), and lysozyme (LSZ: iep = 11.1, Ms = 14,600 Da, basic protein). The TEM, XRD, and gas adsorption measurements ascertained that all of the Hap particles examined were highly crystallized and nonporous. The Hap single phase was continued up to the heat treatment temperature of 600 degrees C. However, after treatment above 800 degrees C in air, the beta-Ca3(PO4)2 (beta-TCP) phase slightly appeared. TG and ICP-AES measurements suggested that all of the Hap particles are Ca2+-deficient. Also, it was indicated from FTIR and XPS measurements that a partially dehydrated oxyhydroxyapatite (pd-OHap) was formed after treatment at high temperature. The saturated amounts of adsorbed BSA (nsBSA) did not vary on the Hap particles after heat treatment at 200 and 400 degrees C. However, nsBSA values were increased by raising the heat treatment temperature above 600 degrees C. The adsorption coverage of BSA was increased up to ca. 1.4. This adsorption coverage of BSA (thetaBSA) over unity suggests that the BSA molecules densely adsorbed and a part of BSA molecules adsorbed as end-on type on the Hap particle surface or BSA molecules became contracted. Similar adsorption behavior was observed on the LSZ system, but the adsorption coverage of LSZ (thetaLSZ) values are much less than thetaBSA. On the other hand, no effect of the heat treatment of Hap particles was observed on the adsorption of MGB. The increases of nsBSA and nsLSZ were explained by the increase of calcium and phosphate ions in the solutions dissolved from beta-TCP formed after heat treatment of Hap, especially treated at high temperature. The dissolved Ca2+ and PO(4)3 - ions may act as binders between proteins and Hap

  19. New Method for Evaluating Irreversible Adsorption and Stationary Phase Bleed in Gas Chromatographic Capillary Columns

    SciTech Connect

    Wright, Bob W.; Wright, Cherylyn W.

    2012-10-26

    A novel method for the evaluation of gas chromatographic (GC) column inertness has been developed using a tandem GC approach. Typically column inertness is measured by analyte peak shape evaluation. In general, silica, glass, and metal surfaces are chemically reactive and can cause analyte adsorption, which typically is observed as chromatographic peak tailing. Adsorption processes produce broad, short chromatographic peaks that confound peak area determinations because a significant portion can reside in the noise. In addition, chromatographic surfaces and stationary phases can irreversibly adsorb certain analytes without obvious degradation of peak shape. The inertness measurements described in this work specifically determine the degree of irreversible adsorption behavior of specific target compounds at levels ranging from approximately 50 picograms to 1 nanogram on selected gas chromatographic columns. Chromatographic columns with 5% phenylmethylsiloxane, polyethylene glycol (wax), trifluoropropylsiloxane, and 78% cyanopropylsiloxane stationary phases were evaluated with a variety of phosphorus- and sulfur- containing compounds selected as test compounds due to their ease of adsorption and importance in trace analytical detection. In addition, the method was shown effective for characterizing column bleed.

  20. Adsorption of albumin on prosthetic materials: implication for tribological behavior.

    PubMed

    Serro, A P; Gispert, M P; Martins, M C L; Brogueira, P; Colaço, R; Saramago, B

    2006-09-01

    The orthopedic prosthesis used to substitute damaged natural joints are lubricated by a pseudosynovial fluid that contains biological macromolecules with potential boundary lubrication properties. Proteins are some of those macromolecules whose role in the lubrication process is not yet completely understood. In a previous work, we investigated the influence of the presence of albumin, the major synovial protein, upon the tribological behavior of three of the most used pairs of artificial joint materials: ultra high molecular weight polyethylene (UHMWPE) against counterfaces of alumina, CoCrMo alloy, and 316L stainless steel. Albumin was found to cause a significant decrease in the friction coefficient when the counterfaces were metallic because transfer of UHMWPE was avoided, but this effect was much weaker in the case of alumina. The objective of the present work was to look for an explanation for these differences in tribological behavior in terms of albumin adsorption. With this goal, studies on adsorption of bovine serum albumin (BSA) on the counterface materials, from a biological model fluid (Hanks' balanced salt solution), were carried out using radiolabeled albumin ((125)I-BSA), X-ray photoelectron spectroscopy, and atomic force microscopy. The conclusion from all techniques is that the driving force for albumin adsorption is higher on the metals than on alumina. These results confirm that the greater the amount of protein adsorbed on the counterface, the more efficient is the protection against the transfer of polymeric film to the counterface.

  1. Phase Behavior of Ionic Microgels

    NASA Astrophysics Data System (ADS)

    Gottwald, D.; Likos, C. N.; Kahl, G.; Löwen, H.

    2004-02-01

    We employ effective interaction potentials between spherical polyelectrolyte microgels in order to investigate theoretically the structure, thermodynamics, and phase behavior of ionic microgel solutions. Combining a genetic algorithm with accurate free energy calculations we are able to perform an unrestricted search of candidate crystal structures. Hexagonal, body-centered orthogonal, and trigonal crystals are found to be stable at high concentrations and charges of the microgels, accompanied by reentrant melting behavior and fluid-fcc-bcc transitions below the overlap concentration.

  2. Phase behavior of ionic microgels.

    PubMed

    Gottwald, D; Likos, C N; Kahl, G; Löwen, H

    2004-02-13

    We employ effective interaction potentials between spherical polyelectrolyte microgels in order to investigate theoretically the structure, thermodynamics, and phase behavior of ionic microgel solutions. Combining a genetic algorithm with accurate free energy calculations we are able to perform an unrestricted search of candidate crystal structures. Hexagonal, body-centered orthogonal, and trigonal crystals are found to be stable at high concentrations and charges of the microgels, accompanied by reentrant melting behavior and fluid-fcc-bcc transitions below the overlap concentration.

  3. Phase 1 Methyl Iodide Deep-Bed Adsorption Tests

    SciTech Connect

    Soelberg, Nick; Watson, Tony

    2014-08-22

    Nuclear fission results in the production of fission products (FPs) and activation products including iodine-129, which could evolve into used fuel reprocessing facility off-gas systems, and could require off-gas control to limit air emissions to levels within acceptable emission limits. Research, demonstrations, and some reprocessing plant experience have indicated that diatomic iodine can be captured with efficiencies high enough to meet regulatory requirements. Research on the capture of organic iodides has also been performed, but to a lesser extent [Jubin 2012b]. Several questions remain open regarding the capture of iodine bound in organic compounds. Deep-bed methyl iodide adsorption testing has progressed according to a multi-laboratory methyl iodide adsorption test plan. This report summarizes the first phase of methyl iodide adsorption work performed according to this test plan using the deep-bed iodine adsorption test system at the Idaho National Laboratory (INL), performed during Fiscal Year (FY) 2013 and early FY-2014. Testing has been performed to address questions posed in the test plan, and followed the testing outline in the test plan. Tests established detection limits, developed procedures for sample analysis with minimal analytical interferences, and confirmed earlier results that show that the methyl iodide reacts when in contact with the AgZ sorbent, and not significantly in the gas flow upstream of the sorbent. The reaction(s) enable separation of the iodine from the organic moiety, so that the iodine can chemisorb onto the sorbent. The organic moiety can form other compounds, some of which are organic compounds that are detected and can be tentatively identified using GC-FID and GCMS. Test results also show that other gas constituents (NOx and/or H2O) can affect the methyl iodide reactions. With NOx and H2O present in the gas stream, the majority of uncaptured iodine exiting iodine-laden sorbent beds is in the form of I2 or HI, species that

  4. Adsorption and recovery issues of recombinant monoclonal antibodies in reversed-phase liquid chromatography.

    PubMed

    Fekete, Szabolcs; Beck, Alain; Wagner, Elsa; Vuignier, Karine; Guillarme, Davy

    2015-01-01

    The poor recovery of large biomolecules is a well-known issue in reversed-phase liquid chromatography. Several papers have reported this problem, but the reasons behind this behavior are not yet fully understood. In the present study, state-of-the-art reversed-phase wide-pore stationary phases were used to evaluate the adsorption of therapeutic monoclonal antibodies. These biomolecules possess molar mass of approximately 150,000 g/mol and isoelectric points between 6.6 and 9.3. Two types of stationary phases were tested, the Phenomenex Aeris Widepore (silica based), with 3.6 μm superficially porous particles, and the Waters Acquity BEH300 (ethylene-bridged hybrid), with 1.7 μm fully porous particles. A systematic investigation was carried out using 11 immunoglobulin G1, G2, and G4 antibodies, namely, panitumumab, natalizumab, cetuximab, bevacizumab, trastuzumab, rituximab, palivizumab, belimumab, adalimumab, denosumab, and ofatumumab. All are approved by the Food and Drug Administration and the European Medicines Agency in various therapeutic indications and are considered as reference antibodies. Several test proteins, such as human serum albumin, transferrin, apoferritin, ovalbumin, and others, possessing a molar mass between 42,000 and 443,000 g/mol were also evaluated to draw reliable conclusions. The purpose of this study was to find a correlation between the adsorption of monoclonal antibodies and their physicochemical properties. Therefore, the impact of isoelectric point, molar mass, protein glycosylation, and hydrophobicity was investigated. The adsorption of intact antibodies on the stationary phase was significantly higher than that of proteins of similar size, isoelectric point, or hydrophobicity. The present study also demonstrates the unique behavior of monoclonal antibodies, contributing some unwanted and unpredictable strong secondary interactions.

  5. Effect of charge asymmetry on adsorption and phase separation of polyampholytes on silica and cellulose surfaces.

    PubMed

    Song, Junlong; Yamagushi, Takashi; Silva, Deusanilde J; Hubbe, Martin A; Rojas, Orlando J

    2010-01-21

    The relation between the properties of polyampholytes in aqueous solution and their adsorption behaviors on silica and cellulose surfaces was investigated. Four polyampholytes carrying different charge densities but with the same nominal ratio of positive to negative segments and two structurally similar polyelectrolytes (a polyacid and a polybase) were investigated by using quartz crystal microgravimetry using silica-coated and cellulose-coated quartz resonators. Time-resolved mass and rigidity (or viscoelasticity) of the adsorbed layer was determined from the shifts in frequency (Deltaf) and energy dissipation (DeltaD) of the respective resonator. Therefore, elucidation of the dynamics and extent of adsorption, as well as the conformational changes of the adsorbed macromolecules, were possible. The charge properties of the solid surface played a crucial role in the adsorption of the studied polyampholytes, which was explained by the capability of the surface to polarize the polyampholyte at the interface. Under the same experimental conditions, the polyampholytes had a higher nominal charge density phase-separated near the interface, producing a soft, dissipative, and loosely bound layer. In the case of cellulose substrates, where adsorption was limited, electrostatic and polarization effects were concluded to be less significant.

  6. Phase behavior of methane haze.

    PubMed

    Signorell, R; Jetzki, M

    2007-01-05

    Methane aerosols play a fundamental role in the atmospheres of Neptune, Uranus, and Saturn's moon Titan as borne out by the recent Cassini-Huygens mission. Here we present the first study of the phase behavior of free methane aerosol particles combining collisional cooling with rapid-scan infrared spectroscopy in situ. We find fast (within minutes) phase transitions to crystalline states directly after particle formation and characteristic surface effects for nanometer-sized particles. From our results, we conclude that in atmospheric clouds solid methane particles are crystalline.

  7. Modulation of mixed-phase titania photoluminescence by oxygen adsorption

    SciTech Connect

    Pallotti, D.; Orabona, E.; Amoruso, S.; Maddalena, P.; Lettieri, S.

    2014-07-21

    We investigate the effect of oxygen (O{sub 2}) adsorption on photoluminescence properties of mixed-phase titania nanoparticle films deposited by femtosecond pulsed laser deposition, aiming to assess preliminary conclusions about the feasibility of opto-chemical sensing based on titania. We evidence that O{sub 2} produces opposite responses in rutile and anatase photoluminescence efficiency, highlighting interesting potentialities for future double-parametric optical sensing based on titania. The results evidence an important role of lattice oxygen atoms, suggesting that the standard Schottky barrier mechanism driving the response toward gas species in most used metal-oxide sensors (e.g., tin dioxide) is not the only active mechanism in titania.

  8. Protein adsorption to poly(ethylenimine)-modified Sepharose FF. IV. Dynamic adsorption and elution behaviors.

    PubMed

    Liu, Na; Yu, Lin-Ling; Sun, Yan

    2014-10-03

    We have previously investigated bovine serum albumin (BSA) uptake to poly(ethylenimine) (PEI)-grafted Sepharose FF. It was found that there was a critical ionic capacity (cIC; 600mmol/L) for BSA, above which the protein adsorption capacity and uptake kinetics increased drastically. In this work, two poly(ethylenimine) (PEI)-grafted resins with IC values of 271mmol/L (FF-PEI-L270) and 683mmol/L (FF-PEI-L680), which were below and above the cIC, respectively, were chosen to investigate the breakthrough and linear gradient elution (LGE) behaviors of BSA. Commercially available anion exchanger, Q Sepharose FF, was used for comparison. The DBC values of FF-PEI-L680 were much higher in the entire residence time range (2-10min) than the other two resins due to its high static adsorption capacity and uptake kinetics. At a residence time of 5.0min, the DBC of FF-PEI-L680 (104mg/mL) was about seven times that of FF-PEI-L270 and three times that of Q Sepharose FF. A rise-fall trend of the DBCs with increasing ionic strength (IS) was found for all the three resins studied, indicating the presence of electrostatic exclusion for protein uptake at low IS. With increasing NaCl concentration from 20 to 200mmol/L, FF-PEI-L680 kept very high DBC values (64-114mg/mL). In addition, FF-PEI-L270 showed more favorable adsorption properties than Q Sepharose FF at 100-300mmol/L NaCl. These results proved that the three-dimensional grafting ion exchange layer on the PEI resins enhanced their tolerance to IS. In the study of LGE, the three resins showed similar elution behaviors and no distinct peak tailings were observed. The salt concentrations at the elution peaks (IR) were in the order of FF-PEI-L680>FF-PEI-L270>Q Sepharose FF, indicating that the elution for the PEI resins needed higher salt concentrations, which was also an appearance of the salt-tolerant feature of the PEI resins. When protein loading amount was increased to the value equivalent to the DBC at 10% breakthrough, the

  9. Multiphase, multicomponent phase behavior prediction

    NASA Astrophysics Data System (ADS)

    Dadmohammadi, Younas

    Accurate prediction of phase behavior of fluid mixtures in the chemical industry is essential for designing and operating a multitude of processes. Reliable generalized predictions of phase equilibrium properties, such as pressure, temperature, and phase compositions offer an attractive alternative to costly and time consuming experimental measurements. The main purpose of this work was to assess the efficacy of recently generalized activity coefficient models based on binary experimental data to (a) predict binary and ternary vapor-liquid equilibrium systems, and (b) characterize liquid-liquid equilibrium systems. These studies were completed using a diverse binary VLE database consisting of 916 binary and 86 ternary systems involving 140 compounds belonging to 31 chemical classes. Specifically the following tasks were undertaken: First, a comprehensive assessment of the two common approaches (gamma-phi (gamma-ϕ) and phi-phi (ϕ-ϕ)) used for determining the phase behavior of vapor-liquid equilibrium systems is presented. Both the representation and predictive capabilities of these two approaches were examined, as delineated form internal and external consistency tests of 916 binary systems. For the purpose, the universal quasi-chemical (UNIQUAC) model and the Peng-Robinson (PR) equation of state (EOS) were used in this assessment. Second, the efficacy of recently developed generalized UNIQUAC and the nonrandom two-liquid (NRTL) for predicting multicomponent VLE systems were investigated. Third, the abilities of recently modified NRTL model (mNRTL2 and mNRTL1) to characterize liquid-liquid equilibria (LLE) phase conditions and attributes, including phase stability, miscibility, and consolute point coordinates, were assessed. The results of this work indicate that the ϕ-ϕ approach represents the binary VLE systems considered within three times the error of the gamma-ϕ approach. A similar trend was observed for the for the generalized model predictions using

  10. Electrochemical adsorptive behavior of some fluoroquinolones at carbon paste electrode.

    PubMed

    El Ries, M A; Wassel, A A; Abdel Ghani, N T; El-Shall, M A

    2005-10-01

    Cyclic voltammetry and differential pulse voltammetry were used to explore the adsorption behavior of three antibacterial agents at a carbon paste electrode. The drugs were accumulated on a carbon paste electrode, and a well-defined oxidation peak was obtained in acetate buffer (pH 5.0). The adsorptive stripping response was evaluated as a function of some variables such as the scan rate, pH and accumulation time. A simple, precise, inexpensive and sensitive voltammetric method has been developed for the determination of the cited drugs (Lomefloxacin (LFX), Sparfloxacin hydrochloride (SFX), and Gatifloxacin (GFX)). A linear calibration was obtained from 2 x 10(-7) M to 4 x 10(-5) M for LFX, 2 x 10(-7) M to 6 x 10(-5) M for SFX, and GFX. The limits of detection (LOD) were 4.2 x 10(-7), 7 x 10(-7) and 6.6 x 10(-7) M, while the limits of quantification (LOQ) were 1.4 x 10(-6), 2.3 x 10(-6) and 2.2 x 10(-6) M for LFX, SFX, and GFX, respectively. The R. S. D. of five measurements at the 1 x 10(-6) M level were 0.4, 0.5 and 0.3 for LFX, SFX and GFX, respectively. The method was applied to the determination of LFX, SFX and GFX in dilute urine samples and dosage forms, and compared with the HPLC method.

  11. Models of adsorption at a line of three-phase contact.

    PubMed

    Widom, B

    2006-11-09

    Two model density distributions at a line of three-phase contact for which the adsorptions are readily calculated are analyzed. One of them provides a numerical illustration of a recently found surprising fact about the thermodynamics of adsorption at such contact lines. A form of the line analogue of the Gibbs adsorption equation is conjectured, and it is noted that the conjecture is in principle testable by computer simulation and by experiment.

  12. Adsorption Behavior of Pb(II) Onto Potassium Polytitanate Nanofibres.

    PubMed

    Shahid, Mohammad; Tiling, Leonard D; El Saliby, Ibrahim; McDonagh, Andrew; Kim, Jong-Beom; Kim, Jong-Ho; Shon, Ho Kyong

    2016-02-01

    Potassium polytitanate nanofibres prepared by a hydrothermal method were investigated for their possible application in removing toxic metals from aqueous solution. Particular attention was paid to employing the titanate as a novel effective adsorbent for the removal of Pb(II). Batch adsorption experiments demonstrated that the adsorption was influenced by various conditions such as solution pH, adsorbent dosage and initial Pb(II) concentration. The results showed that the adsorption rate was faster in the first 5 min and equilibrium was achieved after 180 min. The maximum amount of adsorption was detected at pH 5. Potassium titanate showed much higher adsorption capacity compared to P25. The kinetic studies indicated that the adsorption of Pb(II) onto titanate best fit the pseudo-second-order kinetic model. FTIR spectra revealed that the hydroxyl groups in titanate were responsible for Pb(II) adsorption. The principal mechanism of the adsorption of Pb(II) in the present study is attributed to both ion exchange and oxygen bonding. The adsorption-desorption results demonstrated that the titanate could be readily regenerated after adsorption. Therefore, the present titanate exhibits great potential for the removal of Pb(II) from wastewater.

  13. Solvothermal synthesis of different phase N-TiO2 and their kinetics, isotherm and thermodynamic studies on the adsorption of methyl orange.

    PubMed

    Fan, Jimin; Zhao, Zhihuan; Liu, Wenhui; Xue, Yongqiang; Yin, Shu

    2016-05-15

    The different crystal forms of nitrogen doped-titanium oxide (N-TiO2) with different particle sizes were produced by precipitation-solvothermal method and their adsorption mechanism were also investigated. The adsorption kinetics showed that rutile N-TiO2 displayed higher adsorption capacity than anatase for methyl orange (MO) and its adsorption behavior followed the pseudo-second-order kinetics. The equilibrium adsorption rate of N-TiO2 for MO was well fitted by the Langmuir isotherm model and the adsorption process was monolayer adsorption. The adsorption capacity decreased with increasing temperature. The average correlation coefficient was beyond 97%. The thermodynamic parameters (ΔaGm(ө), ΔaHm(ө), and ΔaSm(ө)) were calculated. It was found that anatase and rutile N-TiO2 had different adsorption enthalpy and entropy. The smaller the particle size, the greater the surface area and surface energy was, then ΔaGm(ө) decreased and the standard equilibrium constant increased at the same time. The adsorption process onto different crystalline phase N-TiO2 was exothermic and non-spontaneous.

  14. Influence of Inorganic Ions on Aggregation and Adsorption Behaviors of Human Adenovirus

    EPA Science Inventory

    In this study, we investigated the influence of inorganic ions on the aggregation and deposition (adsorption) behavior of human adenovirus (HAdV). Experiments were conducted to determine the surface charge and size of HAdV and viral adsorption capacity of sand in different salt c...

  15. Adsorption Behavior of Heat Modified Soybean Oil via Boundary Lubrication Coefficient of Friction Measurements

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The frictional behaviors of soybean oil and heat modified soybean oils with different Gardner scale viscosities as additives in hexadecane have been examined in a boundary lubrication test regime (steel contacts) using Langmuir adsorption model. The free energy of adsorption (delta-Gads) of various...

  16. Adsorption behavior of some radionuclides on the Chinese weathered coal.

    PubMed

    Wu, Jianfeng; Xu, Qichu; Bai, Tao

    2007-08-01

    The equilibrium and kinetic properties of Am(III), Eu(III) and Cs(I) ions adsorption by three weathered coals (WCs) from China, have been investigated in batch stirred-tank experiments. The effects of contact time, solution acidity and initial sorbate concentration on the adsorption of Am(III), Eu(III) and Cs(I) by Yuxian(YX) Tongchuan (TC) and Pingxiang (PX) WC were evaluated. The radionuclide ions are able to form complex compounds with carboxylic and phenolic groups of WCs and they are also bounded with phenolic groups even at high acidity reaction solution (>0.1 mol/L). Mechanisms including ion exchange, complexation and adsorption to the coal surface are possible in the sorption process. The acidity of the solution played an important role in the adsorption. Even acidity as high as 0.1 mol/L, 60% of Am(III) or Eu(III), 40% of Cs(I) were found to be sorbed on the YX WC, which had the best adsorption capacity for Am(III) and Eu(III). Our batch adsorption studies showed the equilibrium adsorption data fit the linear Langmuir and Freundlich adsorption isotherm. The maximum equilibrium uptake of Eu(III) were 0.412, 3.701, 5.446 mmol/g for JXWC, TCWC and YXWC, respectively.

  17. Adsorption behavior of EDTA-graphene oxide for Pb (II) removal.

    PubMed

    Madadrang, Clemonne J; Kim, Hyun Yun; Gao, Guihua; Wang, Ning; Zhu, Jun; Feng, Huan; Gorring, Matthew; Kasner, Marc L; Hou, Shifeng

    2012-03-01

    Chelating groups are successfully linked to graphene oxide (GO) surfaces through a silanization reaction between N-(trimethoxysilylpropyl) ethylenediamine triacetic acid (EDTA-silane) and hydroxyl groups on GO surface. EDTA-GO was found to be an ideal adsorbent for Pb(II) removal with a higher adsorption capacity. EDTA-modification enhances the adsorption capacity of GO because of the chelating ability of ethylene diamine triacetic acid. This study investigates the adsorption and desorption behaviors of heavy metal cations and the effects of solution conditions such as pH on Pb(II) removal. The adsorption capacity for Pb(II) removal was found to be 479 ± 46) mg/g at pH 6.8, and the adsorption process was completed within 20 min. The Langmuir adsorption model agrees well with the experimental data. The experimental results suggest that EDTA-GO can be reused after washed with HCl, suggesting potential applications in the environmental cleanup.

  18. Adsorption characteristics of adsorbent resins and antioxidant capacity for enrichment of phenolics from two-phase olive waste.

    PubMed

    Wang, Zhihong; Wang, Chengzhang; Yuan, Jiaojiao; Zhang, Changwei

    2017-01-01

    In this study, the adsorption properties of nine resins including polyamide resin (30-60), polyamide resin (60-100) AB-8, S-8, D-101, NKA-9, NKA-II, XDA-1 and XDA-4 for enrichment phenolics of the olive waste were investigated. XDA-1 and NKA-II were chosen for further study due to their outstanding adsorption and desorption capacity. XDA-1 and NKA-II had similar adsorption and desorption behaviors for phenolics of olive waste. The adsorption mechanism could be better explained by pseudo second-order kinetics model and Freundlich isotherm model, and the adsorption processes were spontaneously and exothermic. The experiment of gradient elution were carried out through treated XDA-1 resins column, the result indicated the total phenolics were mainly obtained from the 40% and 60% ethanol fraction. The order of antioxidant capacity by DPPH  , ABTS(+) radical and FRAP assay was similar with the content of phenolics from fraction elution. The compositions of phenolics from different elution fractions were determined by reversed phase-HPLC-DAD method. Gallic acid, hydroxytyrosol, tyrosol and ferulic acid were the major constituent in the fraction elute, and the content of hydroxytyrosol reached to the 41.69mg/g. The above results revealed the synergistic effects of the different phenolics contribute to the antioxidant capacity.

  19. [Adsorption behavior of exogenous thorium on soil contaminated by rare earth industries].

    PubMed

    Guo, Peng-ran; Jia, Xiao-yu; Duan, Tai-cheng; Qiu, Rong-liang; Chen, Hang-ting

    2009-10-15

    The adsorption behavior of exogenous thorium on soil was studied to evaluate the contaminated risk on soil. The adsorption capacity, equilibrium time, distribution coefficient and desorption ability were investigated by the experiments of static adsorption. The strong adsorption ability of exogenous thorium on soil samples was observed by high adsorption ratio (> 92%) and low desorption ratio (< 5%) in equilibrium, and the biggest distribution coefficient was over 10(4). The adsorption capacity and equilibrium time were related to soil properties. According to the results of adsorption, Freundlich equation (r > or = 0.9167) and Elovich equation (R2 > or = 0.8980) were primely fit for describing the thermodynamics and kinetics of the adsorption of exogenous thorium on soil samples, respectively, which indicated that the adsorption was belonged to the nonlinear adsorption, and was affected by the diffusion of thorium on soil surface and in mineral interbed. Sequential extraction procedure was employed to evaluate the bound fractions of exogenous thorium adsorbed on soil samples. Based on the extracted results of thorium fractions, exogenous thorium was presented in the labile nonresidual fractions (over 58%) at the low initial concentration (10(-7) - 10(-6) mol x L(-1)), and nonresidual fractions enhanced with the increase of the initial amount, meanwhile more exogenous throium was transferred to the stable residual fractions.

  20. Changes in adsorption and optical properties of liquid crystal langmuir films at structural phase transition

    NASA Astrophysics Data System (ADS)

    Zaitsev, V. B.; Levshin, N. L.; Khlybov, S. V.; Yudin, S. G.

    2012-12-01

    The adsorption isotherms of water molecules, absorption spectra, and spectra of diffuse scattering and polarization of reflected light are studied for ultrathin Langmuir films prepared based on liquid crystals. A structural phase transition near 70°C is detected. Some specific features of the reflection spectra at the phase transition temperature are found. Suggestions are made regarding the nature of the phase transition.

  1. Behavior and Sensitivity of Phase Arrival Times (PHASE)

    DTIC Science & Technology

    2014-09-30

    travel -time perturbations, and, further, to study the behavior of phase arrival times and its predictability, depending on propagation and signal...Using this definition, expressions for the corresponding travel -time perturbations are derived and the sensitivity behavior of phase arrival times...corresponding travel -time sensitivity kernels for peak arrivals. DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited

  2. Oleic acid phase behavior from molecular dynamics simulations.

    PubMed

    Janke, J Joel; Bennett, W F Drew; Tieleman, D Peter

    2014-09-09

    Fatty acid aggregation is important for a number of diverse applications: from origins of life research to industrial applications to health and disease. Experiments have characterized the phase behavior of oleic acid mixtures, but the molecular details are complex and hard to probe with many experiments. Coarse-grained molecular dynamics computer simulations and free energy calculations are used to model oleic acid aggregation. From random dispersions, we observe the aggregation of oleic acid monomers into micelles, vesicles, and oil phases, depending on the protonation state of the oleic acid head groups. Worm-like micelles are observed when all the oleic acid molecules are deprotonated and negatively charged. Vesicles form spontaneously if significant amounts of both neutral and negative oleic acid are present. Oil phases form when all the fatty acids are protonated and neutral. This behavior qualitatively matches experimental observations of oleic acid aggregation. To explain the observed phase behavior, we use umbrella sampling free energy calculations to determine the stability of individual monomers in aggregates compared to water. We find that both neutral and negative oleic acid molecules prefer larger aggregates, but neutral monomers prefer negatively charged aggregates and negative monomers prefer neutral aggregates. Both neutral and negative monomers are most stable in a DOPC bilayer, with implications on fatty acid adsorption and cellular membrane evolution. Although the CG model qualitatively reproduces oleic acid phase behavior, we show that an updated polarizable water model is needed to more accurately predict the shift in pKa for oleic acid in model bilayers.

  3. Vapor phase adsorption of organic compounds on octyl silicas

    NASA Astrophysics Data System (ADS)

    Roshchina, T. M.; Shoniya, N. K.; Tayakina, O. Ya.; Fadeev, A. Y.

    2011-02-01

    The influence of the modification of silica by octyltrichlorosilane with the formation of an oligomeric grafted layer (sample C8(II)) and additional silanization (sample C8(III)) on the thermodynamic adsorption characteristics (TACs) of different classes of organic compounds was investigated by gas chromatography. It was shown that the modification leads to decreased adsorption values for most of the investigated compounds (with the exception of alkanes, for which TACs on sample C8(II) approach the values observed on the initial support, due probably to additional interactions with silanol groups formed in modifying the surface with octyltrichlorosilane). It was established that blocking these silanol groups during additional silanization with trimethylsilane resulted in inert surfaces whose adsorption properties with respect to many compounds (including some capable of participating in strong specific interactions) approaches to the properties of octyl-silica with a close-packed grafted monolayer.

  4. Gas-phase adsorption in dealuminated natural clinoptilolite and liquid-phase adsorption in commercial DAY zeolite and modified ammonium Y zeolite

    NASA Astrophysics Data System (ADS)

    Costa Hernandez, Alba Nydia

    The adsorption of Carbon Dioxide (CO2) is a very important tool for the material characterization. On the other hand, in separation and recovery technology, the adsorption of the CO2 is important to reduce the concentration of this gas considered as one of the greenhouse gases. Natural zeolites, particularly clinoptilolite, are widely applied to eliminate some pollutants from the environment. One of the goals of this research is to study the structure, composition and morphology of one natural clinoptilolite dealuminated with ammonium hexafluorosilicate (AHFi) and with orthophosphoric acid (H3PO4). Each modified sample was characterized using X-ray Diffraction (XRD), Carbon Dioxide adsorption at 0° C, Thermogravimetric Analysis (TGA), and Scanning Electron Microscopy with Energy Dispersive X-Ray Analysis (SEM-EDAX). In addition, the surface chemistry of the modified clinoptilolites was analyzed with Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS). The adsorption measurements were also used to study of the interaction of CO2 molecule within the adsorption space of these modified clinoptilolites. It was concluded that one of the modified clinoptilolites, (CSW-HFSi-0.1M), showed a great quality as adsorbent and as catalytic comparable to commercial synthetic zeolites. As far as we know, the modification of clinoptilolite with HFSi to improve their adsorption properties had not been previously attempted. In the second part of this dissertation, the dynamic adsorption of three isomers of nitrophenols using as adsorbent a commercial DAY zeolite was investigated. Also, the dynamic adsorption of methanol in a less hydrophobic zeolite, Ammonium Y Zeolite was investigated. The obtained breakthrough curves showed that the commercial DAY zeolite could be a suitable adsorbent to the liquid-phase adsorption of the phenolic compounds. Notwithstanding the modified ammonium Y zeolite had a low Si/Al ratio (less hydrophobic) than commercial DAY zeolite; this

  5. Protein adsorption behaviors onto photocatalytic Ti(IV)-doped calcium hydroxyapatite particles.

    PubMed

    Kandori, Kazuhiko; Kuroda, Tomohiko; Wakamura, Masato

    2011-10-15

    The fundamental experiments on the adsorption behaviors of proteins onto photocatalytic Ti(4+)-doped calcium hydroxyapatite (TiHap) particles were examined comparing to those onto the calcium hydroxyapatite (CaHap) and commercially available typical titanium oxide (TiO(2)) photocatalyst (TKP-101). The heat treated TiHap and CaHap particles were also used after treated these particles at 650°C for 1h (abbreviated as TiHap650 and CaHap650, respectively). All the adsorption isotherms of bovine serum albumin (BSA), myoglobin (MGB) and lysozyme (LSZ) from 1×10(-4)mol/dm(3) KCl solution were the Langmuirian type. The saturated amounts of adsorbed BSA (n(s)(BSA)) for the CaHap650 particles was higher than that for CaHap. Similar results were observed for TiHap and TiHap650. The adsorption of LSZ exhibited the same result of BSA, while the saturated amounts of adsorbed LSZ (n(s)(LSZ)) value on the TiHap were much higher than CaHap. However, the saturated amounts of adsorbed MGB (n(s)(MGB)) are almost equal to those for the CaHap and TiHap nevertheless whether these particles were heat treated at 650°C or not. The TKP-101 exhibited extremely small adsorption capacity of all proteins due to its small particle size of ca. 4nm in diameter. The independence of the n(s)(MGB) value on the zeta potential (zp) of the particles was explained by the electrostatical neutrality of MGB molecules. On the other hand, the n(s)(LSZ) values were increased with increase in the negative zp of the particles. This fact was explained by increasing the electrostatic attractive forces between negatively charged particles and positively charged LSZ. However, the n(s)(BSA) values exhibit maxima for the heat treated TiHap650 and CaHap650 particles. This result was interpreted to the formation of β-TCP crystal phase by the heat treatment. The produced Ca(2+) ions by dissolution from β-TCP phase may exert as binders between BSA and surfaces of the heat treated particles.

  6. Adsorption behavior of methylene blue on carbon nanotubes.

    PubMed

    Yao, Yunjin; Xu, Feifei; Chen, Ming; Xu, Zhongxiao; Zhu, Zhiwen

    2010-05-01

    The effect of temperature on the equilibrium adsorption of methylene blue dye from aqueous solution using carbon nanotubes was investigated. The equilibrium adsorption data were analyzed using two widely applied isotherms: Langmuir and Freundlich. The results revealed that Langmuir isotherm fit the experimental results well. Kinetic analyses were conducted using pseudo-first and second-order models and the intraparticle diffusion model. The regression results showed that the adsorption kinetics were more accurately represented by pseudo-second-order model. The activation energy of system (Ea) was calculated as 18.54 kJ/mol. Standard free energy changes (DeltaG(0)), standard enthalpy change (DeltaH(0)), and standard entropy change (DeltaS(0)) were calculated using adsorption equilibrium constants obtained from the Langmuir isotherm at different temperatures. All DeltaG(0) values were negative; the DeltaH(0) values and DeltaS(0) values of CNTs were 7.29 kJ/mol and 64.6 J/mol K, respectively. Results suggested that the methylene blue adsorption on CNTs was a spontaneous and endothermic process.

  7. Adsorption behavior of Zn(II) on calcinated Chinese loess.

    PubMed

    Tang, Xiaowu; Li, Zhenze; Chen, Yunmin

    2009-01-30

    Chinese loess has proven to be effective in removing Zn(II) from aqueous solutions, but the resultant adsorbent-water slurry is difficult to separate. In this paper, the crude loess was calcinated to improve the separation efficiency of slurries in terms of sedimentary rate by increasing the particle sizes of the adsorbent. The sorption capacities of different sorbents, including crude loess, calcinated loess, de-organic crude loess and acid-treated calcinated loess, were obtained and sequenced. The adsorption capacity of the calcinated loess towards Zn(II) was found to be as high as 113.6 mg g(-1). The adsorption isotherms and kinetics of calcinated loess were best-fit with the Freundlich isotherm and the pseudo-second order kinetics, respectively. The thermodynamic analysis revealed that the adsorption was exothermic and spontaneous with a high preference for Zn(II) removal. The adsorption of Zn(II) on calcinated loess implies an ion exchange of the solute with calcite and goethite due to the observed FT-IR and XRD patterns as well as the predicted mean free energies (-11.58 to -9.28 kJ mol(-1) by D-R model). The byproduct of adsorption can be purified and refreshed by using a 0.01 M HCl solution.

  8. Chemical speciation and adsorption behavior of plutonium in natural waters

    SciTech Connect

    Sanchez, A.L.

    1983-01-01

    Dissolved Pu profiles in two partially anoxic basins--Saanich Inlet, an intermittently anoxic marine fiord in Vancouver Island, British Columbia, and Soap Lake, a saline, alkaline lake in eastern Washington state, revealed minimum concentrations at the O/sub 2//H/sub 2/S interface. The Pu concentrations in the anoxic waters of Saanich Inlet were less than the surface concentrations; however, in Soap Lake, a 15- to 50-fold increase in Pu concentration in the anoxic monimolimnion correlated with large increases in the major ions, total alkalinity, and dissolved organic carbon. Laboratory experiments were designed to investigate the effects of pH, ionic strength, dissolved organic carbon, and carbonate ions on the adsorption of tracer amounts of Pu IV and Pu V. The Pu-goethite adsorption system provided the data base for developing a thermodynamic model of Pu interaction with an oxide surface and with dissolved ligands, using the MINEQL computer program. Pu IV and Pu V interacted very differently with goethite, which is consistent with their different hydrolytic character. A reduction of Pu V to Pu IV occurred on the goethite surface and also on montmorillonite and silica gel, suggesting that redox transformations are an important aspect of Pu adsorption. Increases in ionic strength (up to 3 M NaCl or NaNO/sub 3/) did not affect Pu IV or V adsorption. In the presence of dissolved organic carbon (DOC), Pu V reduction to Pu IV occurred in solution. Pu IV adsorption on goethite decreased only 30% in the presence of 240 ppm of natural DOC from Soap Lake; however, carbonate anions inhibited Pu IV adsorption on goethite at the alkalinity levels (1500 meq/L total alkalinity, 0.57 M CO/sub 3/=) measured for Soap Lake monimolimnion waters.

  9. Adsorption behavior of hydrothermally treated municipal sludge & pulp and paper industry sludge.

    PubMed

    Alatalo, Sara-Maaria; Repo, Eveliina; Mäkilä, Ermei; Salonen, Jarno; Vakkilainen, Esa; Sillanpää, Mika

    2013-11-01

    Aim of the study was to investigate how hydrothermal carbonization changes adsorption efficiency toward metal ions of typical sludges. Hydrothermal carbonization is a novel and green method of treating biomasses. Reactions take place in an aqueous environment at relatively mild temperature and high pressure resulting a different end biomass structure than obtained from traditional pyrolysis. Anaerobically digested sludge (ADS) and pulp and paper industry sludge (INS) were utilized as a feedstock. Adsorption behavior of ADS and INS was examined towards Pb(II), Cr(III), Cr(VI), As(III) and As(V). Both ADS and INS were found to remove Pb(II) effectively and followed Sips adsorption isotherm. Adsorption kinetics was fast and followed pseudo-second order model. Furthermore, intraparticle diffusion was observed to be partly responsible in the adsorption process. Hydrothermal carbonization indicated high potential for the production of novel carbonaceous materials for metal removal from waters.

  10. Adsorption of ibuprofen enantiomers on a chiral stationary phase with a grafted antibiotic eremomycin

    NASA Astrophysics Data System (ADS)

    Reshetova, E. N.; Asnin, L. D.

    2015-02-01

    The adsorption of ibuprofen enantiomers on a chiral stationary phase Nautilus-E with a grafted antibiotic eremomycin from aqueous ethanol acetate buffer solutions was studied by chromatography. The ethanol concentration in the mobile phase was varied from 40 to 60 vol %. The adsorption isotherms of both enantiomers had a complex shape characterized by non-Langmuir type curvature and the presence of an inflection point. This is explained by two factors: the energy heterogeneity of the surface of the stationary phase and the dissociation of ibuprofen in the liquid phase. The effect of the system peak on the shape of the chromatograms of the target component was investigated. The temperature effect on the adsorption equilibrium was discussed.

  11. Phase behavior and microstructure of nonaqueous microemulsions

    SciTech Connect

    Martino, A.; Kaler, E.W. )

    1990-02-22

    Phase behavior of glycerol, propylene glycol, hydrocarbon, and alkylpolyglycol ether (C{sub i}E{sub j}) surfactant microemulsions has been studied. Surfactant solubility in the polar organic phase (a mixture of glycerol and propylene glycol) decreases when glycerol content is increased, and a 2-3-2 phase transition is observed at constant temperature. The phase behavior usually observed in water microemulsions as a function of temperature is observed here as a function of the fraction of glycerol in the polar organic phase. Phase behavior is reported as a function of oil solvophobicity and the surfactant solvophilic-lipophilic balance and is compared to a well-established model developed for aqueous microemulsions. Porod analysis of small-angle X-ray scattering (SAX) measurements indicates the presence of interfaces; thus the fluids are microstructured. The SAXS measurements suggest that aqueous and nonaqueous microemulsions are structurally similar.

  12. Adsorption behavior of a surfactant and a monoclonal antibody to sterilizing-grade filters.

    PubMed

    Mahler, Hanns-Christian; Huber, Franziska; Kishore, Ravuri S K; Reindl, Jürgen; Rückert, Peter; Müller, Robert

    2010-06-01

    Formulations of therapeutic proteins usually contain a surfactant such as polysorbate 80 to protect them against interfacial stresses. Since surfactants may interact with surfaces, the aim of the present work was to study the adsorption behavior of low concentrations of polysorbate 80 and of a monoclonal antibody during sterile filtration. Lab-scale tests were performed to study the adsorption behavior of a monoclonal antibody to different filter materials (PVDF, PES, CA, and Nylon) from different suppliers. Subsequently, protein and polysorbate 80 adsorption were tested in manufacturing scale experiments. It was found that the extent of protein adsorption differed with filter materials, but also with different suppliers. Prominently, Nylon filters showed the highest degree of protein adsorption. In manufacturing-scale filtration experiments, significant adsorption of polysorbate 80 to sterilizing-grade filters was found. Thus, the adsorption of both protein and polysorbate to filters should be taken into consideration in the formulation and manufacturing process and assessed on a case-by-case basis depending on the manufacturing process set-up.

  13. Electrostatically-controlled protein adsorption onto lipid bilayer: modeling adsorbate aggregation behavior.

    PubMed

    Trusova, Valeriya M; Gorbenko, Galyna P

    2008-03-01

    Using adsorption models based on scaled particle (SPT) and double layer theories the electrostatically-controlled protein adsorption onto membrane surface has been simulated for non-associating and self-associating ligands. The binding isotherms of monomeric and oligomeric protein species have been calculated over a range of variable parameters including lipid and protein concentrations, protein and membrane charges, pH and ionic strength. Adsorption behavior of monomers appeared to be the most sensitive to the changes in the protein aggregation state. The hallmarks of the protein oligomerization are identified. The practical guides for optimal design of binding experiments focused on obtaining proofs of protein self-association are suggested.

  14. Effects of Ti(IV) substitution on protein adsorption behaviors of calcium hydroxyapatite particles.

    PubMed

    Kandori, Kazuhiko; Oketani, Makoto; Wakamura, Masato

    2013-01-01

    The fundamental experiments on the adsorption behaviors of proteins onto photocatalytic Ti(IV)-doped calcium hydroxyapatite (TiHap) particles with varied amounts of Ti(IV) ions doped (called as original particle) were examined comparing to those onto the calcium hydroxyapatite (CaHap) ones. The heat treated TiHaps and CaHap particles at 650°C for 1h were also examined (called as heat treated particle). The Ti/(Ca+Ti) atomic ratio (X(Ti)) of the TiHap particles was varied between 0 and 0.20. Since the surface acidity of the particles was increased by increase in X(Ti) value, the negative zeta potential (zp) of the particles was increased. All the adsorption isotherms of bovine serum albumin (BSA), myoglobin (MGB) and lysozyme (LSZ) from 1×10(-4)mol/dm(3) KCl solution were the pseudo-Langmuirian type. The saturated amounts of adsorbed LSZ (n(S)(LSZ)) values onto the original particles were increased with increase in the negative zp of the particles. However, the saturated amounts of adsorbed BSA (n(S)(BSA)) values were decreased by increase in the negative zp except at X(Ti)=0.05 where n(S)(BSA) value exhibited a maximum. In the case of MGB, the saturated amounts of adsorbed MGB (n(s)(MGB)) values were less dependent on the zp of the particles. These results were explained by changing the electrostatic forces between protein molecules and TiHap particles by doping Ti(IV) ions. On the other hand, n(S)(BSA), n(S)(LSZ) and n(s)(MGB) values onto the heat treated particles were larger than the original particles in each particle system, though no relationship to the X(Ti) value was recognized in each protein system. This result was interpreted to the formation of β-TCP crystal phase in both the CaHap and TiHap particles by the heat treatment. The Ca(2+) ions produced by dissolution from β-TCP phase may exert as binders between BSA and surfaces of the heat treated particles. The weak binder effects of Ca(2+) and PO(4)(3-) ions were observed for the adsorptions of LSZ

  15. Equilibrium Phase Behavior of Polydisperse Hard Spheres

    NASA Astrophysics Data System (ADS)

    Fasolo, Moreno; Sollich, Peter

    2003-08-01

    We calculate the phase behavior of hard spheres with size polydispersity, using accurate free energies for the fluid and solid phases. Cloud and shadow curves are found exactly by the moment free energy method, but we also compute the complete phase diagram, taking full account of fractionation. In contrast to earlier, simplified treatments we find no point of equal concentration between fluid and solid or reentrant melting at higher densities. Rather, the fluid cloud curve continues to the largest polydispersity that we study (14%); from the equilibrium phase behavior a terminal polydispersity can thus be defined only for the solid, where we find it to be around 7%. At sufficiently large polydispersity, fractionation into several solid phases can occur, consistent with previous approximate calculations; we find, in addition, that coexistence of several solids with a fluid phase is also possible.

  16. Effect of hydrophilicity of end-grafted polymers on protein adsorption behavior: A Monte Carlo study.

    PubMed

    Han, Yuanyuan; Jin, Jing; Cui, Jie; Jiang, Wei

    2016-06-01

    Monte Carlo simulation is employed to investigate protein adsorption behavior on end-grafted polymers. The effect of hydrophilicity of end-grafted polymers on protein adsorption behavior is investigated in detail. The simulation results indicate that the hydrophilicity of the end-grafted polymers can affect both the amount and speed of protein adsorption. An increase in the hydrophilicity of the end-grafted polymers can significantly decrease the amount and speed of protein adsorption first. However, a further increase in the hydrophilicity of the end-grafted polymers results in the increase in the amount and speed of protein adsorption. This phenomenon is easier to be observed in the end-grafted polymer systems with lower grafting density and longer chain length. In addition, the investigation of the chain conformation of the end-grafted polymers reveals that the end-grafted polymers with mediate hydrophilicity have relatively small size difference along the parallel and perpendicular directions to the substrate, and these end-grafted polymers have relatively wide height distribution. Such characteristics favor covering the space above the hydrophobic substrate and thus can effectively resist protein adsorption.

  17. Adsorption behaviors of Hg(II) on chitosan functionalized by amino-terminated hyperbranched polyamidoamine polymers.

    PubMed

    Ma, Fang; Qu, Rongjun; Sun, Changmei; Wang, Chunhua; Ji, Chunnuan; Zhang, Ying; Yin, Ping

    2009-12-30

    The adsorption behaviors of Hg(II) on adsorbents, chitosan functionalized by generation 1.0-3.0 of amino-terminated hyperbranched polyamidoamine polymers (denoted as CTS-1.0, CTS-2.0 and CTS-3.0, respectively), were studied. The optimum pH corresponding to the maximum adsorption capacities was found to be 5.0 for the three adsorbents. The experimental equilibrium data of Hg(II) on the three adsorbents were fitted to the Freundlich and the Langmuir models, and it is found that the Langmuir isotherm was the best fitting model to describe the equilibrium adsorption. The kinetics data indicated that the adsorption process of Hg(II) ions on CTS-1.0, CTS-2.0 and CTS-3.0 were governed by the film diffusion and followed pseudo-second-order rate model. Thermodynamic analysis and FTIR analysis revealed that the adsorption behaviors of Hg(II) ions on the three adsorbents could be considered as spontaneous, endothermic and chemical sorption process, resulting in their higher adsorption capacities at higher temperature.

  18. Adsorption and inactivation behavior of horseradish peroxidase on cellulosic fiber surfaces.

    PubMed

    Di Risio, Sabina; Yan, Ning

    2009-10-15

    The physical immobilization behavior of horseradish peroxidase (HRP) on cellulosic fiber surfaces was characterized using adsorption and inactivation isotherms measured by the depletion method followed by fitting of Langmuir's and Freundlich's models to the experimental data. The adsorption and inactivation behavior of simpler and relatively non-porous high and low crystalline cellulosic substrates (microcrystalline cellulose and regenerated cellulose) as well as more complex and porous cellulosic pulp fibers (bleached kraft softwood fibers) were investigated. The effect of the sorbent surface energy on HRP adsorption was demonstrated by increasing the hydrophobicity of the cellulosic fibers using an internal sizing agent. The influence of the fiber surface charge density on HRP adsorption was studied via modification of the cellulosic fibers using TEMPO (2,2,6,6-tetramethyl-1-piperidiniloxy radical)-mediated oxidation methods. Results showed that hydrophobic interactions had a much larger effect on HRP adsorption than electrostatic interactions. More hydrophobic fiber surfaces (lower polar surface energy) result in larger enzyme-fiber binding affinity constants and higher binding heterogeneity. It was also found that oxidation of the cellulosic fiber substrate reduces enzyme adsorption affinity but significantly increases the loading capacity per unit weight of the surface.

  19. The effect of the adsorption of metal ions on the interfacial behavior of silicate minerals

    SciTech Connect

    Huang, P.; Fuerstenau, D.W.

    1997-08-01

    Because of its importance in the fields of environmental and mineral engineering, the adsorption mechanism of metal ions on oxides has been studied rather extensively using such techniques as titration, adsorption isotherm determination, flotation and spectroscopy. However, limited work has been done to compare the behavior of hydrophilic silicates with those that are naturally hydrophobic. This investigation was undertaken to provide a better understanding of the adsorption mechanism of selected metal ions at the solid/liquid interface through simultaneous measurements of zeta potentials, adsorption densities and turbidity on colloidal suspension of two silicate minerals, as a function of pH, to delineate the effect of hydrophobicity and surface heterogeneity on these processes. In present investigation, quartz and talc are selected as model minerals and lead and cadmium are chosen as the metal ions to investigate because of their importance in industry application.

  20. Phase behavior of patchy spheroidal fluids

    NASA Astrophysics Data System (ADS)

    Carpency, T. N.; Gunton, J. D.; Rickman, J. M.

    2016-12-01

    We employ Gibbs-ensemble Monte Carlo computer simulation to assess the impact of shape anisotropy and particle interaction anisotropy on the phase behavior of a colloidal (or, by extension, protein) fluid comprising patchy ellipsoidal particles, with an emphasis on critical behavior. More specifically, we obtain the fluid-fluid equilibrium phase diagram of hard prolate ellipsoids having Kern-Frenkel surface patches under a variety of conditions and study the critical behavior of these fluids as a function of particle shape parameters. It is found that the dependence of the critical temperature on aspect ratio for particles having the same volume can be described approximately in terms of patch solid angles. In addition, ordering in the fluid that is associated with particle elongation is also found to be an important factor in dictating phase behavior.

  1. Gas adsorption/absorption heat switch, phase 1

    NASA Technical Reports Server (NTRS)

    Chan, C. K.

    1987-01-01

    The service life and/or reliability of far-infrared sensors on surveillance satellites is presently limited by the cryocooler. The life and/or reliability, however, can be extended by using redundant cryocoolers. To reduce parasitic heat leak, each stage of the inactive redundant cryocooler must be thermally isolated from the optical system, while each stage of the active cryocooler must be thermally connected to the system. The thermal break or the thermal contact can be controlled by heat switches. Among different physical mechanisms for heat switching, mechanically activated heat switches tend to have low reliability and, furthermore, require a large contact force. Magnetoresistive heat switches are, except at very low temperatures, of very low efficiency. Heat switches operated by the heat pipe principle usually require a long response time. A sealed gas gap heat switch operated by an adsorption pump has no mechanical motion and should provide the reliability and long lifetime required in long-term space missions. Another potential application of a heat switch is the thermal isolation of the optical plane during decontamination.

  2. Confinement effect on the adsorption from a binary liquid system near liquid/liquid phase separation

    NASA Astrophysics Data System (ADS)

    Rother, Gernot; Woywod, Dirk; Schoen, Martin; Findenegg, Gerhard H.

    2004-06-01

    The preferential adsorption of one component of a binary system at the inner surfaces of mesoporous silica glasses was studied in a wide composition range at temperatures close to liquid/liquid phase separation. Confinement effects on the adsorption were investigated by using three controlled-pore glass (CPG-10) materials of different mean pore size (10 to 50 nm). For the experimental system (2-butoxyethanol+water), which exhibits an upper miscibility gap, strong preferential adsorption of water occurs, as the coexistence curve is approached at bulk compositions, at which water is the minority component. In this strong adsorption regime the area-related surface excess amount of adsorbed water decreases with decreasing pore width, while the shift in the volume-related mean composition of the pore liquid shows an opposite trend, i.e., greatest deviation from bulk composition occurring in the most narrow pores. A simple mean-field lattice model of a liquid mixture confined by parallel walls is adopted to rationalize these experimental findings. This model reproduces the main findings of the confinement effect on the adsorption near liquid/liquid phase separation.

  3. Adsorption and desorption behavior of selected pesticides as influenced by decomposition of maize mulch.

    PubMed

    Aslam, Sohaib; Garnier, Patricia; Rumpel, Cornelia; Parent, Serge E; Benoit, Pierre

    2013-06-01

    Assessing pesticide fate in conservation agricultural systems requires a detailed understanding of their interaction with decomposing surface crop residues (mulch). Adsorption and desorption behavior of glyphosate, s-metolachlor and epoxiconazole was investigated on maize mulch residues decomposed under laboratory and field conditions. Our conceptual approach included characterization of chemical composition and hydrophobicity of mulch residues in order to generate parameters to predict sorption behavior. Adsorption of s-metolachlor and epoxiconazole greatly increased with mulch decomposition, whereas glyphosate adsorption was less affected but its desorption was increased. Mulch characteristics including aromaticity, hydrophobicity and polarity indices were strongly correlated to Koc of the non-ionic pesticides. A predictive model based on compositional data (CoDa) analysis revealed that the sorption capacity of decomposing mulch can be predicted from descriptors such as aromatic and alkyl C corresponding respectively to lignin and NDF biochemical fractions. The decomposition degree of mulch residues should be taken into account while predicting the fate of pesticides.

  4. Adsorption behavior of ternary mixtures of noble gases inside single-walled carbon nanotube bundles

    NASA Astrophysics Data System (ADS)

    Foroutan, Masumeh; Nasrabadi, Amir Taghavi

    2010-09-01

    In order to study the gas-storage and gas-filtering capability of carbon nanotube (CNT) bundles simultaneously, we considered the adsorption behavior of a ternary mixture of noble gases, including Argon (Ar), Krypton (Kr), and Xenon (Xe), i.e., Ar-Kr-Xe mixture, on (10, 10) single-walled carbon nanotube (SWCNT) bundles. Molecular dynamics (MD) simulations at different temperatures of (75, 100, 150, 200, 250, and 300) K were performed, and adsorption energies, self-diffusion coefficients, activation energies, and radial distribution functions (RDFs) were computed to analyze the thermodynamics, transport and structural properties of the adsorption systems. It is observed that the SWCNT bundles have larger contents of heavier noble gases compared to the lighter ones. This interesting behavior of SWCNT bundles makes them proper candidates for gas-storage and gas molecular-sieving processes.

  5. Adsorption behavior of lead on aquatic sediments contaminated with cerium dioxide nanoparticles.

    PubMed

    Wang, Chao; Fan, Xiulei; Wang, Peifang; Hou, Jun; Ao, Yanhui; Miao, Lingzhan

    2016-12-01

    Aquatic sediments serve as an important sink for engineered nanomaterials (ENMs), such as metal oxide nanoparticles (MeO NPs) and carbon nanotubes (CNTs). Owing to their remarkable properties, ENMs demonstrate significant potential to disturb the adsorption behavior of other contaminants in aquatic sediments, thereby altering the bioavailability and toxicity of these contaminants. Thus far, most studies have investigated the effect of CNTs on the adsorption of other contaminants on sediments. Cerium dioxide nanoparticles (CeO2 NPs), as one of the important MeO NPs, are also inevitably discharged into aquatic sediments because of their widespread use. In this study, we investigated the adsorption behavior of Pb(2+) on sediments spiked with CeO2 NPs at a weight ratio of 5.0%. The results showed that the adsorption rates at three stages occurring during adsorption clearly increase for sediments contaminated with CeO2 NPs. Moreover, the results obtained from the adsorption isotherms indicated that the Langmuir isotherm model best fits the isotherm data for both sediments and those contaminated with CeO2 NPs. After spiking the sediments with CeO2 NPs, the theoretical maximum monolayer adsorption capacity (Qmax) for Pb(2+) increased from 4.433 to 4.995 mg/g and the Langmuir isotherm coefficient (KL) decreased from 8.813 to 7.730 L/g. The effects of CeO2 NPs on the surface charge and pore surface properties of sediments were also studied as these properties affect the adsorption of several chemicals in sediments. The results showed that pHzpc, SBET, Sext, and average pore size of sediments clearly decrease for sediments contaminated with CeO2 NPs. Hence, the strong adsorption capacity of CeO2 NPs and the changes of sediment surface charge and pore surface properties caused by CeO2 NPs are important factors affecting the adsorption behavior of Pb(2+). The potential risk of Pb(2+) in aquatic environment may increase with CeO2 NPs buried in sediments.

  6. Delamination behavior of silicate layers by adsorption of cationic surfactants.

    PubMed

    Lee, Seung Yeop; Kim, Soo Jin

    2002-04-15

    Smectite that has reacted for 48 h with hexadecyltrimethylammonium (HDTMA) cations equivalent to 0.01-3.0 times the cation exchange capacity (CEC) converts to HDTMA-smectite. The microstructure of this organoclay is observed using X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). When Na cations in the interlayer of clay are exchanged with HDTMA ions, the changes in internal and external surface configuration are augmented by the intercalation of organic surfactants, showing a heterogeneous increase of interlayer spacings. As HDTMA loading increases, the chance of delaminated layers being developed increases locally in the low-charge interlayer regions by the sufficient adsorption of organic surfactants beyond the CEC due to the tendency of alkyl chain interaction.

  7. Adsorption Behavior of Ferromagnetic Carbon Nanotubes for Methyl Orange from Aqueous Solution.

    PubMed

    Wang, Liping; Zhang, Mingyu; Zhao, Chenxi; Yang, Shan

    2016-03-01

    The ferromagnetic carbon nanotubes which can be easily separated from aqueous solution were prepared and characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). Batch experiments were carried out to investigate the adsorption behavior of ferromagnetic carbon nanotubes for removing methyl orange (MO). The results showed that these ferromagnetic carbon nanotubes were richer in surface function groups than the carbon nanotubes did, furthermore, both γ-Fe2O3 and Fe with ferromagnetism were found on the surface of carbon nanotubes. The results also demonstrated that ferromagnetic carbon nanotubes possessed stronger adsorption ability for MO than carbon nanotubes did. The adsorption isotherms followed Langmuir isotherm equation and the adsorption kinetics could be well described with the pseudo second-order kinetic model. The adsorption process involved an intraparticle diffusion, while it was not the only rate-controlling step. The values of AG were negative and the value of ΔH is -12.37 kJ/mol, proving that the adsorption of MO onto ferromagnetic carbon nanotubes was a spontaneous and exothermic process.

  8. Observation of adsorption behavior of biomolecules on ferroelectric crystal surfaces with polarization domain patterns

    NASA Astrophysics Data System (ADS)

    Nakayama, Tomoaki; Isobe, Akiko; Ogino, Toshio

    2016-08-01

    Lithium tantalate (LiTaO3) is one of the ferroelectric crystals that exhibit spontaneous polarization domain patterns on its surface. We observed the polarization-dependent adsorption of avidin molecules, which are positively charged in a buffer solution at pH 7.0, on LiTaO3 surfaces caused by electrostatic interaction at an electrostatic double layer using atomic force microscopy (AFM). Avidin adsorption in the buffer solution was confirmed by scratching the substrate surfaces using the AFM cantilever, and the adsorption patterns were found to depend on the avidin concentration. When KCl was added to the buffer solution to weaken the electrostatic double layer interaction between avidin molecules and LiTaO3 surfaces, adsorption domain patterns disappeared. From the comparison between the adsorption and chemically etched domain patterns, it was found that avidin molecule adsorption is enhanced on negatively polarized domains, indicating that surface polarization should be taken into account in observing biomolecule behaviors on ferroelectric crystals.

  9. Modeling selenate adsorption behavior on oxides, clay minerals, and soils using the triple layer model

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Selenate adsorption behavior was investigated on amorphous aluminum oxide, amorphous iron oxide, goethite, clay minerals: kaolinites, montmorillonites, illite, and 18 soil samples from Hawaii, and the Southwestern and the Midwestern regions of the US as a function of solution pH. Selenate adsorpti...

  10. Unique adsorption behaviors of carboxylic acids at rutile TiO2(110)

    NASA Astrophysics Data System (ADS)

    Yu, Yan-Yan; Gong, Xue-Qing

    2015-11-01

    The coverage-dependent adsorption behavior of acetic acid (CH3COOH) on rutile TiO2(110) was investigated by means of density functional theory (DFT) calculations, corrected by on-site Coulomb corrections and long-range dispersion interactions. The p(2 × 1) and c(2 × 2) domains of dissociatively adsorbed acetic acid under different coverages have been studied in detail regarding their structural and energetic properties. Adsorptions of formic acid (HCOOH) and carbonic acid (H2CO3) were also considered for better understanding the adsorption behaviors of carboxylic acids. Our calculation results show that carboxylic acids prefer to dissociatively adsorb in bridging bidentate configuration, and it induces significant surface relaxation at the adsorption site, which also affects other surface atoms nearby. Interestingly, we have shown that such adsorption-induced relaxations still maintain bond symmetries for surface Ti cations within the p(2 × 1) domain while they are drastically broken within the c(2 × 2) domain, giving rise to unstable Ti cations at the surface. This work not only explains the long-lasting puzzle of the preferable occurrence of p(2 × 1) domain for the adsorbed carboxylic acids at rutile TiO2(110), it also proposes a novel scheme that metal oxide surfaces may follow when they are involved in the processes like surface functionalization and self-assembly.

  11. Adsorption Behavior of Metasilicate on N-Methyl d-Glucamine Functional Groups and Associated Silicon Isotope Fractionation.

    PubMed

    Wang, Wei; Wei, Hai-Zhen; Jiang, Shao-Yong; Eastoe, Christopher J; Guo, Qi; Lin, Yi-Bo

    2016-09-06

    Significant isotope fractionation of silicon provides a powerful geochemical tracer for biological and physicochemical processes in terrestrial and marine environments. The exact mechanism involved in silicon uptake as part of the biological process is not well known. The silicon uptake in biological processes is investigated using silicate adsorption onto the N-methylglucamine functional group (sugarlike structure, abbreviated as L) of Amberlite IRA-743 resin as an analogue of the formation of silicate-sugar complexes in plants. This study provides new evidence that certain sugars can react readily with basic silicic acid to form sugar-silicate chelating complexes, and the equilibrium adsorption behavior of silicate can be well described by the Langmuir isotherm with a Gibbs free energy (ΔG) of -11.94 ± 0.21 kJ·mol(-1) at 293 K. The adsorption kinetics corresponds well to a first-order kinetic model in which the adsorption rate constant ka of 1.25 × 10(-4) s(-1) and the desorption rate constant kd of 4.00 × 10(-6) s(-1) are obtained at 293 K. Both ka and kd increase with increasing temperature. The bonding configurations of silicate-sugar complexes imply the principal coordination complex of hexacoordinated silicon (silicon/L = 1:3) in the liquid phase and the dominant tetracoordinated silicon in the solid phase. Similar to those of many natural processes, the biological uptake via the sugar-silicate chelating complexes favors the preferential enrichment of light Si isotopes into solids, and the Rayleigh model controls the dynamic isotope fractionation with an estimated silicon isotope fractionation factor (i.e., αsolid-solution = [Formula: see text]) of 0.9971. This study advanced the fundamental understanding of the dynamic isotope fractionation of silicon during silicon cycling from the lithosphere to the biosphere and hydrosphere in surficial processes.

  12. The distribution and adsorption behavior of aliphatic amines in marine and lacustrine sediments

    SciTech Connect

    Wang, Xuchen; Lee, C. )

    1990-10-01

    The methylated amines - monomethyl-, dimethyl-, and trimethyl amine (MMA, DMA, TMA) - are commonly found in aquatic environments, apparently as a result of decomposition processes. Adsorption of these amines to clay minerals and organic matter significantly influences their distribution in sediments. Laboratory measurements using {sup 14}C-radiolabelled amines and application of a linear partitioning model resulted in calculated adsorption coefficients of 2.4-4.7 (MMA), 3.3 (DMA), and 3.3-4.1 (TMA). Further studies showed that adsorption of amines is influenced by salinity of the porewaters, and clay mineral and organic matter content of the sediment solid phase. Concentrations of monomethyl- and dimethyl amine were measured in the porewaters and the solid phase of sediment samples collected from Flax Pond and Lake Ronkonkoma (NY), Long Island Sound, and the coastal Peru upwelling area. These two amines were present in all sediments investigated. A clear seasonal increase in the solid-phase concentration of MMA and DMA in Flax Pond sediments was likely related to the annual senescence of salt marsh grasses, either directly as a source of these compounds or indirectly by providing additional exchange capacity to the sediments. The distribution of amines in the solid and dissolved phases observed in all sediments investigated suggests that the distribution of these compounds results from a balance among production, decomposition, and adsorption processes.

  13. Visualization of Adsorption: Luminescent Mesoporous Silica-Carbon Dots Composite for Rapid and Selective Removal of U(VI) and in Situ Monitoring the Adsorption Behavior.

    PubMed

    Wang, Zhe; Xu, Chao; Lu, Yuexiang; Wu, Fengcheng; Ye, Gang; Wei, Guoyu; Sun, Taoxiang; Chen, Jing

    2017-03-01

    The removal and separation of uranium from aqueous solutions are quite important for resource reclamation and environmental protection. Being one of the most effective techniques for metal separation, adsorption of uranium by a variety of adsorbent materials has been a subject of study with high interest in recent years. However, current methods for monitoring the adsorption process require complicated procedures and tedious measurements, which hinders the development of processes for efficient separation of uranium. In this work, we prepared a type of luminescent mesoporous silica-carbon dots composite material that has high efficiency for the adsorption of uranium and allows simultaneous in situ monitoring of the adsorption process. Carbon dots (CDs) were prepared in situ and introduced onto amino-functionalized ordered mesoporous silica (SBA-NH2) by a facile microplasma-assisted method. The prepared CDs/SBA-NH2 nanocomposites preserved the high specific surface area of the mesoporous silica, as well as the fluorescent properties of the CDs. Compared with bare SBA-NH2, the CDs/SBA-NH2 nanocomposites showed much improved adsorption ability and excellent selectivity for uranyl ions. Moreover, the fluorescence intensity of the composites decreased along with the increase of uranium uptake, indicating that the CDs/SBA-NH2 nanocomposites could be used for on-site monitoring of the adsorption behavior. More interestingly, the adsorption selectivity of the composites for metal ions was in good agreement with the selective fluorescence response of the original CDs, which means that the adsorption selectivity of CDs-based composite materials can be predicted by evaluating the fluorescence selectivity of the CDs for metal ions. As the first study of CDs-based nanocomposites for the adsorption of actinide elements, this work opens a new avenue for the in situ monitoring of adsorption behavior of CDs-based nanocomposites while extending their application areas.

  14. Adsorption behavior of natural anthocyanin dye on mesoporous silica

    NASA Astrophysics Data System (ADS)

    Kohno, Yoshiumi; Haga, Eriko; Yoda, Keiko; Shibata, Masashi; Fukuhara, Choji; Tomita, Yasumasa; Maeda, Yasuhisa; Kobayashi, Kenkichiro

    2014-01-01

    Because of its non-toxicity, naturally occurring anthocyanin is potentially suitable as a colorant for foods and cosmetics. To the wider use of the anthocyanin, the immobilization on the inorganic host for an easy handling as well as the improvement of the stability is required. This study is focused on the adsorption of significant amount of the natural anthocyanin dye onto mesoporous silica, and on the stability enhancement of the anthocyanin by the complexation. The anthocyanin has successfully been adsorbed on the HMS type mesoporous silica containing small amount of aluminum. The amount of the adsorbed anthocyanin has been increased by modifying the pore wall with n-propyl group to make the silica surface hydrophobic. The light fastness of the adsorbed anthocyanin has been improved by making the composite with the HMS samples containing aluminum, although the degree of the improvement is not so large. It has been proposed that incorporation of the anthocyanin molecule deep inside the mesopore is required for the further enhancement of the stability.

  15. The adsorption behavior of octafluoropropane at the water/gas interface

    SciTech Connect

    Giebel, Friederike; Paulus, Michael; Nase, Julia Bieder, Steffen; Kiesel, Irena; Tolan, Metin

    2014-12-14

    We studied the adsorption behavior of the gas octafluoropropane at the water/gas interface as a function of different pressures. In a custom-made measurement cell, the gas pressure was varied in a range between 1 bar and close to the condensation pressure of octafluoropropane. The electron density profiles of the adsorption layers show that the layer thickness increases with pressure. The evolution of the layer electron density indicates that the bulk electron density is reached if a layer consisting of more than one monolayer of octafluoropropane is adsorbed on the water surface.

  16. [Lunar phases as triggers for delinquent behavior?].

    PubMed

    Knecht, Thomas

    2008-01-01

    For many centuries, mankind has been concerned about the potential impact that the moon may have on human behavior, especially delinquency. The author presents a case report, in which the delinquency of the offender seems to show a certain synchronisation with the lunar phases. Finally, the issue is discussed on the basis of today's scientific literature on this topic.

  17. Impact of biochar produced from post-harvest residue on the adsorption behavior of diesel oil on loess soil.

    PubMed

    Jiang, Yu Feng; Sun, Hang; Yves, Uwamungu J; Li, Hong; Hu, Xue Fei

    2016-02-01

    The primary objective of this study was to investigate the effect of biochar, produced from wheat residue at different temperatures, on the adsorption of diesel oil by loess soil. Kinetic and equilibrium data were processed to understand the adsorption mechanism of diesel by biochar-affected loess soil; dynamic and thermodynamic adsorption experiments were conducted to characterize this adsorption. The surface features and chemical structure of biochar, modified at varying pyrolytic temperatures, were investigated using surface scanning electron microscopy and Fourier transform infrared analysis. The kinetic data showed that the adsorption of diesel oil onto loess soil could be described by a pseudo-second-order kinetic model, with the rate-controlling step being intraparticle diffusion. However, in the presence of biochar, boundary layer control and intraparticle diffusion were both involved in the adsorption. Besides, the adsorption equilibrium data were well described by the Freundlich isothermal model. The saturated adsorption capacity weakened as temperature increased, suggesting a spontaneous exothermic process. Thermodynamic parameter analysis showed that adsorption was mainly a physical process and was enhanced by chemical adsorption. The adsorption capacity of loess soil for diesel oil was weakened with increasing pH. The biochar produced by pyrolytic wheat residue increased the adsorption behavior of petroleum pollutants in loess soil.

  18. Aqueous phase adsorption of different sized molecules on activated carbon fibers: Effect of textural properties.

    PubMed

    Prajapati, Yogendra N; Bhaduri, Bhaskar; Joshi, Harish C; Srivastava, Anurag; Verma, Nishith

    2016-07-01

    The effect that the textural properties of rayon-based activated carbon fibers (ACFs), such as the BET surface area and pore size distribution (PSD), have on the adsorption of differently sized molecules, namely, brilliant yellow (BY), methyl orange (MO) and phenol (PH), was investigated in the aqueous phase. ACF samples with different BET areas and PSDs were produced by steam-activating carbonized fibers for different activation times (0.25, 0.5, and 1 h). The samples activated for 0.25 h were predominantly microporous, whereas those activated for relatively longer times contained hierarchical micro-mesopores. The adsorption capacities of the ACFs for the adsorbate increased with increasing BET surface area and pore volume, and ranged from 51 to 1306 mg/g depending on the textural properties of the ACFs and adsorbate size. The adsorption capacities of the hierarchical ACF samples followed the order BY > MO > PH. Interestingly, the number of molecules adsorbed by the ACFs followed the reverse order: PH > MO > BY. This anomaly was attributed to the increasing molecular weight of the PH, MO and BY molecules. The equilibrium adsorption data were described using the Langmuir isotherm. This study shows that suitable textural modifications to ACFs are required for the efficient aqueous phase removal of an adsorbate.

  19. ADSORPTION MECHANISMS AND TRANSPORT BEHAVIOR BETWEEN SELENATE AND SELENITE ON DIFFERENT SORBENTS

    SciTech Connect

    Snyder, Michelle MV; Um, Wooyong

    2014-04-30

    Adsorption of different oxidation species of selenium (Se), selenate (SeO42-) and selenite (SeO32-), with varying pHs (2 - 10) and ionic strengths (I = 0.01 M, 0.1 M and 1.0 M NaNO3) was measured on quartz, aluminum oxide, and synthetic iron oxide (ferrihydrite) using batch reactors to obtain a more detailed understanding of the adsorption mechanisms (e.g., inner- and outer-sphere complex). In addition to the batch experiments with single minerals contained in native Hanford Site sediment, additional batch adsorption studies were conducted with native Hanford Site sediment and groundwater as a function of 1) total Se concentration (from 0.01 to 10 mg L-1) and 2) soil to solution ratios (1:20 and 1:2 grams per mL). Results from these batch studies were compared to a set of saturated column experiments that were conducted with natural Hanford sediment and groundwater spiked with either selenite or selenate to observe the transport behavior of these species. Both batch and column results indicated that selenite adsorption was consistently higher than that of selenate in all experimental conditions used. These different adsorption mechanisms between selenite and selenate result in the varying mobility of Se in the subsurface environment and explain the dependence on the oxidation species.

  20. Microwave-assisted modification on montmorillonite with ester-containing Gemini surfactant and its adsorption behavior for triclosan.

    PubMed

    Liu, Bo; Lu, Junxiang; Xie, Yu; Yang, Bin; Wang, Xiaoying; Sun, Runcang

    2014-03-15

    To obtain effective adsorbent that can remove emerging organic pollutant of triclosan (TCS) in aquatic environment, different ester-containing Gemini surfactant-modified MMT (EMMT) were prepared under microwave irradiation. The whole process was rapid, uniform, easy and energy-efficient. The structures and morphology of EMMT were characterized by XRD, TEM, FT-IR, SEM and TGA. The results revealed that the saturated intercalation amount of this surfactant was 0.8 times to cation exchange capacity (CEC) of MMT, and there was electrostatic interaction between ester-containing Gemini surfactant and MMT. In addition, they bound in the ways of intercalation, intercalation-adsorption or adsorption, which relied on the dosage of the surfactant. The surface of EMMT was hydrophobic, rough and fluffy, which contributed to its strong adsorption capacity. The adsorption equilibrium data of EMMT for TCS were fitted to Langmuir and Freundlich isothermal adsorption model. The result showed that Langmuir isothermal adsorption model could describe the adsorption behavior better, the adsorption behavior of TCS on EMMT was confirmed to a surface monolayer adsorption, and notably the theoretical maximum adsorption capacity was up to 133 mg/g. Therefore, this work lays important foundation on developing effective and safe absorbent materials for the treatment of emerging organic pollutants.

  1. Dissociative Water Adsorption by Al3O4(+) in the Gas Phase.

    PubMed

    Fagiani, Matias R; Song, Xiaowei; Debnath, Sreekanta; Gewinner, Sandy; Schöllkopf, Wieland; Asmis, Knut R; Bischoff, Florian A; Müller, Fabian; Sauer, Joachim

    2017-03-06

    We use cryogenic ion trap vibrational spectroscopy in combination with density functional theory (DFT) to study the adsorption of up to four water molecules on Al3O4(+). The infrared photodissociation spectra of [Al3O4(D2O)1-4](+) are measured in the O-D stretching (3000-2000 cm(-1)) as well as the fingerprint spectral region (1300-400 cm(-1)) and are assigned based on a comparison with simulated harmonic infrared spectra for global minimum-energy structures obtained with DFT. We find that dissociative water adsorption is favored in all cases. The unambiguous assignment of the vibrational spectra of these gas phase model systems allows identifying characteristic spectral regions for O-D and O-H stretching modes of terminal (μ1) and bridging (μ2) hydroxyl groups in aluminum oxide/water systems, which sheds new light on controversial assignments for solid Al2O3 phases.

  2. Selective adsorption behavior of Cd(II) ion imprinted polymers synthesized by microwave-assisted inverse emulsion polymerization: Adsorption performance and mechanism.

    PubMed

    Zhu, Fang; Li, Luwei; Xing, Junde

    2017-01-05

    Microwave-assisted inverse emulsion polymerization method was used to prepare Cd(II) imprinted polymer (IIP) by using β-cyclodextrin (β-CD) and acrylamide (AM) as functional monomer, epichlorohydrin (ECH) as crossing-linking agent, ammonium persulfate as initiator. The Cd(II) imprinted polymer was characterized by SEM, FTIR and TGA. The influences of initial concentration of Cd(II), pH values, temperature, time and competitive ions on adsorption capacity and recognition properties are investigated. Under the optimal conditions, the adsorption capacity could reach 107mg/g. Furthermore, pseudo first order kinetic model, pseudo second order kinetic model and intra-particular diffusion model were used to describe the adsorption kinetic behavior. Results showed that the pseudo-second-order model (R(2) 0.9928-0.9961) had the best agreement with the experimental data. Langmuir adsorption isotherm model described the experimental data well, which indicated that adsorption was mainly monolayer absorption. Moreover, the study of adsorption thermodynamics (ΔG(0)<0, ΔH(0)>0, ΔS(0)>0) suggested that the adsorption process was a spontaneous and endothermic process. Competitive selectivity experiment revealed that imprinted polymer could selectively recognize Cd(II). It provides a new idea for removing Cd(II) from aqueous solution.

  3. Adsorption of water from aqueous acetonitrile on silica-based stationary phases in aqueous normal-phase liquid chromatography.

    PubMed

    Soukup, Jan; Jandera, Pavel

    2014-12-29

    Excess adsorption of water from aqueous acetonitrile mobile phases was investigated on 16 stationary phases using the frontal analysis method and coulometric Karl-Fischer titration. The stationary phases include silica gel and silica-bonded phases with different polarities, octadecyl and cholesterol, phenyl, nitrile, pentafluorophenylpropyl, diol and zwitterionic sulfobetaine and phosphorylcholine ligands bonded on silica, hybrid organic-silica and hydrosilated matrices. Both fully porous and core-shell column types were included. Preferential uptake of water by the columns can be described by Langmuir isotherms. Even though a diffuse rather than a compact adsorbed discrete layer of water on the adsorbent surface can be formed because of the unlimited miscibility of water with acetonitrile, for convenience, the preferentially adsorbed water was expressed in terms of a hypothetical monomolecular water layer equivalent in the inner pores. The uptake of water strongly depends on the polarity and type of the column. Less than one monomolecular water layer equivalent was adsorbed on moderate polar silica hydride-based stationary phases, Ascentis Express F5 and Ascentis Express CN column at the saturation capacity, while on more polar stationary phases, several water layer equivalents were up-taken from the mobile phase. The strongest affinity to water was observed on the ZIC cHILIC stationary phases, where more than nine water layer equivalents were adsorbed onto its surface at its saturation capacity. Columns with bonded hydroxyl and diol ligands show stronger water adsorption in comparison to bare silica. Columns based on hydrosilated silica generally show significantly decreased water uptake in comparison to stationary phases bonded on ordinary silica. Significant correlations were found between the water uptake and the separation selectivity for compounds with strong polarity differences.

  4. Adsorption and desorption behavior of asphaltene on polymer-brush-immobilized surfaces.

    PubMed

    Higaki, Yuji; Hatae, Kaoru; Ishikawa, Tatsuya; Takanohashi, Toshimasa; Hayashi, Jun-ichiro; Takahara, Atsushi

    2014-11-26

    The adsorption behavior of a model compound for surface-active component of asphaltenes, N-(1-hexylheptyl)-N'-(12-carboxylicdodecyl) perylene-3,4,9,10-tetracarboxylic bisimide (C5Pe), and detachment behavior of asphaltene deposit films for high-density polymer brushes were investigated. Zwitterionic poly(3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate (PMAPS) brushes and hydrophobic poly(n-hexyl methacrylate) (PHMA) brushes exhibit less C5Pe adsorption than poly(methyl methacrylate) (PMMA). The asphaltene deposit films on the PHMA brush detached in a model oil (toluene/n-heptane=1/4 (v/v)), and the asphaltene films on the PMAPS brush detached in water. The antifouling character was explained by the interface free energy for the polymer-brush/asphaltenes (γSA) and polymer-brush/toluene (γSO).

  5. Excess adsorption of binary aqueous organic mixtures on various reversed-phase packing materials.

    PubMed

    Buntz, S; Figus, M; Liu, Z; Kazakevich, Y V

    2012-06-01

    Excess adsorption isotherms of acetonitrile and methanol from water were measured on eight commercial columns. Columns used in this study represent latest examples in column development and include three different poroshell columns (Kinetex-C18, Acsentis-C18 and Halo-C18) as well as conventional columns with significantly different adsorbent geometry (Allure-C18, YMC-C18) and various hybrid-silica columns (Gemini-C18, Xterra-C18 and XBridge-C18). Comparison of the excess adsorption isotherms measured on all these columns and expressed in surface specific form demonstrated significant similarity of the adsorption properties of all columns, which allows us to introduce the "standard adsorption isotherm" for reversed-phase C18-type columns. The methodology of the evaluation of the total amount of adsorbent in the column and effective surface area of the C18 modified adsorbent is also discussed. These terms are critical for successful evaluation of surface specific parameters.

  6. Nonuniversal surface behavior of dynamic phase transitions

    NASA Astrophysics Data System (ADS)

    Riego, Patricia; Berger, Andreas

    2015-06-01

    We have studied the dynamic phase transition (DPT) of the kinetic Ising model in systems with surfaces within the mean-field approximation. Varying the surface exchange coupling strength Js, the amplitude of the externally applied oscillating field h0, and its period P , we explore the dynamic behavior of the layer-dependent magnetization and the associated DPTs. The surface phase diagram shows several features that resemble those of the equilibrium case, with an extraordinary bulk transition and a surface transition for high Js values, independent from the value of h0. For low Js, however, h0 is found to be a crucial parameter that leads to nonuniversal surface behavior at the ordinary bulk transition point. Specifically, we observed here a bulk-supported surface DPT for high field amplitudes h0 and correspondingly short critical periods Pc, whereas this surface transition simultaneous to the bulk one is suppressed for slow critical dynamics occurring for low values of h0. The suppression of the DPT for low h0 not only occurs for the topmost surface layer, but also affects a significant number of subsurface layers. We find that the key physical quantity that explains this nonuniversal behavior is the time correlation between the dynamic surface and bulk magnetizations at the bulk critical point. This time correlation has to pass a threshold value to trigger a bulk-induced DPT in the surface layers. Otherwise, dynamic phase transitions are absent at the surface in stark contrast to the equilibrium behavior of the corresponding thermodynamic Ising model. Also, we have analyzed the penetration depth of the dynamically ordered phase for the surface DPT that occurs for large Js values. Here we find that the penetration depth depends strongly on Js and behaves identically to the corresponding equilibrium Ising model.

  7. [Study of the adsorption behaviors of plasma proteins on the single-walled carbon nanotubes nonwoven].

    PubMed

    Meng, Jie; Song, Li; Meng, Jie; Kong, Hua; Wang, Chaoying; Guo, Xiaotian; Xu, Haiyan; Xie, Sishen

    2007-02-01

    Single walled carbon nanotubes (SWNT) have attracted increasing research interests for the purpose of biomedical application because they provide not only nanostructured topography, but also chemical composition of pure carbon atoms, as well as ultra high strength and excellent flexibility. Regarding the interactions of nanomaterials to biological systems, non-specific adsorption of plasma proteins is one of the most important issues to be concerned, which plays a crucial role that would determine how biological systems response to the biomaterials. Motivated by application of SWNT materials in biomedical fields, in this study, the adsorption behaviors of plasma proteins on the surface of SWNT nonwoven, prepared directly by floating chemical vapor observation and energy deposition method were investigated by means of scanning electron microscope (SEM), dispersive X-ray (EDX) analysis and ELISA. Results indicated the SWNT non-woven showed a clear adsorption preference of fibrinogen over albumin. There was no human serum albumin detected using above analysis methods on the SWNT nonwoven even incubated in the albumin solution of 4 mg/ml. While more than 0.15 microg of human fibrinogen was detected by ELISA on the SWNT nonwoven with area of 40 mm x 40 mm incubated in the fibrinogen solution of 5 microg/ml. In addition, IgG of sheep-anti-human serum fibrinogen exhibited strong nonspecific adsorption on the surface of SWNT nonwoven. The adsorption behaviors are different significantly from those of other carbon materials and conventional biomaterials. The unique interaction of SWNT nonwoven to plasma proteins is of significance to further studies of blood cells responses.

  8. Phase Behavior of Lipid Bilayers under Tension

    PubMed Central

    Uline, Mark J.; Schick, M.; Szleifer, Igal

    2012-01-01

    Given the proposed importance of membrane tension in regulating cellular functions, we explore the effects of a finite surface tension on phase equilibrium using a molecular theory that captures the quantitative structure of the phase diagram of the tensionless DPPC/DOPC/Cholesterol lipid bilayer. We find that an increase in the surface tension decreases the temperature of the transition from liquid to gel in a pure DPPC system by ∼1.0 K/(mN/m), and decreases the liquid-disordered to liquid-ordered transition at constant chemical potentials by approximately the same amount. Our results quantitatively isolate the role of tension in comparison to other thermodynamic factors, such as pressure, in determining the phase behavior of lipid bilayers. PMID:22325274

  9. Phase behavior of an amphiphilic fluid.

    PubMed

    Schoen, Martin; Giura, Stefano; Klapp, Sabine H L

    2014-01-01

    We invoke mean-field density functional theory (DFT) to investigate the phase behavior of an amphiphilic fluid composed of a hard-sphere core plus a superimposed anisometric Lennard-Jones perturbation. The orientation dependence of the interactions consists of a contribution analogous to the interaction potential between a pair of "spins" in the classical, three-dimensional Heisenberg fluid and another one reminiscent of the interaction between (electric or magnetic) point dipoles. At fixed orientation both contributions are short-range in nature decaying as r-6 (r being the separation between the centers of mass of a pair of amphiphiles). Based upon two mean-field-like approximations for the pair correlation function that differ in the degree of sophistication we derive expressions for the phase boundaries between various isotropic and polar phases that we solve numerically by the Newton-Raphson method. For sufficiently strong coupling between the Heisenberg "spins" both mean-field approximations generate three topologically different and generic types of phase diagrams that are observed in agreement with earlier work [see, for example, Tavares et al., Phys. Rev. E 52, 1915 (1995)]. Whereas the dipolar contribution alone is incapable of stabilizing polar phases on account of its short-range nature it is nevertheless important for details of the phase diagram such as location of the gas-isotropic liquid critical point, triple, and tricritical points. By tuning the dipolar coupling constant suitably one may, in fact, switch between topologically different phase diagrams. Employing also Monte Carlo simulations in the isothermal-isobaric ensemble the general topology of the DFT phase diagrams is confirmed.

  10. Phase behavior of an amphiphilic fluid

    NASA Astrophysics Data System (ADS)

    Schoen, Martin; Giura, Stefano; Klapp, Sabine H. L.

    2014-01-01

    We invoke mean-field density functional theory (DFT) to investigate the phase behavior of an amphiphilic fluid composed of a hard-sphere core plus a superimposed anisometric Lennard-Jones perturbation. The orientation dependence of the interactions consists of a contribution analogous to the interaction potential between a pair of "spins" in the classical, three-dimensional Heisenberg fluid and another one reminiscent of the interaction between (electric or magnetic) point dipoles. At fixed orientation both contributions are short-range in nature decaying as r-6 (r being the separation between the centers of mass of a pair of amphiphiles). Based upon two mean-field-like approximations for the pair correlation function that differ in the degree of sophistication we derive expressions for the phase boundaries between various isotropic and polar phases that we solve numerically by the Newton-Raphson method. For sufficiently strong coupling between the Heisenberg "spins" both mean-field approximations generate three topologically different and generic types of phase diagrams that are observed in agreement with earlier work [see, for example, Tavares et al., Phys. Rev. E 52, 1915 (1995), 10.1103/PhysRevE.52.1915]. Whereas the dipolar contribution alone is incapable of stabilizing polar phases on account of its short-range nature it is nevertheless important for details of the phase diagram such as location of the gas-isotropic liquid critical point, triple, and tricritical points. By tuning the dipolar coupling constant suitably one may, in fact, switch between topologically different phase diagrams. Employing also Monte Carlo simulations in the isothermal-isobaric ensemble the general topology of the DFT phase diagrams is confirmed.

  11. The effect of weathering on charcoal filter performance. 1; The adsorption and desorption behavior of contaminants

    SciTech Connect

    Wren, J.C.; Moore, C.J. )

    1991-05-01

    This paper reports on triethylenediamine (TEDA) impregnated charcoals, used in nuclear reactors to safeguard against the release of airborne radioiodine, which show high efficiency under various reactor operation and accident conditions when the are new. However, during normal operation, charcoal filters are continuously degraded (or weathered) due to the adsorption of moisture and other air contaminants. The effect of weathering on the efficiency of charcoal for removing radioiodine is of great interest. The results of a study on the adsorption behavior of various contaminants NO{sub 2}, SO{sub 2} 2-butanone (methyl-ethyl ketone (MEK)) and NH{sub 3} on TEDA charcoal are presented. This study is an attempt to characterize and quantify the weathering process of TEDA charcoal by these contaminants. The adsorption and desorption of characteristics of these contaminants range from completely irreversible (NO{sub 2}) to completely reversible (NH{sub 3}). The effect of absorbed water (or humidity) on absorption is different for each contaminant. Absorbed water increases the absorption rate and capacity of TEDA charcoal for NO{sub 2}. However, it appears that SO{sub 2} is absorbed as H{sub 2}SO{sub 4} on the wet charcoal. Absorbed water slightly reduces the adsorption capacity of the charcoal for MEK, but does not affect the absorption of NH{sub 3}.

  12. Behavior of human immunoglobulin G adsorption onto immobilized Cu(II) affinity hollow-fiber membranes.

    PubMed

    Borsoi-Ribeiro, Mariana; Bresolin, Igor Tadeu Lazzarotto; Vijayalakshmi, Mookambeswaran; Bueno, Sônia Maria Alves

    2013-10-01

    Iminodiacetic acid (IDA) and tris(2-aminoethyl)amine (TREN) chelating ligands were immobilized on poly(ethylene vinyl alcohol) (PEVA) hollow-fiber membranes after activation with epichlorohydrin or butanediol diglycidyl ether (bisoxirane). The affinity membranes complexed with Cu(II) were evaluated for adsorption of human immunoglobulin G (IgG). The effects of matrix activation and buffer system on adsorption of IgG were studied. Isotherms of batch IgG adsorption onto finely cut membranes showed that neither of the chelates, IDA-Cu(II) or TREN-Cu(II), had a Langmuirean behavior with negative cooperativity for IgG binding. A comparison of equilibrium and dynamic maximum capacities showed that the dynamic capacity for a mini-cartridge in a cross-flow filtration mode (52.5 and 298.4 mg g(-1) dry weight for PEVA-TREN-Cu(II) and PEVA-IDA-Cu(II), respectively) was somewhat higher than the equilibrium capacity (9.2 and 73.3 mg g(-1) dry weight for PEVA-TREN-Cu(II) and PEVA-IDA-Cu(II), respectively). When mini-cartridges were used, the dynamic adsorption capacity of IDA-Cu(II) was the same for both mini-cartridge and agarose gel.

  13. Computational studies of adsorption in metal organic frameworks and interaction of nanoparticles in condensed phases

    SciTech Connect

    Annapureddy, HVR; Motkuri, RK; Nguyen, PTM; Truong, TB; Thallapally, PK; McGrail, BP; Dang, LX

    2014-02-05

    In this review, we describe recent efforts to systematically study nano-structured metal organic frameworks (MOFs), also known as metal organic heat carriers, with particular emphasis on their application in heating and cooling processes. We used both molecular dynamics and grand canonical Monte Carlo simulation techniques to gain a molecular-level understanding of the adsorption mechanism of gases in these porous materials. We investigated the uptake of various gases such as refrigerants R12 and R143a. We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available measurements from experiments, thus validating our potential models and approaches. In addition, we investigated the structural, diffusive and adsorption properties of different hydrocarbons in Ni-2(dhtp). Finally, to elucidate the mechanism of nanoparticle dispersion in condensed phases, we studied the interactions among nanoparticles in various liquids, such as n-hexane, water and methanol.

  14. Phase behavior of DODAB aqueous solution

    SciTech Connect

    Voronov, V. P.; Kuryakov, V. N.; Muratov, A. R.

    2012-12-15

    Phase behavior of DODAB aqueous solution, prepared without sonication, was studied by adiabatic scanning calorimetry. Measurements revealed four phase transitions with the temperatures 35.2, 39.6, 44.6, and 52.4 Degree-Sign C at heating and one transition at the temperature 40.4 Degree-Sign C at cooling. The first three transitions at heating occur in unilamellar vesicles. The first and third transitions correspond to the subgel-gel and gelliquid phase transitions, corresponding enthalpy jumps are equal to 33 and 49 kJ/mol. The second transition appears after some aging and is similar to gel-ripple phase transition in a DPPC solution, with the enthalpy jump under the transition exceeding 7.4 kJ/mol. The transition occurs in unilamellar vesicles. The transition at the temperature 52.4 Degree-Sign C occurs in another subsystem of the solution, which we believe to be multilamellar vesicles. The enthalpy jump at this transition is equal to 97 kJ/mol, and data analysis suggests that this is a subgel-liquid transition. The phase transition at cooling is the liquid-gel transition in unilamellar vesicles. During the measurements, a slow evolution of the solution occurs, consisting in a change of concentrations of unilamellar and multilamellar vesicles. This transformation mainly occurs at low temperatures.

  15. Locust dynamics: behavioral phase change and swarming.

    PubMed

    Topaz, Chad M; D'Orsogna, Maria R; Edelstein-Keshet, Leah; Bernoff, Andrew J

    2012-01-01

    Locusts exhibit two interconvertible behavioral phases, solitarious and gregarious. While solitarious individuals are repelled from other locusts, gregarious insects are attracted to conspecifics and can form large aggregations such as marching hopper bands. Numerous biological experiments at the individual level have shown how crowding biases conversion towards the gregarious form. To understand the formation of marching locust hopper bands, we study phase change at the collective level, and in a quantitative framework. Specifically, we construct a partial integrodifferential equation model incorporating the interplay between phase change and spatial movement at the individual level in order to predict the dynamics of hopper band formation at the population level. Stability analysis of our model reveals conditions for an outbreak, characterized by a large scale transition to the gregarious phase. A model reduction enables quantification of the temporal dynamics of each phase, of the proportion of the population that will eventually gregarize, and of the time scale for this to occur. Numerical simulations provide descriptions of the aggregation's structure and reveal transiently traveling clumps of gregarious insects. Our predictions of aggregation and mass gregarization suggest several possible future biological experiments.

  16. The Lunacy of It All: Lunar Phases and Human Behavior.

    ERIC Educational Resources Information Center

    Rotton, James; Kelly, Ivan W.

    1986-01-01

    Discusses the relationship between aberrant human behavior and phases of the moon. Reviews media influence, myth, superstition and pseudoscience. Examines studies purporting to have found relationships between moon phases and behavior. (JM)

  17. Phase behavior of semiflexible polymer systems

    NASA Astrophysics Data System (ADS)

    Moonay, David Jordan

    Phase behavior of semiflexible poly(n-hexyl isocyanate) (PHIC) and flexible coil poly(cyclohexyl methacrylate) (PCHMA) were investigated. Room-temperature solubility screenings showed that PCHMA behavior in various solvents agreed with that predicted by Flory-Huggins theory: solvents had interaction parameter values chi1 < 0.5, i.e., less than the critical value for incipient phase separation, while nonsolvents had chi1 > 1, well within the thermodynamically-poor solvency region. PHIC, on the other hand, had interactions which were not in accord with the simple enthalpic theory. A high-boiling solvent, 1-chloronaphthalene, was chosen as suitable for binary and ternary phase behavior work, as a result of the screenings. PCHMA was found to be soluble at all concentrations at room temperature. However, PHIC crystallized at about 5 wt.% a result not previously reported in the literature. The crystallinity, and degradation, interfered with liquid crystalline expression up to the PHIC melting point in binary solution. The novel room-temperature ternary phase diagram, PHIC/PCHMA/CLN, was developed. Particularly striking is its 5 wt.% total polymer solubility limit, which extended to 90:1 (w/w) ratios of PCHMA:PI-HC in CLN, as verified by serial dilution experiments. Novel gels were prepared with PHIC longer-pendant-group homologs poly(n-nonylisocyanate) and poly(n-undecylisocyanate), to investigate their heightened solubility relative to PHIC, in high-boiling alkylaromatic solvents. Apparently homogeneous isotropic gels in two structurally similar solvents, were found. Lengthening pendant groups in the alkyl isocyanate polymers increases solubility in high-boiling solvents, although gelation occurs when the solutions are cooled to room temperature. Elongational flow apparati were constructed. Trumpet-shaped tube experiments indicated no flow-induced crystallinity of isotropic PHIC/CLN solutions. A planar-elongational flow system was constructed and tested, and its central

  18. A simple method for measuring excess adsorption isotherms of organic eluent components on reversed-phase packing materials.

    PubMed

    Ohashi, Junji; Harada, Makoto; Okada, Tetsuo

    2017-02-01

    A simple frontal analysis method has been developed for the reliable measurement of excess adsorption isotherms of an organic component on reversed-phase adsorbents in a series of programmed concentration steps. In the present method, a peak, which is produced by refractive index change in column eluate, is detected at 589 nm; it represents the elution volume of the boundary. The method is applied to the measurement of the excess adsorption isotherms of organic eluent components from water on commercially available reversed-phase stationary phases. The results are in good agreement with the previously reported isotherms. We also measure the excess adsorption isotherms of organic eluent components from solutions containing electrolytes. There are not any interference peaks on the elution traces. The method is thus reliably applicable to the evaluation of the excess adsorption of organic eluent components in practical systems.

  19. Exact results for the behavior of the thermodynamic Casimir force in a model with a strong adsorption

    NASA Astrophysics Data System (ADS)

    Dantchev, Daniel M.; Vassilev, Vassil M.; Djondjorov, Peter A.

    2016-09-01

    When massless excitations are limited or modified by the presence of material bodies one observes a force acting between them generally called Casimir force. Such excitations are present in any fluid system close to its true bulk critical point. We derive exact analytical results for both the temperature and external ordering field behavior of the thermodynamic Casimir force within the mean-field Ginzburg-Landau Ising type model of a simple fluid or binary liquid mixture. We investigate the case when under a film geometry the boundaries of the system exhibit strong adsorption onto one of the phases (components) of the system. We present analytical and numerical results for the (temperature-field) relief map of the force in both the critical region of the film close to its finite-size or bulk critical points as well as in the capillary condensation regime below but close to the finite-size critical point.

  20. Phases of Ba adsorption on Si(100)-(2×1) studied by LEED and AES

    NASA Astrophysics Data System (ADS)

    Hu, Xiaoming; Peterson, C. A.; Sarid, D.; Yu, Z.; Wang, J.; Marshall, D. S.; Droopad, R.; Hallmark, J. A.; Ooms, W. J.

    1999-05-01

    Phase transitions of Ba adsorption on a clean Si(001)-(2×1) studied by low energy electron diffraction (LEED) and Auger electron spectroscopy (AES) are reported. The depositions of the Ba were performed with (a) the substrate held at room temperature followed by annealing at elevated temperatures, and (b) the substrate held at 900°C. While confirming earlier established phases, the existence of 4× streaks in the (3×2)+c(6×2) and (2×1) phases has been identified. Also found was a real-time phase transition from a (3×2) phase to a mixture of (3×2) and c(6×2) phases during sample cooling. Finally, it was found that AES of Ba/Si peak ratios exhibit plateaus in the phase vs. temperature diagram for the (3×2), (3×2)+c(6×2), and (2×1)+4× streak phases, indicating a temperature-dependent mechanism limiting the Ba coverage.

  1. Porous and Magnetic Molecularly Imprinted Polymers via Pickering High Internal Phase Emulsions Polymerization for Selective Adsorption of λ-Cyhalothrin

    PubMed Central

    Wu, Yunlong; Ma, Yue; Pan, Jianming; Gu, Runxing; Luo, Jialu

    2017-01-01

    A novel macroporous magnetic molecularly imprinted polymer (MMIPs) of was prepared by W/O Pickering (high internal phase emulsions) HIPEs polymerization, and then it was adopted as adsorbent for selective adsorption of λ-cyhalothrin (LC). In static conditions, adsorption capacity of LC increased rapidly in the first 60 min and reached to equilibrium in ~2.0 h. Excellent conformity of the second-order model confirmed the chemical nature of the interaction between the LC and imprinted sites. The fitting adsorption isotherm was a Langmuir type, and the maximum monolayer adsorption capacity at 298 K was 404.4 μmol g−1. Thermodynamic parameters suggested the specific adsorption at 298 K was an exothermic, spontaneous, and entropy decreased process. Competitive recognition studies of the MMIPs were performed with diethyl phthalate (DEP) and the structurally similar compound fenvalerate (FL), and the MMIPs, which displayed high selectivity for LC.

  2. Behavior of water in supercritical CO2: adsorption and capillary condensation in porous media

    NASA Astrophysics Data System (ADS)

    Heath, J. E.; Bryan, C. R.; Dewers, T. A.; Wang, Y.

    2011-12-01

    The chemical potential of water in supercritical CO2 (scCO2) may play an important role in water adsorption, capillary condensation, and evaporation under partially saturated conditions at geologic CO2 storage sites, especially if initially anhydrous CO2 is injected. Such processes may affect residual water saturations, relative permeability, shrink/swell of clays, and colloidal transport. We have developed a thermodynamic model of water or brine film thickness as a function of water relative humidity in scCO2. The model is based on investigations of liquid water configuration in the vadose zone and uses the augmented Young-Laplace equation, which incorporates both adsorptive and capillary components. The adsorptive component is based on the concept of disjoining pressure, which reflects force per area normal to the solid and water/brine-scCO2 interfaces. The disjoining pressure includes van der Waals, electrostatic, and structural interactions. The van der Waals term includes the effects of mutual dissolution of CO2 and water in the two fluid phases on partial molar volumes, dielectric coefficients, and refractive indices. Our approach treats the two interfaces as asymmetric surfaces in terms of charge densities and electrostatic potentials. We use the disjoining pressure isotherm to evaluate the type of wetting (e.g., total or partial wetting) for common reservoir and caprock minerals and kerogen. The capillary component incorporates water activity and is applied to simple pore geometries with slits and corners. Finally, we compare results of the model to a companion study by the coauthors on measurement of water adsorption to mineral phases using a quartz-crystal microbalance. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  3. One-pot solvothermal synthesis of dual-phase titanate/titania Nanoparticles and their adsorption and photocatalytic Performances

    SciTech Connect

    Cheng, Yu Hua; Gong, Dangguo; Tang, Yuxin; Ho, Jeffery Weng Chye; Tay, Yee Yan; Lau, Wei Siew; Wijaya, Olivia; Lim, Jiexiang; Chen, Zhong

    2014-06-01

    Dual phase titanate/titania nanoparticles undergo phase transformation gradually with the increase of solvothermal synthesis temperature from 100 °C to 200 °C, and eventually are fully transformed into anatase TiO{sub 2}. The crystal structure change results in the changes of optical absorption, sensitizer/dopant formation and surface area of the materials which finally affect the overall dye removal ability. Reactions under dark and light have been conducted to distinguish the contributions of surface adsorption from photocatalytic degradation. The sample synthesized at 160 °C (S160) shows the best performances for both adsorption under dark and photocatalytic degradation of methylene blue (MB) under visible light irradiation. The adsorption mechanism for S160 is determined as monolayer adsorption based on the adsorption isotherm test under dark condition, and an impressive adsorption capacity of 162.19 mg/g is achieved. For the photocatalytic application, this sample at 0.1 g/L loading is also able to degrade 20 ppm MB within 6 hours under the visible light (>420 nm) condition. - Graphical abstract: The effect of solvothermal synthesis temperature on the formation and dye removal performance of dual phase titanate/titania nanoparticles was unveiled and optimized. - Highlights: • Low temperature one-pot solvothermal synthesis of dual-phase photocatalysts. • Correlation of the synthesis temperature is made with the phase composition. • Adsorption isotherm, kinetics, photocatalytic degradation were studied. • Synthesis at 160 °C yields the best material for adsorption of MB in dark. • The same sample also shows the best visible light degradation of MB.

  4. Phase behavior of carbamyloxyphosphatidylcholine, a sphingolipid analogue.

    PubMed

    Curatolo, W; Bali, A; Gupta, C M

    1985-12-01

    The phase behavior of two series of phosphatidylcholines (PC) possessing carbamyloxy-linked fatty acids has been studied by differential scanning calorimetry. These non-natural phosphatidylcholines are of interest because they possess the capability of forming interlipid hydrogen bonds via the carbamyloxy function and as such can serve as a model for sphingolipids, the phase behavior of which is thought to be dominated by interlipid hydrogen bonding. Furthermore, carbamyloxyphosphatidylcholines form unusually stable liposomes, and thus have potential in drug delivery. Carbamyloxyphosphatidylcholines of the type di-(CnH2n+1NHCOO)-PC, where n = 13, 15, or 17, exhibit metastable polymorphism. Cooling from the liquid crystalline state results in formation of a metastable low-temperature polymorph I, which must transform into a stable low-temperature polymorph II before the liquid crystalline state can be reached again. Carbamyloxyphosphatidylcholines of the type 1-C16:0-2-(CnH2n+1NHCOO)-PC exhibit similar metastable polymorphism. This metastability is similar to that exhibited by certain cerebrosides and sphingomyelins and indicates that the sphingosine backbone is not a prerequisite for this type of metastability. Furthermore, the carbamyloxy group is reversed in orientation compared with the amide of sphingolipids (-NHCO- versus -CONH-), suggesting that the intermolecular hydrogen bonding potential, rather than some highly specific steric or conformational constraint, is responsible for the observed metastability of sphingolipids.

  5. A fundamental study of the impact of pressure on the adsorption mechanism in reversed-phase liquid chromatography.

    PubMed

    Åsberg, Dennis; Samuelsson, Jörgen; Fornstedt, Torgny

    2016-07-29

    A fundamental investigation of the pressure effect on individual adsorption sites was undertaken based on adsorption energy distribution and adsorption isotherm measurements. For this purpose, we measured adsorption equilibrium data at pressures ranging from 100 to 1000bar at constant flow and over a wide concentration range for three low-molecular-weight solutes, antipyrine, sodium 2-naphthalenesulfonate, and benzyltriethylammonium chloride, on an Eternity C18 stationary phase. The adsorption energy distribution was bimodal for all solutes, remaining clearly so at all pressures. The bi-Langmuir model best described the adsorption in these systems and two types of adsorption sites were identified, one with a low and another with a high energy of interaction. Evidence exists that the low-energy interactions occur at the interface between the mobile and stationary phases and that the high-energy interactions occur nearer the silica surface, deeper in the C18 layer. The contribution of each type of adsorption site to the retention factor was calculated and the change in solute molar volume from the mobile to stationary phase during the adsorption process was estimated for each type of site. The change in solute molar volume was 2-4 times larger at the high-energy site, likely because of the greater loss of solute solvation layer when penetrating deeper into the C18 layer. The association equilibrium constant increased with increasing pressure while the saturation capacity of the low-energy site remained almost unchanged. The observed increase in saturation capacity for the high-energy site did not affect the column loading capacity, which was almost identical at 50- and 950-bar pressure drops over the column.

  6. Tuning the adsorption behaviors and conversions of CHx species on metal embedded graphene surfaces

    NASA Astrophysics Data System (ADS)

    Tang, Yanan; Shen, Zigang; Chen, Weiguang; Pan, Lijun; Wang, Xiaolong; Dai, Xianqi

    2016-12-01

    The stable geometries and adsorption behaviors of CHx (x = 0, 1, 2, 3, 4) species on the single-atoms metal embedded graphene (M-graphene) are investigated by first-principles calculations. It is found that the adsorbed CHx species have the different stability on the M-graphene surfaces, and the adsorption energies of CHx species on the Al-graphene are smaller than those on the Au-graphene. Besides, the adsorption of CHx species can regulate the electronic structure and magnetic properties of M-graphene systems. Moreover, the diffusion pathways of CHx (x = 0-3) species and the conversion reactions between CHx (x = 1-4) species on the M-graphene are analyzed systematically. In the conversion reactions, the adsorbed C and CH species can be more easily converted into the CHx+2 species through the hydrogenation reactions, the broken M-H bond and the formation of new Csbnd H bond need overcome the large energy barriers. These results give a clue for designing graphene-based anode materials with high activity and inhibiting carbon deposition.

  7. The (3×2) phase of Ba adsorption on Si(001)-2×1

    NASA Astrophysics Data System (ADS)

    Hu, X.; Yao, X.; Peterson, C. A.; Sarid, D.; Yu, Z.; Wang, J.; Marshall, D. S.; Droopad, R.; Hallmark, J. A.; Ooms, W. J.

    2000-01-01

    The initial stages and surface structures of the (3×2) phase of Ba adsorption on an Si(100)-2×1 surface held at 900°C have been studied by low-energy electron diffraction, Auger electron spectroscopy, and ultra-high vacuum scanning tunneling microscopy (STM). At low coverages (<{1}/{6} ML), the Ba atoms form atomic chains across the Si dimer rows by occupying valley bridge sites, as well as on fourfold sites by replacing Si dimers and exhibiting a local (3×2) phase, with the 3×-phase along the Si dimer row direction. Two different configurations for the (3×2) phase, namely, mono- and dimer-Ba models, are proposed based on the STM images. Below a coverage of {1}/{6} ML, the (3×2) phase is formed by single Ba atoms at fourfold sites by replacing original Si dimers. For a Ba coverage of {1}/{3} ML, the (3×2) phase is formed by buckled Ba dimers, as revealed by high-resolution STM images.

  8. Modeling of phase equilibrium and vapor adsorption on carbon black based on a combination of a lattice theory and equation of state.

    PubMed

    Ustinov, E A; Do, D D

    2002-09-15

    A thermodynamic approach is developed in this paper to describe the behavior of a subcritical fluid in the neighborhood of vapor-liquid interface and close to a graphite surface. The fluid is modeled as a system of parallel molecular layers. The Helmholtz free energy of the fluid is expressed as the sum of the intrinsic Helmholtz free energies of separate layers and the potential energy of their mutual interactions calculated by the 10-4 potential. This Helmholtz free energy is described by an equation of state (such as the Bender or Peng-Robinson equation), which allows us a convenient means to obtain the intrinsic Helmholtz free energy of each molecular layer as a function of its two-dimensional density. All molecular layers of the bulk fluid are in mechanical equilibrium corresponding to the minimum of the total potential energy. In the case of adsorption the external potential exerted by the graphite layers is added to the free energy. The state of the interface zone between the liquid and the vapor phases or the state of the adsorbed phase is determined by the minimum of the grand potential. In the case of phase equilibrium the approach leads to the distribution of density and pressure over the transition zone. The interrelation between the collision diameter and the potential well depth was determined by the surface tension. It was shown that the distance between neighboring molecular layers substantially changes in the vapor-liquid transition zone and in the adsorbed phase with loading. The approach is considered in this paper for the case of adsorption of argon and nitrogen on carbon black. In both cases an excellent agreement with the experimental data was achieved without additional assumptions and fitting parameters, except for the fluid-solid potential well depth. The approach has far-reaching consequences and can be readily extended to the model of adsorption in slit pores of carbonaceous materials and to the analysis of multicomponent adsorption

  9. Photodegradation mechanism of two dyes: the influence of adsorption behavior on the novel TiO2 particles.

    PubMed

    Li, Wei; Wang, Yi-zhong

    2004-01-01

    The relationship between adsorption behavior and photocatalytic mechanism of the two dyes was investigated. Adsorption isotherms showed that the adsorption of cationic pink FG was Langmuir type behavior, while the reactive brilliant red k-2G was Freundlich type behavior. The increasing pH favored the adsorption of FG but have little effect on the photodegradation. The increasing pH favored the adsorption and the photodegradation of k-2G. The presence of scavenger of hvb+ and OH* radical potassium iodide inhibited the degradation of k-2G, free radicals scavenger tetranitromethane inhibited the photodegradation of FG. These results indicated that the photodegradation of FG mainly via free radicals in solution, and the photodegradation of k-2G was mainly on the catalysts surface or near the interface of solid and solution by react with hvb+ and surface-bound OH*. The different effect of SO4(2-), HCO3- on the adsorption and photodegradation of two dyes confirmed these results.

  10. Electroneutrality and phase behavior of colloidal suspensions

    NASA Astrophysics Data System (ADS)

    Denton, A. R.

    2007-11-01

    Several statistical mechanical theories predict that colloidal suspensions of highly charged macroions and monovalent microions can exhibit unusual thermodynamic phase behavior when strongly deionized. Density-functional, extended Debye-Hückel, and response theories, within mean-field and linearization approximations, predict a spinodal phase instability of charged colloids below a critical salt concentration. Poisson-Boltzmann cell model studies of suspensions in Donnan equilibrium with a salt reservoir demonstrate that effective interactions and osmotic pressures predicted by such theories can be sensitive to the choice of reference system, e.g., whether the microion density profiles are expanded about the average potential of the suspension or about the reservoir potential. By unifying Poisson-Boltzmann and response theories within a common perturbative framework, it is shown here that the choice of reference system is dictated by the constraint of global electroneutrality. On this basis, bulk suspensions are best modeled by density-dependent effective interactions derived from a closed reference system in which the counterions are confined to the same volume as the macroions. Lower-dimensional systems (e.g., monolayers, clusters), depending on the strength of macroion-counterion correlations, may be governed instead by density-independent effective interactions tied to an open reference system with counterions dispersed throughout the reservoir, possibly explaining the observed structural crossover in colloidal monolayers and anomalous metastability of colloidal crystallites.

  11. Unique surface adsorption behaviors of serum proteins on chemically uniform and alternating surfaces

    NASA Astrophysics Data System (ADS)

    Song, Sheng

    With increasing interests of studying proteins adsorption on the surfaces with nanoscale features in biomedical field, it is crucial to have fundamental understandings on how the proteins are adsorbed on such a surface and what factors contribute to the driving forces of adsorption. Besides, exploring more available nanoscale templates would greatly offer more possibilities one could design surface bio-detection methods with favorable protein-surface interactions. Thus, to fulfill the purpose, the work in this dissertation has been made into three major sections. First, to probe the intermediate states which possibly exist between stable and unstable phases described in mean-field theory diagram, a solvent vapor annealing method is chosen to slowly induce the copolymer polystyrene-block-polyvinylpyridine (PS-b-PVP)'s both blocks undergoing micro-phase separations from initial spherical nanodomains into terminal cylindrical nanodomains. During this process, real time atomic force microscopy (AFM) has been conducted to capture other six intermediate states with different morphologies on the polymeric film surfaces. Secondly, upon recognizing each intermediate state, the solution of immunoglobulin gamma (IgG) proteins has been deposited on the surface and been rinsed off with buffer solution before the protein-bounded surface is imaged by AFM. It has been found IgG showing a strong adsorption preference on PS over P4VP block. Among all the six intermediate states, the proteins are almost exclusively adsorbed on PS nanodomains regardless the concentration and deposition time. Thirdly, a trinodular shape protein fibrinogen (Fg) is selected for investigating how geometry and surface charge of proteins would interplay with cylindrical nanodomains on a surface developed from Polystyrene -block-Poly-(methyl methacrylate) PS-b-PMMA. Also, Fg adsorptions on chemically homogeneous surfaces are included here to have a better contrast of showing how much difference it can make

  12. Effect of the endcapping of reversed-phase high-performance liquid chromatography adsorbents on the adsorption isotherm

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2005-09-01

    The retention mechanisms of n-propylbenzoate, 4-t ert-butylphenol, and caffeine on the endcapped Symmetry-C{sub 18} and the non-endcapped Resolve-C{sub 18} are compared. The adsorption isotherms were measured by frontal analysis (FA), using as the mobile phase mixtures of methanol or acetonitrile and water of various compositions. The isotherm data were modeled and the adsorption energy distributions calculated. The surface heterogeneity increases faster with decreasing methanol concentration on the non-endcapped than on the endcapped adsorbent. For instance, for methanol concentrations exceeding 30% (v/v), the adsorption of caffeine is accounted for by assuming three and two different types of adsorption sites on Resolve-C{sub 18} and Symmetry-C{sub 18}, respectively. This is explained by the effect of the mobile phase composition on the structure of the C{sub 18}-bonded layer. The bare surface of bonded silica appears more accessible to solute molecules at high water contents in the mobile phase. On the other hand, replacing methanol by a stronger organic modifier like acetonitrile dampens the differences between non-endcapped and endcapped stationary phase and decreases the degree of surface heterogeneity of the adsorbent. For instance, at acetonitrile concentrations exceeding 20%, the surface appears nearly homogeneous for the adsorption of caffeine.

  13. Adsorption mechanisms and effect of temperature in reversed-phase liquid chromatography-Meaning of the classical Van't Hoff plot in chromatography

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2006-07-01

    The effect of temperature on the adsorption and retention behaviors of a low molecular weight compound (phenol) on a C{sub 18}-bonded silica column (C{sub 18}-Sunfire, Waters) from aqueous solutions of methanol (20%) or acetonitrile (15%) was investigated. The results of the measurements were interpreted successively on the basis of the linear (i.e., overall retention factors) and the nonlinear (i.e., adsorption isotherms, surface heterogeneity, saturation capacities, and equilibrium constants) chromatographic methods. The confrontation of these two approaches confirmed the impossibility of a sound physical interpretation of the conventional Van't Hoff plot. The classical linear chromatography theory assumes that retention is determined by the equilibrium thermodynamics of analytes between a homogeneous stationary phase and a homogeneous mobile phase (although there may be two or several types of interactions). From values of the experimental retention factors in a temperature interval and estimates of the activity coefficients at infinite dilution in the same temperature interval provided by the UNIFAC group contribution method, evidence is provided that such a retention model cannot hold. The classical Van't Hoff plot appears meaningless and its linear behavior a mere accident. Results from nonlinear chromatography confirm these conclusions and provide explanations. The retention factors seem to fulfill the Van't Hoff equation, not the Henry constants corresponding to the different types of adsorption sites. The saturation capacities and the adsorption energies are clearly temperature dependent. The temperature dependence of these characteristics of the different assorption sites are different in aqueous methanol and acetonitrile solutions.

  14. Adsorption and Desorption Behavior of NO on H-ZSM-5, Na-ZSM-5, and Na-A as Studied by EPR

    NASA Astrophysics Data System (ADS)

    Rudolf, Thomas; Böhlmann, Winfried; Pöppl, Andreas

    2002-03-01

    Nitric monoxide probe molecules are used to characterize the Lewis acid properties of sodium cations and aluminum defect centers in various zeolite materials. The adsorption-desorption behavior of NO probe molecules is studied at different temperatures for Na-A, Na-ZSM-5, H-ZSM-5, and silicalite. Adsorbed NO molecules form paramagnetic adsorption complexes with Lewis acid sites which can be examined by EPR transitions (ΔmS±1) at g≈2.0. Otherwise the desorption of NO into the gas phase can be monitored by the typical nine-line EPR spectrum (ΔmJ±1) of the 2Π3/2 state at g≈0.7776. This gas-phase signal is used to study the overall adsorption-desorption properties of the zeolites in the temperature range 150 K≲T≲300 K. At lower temperatures the probe molecules are adsorbed at the Lewis acid sites inside the nanoporous materials and produce an intensive spectrum at T≲110 K. But at intermediate temperatures 110 K≲T≲150 K the NO molecules are adsorbed only for a few hundred picoseconds because the lifetime of the adsorption complexes is limited by the beginning desorption processes. The decreasing lifetime of the adsorption complex with rising temperature results in an increasing homogeneous line broadening of their EPR signals. An analysis of the line-broadening effects provides an opportunity for determining the specific desorption energies EA(H-ZSM-5)=(20.2±7.3) kJ/mol, EA(Na-ZSM-5)=(4.1±1.5) kJ/mol, and EA(Na-A)=(7.1±2.1) kJ/mol for NO probe molecules at sodium cations and aluminum defect centers just below the desorption temperature.

  15. Computational studies of adsorption in metal organic frameworks and interaction of nanoparticles in condensed phases

    SciTech Connect

    Annapureddy, Harsha V.; Motkuri, Radha K.; Nguyen, Phuong T.; Truong, T. B.; Thallapally, Praveen K.; McGrail, B. Peter; Dang, Liem X.

    2014-01-08

    In this review, we describe recent efforts in which computer simulations were used to systematically study nano-structured metal organic frameworks, with particular emphasis on their application in heating and cooling processes. These materials also are known as metal organic heat carriers. We used both molecular dynamics and Grand Canonical Monte Carlo simulation techniques to gain a molecular-level understanding of the adsorption mechanism of gases in these porous materials. We investigated the uptake of various gases such as refrigerants R12 and R143a and also the elemental gases Xe and Rn by the metal organic framework (i.e., Ni2(dhtp)). We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available experimental measurements, thus validating our potential models and approaches. In addition, we also investigated the structural, diffusive, and adsorption properties of different hydrocarbons in Ni2(dhtp). To elucidate the mechanism of nanoparticle dispersion in condensed phases, we also studied the interactions among nanoparticles in various liquids, such as n-hexane, water and methanol. This work was performed at Pacific Northwest National Laboratory (PNNL) and was supported by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). PNNL is operated by Battelle for the DOE. The authors also gratefully acknowledge support received from the National Energy Technology Laboratory of DOE's Office of Fossil Energy.

  16. Adsorption behavior and mechanism of chloramphenicols, sulfonamides, and non-antibiotic pharmaceuticals on multi-walled carbon nanotubes.

    PubMed

    Zhao, Heng; Liu, Xue; Cao, Zhen; Zhan, Yi; Shi, Xiaodong; Yang, Yi; Zhou, Junliang; Xu, Jiang

    2016-06-05

    The adsorption behavior of different emerging contaminants (3 chloramphenicols, 7 sulfonamides, and 3 non-antibiotic pharmaceuticals) on five types of multi-walled carbon nanotubes (MWCNTs), and the underlying factors were studied. Adsorption equilibriums were reached within 12h for all compounds, and well fitted by the Freundlich isotherm model. The adsorption affinity of pharmaceuticals was positively related to the specific surface area of MWCNTs. The solution pH was an important parameter of pharmaceutical adsorption on MWCNTs, due to its impacts on the chemical speciation of pharmaceuticals and the surface electrical property of MWCNTs. The adsorption of ionizable pharmaceuticals decreased in varying degrees with the increased ionic strength. MWCNT-10 was found to be the strongest adsorbent in this study, and the Freundlich constant (KF) values were 353-2814mmol(1-n)L(n)/kg, 571-618mmol(1-n)L(n)/kg, and 317-1522mmol(1-n)L(n)/kg for sulfonamides, chloramphenicols, and non-antibiotic pharmaceuticals, respectively. The different adsorption affinity of sulfonamides might contribute to the different hydrophobic of heterocyclic substituents, while chloramphenicols adsorption was affected by the charge distribution in aromatic rings via substituent effects.

  17. Adsorption of organic chemicals in soils.

    PubMed Central

    Calvet, R

    1989-01-01

    This paper presents a review on adsorption of organic chemicals on soils sediments and their constituents. The first part of this review deals with adsorption from gas and liquid phases and gives a discussion on the physical meaning of the shape of adsorption isotherms. Results show that no general rules can be proposed to describe univocally the relation between the shape of isotherms and the nature of adsorbate-adsorbent system. Kinetics of adsorption is discussed through the description of various models. Theoretical developments exist both for the thermodynamics and the kinetics of adsorption, but there is a strong need for experimental results. Possible adsorption mechanisms are ion exchange, interaction with metallic cations, hydrogen bonds, charge transfers, and London-van der Waals dispersion forces/hydrophobic effect. However, direct proofs of a given mechanism are rare. Several factors influence adsorption behavior. Electronic structure of adsorbed molecules, properties of adsorbents, and characteristics of the liquid phase are discussed in relation to adsorption. Such properties as water solubility, organic carbon content of adsorbing materials, and the composition of the liquid phase are particularly important. Evaluation of adsorption can be obtained through either laboratory measurements or use of several correlations. Adsorption measurements must be interpreted, taking into account treatment of adsorbent materials, experimental conditions, and secondary phenomena such as degradations. Correlations between adsorption coefficients and water-octanol partition coefficient or water solubility are numerous. They may be useful tools for prediction purposes. Relations with transport, bioavailability, and degradation are described. PMID:2695323

  18. Assessment of adsorption behavior of dibutyltin (DBT) to clay-rich sediments in comparison to the highly toxic tributyltin (TBT).

    PubMed

    Hoch, Marion; Alonso-Azcarate, Jacinto; Lischick, Martin

    2003-01-01

    The sorption behavior of dibutyltin (DBT) to four types of natural clay-rich sediments as a function of pH and salinity was studied. The strongest affinity of DBT was found to the montmorillonite-rich sediment, which is characterized by the highest specific surface area and cation exchange capacity of the four used sediments. Kd values range between 12 and 40 (l/kg) on simulated marine conditions (pH 8, salinity 32%). A maximum of DBT adsorption was found at a salinity of 0% and pH 6. Desorption occurred over the entire studied pH range (4-8) when contaminated sediments interact with butyltin-free water. The maximum of desorption coincided with the minimum of adsorption, and vice versa. The results of DBT adsorption are compared with tributyltin (TBT), and the mechanism of the adsorption process is discussed.

  19. Soft liquid phase adsorption for fabrication of organic semiconductor films on wettability patterned surfaces.

    PubMed

    Watanabe, Satoshi; Akiyoshi, Yuri; Matsumoto, Mutsuyoshi

    2014-01-01

    We report a soft liquid-phase adsorption (SLPA) technique for the fabrication of organic semiconductor films on wettability-patterned substrates using toluene/water emulsions. Wettability-patterned substrates were obtained by the UV-ozone treatment of self-assembled monolayers of silane coupling agents on glass plates using a metal mask. Organic semiconductor polymer films were formed selectively on the hydrophobic part of the wettability-patterned substrates. The thickness of the films fabricated by the SLPA technique is significantly larger than that of the films fabricated by dip-coating and spin-coating techniques. The film thickness can be controlled by adjusting the volume ratio of toluene to water, immersion angle, immersion temperature, and immersion time. The SLPA technique allows for the direct production of organic semiconductor films on wettability-patterned substrates with minimized material consumption and reduced number of fabrication steps.

  20. Phase transitions, magnetism and surface adsorptions assessed by meta-GGA functionals and random phase approximation

    NASA Astrophysics Data System (ADS)

    Xiao, Bing

    The meta-GGA functionals and random phase approximation are tested for phase transitions and a strongly correlated transition metal oxide in this dissertation. One of the latest meta-GGA functionals is also employed to study the van der Waals bound system in surface science. Our main purpose is to reveal the performance of new exchange-correlation functionals on various properties and systems. We are also interested in seeking the possible relationship between the performance of a semilocal functional and its exchange enhancement factor. We have studied the structural phase transitions in crystalline Si (insulator to metal), SiO2 (insulator to insulator) and Zr (metal to metal) systems, as a test of exchange energy semilocal functionals on Jacob's ladder. Our results confirm the energy-geometry delimma of GGAs in three systems. The most sophisticated non-empirical meta-generalized gradient approximations (meta-GGAs) such as TPSS (Tao-Perdew-Staroveov-Scuseria) and revTPSS (revised TPSS) give better lattice constants than PBE, but the phase transition parameters (energy difference and transition pressure) are smaller and less realistic than those from the latter GGA. However, the recent functionals of meta-GGA made simple family (MGGA_MS) behave differently to those previous meta-GGAs, predicting larger and more realistic phase transition parameters. Meanwhile, MGGA_MS also delivers the equilibrium geometry of crystalline materials similar to previous non-empirical meta-GGAs. In contrast to semilocal functionals, the nonlocal functionals such as the range-separated hybrid functional HSE06 (Heyd-Scuseria-Ernzerhof) and non-self consistent random phase approximation (RPA) are not only able to give the accurate equilibrium geometry , but also predict the realistic phase transition parameters for Si and SiO2 systems. The ground state of rutile-type vanadium dioxide (R-VO2) represents a great challenge to the current density functional theory. In this dissertation, we

  1. Synthesis, characterization and study of arsenate adsorption from aqueous solution by {alpha}- and {delta}-phase manganese dioxide nanoadsorbents

    SciTech Connect

    Singh, Mandeep; Thanh, Dong Nguyen; Ulbrich, Pavel; Strnadova, Nina; Stepanek, Frantisek

    2010-12-15

    Single-phase {alpha}-MnO{sub 2} nanorods and {delta}-MnO{sub 2} nano-fiber clumps were synthesized using manganese pentahydrate in an aqueous solution. These nanomaterials were characterized using the Transmission Electron Microscope (TEM), Field Emission Scanning Electron Microscope (FE-SEM), Powder X-ray diffraction (XRD) and the Brunauer-Elmet-Teller nitrogen adsorption technique (BET-N{sub 2} adsorption). The structural analysis shows that {alpha}-MnO{sub 2} (2x2 tunnel structure) has the form of needle-shaped nanorods and {delta}-MnO{sub 2} (2D-layered structure) consists of fine needle-like fibers arranged in ball-like aggregates. Batch adsorption experiments were carried out to determine the effect of pH on adsorption kinetics and adsorption capacity for the removal of As(V) from aqueous solution onto these two types of nanoadsorbents. The adsorption capacity of As(V) was found to be highly pH dependent. The adsorption of As(V) onto {alpha}-MnO{sub 2} reached equilibrium more rapidly with higher adsorption capacity compared to {delta}-MnO{sub 2}. -- Graphical abstract: {alpha}-MnO{sub 2} (2x2 tunnel structure) nanorods and {delta}-MnO{sub 2} (2-D layered structure) nano-fiber clumps were synthesized in a facile way in an aqueous solution and characterized by TEM, FE-SEM, XRD and BET-N{sub 2} adsorption techniques. The structural analysis shows that {alpha}-MnO{sub 2} is needle shaped nanorods and {delta}-MnO{sub 2} consists of 2-D platelets of fine needle-like fibers arranged in ball-like aggregates. Further batch experiments confirmed that both nanoadsorbents are potential candidates for the adsorption of As(V) with a capacity of 19.41 and 15.33 mg g{sup -1} for {alpha}-MnO{sub 2} and {delta}-MnO{sub 2}, respectively. The presence of As3d peak in XPS study indicates that arsenic on the surface of nanoadsorbents is in the stable form of As(V) with a percentage of arsenate onto {alpha}-MnO{sub 2} is 0.099% as compared to 0.021% onto {delta}-MnO{sub 2

  2. Adsorptive removal of phthalate ester (Di-ethyl phthalate) from aqueous phase by activated carbon: a kinetic study.

    PubMed

    Venkata Mohan, S; Shailaja, S; Rama Krishna, M; Sarma, P N

    2007-07-19

    Adsorptive studies were carried out on Di-ethyl phthalate (DEP) removal from aqueous phase onto activated carbon. Batch sorption studies were performed and the results revealed that activated carbon demonstrated ability to adsorb DEP. Influence of varying experimental conditions such as DEP concentration, pH of aqueous solution, and dosage of adsorbent were investigated on the adsorption process. Sorption interaction of DEP onto activated carbon obeyed the pseudo second order rate equation. Experimental data showed good fit with both the Langmuir and Freundlich adsorption isotherm models. DEP sorption was found to be dependent on the aqueous phase pH and the uptake was observed to be greater at acidic pH.

  3. Fundamentals of asphaltene phase behavior in heavy oil and tar sands

    SciTech Connect

    Carnahan, N.F.; Quintero, L.

    1995-12-31

    As a continuation and update of work presented at the 5th UNITAR International Conference on Heavy Crude and Tar Sands, this presentation addresses the phase behavior of asphaltenes in terms of traditional thermodynamics of mixtures and in terms of interfacial phenomena known to be an integral part of the problem. Recent experimental studies have demonstrated the pressure effect on apparent reverse micelle behavior of asphaltenes in petroleum fluids. Published results have shown that certain commercial surfactants have been effective in ameliorating the problem of asphaltene precipitation in crude oils, and in solubilizing asphaltenes deposited in porous media. These recent observations correspond well with the concepts advanced in our previous studies. Phase behavior of asphaltenes in heavy crude and in tar sands is again addressed from the fundamental point of view, at the molecular level, to interpret observed behavior and to provide a logical means of forecasting expected behavior in these fluids under many different physical and chemical conditions. Interactions between resins and asphaltenes, in the presence of heavy crude or tar sands, do not follow classical thermodynamics, at least, not faithfully. Resins tend to interact as amphiphiles between the asphaltene-free material and the asphaltenes. Resins may be in solution with the asphaltene-free material; however, resins are adsorbed at the surface of the asphaltene aggregations, forming micelles or other amphiphilic structures. Phase behavior of asphaltenes, therefore, depends upon the thermodynamic equilibrium of resins distributed between the asphaltenes and the asphaltene-free material. In crude oils, resins may form solutions which reasonably conform to the Modified Regular Solution Theory, as described previously. At the asphaltene-resin interface, adsorption can be described in terms of classical theories of adsorption and/or similar association mechanisms for interfacial phenomena.

  4. Universal biomimetic preparation and immobilization of layered double hydroxide films and adsorption behavior

    NASA Astrophysics Data System (ADS)

    Zhou, Wei; Zhang, Wenpeng; Chen, Zilin

    2017-01-01

    Preparation and immobilization of layered double hydroxides (LDHs) film onto multiple substrates is important and challenging in functional materials fields by date. In this work, a simple and universal polydopamine (PD)-based layer-by-layer assembly strategy was developed for the immobilization of LDHs film onto surfaces such as polypropylene chip, glass slides and metal coins. The surface of substrates was firstly modified by polydopamine functionalization, and then LDHs film was synthesized via urea method and directly immobilized on the PD layer by in situ growing strategy in one step. The PD layer as well as the final LDHs film was characterized by energy dispersive X-ray spectroscopy, scanning electron microscope, infrared spectroscopy, X-ray diffraction pattern and X-ray photoelectron spectra. It has been demonstrated the formation of the dense and homogeneous nanoscaled LDHs film with 400 nm thickness. Adsorption behavior of the fabricated NiAl-LDHs film toward anionic dyes and pharmaceuticals was further assessed. To demonstrate their extensive application, fast and high efficient adsorption of anionic dyes and pharmaceuticals was achieved by NiAl-LDHs-modified polypropylene centrifugal tube.

  5. Surface field of forces and protein adsorption behavior of poly(hydroxyethylmethacrylate) films deposited from plasma.

    PubMed

    Morra, M; Cassinelli, C

    1995-01-01

    Polymeric films were deposited from hydroxyethylmethacrylate (HEMA) plasma on non-woven poly(butyleneterephtalate) (PBT) filter materials. To test the effect of deposition conditions on surface properties, film were deposited using a constant monomer flow rate and a discharge power ranging from 40-100 W. Surface composition and surface energetics were evaluated by Electron Spectroscopy for Chemical Analysis (ESCA) and contact angle measurement, respectively. Albumin (Alb) and fibrinogen (Fg) adsorption from single protein solutions to the plasma-coated filters was measured. Results illustrate the marked effects of the deposition condition on the surface composition, the surface field of forces, and the protein adsorption behavior. The latter is modeled by the application of the Good-van Oss-Chaudhury theory of Lewis acid-base contribution to interfacial energetics. Materials endowed with widely different properties are obtained from the same monomer and different deposition conditions, a result that must be taken into account both in the production step, to assure constant quality, and in the development of specifically tailored materials.

  6. Organic molecules on metal and oxide semiconductor substrates: Adsorption behavior and electronic energy level alignment

    NASA Astrophysics Data System (ADS)

    Ruggieri, Charles M.

    Modern devices such as organic light emitting diodes use organic/oxide and organic/metal interfaces for crucial processes such as charge injection and charge transfer. Understanding fundamental physical processes occurring at these interfaces is essential to improving device performance. The ultimate goal of studying such interfaces is to form a predictive model of interfacial interactions, which has not yet been established. To this end, this thesis focuses on obtaining a better understanding of fundamental physical interactions governing molecular self-assembly and electronic energy level alignment at organic/metal and organic/oxide interfaces. This is accomplished by investigating both the molecular adsorption geometry using scanning tunneling microscopy, as well as the electronic structure at the interface using direct and inverse photoemission spectroscopy, and analyzing the results in the context of first principles electronic structure calculations. First, we study the adsorption geometry of zinc tetraphenylporphyrin (ZnTPP) molecules on three noble metal surfaces: Au(111), Ag(111), and Ag(100). These surfaces were chosen to systematically compare the molecular self-assembly and adsorption behavior on two metals of the same surface symmetry and two surface symmetries of one metal. From this investigation, we improve the understanding of self-assembly at organic/metal interfaces and the relative strengths of competing intermolecular and molecule-substrate interactions that influence molecular adsorption geometry. We then investigate the electronic structure of the ZnTPP/Au(111), Ag(111), and Ag(100) interfaces as examples of weakly-interacting systems. We compare these cases to ZnTPP on TiO2(110), a wide-bandgap oxide semiconductor, and explain the intermolecular and molecule-substrate interactions that determine the electronic energy level alignment at the interface. Finally we study tetracyanoquinodimethane (TCNQ), a strong electron acceptor, on TiO2

  7. Enhancing the adsorption of vapor-phase mercury chloride with an innovative composite sulfur-impregnated activated carbon.

    PubMed

    Ie, Iau-Ren; Chen, Wei-Chin; Yuan, Chung-Shin; Hung, Chung-Hsuang; Lin, Yuan-Chung; Tsai, Hsieh-Hung; Jen, Yi-Shiu

    2012-05-30

    Mercury chloride (HgCl(2)) is the major mercury derivate emitted from municipal solid waste incinerators, which has high risk to the environment and human health. This study investigated the adsorption of vapor-phase HgCl(2) with an innovative composite sulfurized activated carbon (AC), which was derived from the pyrolysis, activation, and sulfurization of waste tires. The composite sulfur-impregnation process impregnated activated carbon with aqueous-phase sodium sulfide (Na(2)S) and followed with vapor-phase elemental sulfur (S(0)). Thermogravimetric analysis (TGA) was applied to investigate the adsorptive capacity of vapor-phase HgCl(2) using the composite sulfurized AC. The operating parameters included the types of composite sulfurized AC, the adsorption temperature, and the influent HgCl(2) concentration. Experimental results indicated that the sulfur-impregnation process could increase the sulfur content of the sulfurized AC, but decreased its specific surface area. This study further revealed that the composite sulfurized AC impregnated with aqueous-phase Na(2)S and followed with vapor-phase S(0) (Na(2)S+S(0) AC) had much higher saturated adsorptive capacity of HgCl(2) than AC impregnated in the reverse sequence (S(0)+Na(2)S AC). A maximum saturated adsorptive capacity of HgCl(2) up to 5236 μg-HgCl(2)/g-C was observed for the composite Na(2)S+S(0) AC, which was approximately 2.00 and 3.17 times higher than those for the single Na(2)S and S(0) ACs, respectively.

  8. Protein Adsorption as a Key Mediator in the Nanotopographical Control of Cell Behavior

    PubMed Central

    2016-01-01

    Surface nanotopography is widely employed to control cell behavior and in particular controlled disorder has been shown to be important in cell differentiation/maturation. However, extracellular matrix proteins, such as fibronectin (FN), initially adsorbed on a biomaterial surface are known to mediate the interaction of synthetic materials with cells. In this work, we examine the effect of nanotopography on cell behavior through this adsorbed layer of adhesive proteins using a nanostructured polycarbonate surface comprising 150 nm-diameter pits originally defined using electron beam lithography. We address the effect of this nanopitted surface on FN adsorption and subsequently on cell morphology and behavior using C2C12 myoblasts. Wettability measurements and atomic force microscopy imaging showed that protein is adsorbed both within the interpits spaces and inside the nanopits. Cells responded to this coated nanotopography with the formation of fewer but larger focal adhesions and by mimicking the pit patterns within their cytoskeleton, nanoimprinting, ultimately achieving higher levels of myogenic differentiation compared to a flat control. Both focal adhesion assembly and nanoimprinting were found to be dependent on cell contractility and are adversely affected by the use of blebbistatin. Our results demonstrate the central role of the nanoscale protein interface in mediating cell-nanotopographical interactions and implicate this interface as helping control the mechanotransductive cascade. PMID:27391047

  9. [Adsorption and removal of gas-phase Hg(0) over a V2O5/AC catalyst in the presence of SO2].

    PubMed

    Wang, Jun-wei; Yang, Jian-li; Liu, Zhen-yu

    2009-12-01

    The adsorption and removal behaviors of gas-phase Hg(0) over V2O5/AC and AC were studied under a simulated flue gas (containing N2, SO2, O2) in a fixed-bed reactor. The influences of the V2O5, loading, SO2 concentration and adsorption temperature on Hg0 adsorption were investigated. The speciation of mercury adsorbed was determined by X-ray photoelectron spectroscopy (XPS). It was found that the V2O5/AC catalyst has a much higher capability than AC for Hg(0) adsorption and removal, mainly because of the catalytic oxidation activity of V2O5. The Hg(0) adsorption capability depends on the V2O5 content of the V2O5/AC catalyst. The amounts of mercury adsorbed increase from 75.9 microg x g(-1) to 89.6 microg x g(-1) (in the absence of O2) and from 115.9 microg x g(-1) to 185.5 microg x g(-1) (in the presence of O2) as the V2O5 loading increases from 0.5% to 1.0%, which are much higher than those over AC under the same conditions (9.6 microg x g(-1) and 23.3 microg x g(-1)). SO2 in the flue gas enhances Hg(0) adsorption over the V2O5/AC catalyst, which is due to the reaction of SO2 and Hg(0) on V2O3/AC. But as the SO2 concentration increases from 500 x 10(-6) to 2000 x 10(-6), the amount of mercury adsorbed has only a slight increase. The optimal temperature for Hg(0) adsorption over the V2O5/AC catalyst is around 150 degrees C, at which the amounts of mercury adsorbed are up to 98.5 microg x g(-1) (in the absence of O2) and 187.7 microg x g(-1) (in the presence of O2). The XPS results indicate the formation of Hg(0) and HgSO4 on the surface of the V2O5/AC catalyst, which confirms the role of V2O5 and SO2.

  10. Structural transformations in Pb/Si(111) phases induced by C₆₀ adsorption.

    PubMed

    Matetskiy, A V; Bondarenko, L V; Gruznev, D V; Zotov, A V; Saranin, A A; Tringides, M C

    2013-10-02

    Structural transformations at the Pb/Si(111) surface occurring upon C₆₀ adsorption onto Pb/Si(111)1 × 1 phase at room temperature and Pb/Si(111)[Formula: see text] at low temperatures between 30 and 210 K, have been studied using scanning tunneling microscopy and low-energy electron diffraction observations. Typically, C₆₀ fullerenes agglomerate into random molecular islands nucleated at the surface defects. C₆₀ island formation is accompanied by expelling Pb atoms to the surrounding surface area where more dense Pb/Si(111) phases form. Productivity of C₆₀-induced expelling of Pb atoms is controlled by surface defects and is suppressed dramatically when regular ('crystalline') C₆₀ islands self-assemble at the defect-free Pb/Si(111) surface. When Pb atoms are ejected by the random C₆₀ islands, extended structural transformations involving reordering of numerous Pb atoms are fully completed at the surface within the shortest possible time (a few dozen seconds) to reapproach and image the surface after C₆₀ deposition. Estimations show that the observed transformations cannot be controlled by random walk diffusion of Pb adatoms, which implies a highly correlated motion of the Pb atom displacements within the layer.

  11. Batch study of liquid-phase adsorption of methylene blue using cedar sawdust and crushed brick.

    PubMed

    Hamdaoui, Oualid

    2006-07-31

    This paper presents a study on the batch adsorption of basic dye, methylene blue, from aqueous solution (40 mg L(-1)) onto cedar sawdust and crushed brick in order to explore their potential use as low-cost adsorbents for wastewater dye removal. Adsorption isotherms were determined at 20 degrees C and the experimental data obtained were modelled with the Langmuir, Freundlich, Elovich and Temkin isotherm equations. Adsorption kinetic data determined at a temperature of 20 degrees C were modelled using the pseudo-first and pseudo-second-order kinetic equations, liquid-film mass transfer and intra-particle diffusion models. By considering the experimental results and adsorption models applied in this study, it can be concluded that equilibrium data were represented well by a Langmuir isotherm equation with maximum adsorption capacities of 142.36 and 96.61 mg g(-1) for cedar sawdust and crushed brick, respectively. The second-order model best describes adsorption kinetic data. Analysis of adsorption kinetic results indicated that both film- and particle-diffusion are effective adsorption mechanisms. The Influence of temperature and pH of the solution on adsorption process were also studied. The extent of the dye removal decreased with increasing the solution temperature and optimum pH value for dye adsorption was observed at pH 7 for both adsorbents. The results indicate that cedar sawdust and crushed brick can be attractive options for dye removal from dilute industrial effluents.

  12. Phase Behavior and Implications for Travel time Observables (PHASE 2)

    DTIC Science & Technology

    2015-09-30

    perturbation behavior of travel time observables due to sound -speed perturbations. OBJECTIVES The objective is to study the behavior of the wave-theoretic...location, as well as on the sound -speed distribution ( )c x , where x is the spatial variable. Thus, perturbations ( )c x give rise to perturbations in...arrival pattern, where the index spans the arrival peaks. As the sound speed changes the peaks of the arrival pattern are deformed and displaced

  13. Neutrons measure phase behavior in pores at Angstrom size

    SciTech Connect

    Bardoel, Agatha A; Melnichenko, Yuri B

    2012-01-01

    Researchers have measured the phase behavior of green house gases in pores at the Angstrom-level, using small angle neutron scattering (SANS) at the Oak Ridge National Laboratory's High Flux Isotope Reactor. Yuri Melnichenko, an instrument scientist on the General Purpose Small Angle Neutron Scattering (GP SANS) Diffractometer at ORNL's High Flux Isotope Reactor, his postdoctoral associate Lilin He and collaborators Nidia Gallego and Cristian Contescu from the Material Sciences Division (ORNL) were engaged in the work. They were studying nanoporous carbons to assess their attractiveness as storage media for hydrogen, with a view to potential use for on-board hydrogen storage for transportation applications. Nanoporous carbons can also serve as electrode material for supercapacitors and batteries. The researchers successfully determined that the most efficiently condensing pore size in a carbon nanoporous material for hydrogen storage is less than one nanometer. In a paper recently published by the Journal of the American Chemical Society, the collaborators used small angle neutron scattering to study how hydrogen condenses in small pores at ambient temperature. They discovered that the surface-molecule interactions create internal pressures in pores that may exceed the external gas pressure by a factor of up to 50. 'This is an exciting result,' Melnichenko said, 'as you achieve extreme densification in pores 'for free', i.e. without spending any energy. These results can be used to guide the development of new carbon adsorbents tailored to maximize hydrogen storage capacities.' Another important factor that defines the adsorption capacity of sub-nanometer pores is their shape. In order to get accurate structural information and maximize sorption capacity, it is important that pores are small and of approximately uniform size. In collaboration with Drexel University's Yury Gogotsi who supplied the samples, Melnichenko and his collaborators used the GP SANS

  14. Adsorption mechanism of acids and bases in reversed-phase liquid chromatography in weak buffered mobile phases designed for liquid chromatography/mass spectrometry.

    PubMed

    Gritti, Fabrice; Guiochon, Georges

    2009-03-06

    The overloaded band profiles of five acido-basic compounds were measured, using weakly buffered mobile phases. Low buffer concentrations were selected to provide a better understanding of the band profiles recorded in LC/MS analyses, which are often carried out at low buffer concentrations. In this work, 10 microL samples of a 50 mM probe solution were injected into C(18)-bonded columns using a series of five buffered mobile phases at (SW)pH between 2 and 12. The retention times and the shapes of the bands were analyzed based on thermodynamic arguments. A new adsorption model that takes into account the simultaneous adsorption of the acidic and the basic species onto the endcapped adsorbent, predicts accurately the complex experimental profiles recorded. The adsorption mechanism of acido-basic compounds onto RPLC phases seems to be consistent with the following microscopic model. No matter whether the acid or the base is the neutral or the basic species, the neutral species adsorbs onto a large number of weak adsorption sites (their saturation capacity is several tens g/L and their equilibrium constant of the order of 0.1 L/g). In contrast, the ionic species adsorbs strongly onto fewer active sites (their saturation capacity is about 1g/L and their equilibrium constant of the order of a few L/g). From a microscopic point of view and in agreement with the adsorption isotherm of the compound measured by frontal analysis (FA) and with the results of Monte-Carlo calculations performed by Schure et al., the first type of adsorption sites are most likely located in between C(18)-bonded chains and the second type of adsorption sites are located deeper in contact with the silica surface. The injected concentration (50 mM) was too low to probe the weakest adsorption sites (saturation capacity of a few hundreds g/L with an equilibrium constant of one hundredth of L/g) that are located at the very interface between the C(18)-bonded layer and the bulk phase.

  15. Adsorption behavior of methacryloyloxydecyl dihydrogen phosphate on an apatite surface at neutral pH.

    PubMed

    Bista, Baba; Nakashima, Syozi; Nikaido, Toru; Sadr, Alireza; Takagaki, Tomohiro; Romero, Maria J R H; Sato, Takaaki; Tagami, Junji

    2016-04-01

    This study aimed to quantify the adsorption affinity of neutralized 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP-N) toward hydroxyapatite (HA) and dicalcium phosphate dihydrate (DCPD) at pH 7.0 by employing the Langmuir isotherm model. Furthermore, the effects of inorganic phosphate (Pi) and fluoride (F(-) ) ions on the adsorption of 10-MDP-N onto HA and DCPD were examined. Fixed amounts of HA and DCPD powders were suspended in different concentrations of 10-MDP-N solutions and were incubated for 18 h. Equilibrated concentrations of 10-MDP-N were measured by spectrophotometry and the adsorption affinity was estimated using the Langmuir model. Moreover, the adsorption was examined by zeta-potential analysis. The results indicated that significant Langmuir correlation was noted in both substrates, along with an increasing negative zeta-potential; however, in DCPD the correlation was less strong. The addition of 1.0 mM Pi slightly delayed the adsorption of 10-MDP-N onto both substrates, whereas 3.0 mM Pi drastically delayed adsorption onto HA but completely inhibited adsorption onto DCPD. Up to 50 ppm, F(-) enhanced the adsorption onto HA, and the adsorption plateaued at higher concentrations of F(-) , whereas no obvious influence of F(-) on the adsorption onto DCPD was noted.

  16. Co-solvent enhanced adsorption with magnetic velvet-like carbon nitride for high efficiency solid phase extraction.

    PubMed

    Fan, Shanshan; Zhu, Jun; Ren, Lixuan; Wang, Man; Bi, Wentao; Li, Huihui; Huang, Xiaohua; Chen, David Da Yong

    2017-04-01

    Magnetic velvet-like graphitic carbon nitride (V-g-C3N4/Fe3O4) was used for rapid 1 min extraction of flavonoids from different tea extracts by co-solvent enhanced adsorptive magnetic solid phase extraction. The nanocomposite can interact with flavonoids, in which Fe3O4 provide hydrogen bond and V-g-C3N4 has hydrophobic and π-π interaction to promote adsorption. The enhanced adsorptive magnetic solid phase extraction method is developed with the addition of a co-solvent (water) to dramatically change the solvent environment, which enhanced the speed of movement of target compounds from the solvent to the sorbent and increase the adsorption capacity. The synergistic effects improved the extraction rate of flavonoids with excellent reproducibility (88.2-107.2%), sensitivity (limits of detection (S/N = 3): 0.075-0.1 μg/mL) and recoveries (88.2-107.2%). This study demonstrated the potential to apply this method for various target analytes from complex sample matrices.

  17. [Simulation study on the effect of salinity on the adsorption behavior of mercury in wastewater-irrigated area].

    PubMed

    Zheng, Shun-An; Li, Xiao-Hua; Xu, Zhi-Yu

    2014-05-01

    This study was designed to pinpoint the impact of salinity ( NaCl and Na2SO4, added at salinity levels of 0-5%, respectively) on the adsorption behavior of mercury in wastewater-irrigated areas of Tianjin City by batch and kinetic experiments. The results showed that, the Langmuir isotherm and the Elovich equation can well fitted batch and kinetic experimental data, respectively. As NaCI spiked in soil, Hg( II) adsorption capacity and strength had marked decreases, from 868.64 mgkg-1 and 1. 32 at control to 357.48 mgkg-1 and 0.63 at 5% salinity level of NaCI, respectively. As Na2SO4 spiked in soil, Hg(II) adsorption capacity (parameter qm in Langmuir isotherm) and strength (parameter k in Langmuir isotherm) changed slightly, from 868.64 mg kg-1 and 1.32 at control to 739.44 mg.kg-1 and 1. 18 at 5% salinity level of Na2 SO4, respectively. Kinetic data showed that, Hg( II) adsorption rate (parameter b in Elovich equation) in soil was not influenced by Na2SO, addition. However, the addition of NaC1 had a great effect on mercury adsorption rate. Hg(II ) adsorption capacity as a function of CI- or SO(2-)(4) content in soil could be simulated by the natural logarithm model, while Hg( II ) adsorption rate as a function of CI- content in soil could be simulated by the linear model. The study manifested that NaCI can significantly increase migration of Hg( II ) in the soil irrigated with wastewater, which may enhance Hg( II) bioavailability in the soil and cause a hazard to surface water. Especially, it will be harmful to human body through the food chain.

  18. Phase diagram and adsorption-desorption kinetics of CO on Ru(0001) from first principles.

    PubMed

    McEwen, J-S; Eichler, A

    2007-03-07

    A kinetic lattice gas model is used to study the equilibrium properties and the desorption kinetics of CO on Ru(0001). The authors compute all relevant on-site binding and interaction energies of CO molecules within density functional theory and import them in two different models. The first model allows the CO molecules to adsorb upright on top and hollow sites. The authors calculate the phase diagram, coverage isobars, and temperature programed desorption spectra. Up to a coverage of 1/3 ML, very good agreement is obtained between theory and experiment when considering top sites only. For coverages beyond 1/3 ML, hollow sites are included and disagreement between theory and experiment occurs. The second model allows adsorption on top sites only but allows them to tilt and shift from their upright positions. The authors show that this model resolves many of the deficiencies of their first one. Furthermore, the authors demonstrate that this model is more consistent with experiment since it is the only model that is able to explain the results from IR-spectroscopy experiments.

  19. Removal of the antibiotic metronidazole by adsorption on various carbon materials from aqueous phase.

    PubMed

    Carrales-Alvarado, D H; Ocampo-Pérez, R; Leyva-Ramos, R; Rivera-Utrilla, J

    2014-12-15

    The adsorption of the antibiotic metronidazole (MNZ) on activated carbon (F400), activated carbon cloth (ACF), mesoporous activated carbon (CMK-3), and carbon nanotubes (MWCNT) was investigated in this work. The effect of the adsorbent-adsorbate interactions as well as the operating conditions (ionic strength, solution pH, temperature, chemical modification of the adsorbents by HNO3 treatment, and water matrix) on the adsorption capacity were analyzed to substantiate the adsorption mechanism. The adsorption capacity markedly varied as function of the carbon material, decreasing in the following order: F400>ACF>F400-HNO3>CMK-3>MWCNT>MWCNT-HNO3, and depended not only on their surface area and pore size distribution, but also on their chemical nature. The adsorption of MNZ was influenced by the solution pH, but was not significantly affected by the ionic strength and temperature. The adsorption of MNZ was enhanced when the MNZ solutions were prepared using wastewater. Therefore, the electrolytes present in the wastewater cooperated rather than competed with the MNZ molecules for the adsorption sites. Desorption equilibrium data of MNZ on all carbon materials demonstrated that the adsorption was reversible corroborating the weakness of the adsorbent-adsorbate interactions.

  20. Removal of phenolic compounds from aqueous phase by adsorption onto polymer supported iron nanoparticles.

    PubMed

    Sen, Bhupendra K; Deshmukh, Dhananjay K; Deb, Manas K; Verma, Devsharan; Pal, Jolly

    2014-11-01

    The removal of phenolic compounds, i.e., o-cresol, m-cresol, and p-cresol from aqueous solution have been evaluated employing activated carbon (AC) coated with polymer supported iron nanoparticles (FeNPs). The synthesized FeNPs were characterized by scanning electron microscope and X-ray diffraction analysis. High correlation coefficient values indicated that the adsorption of phenolic compounds onto AC coated with polyvinylpyrrolidon (PVP) supported FeNPs obey Freundlich and Langmuir adsorption isotherms. Higher Freundlich and Langmuir constant values for AC coated with PVP supported FeNPs indicated its greater efficiency than AC. The adsorption data are well represented by both the Freundlich and Langmuir isotherms, indicating favourable adsorption of cresols by the adsorbents. Cresols were effectively removed (90 %) by adsorption process from aqueous solution using AC coated with FeNPs. The percentage removal of above phenolic compounds was studied under varying experimental conditions such as pH, temperature, adsorbent dosage, and contact time. The adsorption of phenolic compounds is quite sensitive to pH of the suspension and optimum uptake value was found at pH 7.0. Temperature also has a favorable effect on adsorption when varied from 20 to 50°C. On the contrary, beyond 30°C, a decrease in the adsorption was noticed.

  1. Kinetic modeling of liquid-phase adsorption of phosphate on dolomite.

    PubMed

    Karaca, S; Gürses, A; Ejder, M; Açikyildiz, M

    2004-09-15

    The adsorption of phosphate from aqueous solution on dolomite was investigated at 20 and 40 degrees C in terms of pseudo-second-order mechanism for chemical adsorption as well as an intraparticle diffusion mechanism process. Adsorption was changed with increased contact time, initial phosphate concentration, temperature, solution pH. A pseudo-second-order model and intraparticle diffusion model have been developed to predict the rate constants of adsorption and equilibrium capacities. The activation energy of adsorption can be evaluated using the pseudo-second-order rate constants. The adsorption of phosphate onto dolomite are an exothermically activated process. A relatively low activation energy and a model highly fitting to intraparticle diffusion suggest that the adsorption of phosphate by dolomite may involve not only physical but also chemisorption. This was likely due to its combined control of chemisorption and intraparticle diffusion. However, for phosphate/dolomite system chemical reaction is important and significant in the rate-controlling step, and for the adsorption of phosphate onto dolomite the pseudo-second-order chemical reaction kinetics provides the best correlation of the experimental data.

  2. Preparation and adsorption behavior of berberine hydrochloride imprinted polymers by using silica gel as sacrificed support material

    NASA Astrophysics Data System (ADS)

    Li, Hui; Li, Yuzhuo; Li, Zhiping; Peng, Xiyang; Li, Yanan; Li, Gui; Tan, Xianzhou; Chen, Gongxi

    2012-03-01

    Preparation of berberine hydrochloride (B-Cl) imprinted polymers (MIPs) based on surface imprinting technique with silica gel as sacrificial support material was performed successfully by using B-Cl as template, methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) as functional monomer and cross-linker, respectively. The prepared polymers were characterized by Fourier transmission infrared spectrometry (FTIR) and scanning electron microscopy (SEM). Adsorption behavior of the MIPs for the template and its structural analogues was investigated. Sites distribution on the surface of MIPs was explored by using different isotherm adsorption models and thermodynamic parameters for the adsorption of B-Cl on the MIPs determined. Sample application and reusability for the MIPs was also evaluated. Results indicated the strong adsorption and high selectivity of the MIPs for B-Cl. Saturated adsorption capacity reached 27.2 μmol g-1 and the selectivity coefficient of the MIPs for B-Cl relative to jatrorrhizine hydrochloride (J-Cl) and palmatine palmatus hydrochloride (P-Cl) are 3.70 and 6.03, respectively. In addition, the MIPs were shown with good reusability and selectively retention ability in sample application.

  3. Nano-organized collagen layers obtained by adsorption on phase-separated polymer thin films.

    PubMed

    Zuyderhoff, Emilienne M; Dupont-Gillain, Christine C

    2012-01-31

    The organization of adsorbed type I collagen layers was examined on a series of polystyrene (PS)/poly(methyl methacrylate) (PMMA) heterogeneous surfaces obtained by phase separation in thin films. These thin films were prepared by spin coating from solutions in either dioxane or toluene of PS and PMMA in different proportions. Their morphology was unraveled combining the information coming from X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and water contact angle measurements. Substrates with PMMA inclusions in a PS matrix and, conversely, substrates with PS inclusions in a PMMA matrix were prepared, the inclusions being either under the form of pits or islands, with diameters in the submicrometer range. The organization of collagen layers obtained by adsorption on these surfaces was then investigated. On pure PMMA, the layer was quite smooth with assemblies of a few collagen molecules, while bigger assemblies were found on pure PS. On the heterogeneous surfaces, it appeared clearly that the diameter and length of collagen assemblies was modulated by the size and surface coverage of the PS domains. If the PS domains, either surrounding or surrounded by the PMMA phase, were above 600 nm wide, a heterogeneous distribution of collagen was found, in agreement with observations made on pure polymers. Otherwise, fibrils could be formed, that were longer compared to those observed on pure polymers. Additionally, the surface nitrogen content determined by XPS, which is linked to the protein adsorbed amount, increased roughly linearly with the PS surface fraction, whatever the size of PS domains, suggesting that adsorbed collagen amount on heterogeneous PS/PMMA surfaces is a combination of that observed on the pure polymers. This work thus shows that PS/PMMA surface heterogeneities can govern collagen organization. This opens the way to a better control of collagen supramolecular organization at interfaces, which could in turn allow cell

  4. Phase behavior of a family of truncated hard cubes

    SciTech Connect

    Gantapara, Anjan P. Dijkstra, Marjolein; Graaf, Joost de; Roij, René van

    2015-02-07

    In continuation of our work in Gantapara et al., [Phys. Rev. Lett. 111, 015501 (2013)], we investigate here the thermodynamic phase behavior of a family of truncated hard cubes, for which the shape evolves smoothly from a cube via a cuboctahedron to an octahedron. We used Monte Carlo simulations and free-energy calculations to establish the full phase diagram. This phase diagram exhibits a remarkable richness in crystal and mesophase structures, depending sensitively on the precise particle shape. In addition, we examined in detail the nature of the plastic crystal (rotator) phases that appear for intermediate densities and levels of truncation. Our results allow us to probe the relation between phase behavior and building-block shape and to further the understanding of rotator phases. Furthermore, the phase diagram presented here should prove instrumental for guiding future experimental studies on similarly shaped nanoparticles and the creation of new materials.

  5. The computational study of amino group impregnation on the zeolite surface toward the behaviors of adsorption and diffusion

    NASA Astrophysics Data System (ADS)

    Kim, Kiwoong; Lee, Sooho; Lee, Kwang Soon; Lee, Won Bo

    2014-03-01

    The molecular dynamic and Grand Canonical Monte Carlo simulation study were conducted to investigate the adsorption and diffusion behaviors of mixture of CO2 and N2. Pure silicalite structures of zeolites TON, AFI, and LTL were selected as the host materials to be evaluated in this study. The effect of surface modification of TON, realized by impregnating the amino functional group on TON surface, on the adsorption and the diffusion were analyzed and compared with the normal TON structure. The results show that, in the adsorption behaviors, the modified TON adsorbs more CO2 than the normal TON structure, however, at high pressure regions, CO2 uptake is lower than the normal TON due to reductions of pore volume. This effect was quantitatively analyzed for the various amino functional group; methyl-, ethylamine, and ammonia. In the diffusion behaviors, the mixture in the modified TON has a lower diffusivity than the mixture in the normal TON due to additional attractive interaction between the amino group and mixture. In addition, the single file mobilities as well as the self-diffusion coefficients were employed to describe the observed diffusion behaviors.

  6. Phase behavior of charged colloids at a fluid interface

    NASA Astrophysics Data System (ADS)

    Kelleher, Colm P.; Guerra, Rodrigo E.; Hollingsworth, Andrew D.; Chaikin, Paul M.

    2017-02-01

    We study the phase behavior of a system of charged colloidal particles that are electrostatically bound to an almost flat interface between two fluids. We show that, despite the fact that our experimental system consists of only 103-104 particles, the phase behavior is consistent with the theory of melting due to Kosterlitz, Thouless, Halperin, Nelson, and Young. Using spatial and temporal correlations of the bond-orientational order parameter, we classify our samples into solid, isotropic fluid, and hexatic phases. We demonstrate that the topological defect structure we observe in each phase corresponds to the predictions of Kosterlitz-Thouless-Halperin-Nelson-Young theory. By measuring the dynamic Lindemann parameter γL(τ ) and the non-Gaussian parameter α2(τ ) of the displacements of the particles relative to their neighbors, we show that each of the phases displays distinctive dynamical behavior.

  7. Phase Formation Behavior in Ultrathin Iron Oxide.

    PubMed

    Jõgi, Indrek; Jacobsson, T Jesper; Fondell, Mattis; Wätjen, Timo; Carlsson, Jan-Otto; Boman, Mats; Edvinsson, Tomas

    2015-11-17

    Nanostructured iron oxides, and especially hematite, are interesting for a wide range of applications ranging from gas sensors to renewable solar hydrogen production. A promising method for deposition of low-dimensional films is atomic layer deposition (ALD). Although a potent technique, ALD of ultrathin films is critically sensitive to the substrate and temperature conditions where initial formation of islands and crystallites influences the properties of the films. In this work, deposition at the border of the ALD window forming a hybrid ALD/pulsed CVD (pCVD) deposition is utilized to obtain a deposition less sensitive to the substrate. A thorough analysis of iron oxide phases formation on two different substrates, Si(100) and SiO2, was performed. Films between 3 and 50 nm were deposited and analyzed with diffraction techniques, high-resolution Raman spectroscopy, and optical spectroscopy. Below 10 nm nominal film thickness, island formation and phase dependent particle crystallization impose constraints for deposition of phase pure iron oxides on non-lattice-matching substrates. Films between 10 and 20 nm thickness on SiO2 could effectively be recrystallized into hematite whereas for the corresponding films on Si(100), no recrystallization occurred. For films thicker than 20 nm, phase pure hematite can be formed directly with ALD/pCVD with very low influence of the substrate on either Si or SiO2. For more lattice matched substrates such as SnO2:F, Raman spectroscopy indicated formation of the hematite phase already for films with 3 nm nominal thickness and clearly for 6 nm films. Analysis of the optical properties corroborated the analysis and showed a quantum confined blue-shift of the absorption edge for the thinnest films.

  8. Anomalous compression behavior of germanium during phase transformation

    SciTech Connect

    Yan, Xiaozhi; Tan, Dayong; Ren, Xiangting; Yang, Wenge E-mail: duanweihe@scu.edu.cn; He, Duanwei E-mail: duanweihe@scu.edu.cn; Mao, Ho-Kwang

    2015-04-27

    In this article, we present the abnormal compression and plastic behavior of germanium during the pressure-induced cubic diamond to β-tin structure transition. Between 8.6 GPa and 13.8 GPa, in which pressure range both phases are co-existing, first softening and followed by hardening for both phases were observed via synchrotron x-ray diffraction and Raman spectroscopy. These unusual behaviors can be interpreted as the volume misfit between different phases. Following Eshelby, the strain energy density reaches the maximum in the middle of the transition zone, where the switch happens from softening to hardening. Insight into these mechanical properties during phase transformation is relevant for the understanding of plasticity and compressibility of crystal materials when different phases coexist during a phase transition.

  9. Kinetic and thermodynamic studies of sulforaphane adsorption on macroporous resin.

    PubMed

    Yuanfeng, Wu; Lei, Zhang; Jianwei, Mao; Shiwang, Liu; Jun, Huang; Yuru, You; Lehe, Mei

    2016-08-15

    The adsorption equilibrium, kinetic and thermodynamic of sulforaphane (SF) adsorption onto macroporous resin in aqueous phase were studied. The SP850 resin was screened as the appropriate resin for SF purification. From the equilibrium studies, the Redlich-Peterson model was found to be the best for description of the adsorption behavior of SF onto SP850 resin, followed by the Freundlich model and the Langmuir model. Batch equilibrium experiments demonstrated that, in the examined temperature range, the equilibrium adsorption capacity of SP850 resin decreased with increasing adsorption temperature. Thermodynamics studies indicated that the adsorption of SF was a physical, exothermic, and spontaneous process. The adsorption kinetics revealed that the pseudo-second-order kinetic model was suitable to characterize the kinetics of adsorption of SF onto SP850. Finally, the intra-particle diffusion model demonstrated that SF diffused quickly into macropores, and that diffusion slowed down in the meso- and micropores.

  10. The microwave adsorption behavior and microwave-assisted heteroatoms doping of graphene-based nano-carbon materials.

    PubMed

    Tang, Pei; Hu, Gang; Gao, Yongjun; Li, Wenjing; Yao, Siyu; Liu, Zongyuan; Ma, Ding

    2014-08-11

    Microwave-assisted heating method is used to treat graphite oxide (GO), pyrolytic graphene oxide (PGO) and hydrogen-reduced pyrolytic graphene oxide (HPGO). Pure or doped graphene are prepared in the time of minutes and a thermal deoxygenization reduction mechanism is proposed to understand their microwave adsorption behaviors. These carbon materials are excellent catalysts in the reduction of nitrobenzene. The defects are believed to play an important role in the catalytic performance.

  11. The microwave adsorption behavior and microwave-assisted heteroatoms doping of graphene-based nano-carbon materials

    NASA Astrophysics Data System (ADS)

    Tang, Pei; Hu, Gang; Gao, Yongjun; Li, Wenjing; Yao, Siyu; Liu, Zongyuan; Ma, Ding

    2014-08-01

    Microwave-assisted heating method is used to treat graphite oxide (GO), pyrolytic graphene oxide (PGO) and hydrogen-reduced pyrolytic graphene oxide (HPGO). Pure or doped graphene are prepared in the time of minutes and a thermal deoxygenization reduction mechanism is proposed to understand their microwave adsorption behaviors. These carbon materials are excellent catalysts in the reduction of nitrobenzene. The defects are believed to play an important role in the catalytic performance.

  12. The phase behavior of cationic lipid-DNA complexes.

    PubMed Central

    May, S; Harries, D; Ben-Shaul, A

    2000-01-01

    We present a theoretical analysis of the phase behavior of solutions containing DNA, cationic lipids, and nonionic (helper) lipids. Our model allows for five possible structures, treated as incompressible macroscopic phases: two lipid-DNA composite (lipoplex) phases, namely, the lamellar (L(alpha)(C)) and hexagonal (H(II)(C)) complexes; two binary (cationic/neutral) lipid phases, that is, the bilayer (L(alpha)) and inverse-hexagonal (H(II)) structures, and uncomplexed DNA. The free energy of the four lipid-containing phases is expressed as a sum of composition-dependent electrostatic, elastic, and mixing terms. The electrostatic free energies of all phases are calculated based on Poisson-Boltzmann theory. The phase diagram of the system is evaluated by minimizing the total free energy of the three-component mixture with respect to all the compositional degrees of freedom. We show that the phase behavior, in particular the preferred lipid-DNA complex geometry, is governed by a subtle interplay between the electrostatic, elastic, and mixing terms, which depend, in turn, on the lipid composition and lipid/DNA ratio. Detailed calculations are presented for three prototypical systems, exhibiting markedly different phase behaviors. The simplest mixture corresponds to a rigid planar membrane as the lipid source, in which case, only lamellar complexes appear in solution. When the membranes are "soft" (i.e., low bending modulus) the system exhibits the formation of both lamellar and hexagonal complexes, sometimes coexisting with each other, and with pure lipid or DNA phases. The last system corresponds to a lipid mixture involving helper lipids with strong propensity toward the inverse-hexagonal phase. Here, again, the phase diagram is rather complex, revealing a multitude of phase transitions and coexistences. Lamellar and hexagonal complexes appear, sometimes together, in different regions of the phase diagram. PMID:10733951

  13. [Preparation of weak light driven TiO2 multi composite photocatalysts via adsorption phase synthesis].

    PubMed

    Wang, Ting; Zhu, Yi-Chen; Sun, Zhi-Xuan; Wu, Li-Guang

    2015-02-01

    Photodegradation of pollutions by TiO2 under irradiation of weak UV and visible lights was one of the key points to expand the application of heterogeneous photocatalysis. Based on the adsorption phase synthesis, N doping and co-doping with N and Fe2O3 were employed to prepare TiO2 multi composite photocatalysts. The activity of these photocatalyts was evaluated by photodegradation of methyl-orange illuminated under weak UV and visible lights. Via UV-Vis diffuse reflectance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and photoluminescence spectra, the effects on the light absorption and visible response expansion of catalysts caused by different conditions were explored, such as sintering temperature, doping content of N and co-doping. Followed that, the changes in the photocatalytic activities were studied under the irradiation of weak light. The results showed that, N doping could enhance the light absorption of the catalysts, thus significantly enhanced their photocatalytic activity illuminated under UV weak light. All N-doped photocatalysts had a higher activity than the commercial available P25 photocatalyst. The visible response of catalysts was expanded little caused by N doping, thereby most catalysts doped by single N element had no activity illuminated by weak visible light. Only the catalyst doped with 5% of N element showed a weak activity after calcined at 900 degrees C . Due to the synergy effects between N doping and Fe2O3 coupling, co-doping did not only enhance the light absorption of the catalysts, but also significantly expanded the visible response of catalysts. So, co-doped catalysts showed a good catalytic activity when excited by weak visible light.

  14. Phase behavior of coal fluids: Data for correlation development

    SciTech Connect

    Robinson, R.L. Jr.

    1990-02-06

    The effective design and operation of processes for conversion of coal to fluid fuels requires accurate knowledge of the phase behavior of the fluid mixtures encountered in the conversion process. Multiple phases are present in essentially all stages of feed preparation, conversion reactions and product separation; thus, knowledge of the behavior of these multiple phases is important in each step. The overall objective of the author's work is to develop accurate predictive methods for representation of vapor-liquid equilibria in systems encountered in coal conversion processes. 59 refs., 6 figs., 7 tabs.

  15. Effects of modification of calcium hydroxyapatites by trivalent metal ions on the protein adsorption behavior.

    PubMed

    Kandori, Kazuhiko; Toshima, Satoko; Wakamura, Masato; Fukusumi, Masao; Morisada, Yoshiaki

    2010-02-25

    The effects of modification of calcium hydroxyapatites (Hap; Ca10(PO4)6(OH)2) by trivalent metal ions (Al(III), La(III), and Fe(III)) on protein adsorption behavior were examined using bovine serum albumin (BSA; isoelectric point (iep) = 4.7 and molecular mass (M(s)) = 67,200 Da). The Al(III)-, La(III)-, and Fe(III)-substituted Hap particles were prepared by the coprecipitation method with different atomic ratios, metal/(Ca + metal), abbreviated as X(metal). The particles precipitated at X(metal) = 0 (original-Hap) were rod-like and 10 x 36 nm2 in size. The short, rod-like original-Hap particles were elongated upon adding metal ions up to X(metal) = 0.10, and the extent of the particle growth was in the order of La(III) < Al(III) < Fe(III). The crystallinity of the materials was slightly lowered by increasing X(metal) for all systems. The adsorption isotherms of BSA onto the Al(III)-, La(III)-, and Fe(III)-substituted Hap particles showed the Langmuirian type. The saturated amounts of adsorbed BSA (n(s)(BSA)) values were strongly dependent on X(metal) in each system. The n(s)(BSA) values for the Fe(III)-substituted Hap system were increased with an increase in X(Fe) (X(metal) value of Hap particles substituted with Fe(III)); the n(s)(BSA) value obtained at X(Fe) = 0.10 was 2.7-fold more than that for the original-Hap particle, though those for the La(III) system were decreased to ca. 1/5. On the other hand, the n(s)(BSA) values for the Al(III) system were decreased with substitution of small amounts of Al(III), showing a minimum point at X(Al) = 0.01, but they were increased again at X(Al) over 0.03. Since the concentrations of hetero metal ions dissolved from the particles exhibited extremely low values, the possibility of binder effects of trivalent cations dissolved from the particle surface for adsorbing BSA to trivalent-ion-substituted Hap particles was excluded. The increase of n(s)(BSA) by an increase in X(Fe) was explained by elongation of mean particle

  16. Liquid-phase adsorption and desorption of phenol onto activated carbons with ultrasound.

    PubMed

    Juang, Ruey-Shin; Lin, Su-Hsia; Cheng, Ching-Hsien

    2006-04-01

    The effect of 48-kHz ultrasound on the adsorption and desorption of phenol from aqueous solutions onto coconut shell-based granular activated carbons was studied at 25 degrees C. Experiments were performed at different carbon particle sizes (1.15, 2.5, 4.0 mm), initial phenol concentrations (1.06-10.6 mol/m3), and ultrasonic powers (46-133 W). Regardless of the absence and presence of ultrasound, the adsorption isotherms were well obeyed by the Langmuir equation. When ultrasound was applied in the whole adsorption process, the adsorption capacity decreased but the Langmuir constant increased with increasing ultrasonic power. According to the analysis of kinetic data by the Elovich equation, it was shown that the initial rate of adsorption was enhanced after sonication and the number of sites available for adsorption was reduced. The effect of ultrasonic intensity on the initial rate and final amount of desorption of phenol from the loaded carbons using 0.1 mol/dm3 of NaOH were also evaluated and compared.

  17. Liquid phase adsorption of Crystal violet onto activated carbons derived from male flowers of coconut tree.

    PubMed

    Senthilkumaar, S; Kalaamani, P; Subburaam, C V

    2006-08-25

    Adsorption of Crystal violet, a basic dye onto phosphoric and sulphuric acid activated carbons (PAAC and SAAC), prepared from male flowers coconut tree has been investigated. Equilibrium data were successfully applied to study the kinetics and mechanism of adsorption of dye onto both the carbons. The kinetics of adsorption was found to be pseudo second order with regard to intraparticle diffusion. The pseudo second order is further supported by the Elovich model, which in turn intensifies the fact of chemisorption of dye onto both the carbons. Quantitative removal of dye at higher initial pH of dye solution reveals the basic nature of the Crystal violet and acidic nature of the activated carbons. Influence of temperature on the removal of dye from aqueous solution shows the feasibility of adsorption and its endothermic nature. Mass transfer studies were also carried out. The adsorption capacities of both the carbons were found to be 60.42 and 85.84 mg/g for PAAC and SAAC, respectively. Langmuir's isotherm data were used to design single-stage batch adsorption model.

  18. Phase behavior of the 38-atom Lennard-Jones cluster.

    PubMed

    Sehgal, Ray M; Maroudas, Dimitrios; Ford, David M

    2014-03-14

    We have developed a coarse-grained description of the phase behavior of the isolated 38-atom Lennard-Jones cluster (LJ38). The model captures both the solid-solid polymorphic transitions at low temperatures and the complex cluster breakup and melting transitions at higher temperatures. For this coarse model development, we employ the manifold learning technique of diffusion mapping. The outcome of the diffusion mapping analysis over a broad temperature range indicates that two order parameters are sufficient to describe the cluster's phase behavior; we have chosen two such appropriate order parameters that are metrics of condensation and overall crystallinity. In this well-justified coarse-variable space, we calculate the cluster's free energy landscape (FEL) as a function of temperature, employing Monte Carlo umbrella sampling. These FELs are used to quantify the phase behavior and onsets of phase transitions of the LJ38 cluster.

  19. Phase behavior of the 38-atom Lennard-Jones cluster

    SciTech Connect

    Sehgal, Ray M.; Maroudas, Dimitrios E-mail: ford@ecs.umass.edu; Ford, David M. E-mail: ford@ecs.umass.edu

    2014-03-14

    We have developed a coarse-grained description of the phase behavior of the isolated 38-atom Lennard-Jones cluster (LJ{sub 38}). The model captures both the solid-solid polymorphic transitions at low temperatures and the complex cluster breakup and melting transitions at higher temperatures. For this coarse model development, we employ the manifold learning technique of diffusion mapping. The outcome of the diffusion mapping analysis over a broad temperature range indicates that two order parameters are sufficient to describe the cluster's phase behavior; we have chosen two such appropriate order parameters that are metrics of condensation and overall crystallinity. In this well-justified coarse-variable space, we calculate the cluster's free energy landscape (FEL) as a function of temperature, employing Monte Carlo umbrella sampling. These FELs are used to quantify the phase behavior and onsets of phase transitions of the LJ{sub 38} cluster.

  20. Re-entrant phase behavior for systems with competition between phase separation and self-assembly.

    PubMed

    Reinhardt, Aleks; Williamson, Alexander J; Doye, Jonathan P K; Carrete, Jesús; Varela, Luis M; Louis, Ard A

    2011-03-14

    In patchy particle systems where there is a competition between the self-assembly of finite clusters and liquid-vapor phase separation, re-entrant phase behavior can be observed, with the system passing from a monomeric vapor phase to a region of liquid-vapor phase coexistence and then to a vapor phase of clusters as the temperature is decreased at constant density. Here, we present a classical statistical mechanical approach to the determination of the complete phase diagram of such a system. We model the system as a van der Waals fluid, but one where the monomers can assemble into monodisperse clusters that have no attractive interactions with any of the other species. The resulting phase diagrams show a clear region of re-entrance. However, for the most physically reasonable parameter values of the model, this behavior is restricted to a certain range of density, with phase separation still persisting at high densities.

  1. Adsorption behavior of tetracycline by extracellular polymeric substrates extracted from Klebsiella sp. J1.

    PubMed

    Li, Ang; Pi, Shanshan; Wei, Wei; Chen, Ting; Yang, Jixian; Ma, Fang

    2016-12-01

    The extracellular polymeric substrate (EPS) extracted from Klebsiella sp. J1 was used to adsorb low concentrations of tetracycline, and the efficiency and mechanism of tetracycline adsorption by EPS from strain J1 were studied. Adsorption efficiency was evaluated at different conditions. Results showed that optimal adsorption efficiency was 71.68 % with 60 mg L(-1) of EPS from strain J1 and 90 μL of 10 % (w/v) CaCl2 in 100 mL of tetracycline solution (80 μg L(-1)) with pH of 8.0. Experimental data was fitted well with Langmuir, Freundlich isotherm, and pseudo-second-order models. Analyses of E value, Ea value, thermodynamics, zeta potential variation, and Fourier transform infrared spectroscopy (FTIR) spectra proved that chemisorption was the main adsorption type and bridging was the main adsorption mechanism. Thermodynamic analysis indicated that adsorptive reaction was exothermic from 20 to 40 °C. In addition, humic acid (HA) showed little effect on the tetracycline adsorption by MFX.

  2. Adsorption characteristics and behaviors of graphene oxide for Zn(II) removal from aqueous solution

    NASA Astrophysics Data System (ADS)

    Wang, Hou; Yuan, Xingzhong; Wu, Yan; Huang, Huajun; Zeng, Guangming; Liu, Yan; Wang, Xueli; Lin, Ningbo; Qi, Yu

    2013-08-01

    In this study, graphene oxide (GO) was synthesized via modified Hummers’ method, and characterized by scanning electron microscopy (SEM), atomic force microscope (AFM), X-ray diffraction (XRD), and Fourier transform infrared spectrum (FT-IR), X-ray photoelectron spectroscopy (XPS). The adsorption of Zn(II) on GO as a function of pH, adsorbent dosage, foreign ions, contact time, and temperature was investigated using batch technique. Results showed that the suitable pH for Zn(II) removal was about 7.0, and the optimal dosage was 2 mg. The adsorption of Zn(II) onto GO increased sharply within 20 min and obtained equilibrium gradually. Meanwhile, foreign ion and temperature also affected the adsorption performance of GO. The adsorption process was found to be well described by the pseudo-second-order rate model. Equilibrium studies indicated that the data of Zn(II) adsorption followed the Langmuir model. The maximum adsorption capacity for Zn(II) was up to 246 mg/g with a Langmuir adsorption equilibrium constant of 5.7 L/g at 20 °C. The thermodynamic parameters calculated from temperature-dependent sorption isotherms suggested that Zn(II) sorption on GO was an exothermic and spontaneous process in nature. The possibility of Zn(II) recovery was investigated and the result revealed that the maximum Zn(II) recovery yield was achieved with hydrochloric acid.

  3. Investigation of adsorption behavior of mercury on Au(111) from first principles.

    PubMed

    Lim, Dong-Hee; Aboud, Shela; Wilcox, Jennifer

    2012-07-03

    The structural and electronic properties of Hg, SO(2), HgS, and HgO adsorption on Au(111) surfaces have been determined using density functional theory with the generalized gradient approximation. The adsorption strength of Hg on Au(111) increases by a factor of 1.3 (from -9.7 to -12.6 kcal/mol) when the number of surface vacancies increases from 0 to 3; however, the adsorption energy decreases with more than three vacancies. In the case of SO(2) adsorption on Au(111), the Au surface atoms are better able to stabilize the SO(2) molecule when they are highly undercoordinated. The SO(2) adsorption stability is enhanced from -0.8 to -9.3 kcal/mol by increasing the number of vacancies from 0 to 14, with the lowest adsorption energy of -10.2 kcal/mol at 8 Au vacancies. Atomic sulfur and oxygen precovered-Au(111) surfaces lower the Hg stability when Hg adsorbs on the top of S and O atoms. However, a cooperative effect between adjacent Hg atoms is observed as the number of S and Hg atoms increases on the perfect Au(111) surface, resulting in an increase in the magnitude of Hg adsorption. Details of the electronic structure properties of the Hg-Au systems are also discussed.

  4. Dye Adsorption Behavior of Polyvinyl Alcohol/Glutaraldehyde/β-Cyclodextrin Polymer Membranes

    NASA Astrophysics Data System (ADS)

    Ghemati, Dj.; Aliouche, Dj.

    2014-05-01

    Crosslinked polyvinyl alcohol/glutaraldehyde (PVA/GA) membranes were prepared, and attempts to obtain hydrophilic crosslinked PVA membranes were made by adding various amounts of β-cyclodexrin (β-CD), which is a typical cyclic oligosaccharide able to form inclusion complexes with organic host molecules (host-guest complexes). Thus, membranes of PVA/GA/β-CD were synthesized. The membranes were characterized by infrared spectroscopy (FTIR) and swelling measurements. The ability of cyclodextrin to include a wide variety of chemicals was also exploited for the dye adsorption to show the potentialities of the membranes in textile liquid waste processing. Adsorption of reactive methyl orange, and methylene blue dyes on PVA/GA/β-CD membranes was consequently studied using UV-Vis spectroscopy at wavelengths of 547, 463, and 660 nm. Adsorption reached equilibrium after 24 h. Results indicated that there is no covalent bond formation between PVA and β-CD; the β-CD is completely mixed into the PVA matrix polymer. The adsorption capacity increases with increasing amounts of cyclodextrin; the maximum adsorption capacity was obtained with 8% β-CD. Therefore, the change in adsorption capacities may be due to the dye structure effect, and the negative value of free energy indicated the spontaneous nature of adsorption.

  5. Nickel oxide grafted andic soil for efficient cesium removal from aqueous solution: adsorption behavior and mechanisms.

    PubMed

    Ding, Dahu; Lei, Zhongfang; Yang, Yingnan; Feng, Chuanping; Zhang, Zhenya

    2013-10-23

    An andic soil, akadama clay, was modified with nickel oxide and tested for its potential application in the removal of cesium from aqueous solution. Scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS), and powder X-ray diffraction (XRD) results revealed the nickel oxide was successfully grafted into akadama clay. N2 adsorption-desorption isotherms indicated the surface area decreased remarkably after modification while the portion of mesopores increased greatly. Thermogravimetric-differential thermal analysis (TG-DTA) showed the modified akadama clay had better thermostability than the pristine akadama clay. Decreases in cation exchange capacity (CEC) and ζ-potential were also detected after the modification. Adsorption kinetic and isotherm studies indicated the adsorption of Cs+ on the modified akadama clay was a monolayer adsorption process. Adsorption capacity was greatly enhanced for the modified akadama clay probably due to the increase in negative surface charge caused by the modification. The adsorption of Cs+ on the modified akadama clay was dominated by an electrostatic adsorption process. Results of this work are of great significance for the application of akadama clay as a promising adsorbent material for cesium removal from aqueous solutions.

  6. Adsorption behaviors of thiophene, benzene, and cyclohexene on FAU zeolites: Comparison of CeY obtained by liquid-, and solid-state ion exchange

    NASA Astrophysics Data System (ADS)

    Qin, Yucai; Mo, Zhousheng; Yu, Wenguang; Dong, Shiwei; Duan, Linhai; Gao, Xionghou; Song, Lijuan

    2014-02-01

    Cerium containing Y zeolites were prepared by liquid- (L-CeY) and solid- (S-CeY) state ion exchange from NaY and HY, respectively. The structural and textural properties were characterized by XRD and N2 adsorption, and acidity properties were characterized by NH3 temperature-programmed desorption (NH3-TPD) and in situ FTIR spectrum of chemisorbed pyridine (in situ Py-FTIR). Furthermore, the single component adsorption and multi-component competitive adsorption behavior of thiophene, benzene and cyclohexene on those zeolites have also been studied by using vapor adsorption isotherms, solution adsorption breakthrough curves, thermogravimetry and derivative thermogravimetry (TG/DTG), frequency response (FR) and in situ FTIR techniques. The results indicate that the primary adsorption mode of benzene is simply micropore filling process, but the nature of effect of aromatics on selective adsorption of thiophene is competitive adsorption. The strong chemical adsorptions and protonization reactions of thiophene and cyclohexene occur upon the Brönsted acid sites of the HY and L-CeY zeolites, and the preferable acid catalytic protonization reactions of olefins hinder the further adsorption of sulfur compounds.

  7. Easy extrusion of honeycomb-shaped monoliths using Moroccan natural clays and investigation of their dynamic adsorptive behavior towards VOCs.

    PubMed

    Chafik, T; Harti, S; Cifredo, G; Gatica, J M; Vidal, H

    2009-10-15

    In the present work, honeycomb-shaped monoliths were easily extruded using local natural clays without the need of chemical binders. This finding allows significant cost reduction, in terms of not only additives and solvents but also the energy consumption required for their elimination by thermal treatment. The extruded monoliths were subject to mechanical strength testing in addition to the study of their thermal behavior, structural and textural properties. Moreover, one of their potential uses as VOCs adsorbents was evaluated in comparison with conventional packed bed by investigating their dynamic adsorptive and desorption behavior towards a model VOC of o-xylene type.

  8. Physico-chemical characterization of metal-doped bone chars and their adsorption behavior for water defluoridation

    NASA Astrophysics Data System (ADS)

    Rojas-Mayorga, C. K.; Bonilla-Petriciolet, A.; Silvestre-Albero, J.; Aguayo-Villarreal, I. A.; Mendoza-Castillo, D. I.

    2015-11-01

    New bone chars for fluoride adsorption from drinking water have been synthetized via metallic doping using aluminum and iron salts. A detailed statistical analysis of the metal doping process using the signal-to-noise ratios from Taguchi's experimental designs and its impact on the fluoride adsorption properties of modified bone chars have been performed. The best conditions, including the proper metallic salt, for metal doping were identified to improve the fluoride uptakes of modified bone chars. Results showed that the fluoride adsorption properties of bone chars can be enhanced up to 600% using aluminum sulfate for the surface modification. This aluminum-based adsorbent showed an adsorption capacity of 31 mg/g, which outperformed the fluoride uptakes reported for several adsorbents. Surface interactions involved in the defluoridation process were established using FTIR, DRX and XPS analysis. Defluoridation using the metal-doped bone chars occurred via an ion exchange process between fluoride ions and the hydroxyl groups on the adsorbent surface, whereas the Al(OH)xFy, FexFy, and CaF2 interactions could play also an important role in the removal process. These metal-doped adsorbents anticipate a promising behavior in water treatment, especially in developing countries where the efficiency - cost tradeoff is crucial for implementing new defluoridation technologies.

  9. Comparative study on composition, structure, and adsorption behavior of activated carbons derived from different synthetic waste polymers.

    PubMed

    Lian, Fei; Xing, Baoshan; Zhu, Lingyan

    2011-08-15

    The composition, structure, and adsorption behavior of activated carbons (ACs) derived from three different types of waste polymers, i.e., tire rubber (TR), polyvinyl chloride (PVC), and polyethyleneterephtalate (PET), by KOH activation were compared. The AC derived from PET exhibited the largest surface area (2831 m(2)/g) and pore volume (1.68 cm(3)/g) due to the homogenous aromatic composition of PET. The AC derived from PVC exhibited relatively lower surface area (2666 m(2)/g) but more narrowed pore size distribution (2-3 nm). The complex composition and high ash content of tire particles resulted in AC product with significantly lower surface area (398.5 m(2)/g) and heterogeneous pore width. Adsorption data of methylene blue (MB) were fitted well by Langmuir equation, indicating monolayer coverage on the ACs. The high oxygen content of PET-derived AC heavily affected its adsorption to MB and iodine. Due to the remarkable surface area and highly mesoporous structures, ACs based on both PET and PVC exhibited much higher adsorption capacities than that of TR and commercial coal-based AC (F400). This study demonstrates that the properties of ACs are highly dependent on their starting polymers and the potential of converting synthetic polymer waste into effective adsorbents for environmental remediation and cleanup.

  10. Dependence of Protein Adsorption on Wetting Behavior of UHMWPE-HA-Al2O3-CNT Hybrid Biocomposites

    NASA Astrophysics Data System (ADS)

    Gupta, Ankur; Tripathi, Garima; Basu, Bikramjit; Balani, Kantesh

    2012-04-01

    Ultrahigh-molecular-weight polyethylene (UHMWPE) is used as an articulating surface in total hip and knee joint replacement. In order to enhance long-term durability/wear resistance properties, UHMWPE-based polymer-ceramic hybrid composites are being developed. Surface properties such as wettability and protein adsorption alter with reinforcement or with change in surface chemistry. From this perspective, the wettability and protein adsorption behavior of compression-molded UHMWPE-hydroxyapatite (HA)-aluminum oxide (Al2O3)-carbon nanotube (CNT) composites were analyzed in conjunction with surface roughness. The combined effect of Al2O3 and CNT shows enhancement of the contact angle by ~37° compared with the surface of the UHMWPE matrix reinforced with HA. In reference to unreinforced UHMWPE, protein adsorption density also increased by ~230% for 2 wt.%HA-5 wt.%Al2O3-2 wt.%CNT addition to UHMWPE. An important conclusion is that the polar and dispersion components of the surface free energy play a significant role in wetting and protein adsorption than do the total free energy or chemistry of the surface. The results of this study have major implications for the biocompatibility of these newly developed biocomposites.

  11. Acquisition and Tracking Behavior of Phase-Locked Loops

    NASA Technical Reports Server (NTRS)

    Viterbi, A. J.

    1958-01-01

    Phase-locked or APC loops have found increasing applications in recent years as tracking filters, synchronizing devices, and narrowband FM discriminators. Considerable work has been performed to determine the noise-squelching properties of the loop when it is operating in or near phase lock and is functioning as a linear coherent detector. However, insufficient consideration has been devoted to the non-linear behavior of the loop when it is out of lock and in the process of pulling in. Experimental evidence has indicated that there is a strong tendency for phase-locked loops to achieve lock under most circumstances. However, the analysis which has appeared in the literature iis limited to the acquisition of a constant frequency reference signal with only one phase-locked loop filter configuration. This work represents an investigation of frequency acquisition properties of phase-locked loops for a variety of reference-signal behavior and loop configurations

  12. Use of in situ solid-phase adsorption in microbial natural product fermentation development.

    PubMed

    Phillips, Thomas; Chase, Matthew; Wagner, Stephanie; Renzi, Chris; Powell, Marcella; DeAngelo, Joseph; Michels, Peter

    2013-05-01

    It has been half a century since investigators first began experimenting with adding ion exchange resins during the fermentation of microbial natural products. With the development of nonionic polymeric adsorbents in the 1970s, the application of in situ product adsorption in bioprocessing has grown slowly, but steadily. To date, in situ product adsorption strategies have been used in biotransformations, plant cell culture, the production of biofuels, and selected bulk chemicals, such as butanol and lactic acid, as well as in more traditional natural product fermentation within the pharmaceutical industry. Apart from the operational gains in efficiency from the integration of fermentation and primary recovery, the addition of adsorbents during fermentation has repeatedly demonstrated the capacity to significantly increase titers by sequestering the product and preventing or mitigating degradation, feedback inhibition and/or cytotoxic effects. Adoption of in situ product adsorption has been particularly valuable in the early stages of natural product-based drug discovery programs, where quickly and cost-effectively generating multigram quantities of a lead compound can be challenging when using a wild-type strain and fermentation conditions that have not been optimized. While much of the literature involving in situ adsorption describes its application early in the drug development process, this does not imply that the potential for scale-up is limited. To date, commercial-scale processes utilizing in situ product adsorption have reached batch sizes of at least 30,000 l. Here we present examples where in situ product adsorption has been used to improve product titers or alter the ratios among biosynthetically related natural products, examine some of the relevant variables to consider, and discuss the mechanisms by which in situ adsorption may impact the biosynthesis of microbial natural products.

  13. Thermodynamic and kinetic behaviors of trinitrotoluene adsorption on powdered activated carbons

    SciTech Connect

    Lee, J.W.; Hwang, K.J.; Shim, W.G.; Moon, I.S.

    2006-07-01

    Regulations on the removal of trinitrotoluene (TNT) from wastewater have become increasingly more stringent, demanding faster, less expensive, and more efficient treatment. This study focuses on the adsorption equilibrium and kinetics of TNT on powered activated carbons (PAC). Three types of PACs (i.e., wood based, coal based, and coconut-shell based) were studied as functions of temperature and pH. Thermodynamic properties including Gibbs free energy, enthalpy, and entropy, were evaluated by applying the Van't Hoff equation. In addition, the adsorption energy distribution functions which describe heterogeneous characteristics of porous solid sorbents were calculated by using the generalized nonlinear regularization method. Adsorption kinetic studies were carried out in batch adsorber under important conditions such as PAC types, temperature, pH, and concentration. We found that fast and efficient removal of TNT dissolved in water can be successfully achieved by PAC adsorption.

  14. Metals on graphene: correlation between adatom adsorption behavior and growth morphology

    SciTech Connect

    Liu, Xiaojie; Wang, Cai-Zhuang; Hupalo, Myron; Lu, Wencai; Tringides, Michael C.; Yao, Yongxin; Ho, Kai-Ming

    2012-05-19

    We present a systematic study of metal adatom adsorption on graphene by ab initio calculations. The calculations cover alkali metals, sp-simple metals, 3d and group 10 transition metals, noble metals, as well as rare earth metals. The correlation between the adatom adsorption properties and the growth morphology of the metals on graphene is also investigated. We show that the growth morphology is related to the ratio of the metal adsorption energy to its bulk cohesive energy (E(a)/E(c)) and the diffusion barrier (ΔE) of the metal adatom on graphene. Charge transfer, electric dipole and magnetic moments, and graphene lattice distortion induced by metal adsorption would also affect the growth morphologies of the metal islands. We also show that most of the metal nanostructures on graphene would be thermally stable against coarsening.

  15. Adsorption behaviors of fungicide-derived copper onto various size fractions of aggregates from orchard soil.

    PubMed

    Wang, Quan-Ying; Hu, Bo; Yu, Hong-Wen

    2016-12-01

    Although the gradual accumulations of Cu in orchard soils due to the application of Cu-based fungicides have been widely reported, limited information is available about the retention characteristics of fungicide-derived Cu in soil, especially in various size soil aggregates. This study described the adsorption characteristics of Cu from commonly used fungicide, Bordeaux mixture (CuSO4 + Ca(OH)2), onto various aggregate fractions (2000-1000, 1000-500, 500-250, 250-106, and <106 μm) of orchard soil. The Cu(NO3)2 was selected as a comparison. Two different types of adsorption experiments were conducted as follows: variable pH and variable Cu concentration experiments. The adsorption processes of Bordeaux mixture and Cu(NO3)2 onto the studied soil samples followed well with the Freundlich isotherm, and the adsorption isotherms were the S shaped. The adsorption amounts of Cu from different Cu compounds differed, and Bordeaux mixture can result in more Cu retention in soil than Cu(NO3)2. The adsorption ability of different size soil aggregates varied, and it was mainly governed by soil properties. The findings of this study suggested that both the chemical compositions of Cu compounds and the soil physical structure should be taken into account when performing soil Cu retention experiments with fungicide-derived Cu.

  16. Adsorption behavior and mechanism of Cd(II) on loess soil from China.

    PubMed

    Wang, Yan; Tang, Xiaowu; Chen, Yunmin; Zhan, Liangtong; Li, Zhenze; Tang, Qiang

    2009-12-15

    Cadmium is a toxic heavy metal that has caused serious public health problems. It is necessary to find a cost effective method to deal with wastewater containing Cd(II). Loess soils in China have proven to be a potential adsorbent for Cd(II) removal from wastewater. The adsorption capacity of loess towards Cd(II) has been determined to be about 9.37 mg g(-1). Slurry concentration, initial solution pH, reaction time and temperature have also been found to significantly influence the efficiency of Cd(II) removal. The adsorption isotherms and kinetics of loess soil from China can be best-fit with the Langmuir model and pseudo-second order kinetics model, respectively. The thermodynamic analysis revealed that the adsorption process was spontaneous, endothermic and the system disorder increased with duration. The natural organic matter in loess soil is mainly responsible for Cd(II) removal at pH < 4.2, while clay minerals contribute to a further gradual adsorption process. Chemical precipitation dominates the adsorption stage at pH > 8.97. Further studies using X-ray diffraction, Fourier transform infrared spectra of Cd(II) laden loess soil and Cd(II) species distribution have confirmed the adsorption mechanism.

  17. Alumina interaction with AMPS-MPEG random copolymers I. Adsorption and electrokinetic behavior.

    PubMed

    Bouhamed, H; Boufi, S; Magnin, A

    2003-05-15

    Adsorption of brush copolymers, bearing sulfonate groups and polyethylene glycol segments, on to alumina particles in suspension in water has been investigated. Study of the adsorption isotherms revealed that the copolymers displayed a strong affinity for the surface of the alumina regardless of the fraction of ionic groups on the polymer. For poly(ethylene glycol) content greater than 50%, the adsorption isotherms revealed an initial adsorption plateau followed by a second one. The shape of the adsorption isotherms was interpreted in terms of the polymer configuration at the solid-to-liquid interface. The effects of the pH and the ionic force on adsorption were studied and connected to the effects of interaction between chain segments at the surface of the alumina particles. Changes in the electrokinetic properties of the alumina particles after addition of the copolymers were investigated by following the zeta potential of particles as a function of pH. In the presence of the copolymer continuous shift of the isoelectric point IEP to a more acidic values was observed. Beyond a certain concentration the zeta potential remained negative regardless of the pH.

  18. Adsorption behavior of hydrophobin and hydrophobin/surfactant mixtures at the solid-solution interface.

    PubMed

    Zhang, Xiaoli L; Penfold, Jeffrey; Thomas, Robert K; Tucker, Ian M; Petkov, Jordan T; Bent, Julian; Cox, Andrew

    2011-09-06

    The adsorption of surface-active protein hydrophobin, HFBII, and HFBII/surfactant mixtures at the solid-solution interface has been studied by neutron reflectivity, NR. At the hydrophilic silicon surface, HFBII adsorbs reversibly in the form of a bilayer at the interface. HFBII adsorption dominates the coadsorption of HFBII with cationic and anionic surfactants hexadecyltrimethyl ammonium bromide, CTAB, and sodium dodecyl sulfate, SDS, at concentrations below the critical micellar concentration, cmc, of conventional cosurfactants. For surfactant concentrations above the cmc, HFBII/surfactant solution complex formation dominates and there is little HFBII adsorption. Above the cmc, CTAB replaces HFBII at the interface, but for SDS, there is no affinity for the anionic silicon surface hence there is no resultant adsorption. HFBII adsorbs onto a hydrophobic surface (established by an octadecyl trimethyl silane, OTS, layer on silicon) irreversibly as a monolayer, similar to what is observed at the air-water interface but with a different orientation at the interface. Below the cmc, SDS and CTAB have little impact upon the adsorbed layer of HFBII. For concentrations above the cmc, conventional surfactants (CTAB and SDS) displace most of the HFBII at the interface. For nonionic surfactant C(12)E(6), the pattern of adsorption is slightly different, and although some coadsorption at the interface takes place, C(12)E(6) has little impact on the HFBII adsorption.

  19. Preparation of activated carbon from corn cob and its adsorption behavior on Cr(VI) removal.

    PubMed

    Tang, Shuxiong; Chen, Yao; Xie, Ruzhen; Jiang, Wenju; Jiang, Yanxin

    2016-01-01

    Operation experiments were conducted to optimize the preparation of activated carbons from corn cob. The Cr(VI) adsorption capacity of the produced activated carbons was also evaluated. The impact of the adsorbent dosage, contact time, initial solution pH and temperature was studied. The results showed that the produced corn cob activated carbon had a good Cr(VI) adsorptive capacity; the theoretical maximum adsorption was 34.48 mg g(-1) at 298 K. The Brunauer-Emmett-Teller and iodine adsorption value of the produced activated carbon could be 924.9 m(2) g(-1) and 1,188 mg g(-1), respectively. Under the initial Cr(VI) concentration of 10 mg L(-1) and the original solution pH of 5.8, an adsorption equilibrium was reached after 4 h, and Cr(VI) removal rate was from 78.9 to 100% with an adsorbent's dosage increased from 0.5 to 0.7 g L(-1). The kinetics and equilibrium data agreed well with the pseudo-second-order kinetics model and the Langmuir isotherm model. The equilibrium adsorption capacity improved with the increment of the temperature.

  20. Improved efficiency in micellar liquid chromatography using triethylamine and 1-butanol as mobile phase additives to reduce surfactant adsorption.

    PubMed

    Thomas, David P; Foley, Joe P

    2008-09-26

    The effect of triethylamine as a mobile phase modifier on chromatographic efficiency in micellar liquid chromatography (MLC) is reported for nine different columns with various bonded stationary phases and silica pore sizes, including large-pore short alkyl chain, non-porous, and perfluorinated. Reduced plate height (h) versus reduced velocity (nu) plots were constructed for each column and the A' and C' terms calculated using a simplified Van Deemter equation introduced in our previous work. To further explore the practicality of using triethylamine in the micellar mobile phase, the efficiency of nine polar and non-polar substituted benzenes was studied on seven columns. Surfactant adsorption isotherms were measured for five columns with three micellar mobile phases to understand the relationship between adsorbed surfactant, mobile phase additive, and column efficiency. Clear improvements in efficiency were observed with the addition of 2% (v/v) triethylamine to a 1-butanol modified aqueous micellar mobile phase. This finding is supported by the lower amount of surfactant adsorbed onto the stationary phase when TEA is present in the mobile phase compared to an SDS only or a 1-butanol modified SDS mobile phase.

  1. Alumina interaction with AMPS-MPEG random copolymers III. Effect of PEG segment length on adsorption, electrokinetic and rheological behavior.

    PubMed

    Bouhamed, H; Magnin, A; Boufi, S

    2006-06-01

    The effect of different 2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS)-methoxypolyethyleneglycol methacrylate (MPEG) comb-like copolymers on the adsorption behavior, electrokinetic and rheological properties of alumina suspensions has been investigated. The change in adsorption isotherms with the content of the two monomers, the medium pH and the ionic strength indicated that the interaction of these copolymers was found to be controlled by both the fraction of ionic groups on the polymer and by the length of the polyethyleneglycol (PEG) segments. Adsorption of the copolymers on alumina particles is accompanied by a shift in the IEP toward acid pH values and may lead to a charge reversal above a certain level. The presence of the PEG segment equally affects the magnitude of the zeta potential by moving the shear plane forward. Addition of the copolymers greatly affects the rheological behavior of the suspension; the viscosity at a defined shear rate decreases and reaches an optimum, which is all the lower as the fraction of the ionic groups is higher. The dispersing effect of the copolymer was controlled by both the ionization level of the copolymer and by the length of the PEG segments.

  2. Effect of polymer rigidity on the phase behaviour of polymer adsorption on to planar surface

    PubMed Central

    Yang, Zhiyong; Chai, Aihua; Zhou, Peicong; Li, Ping; Yang, Yongfu

    2016-01-01

    We study the process of a semiflexible polymer chain adsorption on to planar surface by the dynamic Monte Carlo (DMC) method, based on the 3D off-lattice model. Both the strength of attractive monomer–surface interaction (εa) and bending energy (b) have pronounced effect on the adsorption and shape of semiflexible polymer chain. The semiflexible polymer can just fully adsorb on to the surface at certain εa, which is defined as critical εa. The essential features of the semiflexible polymer adsorption on to surface are that (i) the critical εa increases with increase in b; (ii) the shape of the fully adsorbed semiflexible polymer chain is film-like toroid, and the toroid becomes more and more perfect with increase in b. In addition, the size of toroid and the number of turns of toroid can be controlled by the b and εa. PMID:27756826

  3. 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.

  4. Investigating the Co-Adsorption Behavior of Nucleic-Acid Base (Thymine and Cytosine) and Melamine at Liquid/Solid Interface

    NASA Astrophysics Data System (ADS)

    Zhao, Huiling; Li, Yinli; Chen, Dong; Liu, Bo

    2016-12-01

    The co-adsorption behavior of nucleic-acid base (thymine; cytosine) and melamine was investigated by scanning tunneling microscopy (STM) technique at liquid/solid (1-octanol/graphite) interface. STM characterization results indicate that phase separation happened after dropping the mixed solution of thymine-melamine onto highly oriented pyrolytic graphite (HOPG) surface, while the hetero-component cluster-like structure was observed when cytosine-melamine binary assembly system is used. From the viewpoints of non-covalent interactions calculated by using density functional theory (DFT) method, the formation mechanisms of these assembled structures were explored in detail. This work will supply a methodology to design the supramolecular assembled structures and the hetero-component materials composed by biological and chemical compound.

  5. On the Henry constant and isosteric heat at zero loading in gas phase adsorption.

    PubMed

    Do, D D; Nicholson, D; Do, H D

    2008-08-01

    The Henry constant and the isosteric heat of adsorption at zero loading are commonly used as indicators of the strength of the affinity of an adsorbate for a solid adsorbent. It is assumed that (i) they are observable in practice, (ii) the Van Hoff's plot of the logarithm of the Henry constant versus the inverse of temperature is always linear and the slope is equal to the heat of adsorption, and (iii) the isosteric heat of adsorption at zero loading is either constant or weakly dependent on temperature. We show in this paper that none of these three points is necessarily correct, first because these variables might not be observable since they are outside the range of measurability; second that the linearity of the Van Hoff plot breaks down at very high temperature, and third that the isosteric heat versus loading is a strong function of temperature. We demonstrate these points using Monte Carlo integration and Monte Carlo simulation of adsorption of various gases on a graphite surface. Another issue concerning the Henry constant is related to the way the adsorption excess is defined. The most commonly used equation is the one that assumes that the void volume is the volume extended all the way to a boundary passing through the centres of the outermost solid atoms. With this definition the Henry constant can become negative at high temperatures. Although adsorption at these temperatures may not be practical because of the very low value of the Henry constant, it is more useful to define the Henry constant in such a way that it is always positive at all temperatures. Here we propose the use of the accessible volume; the volume probed by the adsorbate when it is in nonpositive regions of the potential, to calculate the Henry constant.

  6. The adsorption and lubrication behavior of synovial fluid proteins and glycoproteins on the bearing-surface materials of hip replacements.

    PubMed

    Roba, Marcella; Naka, Marco; Gautier, Emanuel; Spencer, Nicholas D; Crockett, Rowena

    2009-04-01

    The selectivity of synovial fluid protein adsorption onto ultra-high molecular weight polyethylene (UHMWPE) and alumina (Al(2)O(3)), and in particular the ability of glycoproteins to adsorb in the presence of all the other synovial fluid proteins, was investigated by means of fluorescence microscopy and gel electrophoresis (SDS-PAGE). The non-specific nature of protein adsorption from synovial fluid indicated that the lubrication of artificial hip-joint materials may not be attributable to a single protein as has been frequently suggested. The friction behavior of polyethylene (PE) sliding against Al(2)O(3) in solutions of bovine serum albumin (BSA), alpha-1-acid glycoprotein (AGP) and alpha-1-antitrypsin (A1AT) was investigated by means of colloidal probe atomic force microscopy. BSA was shown to be a poorer boundary lubricant than the phosphate buffered saline used as a control. This was attributed to denaturation of the BSA upon adsorption, which provided a high-shear-strength layer at the interface, impairing the lubrication. Interestingly, both the glycoproteins AGP and A1AT, despite their low concentrations, improved lubrication. The lubricating properties of AGP and A1AT were attributed to adsorption via the hydrophobic backbone, allowing the hydrophilic carbohydrate moieties to be exposed to the aqueous solution, thus providing a low-shear-strength fluid film that lubricated the system. The amount of glycoprotein adsorbed on hydrophobic surfaces was determined by means of optical waveguide lightmode spectroscopy (OWLS), allowing conclusions to be drawn about the conformation of the glycan residues following adsorption.

  7. Phase and sedimentation behavior of oil (octane) dispersions in the presence of model mineral aggregates.

    PubMed

    Gupta, Anju; Sender, Maximilian; Fields, Sarah; Bothun, Geoffrey D

    2014-10-15

    Adsorption of suspended particles to the interface of surfactant-dispersed oil droplets can alter emulsion phase and sedimentation behavior. This work examines the effects of model mineral aggregates (silica nanoparticle aggregates or SNAs) on the behavior of oil (octane)-water emulsions prepared using sodium bis(2-ethylhexyl) sulfosuccinate (DOSS). Experiments were conducted at different SNA hydrophobicities in deionized and synthetic seawater (SSW), and at 0.5mM and 2.5mM DOSS. SNAs were characterized by thermogravimetric analysis (TGA) and dynamic light scattering (DLS), and the emulsions were examined by optical and cryogenic scanning electron microscopy. In deionized water, oil-in-water emulsions were formed with DOSS and the SNAs did not adhere to the droplets or alter emulsion behavior. In SSW, water-in-oil emulsions were formed with DOSS and SNA-DOSS binding through cation bridging led to phase inversion to oil-in-water emulsions. Droplet oil-mineral aggregates (OMAs) were observed for hydrophilic SNAs, while hydrophobic SNAs yielded quickly sedimenting agglomerated OMAs.

  8. Improving Coalition Performance by Exploiting Phase Transition Behavior

    DTIC Science & Technology

    2004-09-01

    CODE 13. ABSTRACT (Maximum 200 Words) This document describes research into the effects of phase transitions and related phenomena on the design...implications of these thresholds for "anytime", "good enough soon enough" behavior are discussed. Second, the effects of solution-clustering behavior on...20 Figure 4.4: Example of effects , in oPARIS, of learning simple CNF clauses versus learning of cardinality constraints

  9. Phase Behavior of Polymer Blends for Organic Photovoltaic Applications

    NASA Astrophysics Data System (ADS)

    Emerson, Jillian; Furst, Eric; Epps, Thomas, III

    2014-03-01

    Polymer blends offer a promising and economically-viable route to creating organic photovoltaic (OPV) devices, as blends can form bicontinuous domains via spinodal decomposition. Understanding the phase behavior of conjugated polymer blends commonly used in OPVs is vital to producing more efficient devices. In this work, we determined the Flory-Huggins solvent-polymer and polymer-polymer interaction parameters for a model system of poly(3-hexylthiophene) (P3HT) and polystyrene (PS) through solvent vapor swelling of thin polymer films. From these interaction parameters, we constructed a polymer/polymer/solvent phase diagram. The phase diagram was validated experimentally with solution-based transmission measurements of PS/P3HT. This work highlights a method to determine the phase behavior in polymer/polymer/solvent blends that can be extended to other combinations of macromolecules relevant to organic photovoltaics, composites, and other materials systems.

  10. Phase behavior and rheological characterization of silica nanoparticle gel

    NASA Astrophysics Data System (ADS)

    Metin, Cigdem O.; Rankin, Kelli M.; Nguyen, Quoc P.

    2014-01-01

    Preferential injection into high permeability thief zones or fractures can result in early breakthrough at production wells and large unswept areas of high oil saturation, which impact the economic life of a well. A variety of conformance control techniques, including polymer and silica gel treatments, have been designed to block flow through the swept zones. Over a certain range of salinities, silica nanoparticle suspensions form a gel in bulk phase behavior tests. These gels have potential for in situ flow diversion, but in situ flow tests are required to determine their applicability. To determine the appropriate scope of the in situ tests, it is necessary to obtain an accurate description of nanoparticle phase behavior and gel rheology. In this paper, the equilibrium phase behavior of silica nanoparticle solutions in the presence of sodium chloride (NaCl) is presented with four phase regions classified as a function of salinity and nanoparticle concentration. Once the gelation window was clearly defined, rheology experiments of silica nanoparticle gels were also carried out. Gelation time decreases exponentially as a function of silica concentration, salinity, and temperature. Following a power law behavior, the storage modulus, G', increases with particle concentration. Steady shear measurements show that silica nanoparticle gels exhibit non-Newtonian, shear thinning behavior. This comprehensive study of the silica nanoparticle gels has provided a clear path forward for in situ tests to determine the gel's applicability for conformance control operations.

  11. Molecular Simulation of Olefin Oligomer Blend Phase Behavior

    NASA Astrophysics Data System (ADS)

    Chen, Qile; Lodge, Timothy; Siepmann, Ilja; Mrsec Collaboration

    Material properties (e.g. toughness) of polyolefin mixtures are closely tied to their phase behavior that often cannot be accurately predicted by the widely used Flory-Huggins (FH) theory. In this work, configurational-bias Monte Carlo (CBMC) simulations in the Gibbs ensemble were used to compute the phase behavior of oligomeric olefins. The cohesive energy density of pure melts and the free energy of mixing were obtained from these simulations, and the discrepancy between the binary interaction χ parameter from simulation and from the FH theory was quantified. Structural analysis and the calculated excess mixing properties provided some rationale into the interpretation of these results.

  12. Density, phase behavior keys to acid gas injection

    SciTech Connect

    Carroll, J.J.; Lui, D.W.

    1997-06-23

    Acid gas injection requires an understanding of the complexities of gas phase behavior and physical properties. Injected acid gas streams typically come from the top of the regenerator reflux accumulator of an amine unit. Thus, they are composed mainly of hydrogen sulfide (H{sub 2}S) and carbon dioxide (CO{sub 2}) with significant amounts of methane and lesser amounts of other hydrocarbons. The stream is also saturated with water. The stream from the amine plant has a low pressure and must be compressed to a higher pressure for injection into a disposal well. This article summarizes the available research on acid gas phase behavior and density calculations.

  13. Heterogeneous adsorption behavior of landfill leachate on granular activated carbon revealed by fluorescence excitation emission matrix (EEM)-parallel factor analysis (PARAFAC).

    PubMed

    Lee, Sonmin; Hur, Jin

    2016-04-01

    Heterogeneous adsorption behavior of landfill leachate on granular activated carbon (GAC) was investigated by fluorescence excitation-emission matrix (EEM) combined with parallel factor analysis (PARAFAC). The equilibrium adsorption of two leachates on GAC was well described by simple Langmuir and Freundlich isotherm models. More nonlinear isotherm and a slower adsorption rate were found for the leachate with the higher values of specific UV absorbance and humification index, suggesting that the leachate containing more aromatic content and condensed structures might have less accessible sites of GAC surface and a lower degree of diffusive adsorption. Such differences in the adsorption behavior were found even within the bulk leachate as revealed by the dissimilarity in the isotherm and kinetic model parameters between two identified PARAFAC components. For both leachates, terrestrial humic-like fluorescence (C1) component, which is likely associated with relatively large sized and condensed aromatic structures, exhibited a higher isotherm nonlinearity and a slower kinetic rate for GAC adsorption than microbial humic-like (C2) component. Our results were consistent with size exclusion effects, a well-known GAC adsorption mechanism. This study demonstrated the promising benefit of using EEM-PARAFAC for GAC adsorption processes of landfill leachate through fast monitoring of the influent and treated leachate, which can provide valuable information on optimizing treatment processes and predicting further environmental impacts of the treated effluent.

  14. Liquid Phase adsorption kinetics and equilibrium of toluene by novel modified-diatomite.

    PubMed

    Sheshdeh, Reza Khalighi; Abbasizadeh, Saeed; Nikou, Mohammad Reza Khosravi; Badii, Khashayar; Sharafi, Mohammad Sadegh

    2014-01-01

    The adsorption equilibria of toluene from aqueous solutions on natural and modified diatomite were examined at different operation parameters such as pH, contact time, initial toluene concentration was evaluated and optimum experimental conditions were identified. The surface area and morphology of the nanoparticles were characterized by SEM, BET, XRD, FTIR and EDX analysis. It was found that in order to obtain the highest possible removal of toluene, the experiments can be carried out at pH 6, temperature 25°C, an agitation speed of 200 rpm, an initial toluene concentration of 150 mg/L, a centrifugal rate of 4000 rpm, adsorbent dosage = 0.1 g and a process time of 90 min. The results of this work show that the maximum percentage removal of toluene from aqueous solution in the optimum conditions for NONMD was 96.91% (145.36 mg/g). Furthermore, under same conditions, the maximum adsorption of natural diatomite was 71.45% (107.18 mg/g). Both adsorption kinetic and isotherm experiments were carried out. The experimental data showed that the adsorption follows the Langmuir model and Freundlich model on natural and modified diatomite respectively. The kinetics results were found to conform well to pseudo-second order kinetics model with good correlation. Thus, this study demonstrated that the modified diatomite could be used as potential adsorbent for removal of toluene from aqueous solution.

  15. Final Report on Phase III Testing of Monosodium Titanate Adsorption Kinetics

    SciTech Connect

    Hobbs, D.T.

    1999-09-29

    This study consisted of a statistically designed set of tests to determine the extent and rate of adsorption of strontium, plutonium, uranium, and neptunium as a function of temperature, monosodium titanate (MST) concentration, and concentrations of sodium, strontium, plutonium, uranium, and neptunium.

  16. Stimulatory effect and adsorption behavior of rhamnolipids on lignocelluloses degradation system.

    PubMed

    Hou, Jinju; Zhang, Shudong; Qiu, Zhen; Han, Hui; Zhang, Qiuzhuo

    2017-01-01

    Di-rhamnolipid and mixed rhamnolipid were added to rice straw degrading system to investigate their mechanism of stimulatory effect. By batch adsorption experiments, it was shown that the equilibrium adsorption time of rhamnolipids on rice straw single system was the shortest (50min). The adsorption capacity of Trichoderma reesei single system was the strongest, whose Qe,exp for di-rhamnolipid and mixed rhamnolipid was 10.57×10(-2)mg·g(-1) and 8.13×10(-2)mg·g(-1), respectively. The adsorption of rhamnolipids on consortia system was not the simple adduct of the two single systems. The adsorption of rhamnolipids on the three different systems might belong to chemisorptions. SEM and FTIR analyses were used to observe the morphology and to analyze the chemical functions in lignocellulosic biomass degradation with rhamnolipid. It was shown that after addition of rhamnolipids, the basic tissue in rice straw was severely destroyed and hydrogen bond was formed between biosurfactant and bacteria in lignocellulose degrading system.

  17. Adsorption behavior and mechanism of Cr(VI) using Sakura waste from aqueous solution

    NASA Astrophysics Data System (ADS)

    Qi, Wenfang; Zhao, Yingxin; Zheng, Xinyi; Ji, Min; Zhang, Zhenya

    2016-01-01

    A forestall waste, Sakura leave, has been studied for the adsorption of Cr(VI) from aqueous solution. The materials before and after adsorption were characterized by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). To investigate the adsorption performance of Sakura waste, batch experiments were conducted under different adsorbent dosage, contact time, initial concentration of Cr(VI), and co-existing ions. Results showed the data fitted pseudo-second-order better than pseudo-first-order kinetic model. Equilibrium data was analyzed with Langmuir, Freundlich and Redlich-Peterson isotherm models at temperature ranges from 25 °C to 45 °C. The maximum adsorption capacity from the Langmuir model was 435.25 mg g-1 at pH 1.0. The presence of Cl-, SO42- and PO43- would lead to an obvious negative effect on Cr(VI) adsorption, and their influence order follows PO43- > SO42- > Cl-. The study developed a new way to reutilize wastes and showed a great potential for resource recycling.

  18. Removal of gas phase low-concentration toluene over Mn, Ag and Ce modified HZSM-5 catalysts by periodical operation of adsorption and non-thermal plasma regeneration.

    PubMed

    Wang, Wenzheng; Wang, Honglei; Zhu, Tianle; Fan, Xing

    2015-07-15

    Ag/HZSM-5, Mn/HZSM-5, Ce/HZSM-5, Ag-Mn/HZSM-5 and Ce-Mn/HZSM-5 were prepared by impregnation method. Both their adsorption capacity and catalytic activity were investigated for the removal of gas phase low-concentration toluene by periodical operation of adsorption and non-thermal plasma regeneration. Results show that catalysts loaded with Ag (Ag/HZSM-5 and Ag-Mn/HZSM-5) had larger adsorption capacity for toluene than the other catalysts. And Ag-Mn/HZSM-5 displayed the best catalytic performance for both toluene oxidation by non-thermal plasma and byproducts suppression. On the other hand, the deactivated catalyst can be fully regenerated by calcining in air stream when its adsorption capacity and catalytic activity of the Ag-Mn/HZSM-5 catalyst was found to be decreased after 10 cycles of periodical adsorption and non-thermal regeneration.

  19. Tuning the Adsorption-Induced Phase Change in the Flexible Metal-Organic Framework Co(bdp).

    PubMed

    Taylor, Mercedes K; Runčevski, Tomče; Oktawiec, Julia; Gonzalez, Miguel I; Siegelman, Rebecca L; Mason, Jarad A; Ye, Jinxing; Brown, Craig M; Long, Jeffrey R

    2016-11-16

    Metal-organic frameworks that flex to undergo structural phase changes upon gas adsorption are promising materials for gas storage and separations, and achieving synthetic control over the pressure at which these changes occur is crucial to the design of such materials for specific applications. To this end, a new family of materials based on the flexible metal-organic framework Co(bdp) (bdp(2-) = 1,4-benzenedipyrazolate) has been prepared via the introduction of fluorine, deuterium, and methyl functional groups on the bdp(2-) ligand, namely, Co(F-bdp), Co(p-F2-bdp), Co(o-F2-bdp), Co(D4-bdp), and Co(p-Me2-bdp). These frameworks are isoreticular to the parent framework and exhibit similar structural flexibility, transitioning from a low-porosity, collapsed phase to high-porosity, expanded phases with increasing gas pressure. Powder X-ray diffraction studies reveal that fluorination of the aryl ring disrupts edge-to-face π-π interactions, which work to stabilize the collapsed phase at low gas pressures, while deuteration preserves these interactions and methylation strengthens them. In agreement with these observations, high-pressure CH4 adsorption isotherms show that the pressure of the CH4-induced framework expansion can be systematically controlled by ligand functionalization, as materials without edge-to-face interactions in the collapsed phase expand at lower CH4 pressures, while frameworks with strengthened edge-to-face interactions expand at higher pressures. Importantly, this work puts forth a general design strategy relevant to many other families of flexible metal-organic frameworks, which will be a powerful tool in optimizing these phase-change materials for industrial applications.

  20. Thermorheologically complex behavior of multi-phase viscoelastic materials

    NASA Astrophysics Data System (ADS)

    Brinson, L. C.; Knauss, W. G.

    T HE DYNAMIC correspondence principle of viscoelasticity is used to study the nature of time-temperature behavior of multi-phase composites by means of finite element computation. The composite considered contains viscoelastic inclusions embedded in a viscoelastic matrix. Each phase of the composite is considered to be thermorheologically simple, but the resulting mechanical properties of the composite are thermorheologically complex. The deviation of the composite moduli from thermorheologically simple behavior of the matrix material is shown to occur at frequencies and temperatures where the glass-to-rubber transition of the included phases are reached. Properties of a styrene-butadiene-styrene (SBS) block copolymer are investigated based on the individual phase properties of polystyrene and polybutadiene. To achieve congruence of the results with experimental data, it is necessary to consider a transition phase of properties "intermediate" to those of polystyrene and polybutadiene. Using accurate physical information on the individual phase properties and on the interphase region, it is possible to predict properties of multiphase composites. Although detailed a priori knowledge of such an interphase is usually lacking, it is shown that the computational procedure presented here together with an extended range of test frequencies will aid in estimating the properties of the phase in question.

  1. Phase Transition Behavior in a Neutral Evolution Model

    NASA Astrophysics Data System (ADS)

    King, Dawn; Scott, Adam; Maric, Nevena; Bahar, Sonya

    2014-03-01

    The complexity of interactions among individuals and between individuals and the environment make agent based modeling ideal for studying emergent speciation. This is a dynamically complex problem that can be characterized via the critical behavior of a continuous phase transition. Concomitant with the main tenets of natural selection, we allow organisms to reproduce, mutate, and die within a neutral phenotype space. Previous work has shown phase transition behavior in an assortative mating model with variable fitness landscapes as the maximum mutation size (μ) was varied (Dees and Bahar, 2010). Similarly, this behavior was recently presented in the work of Scott et al. (2013), even on a completely neutral landscape, for bacterial-like fission as well as for assortative mating. Here we present another neutral model to investigate the `critical' phase transition behavior of three mating types - assortative, bacterial, and random - in a phenotype space as a function of the percentage of random death. Results show two types of phase transitions occurring for the parameters of the population size and the number of clusters (an analogue of species), indicating different evolutionary dynamics for system survival and clustering. This research was supported by funding from: University of Missouri Research Board and James S. McDonnell Foundation.

  2. Phase behavior of coal fluids: Data for correlation development

    SciTech Connect

    Robinson, R.J. Jr.; Gasem, K.A.M.; Shaver, R.D.

    1990-01-01

    The effective design and operation of processes for conversion of coal to fluid fuels requires accurate knowledge of the phase behavior of the fluid mixtures encountered in the conversion process. The overall objective of the author's work is to develop accurate predictive methods for representation of vapor-liquid equilibria in systems encountered in coal conversion processes. The objectives of the present project include: (1) measurements of binary vapor-liquid phase behavior data for selected solute gases (e.g. CO{sub 2} and C{sub 2}H{sub 6}) in a series of heavy hydrocarbon solvents to permit evaluation of interaction parameters in models for phase behavior, (2) measurements on ternary systems in which high-melting-point solvents are dissolved in more volatile aromatics to provide mixed solvents, (3) evaluation of existing equations-of-state and other models for representation of phase behavior in systems of the type studied experimentally; development of new correlation frameworks as needed, and (4) generalization of the interaction parameters for the solutes studied to a wide spectrum of heavy solvents; presentations of final results in formats useful in the design/optimization of coal liquefaction processes. This quarter, our framework for correlating saturation properties using a scaled-variable-reduced-coordinate'' approach was further developed to provide for generalized vapor pressure predictions. 59 refs., 6 figs., 8 tabs.

  3. Synthesis of magnetic epichlorohydrin cross-linked carboxymethyl cellulose microspheres and their adsorption behavior for methylene blue.

    PubMed

    Lin, Qingwen; Chang, Jiali; Gao, Mengfan; Ma, Hongzhu

    2017-01-28

    Epichlorohydrin cross-linked carboxymethyl cellulose microspheres (ECH/CMC) obtained by inverse suspension method and magnetic Fe3O4 nanoparticles encasing the ECH/CMC microspheres (M-ECH/CMC) obtained by two different methods were successfully prepared and compared. Their structures and morphologies were analyzed using polarizing microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The adsorption behaviors of M1-ECH/CMC for methylene blue (MB) in the single cationic dye wastewater, the cationic/anionic dye mixture in the absence or presence of co-existed additives (salt and surfactant) wastewater, were also investigated with UV-vis spectrometer. The results showed that the magnetic Fe3O4 nanoparticles were loaded readily in situ into ECH/CMC by specific, chemical interactions between COO(-) groups of ECH/CMC and magnetic responsive Fe3O4. The Langmuir isotherm and pseudo-second-order kinetic model provide best correlation with the experimental data for the adsorption of MB onto ECH/CMC and M1-ECH/CMC microspheres, while the Langmuir isotherm and pseudo-first-order kinetic model for M2-ECH/CMC. These microspheres are easily recyclable and exhibit high desorption and adsorption, which suggests that they can be applied as potential environmental adsorbents.

  4. Adsorption mechanism in reversed-phase liquid chromatography. Effect of the surface coverage of a monomeric C18-silica stationary phase

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2006-04-01

    The effect of the bonding density of the octadecyl chains onto the same silica on the adsorption and retention properties of low molecular weight compounds (phenol, caffeine, and sodium 2-naphthalene sulfonate) was investigated. The same mobile phase (methanol:water, 20:80, v/v) and temperature (T = 298 K) were applied and two duplicate columns (A and B) from each batch of packing material (neat silica, simply endcapped or C{sub 1} phase, 0.42, 1.01, 2.03, and 3.15 {micro}mol/m{sup 2} of C{sub 18} alkyl chains) were tested. Adsorption data of the three compounds were acquired by frontal analysis (FA) and the adsorption energy distributions (AEDs) were calculated using the expectation-maximization method. Results confirmed earlier findings in linear chromatography of a retention maximum at an intermediate bonding density. From a general point of view, the saturation capacity of the adsorbent tends to decrease with increasing bonding density, due to the vanishing space intercalated between the C{sub 18} bonded chains and to the decrease of the specific surface area of the stationary phase. The equilibrium constants are maximum for an intermediary bonding density ({approx}2 {micro}mol/m{sup 2}). An enthalpy-entropy compensation was found for the thermodynamic parameters of the isotherm data. Weak equilibrium constants (small {Delta}H) and high saturation capacities (large {Delta}S) were observed at low bonding densities, higher equilibrium constants and lower saturation capacities at high bonding densities, the combinations leading to similar apparent retention in RPLC. The use of a low surface coverage column is recommended for preparative purposes.

  5. Removal of Pb(II) from aqueous solution by hydrous manganese dioxide: adsorption behavior and mechanism.

    PubMed

    Xu, Meng; Wang, Hongjie; Di, Lei; Qu, Dan; Zhai, Yujia; Wang, Yili

    2013-03-01

    Hydrous manganese dioxide (HMO) synthesized by redox of potassium permanganate and hydrogen peroxide was used as an adsorbent for Pb(II) removal. The specific surface area, pore volume and BJH pore diameter of the HMO were 79.31 m2/g, 0.07 cm3/g and 3.38 nm, respectively. The adsorption equilibrium at 298 K could be well described by the Langmuir isotherm equation with qmax value of 352.55 mg/g. The negative values of deltaG and the positive values of deltaH and deltaS indicated the adsorption process was spontaneous and endothermic. The pseudo second-order equation could best fit the adsorption data. The value of the calculated activation energy for Pb(II) adsorption onto the HMO was 38.23 kJ/mol. The uptake of Pb(II) by HMO was correlated with increasing surface hydroxyl group content and the main adsorbed speciation was PbOH+. The final chemical state of Pb(II) on the surface of HMO was similar to PbO. HMO was a promising candidate for Pb(II) removal from aqueous solution.

  6. Adsorption behavior comparison of trivalent and hexavalent chromium on biochar derived from municipal sludge.

    PubMed

    Chen, Tan; Zhou, Zeyu; Xu, Sai; Wang, Hongtao; Lu, Wenjing

    2015-08-01

    In this work, static equilibrium experiments were conducted to distinguish the adsorption performance between the two valence states of chromium on biochar derived from municipal sludge. The removal capacity of Cr(VI) is lower than 7mg/g at the initial chromium concentration range of 50-200mg/L, whereas that of Cr(III) higher than 20mg/g. It indicates that Cr(III) is much easier to be stabilized than Cr(VI). No significant changes in the biochar surface functional groups are observed before and after the adsorption equilibrium, demonstrating the poor contribution of organic matter in chromium adsorption. The main mechanism of heavy metal adsorption by biochar involves (1) surface precipitation through pH increase caused by biochar buffer ability, and (2) exchange between cations in solution (Cd(2+)) and in biochar matrix (e.g. Ca(2+) and Mg(2+)). The reduction of Cr(VI) to Cr(III) is necessary to improve removal efficiency of chromium.

  7. On the potential of phase-change adsorbents for CO2 capture by temperature swing adsorption.

    PubMed

    Hefti, Max; Joss, Lisa; Bjelobrk, Zoran; Mazzotti, Marco

    2016-10-20

    We investigate the potential of a class of recently discovered metal-organic-framework materials for their use in temperature swing adsorption (TSA) processes for CO2 capture; the particularity of the considered materials is their reversible and temperature dependent step-shaped CO2 adsorption isotherm. Specifically, we present a comprehensive modeling study, where the performance of five different materials with step-shaped isotherms [McDonald et al., Nature, 2015, 519, 303] in a four step TSA cycle is assessed. The specific energy requirement of the TSA process operated with these materials is lower than for a commercial 13X zeolite, and a smaller temperature swing is required to reach similar levels of CO2 purity and recovery. The effect of a step in the adsorption isotherm is illustrated and discussed, and design criteria that lead to an optimal and robust operation of the considered TSA cycle are identified. The presented criteria could guide material scientists in designing novel materials whose step position is tailored to specific CO2 separation tasks.

  8. Enthalpy-entropy compensation effect on adsorption of light hydrocarbons on monolithic stationary phases.

    PubMed

    Korolev, Alexander A; Shiryaeva, Valeria E; Popova, Tamara P; Kurganov, Alexander A

    2011-08-01

    Enthalpy and entropy of adsorption of light hydrocarbons C1-C4 have been measured for three monoliths of different polarity and for five different carrier gases: helium, hydrogen, nitrogen, carbon dioxide and dinitrogen oxide. Using carrier gas helium the highest values of enthalpy and entropy were observed for monolith based on ethylenedimethacrylate and the lowest values were observed for monolith based on silica, while monolith based on divinylbenzene demonstrated intermediate values. Entropy-enthalpy correlations were observed with carrier gas helium for all thee monoliths and possess similar slope indicating similar adsorption mechanism on all monoliths studied. Comparing different carrier gases entropy-enthalpy correlations within a homological series of solutes were observed for light carrier gases (He, H2 and N2) and were not observed for heavy carrier gases (CO2 and N2O). Instead, entropy-enthalpy correlations for heavy carrier gases were observed with pressure as variable and the higher the carrier gas pressure the lower the values of enthalpy and entropy observed. The observed changes in entropy-enthalpy correlations were explained by competitive adsorption of heavy carrier gas on monoliths.

  9. Adsorption Behavior of Cellulose and Its Derivatives toward Ag(I) in Aqueous Medium: An AFM, Spectroscopic, and DFT Study.

    PubMed

    Zhu, Chuantao; Dobryden, Illia; Rydén, Jens; Öberg, Sven; Holmgren, Allan; Mathew, Aji P

    2015-11-17

    The aim of this study was to develop a fundamental understanding of the adsorption behavior of metal ions on cellulose surfaces using experimental techniques supported by computational modeling, taking Ag(I) as an example. Force interactions among three types of cellulose microspheres (native cellulose and its derivatives with sulfate and phosphate groups) and the silica surface in AgNO3 solution were studied with atomic force microscopy (AFM) using the colloidal probe technique. The adhesion force between phosphate cellulose microspheres (PCM) and the silica surface in the aqueous AgNO3 medium increased significantly with increasing pH while the adhesion force slightly decreased for sulfate cellulose microspheres (SCM), and no clear adhesion force was observed for native cellulose microspheres (CM). The stronger adhesion enhancement for the PCM system is mainly attributed to the electrostatic attraction between Ag(I) and the negative silica surface. The observed force trends were in good agreement with the measured zeta potentials. The scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) analyses confirmed the presence of silver on the surface of cellulose microspheres after adsorption. This study showed that PCM with a high content of phosphate groups exhibited a larger amount of adsorbed Ag(I) than CM and SCM and possible clustering of Ag(I) to nanoparticles. The presence of the phosphate group and a wavenumber shift of the P-OH vibration caused by the adsorption of silver ions on the phosphate groups were further confirmed with computational studies using density functional theory (DFT), which gives support to the above findings regarding the adsorption and clustering of Ag(I) on the cellulose surface decorated with phosphate groups as well as IR spectra.

  10. Markedly different adsorption behaviors of gas molecules on defective monolayer MoS2: a first-principles study.

    PubMed

    Li, Hongxing; Huang, Min; Cao, Gengyu

    2016-06-01

    Sulfur vacancy (SV) is one of the most typical defects in two-dimensional monolayer MoS2, leading to reactive sites. We presented a systematic study of the adsorption behaviors of gas molecules, CO2, N2, H2O, CO, NH3, NO, O2, H2 and NO2, on monolayer MoS2 with single SV by first-principles calculations. It was found that CO2, N2 and H2O molecules physisorbed at the proximity of single SV. Our adsorption energy calculations and charge transfer analysis showed that the interactions between CO2, N2 and H2O molecules and defective MoS2 are stronger than the cases of CO2, N2 and H2O molecules adsorbed on pristine MoS2, respectively. The defective MoS2 based gas sensors may be more sensitive to CO2, N2 and H2O molecules than pristine MoS2 based ones. CO, NO, O2 and NH3 molecules were found to chemisorb at the S vacancy site and thus modify the electronic properties of defective monolayer MoS2. Magnetism was induced upon adsorption of NO molecules and the defective states induced by S vacancy can be completely removed upon adsorption of O2 molecules, which may provide some helpful information for designing new MoS2 based nanoelectronic devices in future. The H2 and NO2 molecules were found to dissociate at S vacancy. The dissociation of NO2 molecules resulted in O atoms located at the S vacancy site and NO molecules physisorbed on O-doped MoS2. The calculated results showed that NO2 molecules can help heal the S vacancy of the MoS2 monolayer.

  11. Adsorption and attenuation behavior of 3-nitro-1,2,4-triazol-5-one (NTO) in eleven soils.

    PubMed

    Mark, Noah; Arthur, Jennifer; Dontsova, Katerina; Brusseau, Mark; Taylor, Susan

    2016-02-01

    NTO (3-nitro-1,2,4-triazol-5-one) is one of the new explosive compounds used in insensitive munitions (IM) developed to replace traditional explosives, TNT and RDX. Data on NTO fate and transport is needed to determine its environmental behavior and potential for groundwater contamination. We conducted a series of kinetic and equilibrium batch experiments to characterize the fate of NTO in soils and the effect of soil geochemical properties on NTO-soil interactions. A set of experiments was also conducted using sterilized soils to evaluate the contribution of biodegradation to NTO attenuation. Measured pH values for NTO solutions decreased from 5.98 ± 0.13 to 3.50 ± 0.06 with increase in NTO concentration from 0.78 to 100 mg L(-1). Conversely, the pH of soil suspensions was not significantly affected by NTO in this concentration range. NTO experienced minimal adsorption, with measured adsorption coefficients being less than 1 cm(3) g(-1) for all studied soils. There was a highly significant inverse relationship between the measured NTO adsorption coefficients and soil pH (P = 0.00011), indicating the role of NTO and soil charge in adsorption processes. In kinetic experiments, 1st order transformation rate constant estimates ranged between 0.0004 h(-1) and 0.0142 h(-1) (equivalent to half-lives of 72 and 2 d, respectively), and correlated positively with organic carbon in the soil. Total attenuation of NTO was higher in untreated versus sterilized samples, suggesting that NTO was being biodegraded. The information presented herein can be used to help evaluate NTO potential for natural attenuation in soils.

  12. Adsorption behavior of pesticide methomyl on activated carbon in a high gravity rotating packed bed reactor.

    PubMed

    Chang, Chiung-Fen; Lee, Shu-Chi

    2012-06-01

    High gravity rotating packed bed (HGRPB) reactor possesses the property of high mass transfer rate, which is expected to promote the adsorption rate for the process. In this study, HGRPB has been applied on adsorption removal of methomyl from solution, adopting the adsorbent of activated carbon F400. The influence of operating parameters of HGRPB on mass transfer such as the rotating speed (N(R)), the flow rate of solution (F(L)) and initial concentration of methomyl (C(b0)) were examined. The traditionally internal mass transfer models combined with Freundlich isotherm were used to predict the surface and effective diffusion coefficients. In addition, the results have also been compared with those obtained from the traditional basket stirred batch reactor (BBR). The results showed that the larger values of N(R) and F(L) enhanced the effective intraparticle diffusion and provided more accessible adsorption sites so as to result in lower equilibrium concentration in HGRPB system when compared to SBR system. The results of adsorption kinetics demonstrated that surface and effective diffusions were both significantly greater in HGRPB system instead of BBR system. Furthermore, the values of Bi(S) also manifested less internal mass transfer resistance in HGRPB system. The contribution ratio (R(F)) of the surface to pore diffusion mass transport showed that the larger contribution resulted from the surface diffusion in HGRPB system. Therefore, the results reasonably led to the conclusion that when the HGRPB system applied on the adsorption of methomyl on F400, the lower equilibrium concentration and faster internal mass transfer can be obtained so as to highly possess great potential to match the gradually stricter environmental standard.

  13. Adsorption of ethanol and water on calcite: dependence on surface geometry and effect on surface behavior.

    PubMed

    Keller, K S; Olsson, M H M; Yang, M; Stipp, S L S

    2015-04-07

    Molecular dynamics (MD) simulations were used to explore adsorption on calcite, from a 1:1 mixture of ethanol and water, on planar {10.4} and stepped, i.e. vicinal, surfaces. Varying the surface geometry resulted in different adsorption patterns, which would directly influence the ability of ethanol to control calcite crystal growth, dissolution, and adsorption/desorption of other ions and molecules. Ethanol forms a well-ordered adsorbed layer on planar faces and on larger terraces, such as between steps and defects, providing little chance for water, with its weaker attachment, to displace it. However, on surfaces with steps, adsorption affinity depends on the length of the terraces between the steps. Long terraces allow ethanol to form a well-ordered, hydrophobic layer, but when step density is high, ethanol adsorption is less ordered, allowing water to associate at and near the steps and even displacing pre-existing ethanol. Water adsorbed at steps forms mass transport pathways between the bulk solution and the solid surface. Our simulations confirm the growth inhibiting properties of ethanol, also explaining how certain crystal faces are more stabilized because of their surface geometry. The -O(H) functional group on ethanol forms tight bonds with calcite; the nonpolar, -CH3 ends, which point away from the surface, create a hydrophobic layer that changes surface charge, thus wettability, and partly protects calcite from precipitation and dissolution. These tricks could easily be adopted by biomineralizing organisms, allowing them to turn on and off crystal growth. They undoubtedly also play a role in the wetting properties of mineral surfaces in commercial CaCO3 manufacture, oil production, and contamination remediation.

  14. Separation of phenolic compounds with modified adsorption resin from aqueous phase products of hydrothermal liquefaction of rice straw.

    PubMed

    Chen, Kaifei; Lyu, Hang; Hao, Shilai; Luo, Gang; Zhang, Shicheng; Chen, Jianmin

    2015-04-01

    Hydrothermal liquefaction can be used to convert rice straw into an aqueous phase product that contains valuable phenolic compounds. In experiments, commercial adsorption resin XAD-4 was modified by a benzene ring - α,α'-dichloro-p-xylene (DCX) - in order to separate the phenolic compounds from the aqueous phase product; and, the optimal conditions for separation were explored. The results showed that, after modification of the resin, its adsorption capacity improved by 50%, due to increases in surface area, pore volume and micropore volume. The selectivity of the resin increased when the benzene ring was introduced as the ring formed hydrogen bonds with the compounds. The optimal conditions for separation were desorption agent of 40%, 45% and 55% ethanol solution, a flow rate of 2.5-5 mL/min, and a ratio of the sample volume to the column volume was 1:1. The total content of phenolic compounds in aqueous solution increased from 18% to 78% after separation.

  15. Different Adsorption Behavior of Rare Earth and Metallic Ion Complexes on Langmuir Mono layers Probed by Sum-Frequency Generation Spectroscopy

    SciTech Connect

    Song, Woongmo; Vaknin, David; Kim, Doseok

    2013-02-25

    Adsorption behavior of counterions under a Langmuir monolayer was investigated by sum-frequency generation (SFG) spectroscopy. By comparing SFG spectra of arachidic acid (AA) Langmuir monolayer/water interface with and without added salt, it was found that the simple trivalent cation La3+ adsorbed on AA monolayer only when the carboxylic headgroups are charged (deprotonated), implying that counterion adsorption is induced by Coulomb interaction. On the other hand, metal hydroxide complex Fe(OH)3 adsorbed even on a charge-neutral AA monolayer, indicating that the adsorption of iron hydroxide is due to chemical interaction such as covalent or hydrogen bonding to the headgroup of the molecules at the monolayer.

  16. Phase Behavior of Ternary Polymer Blends: Asymmetry, Segregation Strength, and Coexisting Phases

    NASA Astrophysics Data System (ADS)

    Habersberger, Brian McLean

    The bicontinuous microemulsion phase, found in ternary polymer blends containing immiscible A and B homopolymers and an amphiphilic A-B diblock copolymer, has attracted interest due to its combination of properties that make it attractive for use as a template for nanoporous materials. While recent work has demonstrated that a variety of materials can be templated from a single blend system, future work may demand incorporation of a variety of polymers into microemulsion-forming blends. Such systems fall beyond the currently understood model phase behavior for ternary blends. In this thesis, the effect of well-controlled nonidealities and other extensions of ternary blend phase behavior are described. Systems were designed to investigate the influence of conformational asymmetry---a difference in the radius of gyration per molar volume of two polymers---on blend phase behavior. Previous work suggested that the influence was significant, and resulted in a broad region of a hexagonally symmetric phase in the vicinity of the microemulsion. This behavior could inhibit the process of capturing of microemulsion for templating purposes, so it is important to understand conformational asymmetry's influence. A related series of systems was designed to investigate the effect of increased segregation strength by using amphiphilic diblocks of varying molecular weight. Finally, a previous study incorporating an ABA triblock, C homopolymer, and ABABA--C amphiphilic hexablock was expanded to incorporate ordered components, allowing for hierarchical microphase separation. This study demonstrates that model ternary blend phase behavior can be extended to systems containing more complex linear polymer architectures. Additionally, two phenomena observed in these systems were investigated in detail. First, light scattering was observed in the vicinity of the order-disorder transition of blends; this scattering is a result of coexisting ordered and disordered phases. Finally, catalytic

  17. Application of Phase Field Simulations to Fuel Behavior

    SciTech Connect

    Radhakrishnan, Balasubramaniam; Gorti, Sarma B; Clarno, Kevin T

    2015-01-01

    The application of the phase filed method to simulate the formation and the stress induced re-orientation of zirconium hydride during dry storage of the spent fuel and clad assembly is discussed. The phase field technique is able to capture qualitatively the effect of external stress on the hydride orientation in Zr-H system. However, the modeling effort to-date is far from adequate and several issues remain to be addressed before the simulations can be used as a predictive tool for the behavior of the clad during long time dry storage.

  18. Phase behaviors of polymer solutions using molecular simulation technique.

    PubMed

    Yang, Jung Ho; Bae, Young Chan

    2008-08-14

    Phase behaviors of polymer solutions are estimated using a combination of thermodynamic models and molecular simulation technique. In general, many parameters of binary systems are determined by fitting a thermodynamic model with experimental data. In this study, we obtained all parameters using molecular simulation. To take the specific interaction into account, we assume that it only occurs between a solvent molecule and a specific group. Our results show that the theoretical treatment accounting for the specific interaction gives more accurate predictions than those without consideration of specific interaction. Also, our approach describes the phase equilibria of various polymer solutions over the entire concentration remarkably well.

  19. Adsorption of nickel on husk of Lathyrus sativus: behavior and binding mechanism.

    PubMed

    Panda, G C; Das, S K; Bandopadhyay, T S; Guha, A K

    2007-06-15

    Husk of Lathyrus sativus (HLS) has been found to be a good sorbent for the removal of nickel(II) from its aqueous solution. The adsorption process depends on pH of the solution with an optimum at 5.0, and follows Langmuir isotherm model (correlation coefficient 0.998). Initial adsorption rate is very fast and reaches equilibrium following pseudo-second order kinetics within 60 min. Amino, carboxyl, hydroxyl and phosphate groups of the biomass are involved in chemical interaction with nickel ions as revealed from SEM-EDX and FTIR studies. Chemical modifications of the functional groups of the biosorbent show that amino groups contribute largely (approximately 57%) for the binding of nickel ions and probably undergo chelation through dative bond formation. HLS biomass has been found to adsorb both nickel and cadmium equally from their mixed solution to the extent of approximately 70% indicating the importance of this sorbent in industrial effluent treatment.

  20. Breakthrough behavior of granular ferric hydroxide (GFH) fixed-bed adsorption filters: modeling and experimental approaches.

    PubMed

    Sperlich, Alexander; Werner, Arne; Genz, Arne; Amy, Gary; Worch, Eckhard; Jekel, Martin

    2005-03-01

    Breakthrough curves (BTC) for the adsorption of arsenate and salicylic acid onto granulated ferric hydroxide (GFH) in fixed-bed adsorbers were experimentally determined and modeled using the homogeneous surface diffusion model (HSDM). The input parameters for the HSDM, the Freundlich isotherm constants and mass transfer coefficients for film and surface diffusion, were experimentally determined. The BTC for salicylic acid revealed a shape typical for trace organic compound adsorption onto activated carbon, and model results agreed well with the experimental curves. Unlike salicylic acid, arsenate BTCs showed a non-ideal shape with a leveling off at c/c0 approximately 0.6. Model results based on the experimentally derived parameters over-predicted the point of arsenic breakthrough for all simulated curves, lab-scale or full-scale, and were unable to catch the shape of the curve. The use of a much lower surface diffusion coefficient D(S) for modeling led to an improved fit of the later stages of the BTC shape, pointing on a time-dependent D(S). The mechanism for this time dependence is still unknown. Surface precipitation was discussed as one possible removal mechanism for arsenate besides pure adsorption interfering the determination of Freundlich constants and D(S). Rapid small-scale column tests (RSSCT) proved to be a powerful experimental alternative to the modeling procedure for arsenic.

  1. Adsorption behavior of a textile dye of Reactive Blue 19 from aqueous solutions onto modified bentonite

    NASA Astrophysics Data System (ADS)

    Gök, Özer; Özcan, A. Safa; Özcan, Adnan

    2010-06-01

    The aim of this study is to evaluate adsorption kinetics, isotherms and thermodynamic parameters of Reactive Blue 19 (RB19) onto modified bentonite from aqueous solutions. The effects of pH, contact time, initial dye concentration and temperature were investigated in the experimentally. Natural bentonite was modified by using 1,6-diamino hexane (DAH) as a modifying agent. The characterization of modified bentonite (DAH-bentonite) was accomplished by using FTIR, TGA, BET and elemental analysis techniques. The optimum pH value for the adsorption experiments was found to be 1.5 and all the experiments were carried out at this pH value. The pseudo-second-order kinetic model agrees very well with the experimental results. Equilibrium data were also fitted well to the Langmuir isotherm model in the studied concentration range of RB19 at 20 °C. The results indicate that DAH-modified bentonite is a suitable adsorbent for the adsorption of textile dyes.

  2. Human behavioral regularity, fractional Brownian motion, and exotic phase transition

    NASA Astrophysics Data System (ADS)

    Li, Xiaohui; Yang, Guang; An, Kenan; Huang, Jiping

    2016-08-01

    The mix of competition and cooperation (C&C) is ubiquitous in human society, which, however, remains poorly explored due to the lack of a fundamental method. Here, by developing a Janus game for treating C&C between two sides (suppliers and consumers), we show, for the first time, experimental and simulation evidences for human behavioral regularity. This property is proved to be characterized by fractional Brownian motion associated with an exotic transition between periodic and nonperiodic phases. Furthermore, the periodic phase echoes with business cycles, which are well-known in reality but still far from being well understood. Our results imply that the Janus game could be a fundamental method for studying C&C among humans in society, and it provides guidance for predicting human behavioral activity from the perspective of fractional Brownian motion.

  3. Second Virial Coefficient As Determined from Protein Phase Behavior.

    PubMed

    Platten, Florian; Hansen, Jan; Wagner, Dana; Egelhaaf, Stefan U

    2016-10-06

    We quantitatively link the macroscopic phase behavior of protein solutions to protein-protein interactions based on a coarse-grained colloidal approach. We exploit the extended law of corresponding states and apply the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory in order to infer the second virial coefficient b2, an integral measure of the interaction potential, from the phase behavior, namely, cloud-point temperature (CPT) measurements under conditions favoring protein crystallization. This determination of b2 yields values that quantitatively agree with the results of static light scattering (SLS) experiments. The strength of the attractions is quantified in terms of an effective Hamaker constant, which accounts for van der Waals attractions as well as non-DLVO forces, such as hydration and hydrophobic interactions. Our approach based on simple lab experiments to determine the CPT in combination with the DLVO theory is expected to facilitate further biophysical research on protein-protein interactions in complex solution environments.

  4. Effect of Nanoparticle Surface Chemistry on Adsorption and Fluid Phase Partitioning in Aqueous/Toluene and Cellular Systems.

    PubMed

    Gambinossi, Filippo; Lapides, Dana; Anderson, Chris; Chanana, Munish; Ferri, James K

    2015-05-01

    Copolymers of di(ethylene glycol) methyl ether methacrylate (x = MeO2MA) and oligo(ethylene glycol) methyl ether methacrylate (y = OEGMA) display lower critical solution phenomena in aqueous systems that are tunable by the copolymer ratio (x:y), ionic strength, and temperature. These properties enable tuning the hydrophobicity of macromolecular systems by variation of (x:y). For nanoparticles stabilized with these macromolecules, this provides a systematic approach to understanding the impact of surface chemistry, specifically hydrophobicity, on the equilibrium and transport properties of nanomaterials in biphasic systems. We synthesized a homologous series of gold nanoparticles capped by these copolymers, Au@(MeO2MA(x)-co-OEGMA(y)). By varying the copolymer 95:5 < (x:y) < 80:20 ratio, we studied the effect of surface hydrophobicity on the nanoparticle equilibrium adsorption isotherm and phase transfer at the aqueous-toluene interface. The increase in hydrophobicity from (x:y) = 80:20 to (x:y) = 95:5 is accompanied by an increase in the fractional coverage of the aqueous-toluene interface from f = 0.3 to f > 1, or multilayer adsorption and an increase in the characteristic adsorption timescale from τ(D) = 31 to τ(D) = 450 seconds. The equilibrium partition coefficient for the aqueous/toluene systems, K(T/W) is also a strong function of (x:y), increasing from K(T/W) (80:20) = 0.7 to K(T/W) (95:5) = 9.8. We also observed an increase in cellular uptake for increasing (x:y) suggesting that surface chemistry alone plays a significant role in intercellular transport processes.

  5. Effect of phase behavior on bypassing in enriched gas floods

    SciTech Connect

    Burger, J.E.; Bhogeswara, R.; Mohanty, K.K. )

    1994-05-01

    Enriched gas floods incorporate a complex interaction of heterogeneity, fingering, multiphase flow, and phase behavior. Experiments and simulations indicate that the optimum solvent enrichment in high-viscosity-ratio secondary gas floods can be below minimum miscibility enrichment (MME). The compositional path and resulting mobility profile in multidimensional multiple-contact miscible (MCM) or immiscible floods are different from their 1D counterparts for high-viscosity-ratio floods in heterogeneous media.

  6. Critical behaviors and phase transitions of black holes in higher order gravities and extended phase spaces

    NASA Astrophysics Data System (ADS)

    Sherkatghanad, Zeinab; Mirza, Behrouz; Mirzaiyan, Zahra; Mansoori, Seyed Ali Hosseini

    We consider the critical behaviors and phase transitions of Gauss-Bonnet-Born-Infeld-AdS black holes (GB-BI-AdS) for d = 5, 6 and the extended phase space. We assume the cosmological constant, Λ, the coupling coefficient α, and the BI parameter β to be thermodynamic pressures of the system. Having made these assumptions, the critical behaviors are then studied in the two canonical and grand canonical ensembles. We find “reentrant and triple point phase transitions” (RPT-TP) and “multiple reentrant phase transitions” (multiple RPT) with increasing pressure of the system for specific values of the coupling coefficient α in the canonical ensemble. Also, we observe a reentrant phase transition (RPT) of GB-BI-AdS black holes in the grand canonical ensemble and for d = 6. These calculations are then expanded to the critical behavior of Born-Infeld-AdS (BI-AdS) black holes in the third-order of Lovelock gravity and in the grand canonical ensemble to find a van der Waals (vdW) behavior for d = 7 and a RPT for d = 8 for specific values of potential ϕ in the grand canonical ensemble. Furthermore, we obtain a similar behavior for the limit of β →∞, i.e. charged-AdS black holes in the third-order of the Lovelock gravity. Thus, it is shown that the critical behaviors of these black holes are independent of the parameter β in the grand canonical ensemble.

  7. PHASE BEHAVIOR OF LIGHT GASES IN HYDROCARBON AND AQUEOUS SOLVENTS

    SciTech Connect

    KHALED A.M. GASEM; ROBERT L. ROBINSON, JR.

    1998-08-31

    Under previous support from the Department of Energy, an experimental facility has been established and operated to measure valuable vapor-liquid equilibrium data for systems of interest in the production and processing of coal fluids. To facilitate the development and testing of models for prediction of the phase behavior for such systems, we have acquired substantial amounts of data on the equilibrium phase compositions for binary mixtures of heavy hydrocarbon solvents with a variety of supercritical solutes, including hydrogen, methane, ethane, carbon monoxide, and carbon dioxide. The present project focuses on measuring the phase behavior of light gases and water in Fischer-Tropsch (F-T) type solvents at conditions encountered in indirect liquefaction processes and evaluating and developing theoretically-based correlating frameworks to predict the phase behavior of such systems. Specific goals of the proposed work include (a) developing a state-of-the-art experimental facility to permit highly accurate measurements of equilibrium phase compositions (solubilities) of challenging F-T systems, (b) measuring these properties for systematically-selected binary, ternary and molten F-T wax mixtures to provide critically needed input data for correlation development, (c) developing and testing models suitable for describing the phase behavior of such mixtures, and (d) presenting the modeling results in generalized, practical formats suitable for use in process engineering calculations. During the present period, the Park-Gasem-Robinson (PGR) equation of state (EOS) has been modified to improve its volumetric and equilibrium predictions. Specifically, the attractive term of the PGR equation was modified to enhance the flexibility of the model, and a new expression was developed for the temperature dependence of the attractive term in this segment-segment interaction model. The predictive capability of the modified PGR EOS for vapor pressure, and saturated liquid and

  8. Controlling block copolymer phase behavior using ionic surfactant

    NASA Astrophysics Data System (ADS)

    Ray, D.; Aswal, V. K.

    2016-05-01

    The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO26PO39EO26)] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle-surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at higher temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.

  9. The adsorption behavior of mercury on the hematite (1-102) surface from coal-fired power plant emissions

    NASA Astrophysics Data System (ADS)

    Jung, J. E.; Jew, A. D.; Rupp, E.; Aboud, S.; Brown, G. E.; Wilcox, J.

    2014-12-01

    One of the biggest environmental concerns caused by coal-fired power plants is the emission of mercury (Hg). Worldwide, 475 tons of Hg are released from coal-burning processes annually, comprising 24% of total anthropogenic Hg emissions. Because of the high toxicity of Hg species, US Environmental Protection Agency (EPA) proposed a standard on Hg and air toxic pollutants (Mercury and Air Toxics Standards, MATS) for new and existing coal-fired power plants in order to eliminate Hg in flue gas prior to release through the stack. To control the emission of Hg from coal-derived flue gas, it is important to understand the behavior, speciation of Hg as well as the interaction between Hg and solid materials, such as fly ash or metal oxides, in the flue gas stream. In this study, theoretical investigations using density functional theory (DFT) were carried out in conjunction with experiments to investigate the adsorption behavior of oxidized Hg on hematite (α-Fe2O3), an important mineral component of fly ash which readily sorbes Hg from flue gas. For DFT calculation, the two α-Fe2O3 (1-102) surfaces modeled consisted of two different surface terminations: (1) M2-clean, which corresponds to the oxygen-terminated surface with the first layer of cations removed and with no hydroxyl groups and (2) M2-OH2-OH, which has bihydroxylated top oxygen atoms and a second layer of hydroxylated oxygen atoms. These surface terminations were selected because both surfaces are highly stable in the temperature range of flue gases. The most probable adsorption sites of Hg, Cl and HgCl on the two α-Fe2O3 surface terminations were suggested based on calculated adsorption energies. Additionally, Bader charge and projected density of states (PDOS) analyses were conducted to characterize the oxidation state of adsorbates and their bonding interactions with the surfaces. Results indicate that oxidized Hg physically adsorbs on the M2-clean surface with a binding energy of -0.103 eV and that

  10. Adsorption-Driven Catalytic and Photocatalytic Activity of Phase Tuned In2S3 Nanocrystals Synthesized via Ionic Liquids.

    PubMed

    Sharma, Rahul Kumar; Chouryal, Yogendra Nath; Chaudhari, Sushmita; Saravanakumar, Jeganathan; Dey, Suhash Ranjan; Ghosh, Pushpal

    2017-03-14

    Phase tuned quantum confined In2S3 nanocrystals are accessible solvothermally using task-specific ionic liquids (ILs) as structure directing agents. Selective tuning of size, shape, morphology and, most importantly, crystal phase of In2S3 is achieved by changing the alkyl side chain length, the H-bonding and aromatic -stacking ability of the 1-alkyl-3- methylimidazolium bromide ILs, [Cnmim]Br (n=2,4,6,8 and 10). It is observed that crystallite size is significantly less when ILs are used compared to the synthesis without ILs keeping the other reaction parameters same. At 150oC, when no IL is used, pure tetragonal form of -In2S3 appears however in presence of [Cnmim]Br [n=2,4], at the same reaction condition, a pure cubic phase crystallizes. However in case of methylimidazolium bromides with longer pendant alkyl chains such as hexyl (C6), octyl (C8) or decyl (C10), nanoparticles of the tetragonal polymorph form. Likewise, judicious choice of reaction temperature and precursors has a profound effect to obtain phase pure and morphology controlled nanocrystals. Furthermore, the adsorption driven catalytic and photocatalytic activity of as-prepared nanosized indium sulphide is confirmed by studying the degradation of crystal violet (CV) dye in presence of dark and visible light. Maximum 94.8 % catalytic efficiency is obtained for the In2S3 nanocrystals using tetramethylammonium bromide (TMAB) ionic liquid.

  11. Phase behavior of polarizable spherocylinders in external fields.

    PubMed

    Rotunno, Melissa; Bellini, Tommaso; Lansac, Yves; Glaser, Matthew A

    2004-09-15

    Applied electric fields are known to induce significant changes in the properties of systems of polarizable molecules or particles. For rod-shaped molecules, the field-induced behavior can be rather surprising, as in the case of the negative electric birefringence of concentrated solutions of rodlike polyelectrolytes. We have investigated the interplay of shape anisotropy and field-induced anisotropy in molecular dynamics simulations of systems of polarizable soft spherocylinders in an electric field, in the limit of infinitely anisotropic polarizability, taking full account of mutual induction effects. We find a novel crystalline structure (K(2)) in the high-field limit, whose formation is driven by interactions between induced dipoles. For high pressures, the phase diagram exhibits a polar nematic phase between the hexagonal close-packed crystal phase and the K(2) phase. We also compare this system with an analogous system of spherocylinders with permanent electric dipoles and find that qualitatively similar behavior is obtained in the limit of strong coupling of the permanent dipoles to the external field.

  12. [Adsorption behavior and influence factors of p-nitroaniline on high surface area activated carbons prepared from plant stems].

    PubMed

    Li, Kun-quan; Zheng, Zheng; Luo, Xing-zhang

    2010-08-01

    Low-cost and high surface area microporous activated carbons were prepared from Spartina alternilora and cotton stalk with KOH activation under the conditions of impregnation ratio of 3.0, activation temperature at 800 degrees C and activation time of 1.5 h. The adsorption behavior of p-nitroaniline on the activated carbons was investigated by batch sorption experiments. The influences of solution pH value, adsorbent dose and temperature were investigated. The adsorption isotherm and thermodynamic characteristics were also discussed. The Spartina alterniflora activated carbon (SA-AC) has a high surface area of 2825 m2 x g(-1) and a micropore volume of 1.192 cm3 x g(-1). The BET surface area and micropore volume of the cotton stalk activated carbon (CS-AC) are 2135 m2 x g(-1) and 1.011 cm3 x g(-1), respectively. The sorption experiments show that both the activated carbons have high sorption capacity for p-nitroaniline. The Langmuir maximum sorption amount was found to be 719 mg x g(-1) for SA-AC and 716 mg x g(-1) for CS-AC, respectively. The sorption was found to depend on solution pH, adsorbent dose, and temperature. The optimum pH for the removal of p-nitroaniline was found to be 7.0. The Freundlich model and Redlich-Peterson model can describe the experimental data effectively. The negative changes in free energy (delta G0) and enthalpy (delta H0) indicate that the sorption is a spontaneous and exothermic procedure. The negative values of the adsorption entropy delta S0 indicate that the mobility of p-nitroaniline on the carbon surface becomes more restricted as compared with that of those in solution.

  13. Structure and Interaction in the pH-Dependent Phase Behavior of Nanoparticle-Protein Systems.

    PubMed

    Yadav, Indresh; Kumar, Sugam; Aswal, Vinod K; Kohlbrecher, Joachim

    2017-02-07

    The pH-dependent structure and interaction of anionic silica nanoparticles (diameter 18 nm) with two globular model proteins, lysozyme and bovine serum albumin (BSA), have been studied. Cationic lysozyme adsorbs strongly on the nanoparticles, and the adsorption follows exponential growth as a function of lysozyme concentration, where the saturation value increases as pH approaches the isoelectric point (IEP) of lysozyme. By contrast, irrespective of pH, anionic BSA does not show any adsorption. Despite having a different nature of interactions, both proteins render a similar phase behavior where nanoparticle-protein systems transform from being one-phase (clear) to two-phase (turbid) above a critical protein concentration (CPC). The measurements have been carried out for a fixed concentration of silica nanoparticles (1 wt %) with varying protein concentrations (0-5 wt %). The CPC is found to be much higher for BSA than for lysozyme and increases for lysozyme but decreases for BSA as pH approaches their respective IEPs. The structure and interaction in these systems have been examined using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The effective hydrodynamic size of the nanoparticles measured using DLS increases with protein concentration and is related to the aggregation of the nanoparticles above the CPC. The propensity of the nanoparticles to aggregate is suppressed for lysozyme and enhanced for BSA as pH approached their respective IEPs. This behavior is understood from SANS data through the interaction potential determined by the interplay of electrostatic repulsion with a short-range attraction for lysozyme and long-range attraction for BSA. The nanoparticle aggregation is caused by charge neutralization by the oppositely charged lysozyme and through depletion for similarly charged BSA. Lysozyme-mediated attractive interaction decreases as pH approaches the IEP because of a decrease in the charge on the protein. In the case of

  14. Aqueous-Phase Preparation of Model HDS Catalysts on Planar Alumina Substrates: Support Effect on Mo Adsorption and Sulfidation.

    PubMed

    Bara, Cédric; Plais, Lucie; Larmier, Kim; Devers, Elodie; Digne, Mathieu; Lamic-Humblot, Anne-Félicie; Pirngruber, Gerhard D; Carrier, Xavier

    2015-12-23

    The role of the oxide support on the structure of the MoS2 active phase (size, morphology, orientation, sulfidation ratio, etc.) remains an open question in hydrotreating catalysis and biomass processing with important industrial implications for the design of improved catalytic formulations. The present work builds on an aqueous-phase surface-science approach using four well-defined α-alumina single crystal surfaces (C (0001), A (112̅0), M (101̅0), and R (11̅02) planes) as surrogates for γ-alumina (the industrial support) in order to discriminate the specific role of individual support facets. The reactivity of the various surface orientations toward molybdenum adsorption is controlled by the speciation of surface hydroxyls that determines the surface charge at the oxide/water interface. The C (0001) plane is inert, and the R (11̅02) plane has a limited Mo adsorption capacity while the A (112̅0) and M (101̅0) surfaces are highly reactive. Sulfidation of model catalysts reveals the highest sulfidation degree for the A (112̅0) and M (101̅0) planes suggesting weak metal/support interactions. Conversely, a low sulfidation rate and shorter MoS2 slabs are found for the R (11̅02) plane implying stronger Mo-O-Al bonds. These limiting cases are reminiscent of type I/type II MoS2 nanostructures. Structural analogies between α- and γ- alumina surfaces allow us to bridge the material gap with real Al2O3-supported catalysts. Hence, it can be proposed that Mo distribution and sulfidation rate are heterogeneous and surface-dependent on industrial γ-Al2O3-supported high-surface-area catalysts. These results demonstrate that a proper control of the γ-alumina morphology is a strategic lever for a molecular-scale design of hydrotreating catalysts.

  15. Unusual pH-regulated surface adsorption and aggregation behavior of a series of asymmetric gemini amino-acid surfactants.

    PubMed

    Lv, Jing; Qiao, Weihong

    2015-04-07

    A new series of pH-regulated asymmetric amino-acid gemini surfactants N,N'-dialkyl-N,N'-diacetate ethylenediamine (Ace(m)-2-Ace(n)), differing by the asymmetric degree and length of the carbon tails (m = 8 and 10, n = 10, 12, 14, and 16), were synthesized in three steps. On the basis of pKa values obtained by pH titration, surface tension, fluorescence, dynamic light scattering (DLS), and transmission electron microscopy (TEM) measurements were performed to study the surface adsorption and aggregation properties in aqueous Ace(m)-2-Ace(n) solution. The new compounds have higher surface activity and better pH adaptability in comparison with that of symmetric gemini surfactants Ace(n)-2-Ace(n). The molecule behavior of Ace(m)-2-Ace(n) can be adjusted by either the hydrophobic group or the pH. With increasing alkyl chain length, the surface adsorption declines but its ability to form aggregates increases. We find that pH can promote the self-assembly transition of Ace(m)-2-Ace(n) from surfactant monomers to aggregates through protonation between H(+) and the tertiary nitrogen group. TEM data further confirm the pH-regulated molecular self-assembly process and the existence of vesicles at neutral or weak acidic pH. pH-recyclability is found to be reversible by pH-light transmittance recycle tests.

  16. Thermotropic phase behavior of multilamellar membranes of dioleoylphosphatidylcholine.

    PubMed

    Zhang, Yu-Dong; Lu, Ying; Hu, Shu-Xin; Li, Ming

    2010-02-18

    We use the X-ray diffraction method to examine the thermotropic phase behavior of multilamellar membranes of dioleoylphosphatidylcholine. We find that when the temperature is reduced from room temperature to below 0 degrees C, both the lipid bilayers and the amount of water in the bilayers increase. But the interbilayer distance descends abruptly at a certain temperature between -6 and -15 degrees C, the actual value depending on the relative humidity of the atmosphere, solely due to the thinning of the water layer, d(w). There are several L(alpha) and L(c) phase coexistence states both in the cooling process and in the heating process. In the cooling process, only a part of the lipid molecules accomplish the L(alpha)-to-L(c) main phase transition at -16 degrees C, with the rest of the lipids being frozen down to a very low temperature. In the heating process, however, these frozen lipid molecules are able to move to complete the L(alpha)-to-L(c) main phase transition at -12 degrees C. The reverse of the main phase transition begins at -9 degrees C and is completed at -5 degrees C, after which the water is absorbed into the lipid bilayer to increase the thickness of the water layer, while the thickness of the lipid membranes remain unchanged. This process continues until all the ice on top of the samples melts.

  17. Phase behavior and shear alignment in SWNT-surfactant dispersions.

    PubMed

    Nativ-Roth, Einat; Yerushalmi-Rozen, Rachel; Regev, Oren

    2008-09-01

    The effect of single-walled carbon nanotubes (SWNT) on the phase behavior of the cationic surfactant cetyltrimethylammonium bromide (CTAB) in aqueous solutions is investigated at room temperature. Small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM) are used for characterization of bulk dispersions and nanometrically thin films. Additional carbonaceous additives (fullerenes, multi-walled carbon nanotubes, and carbon black) serve as reference systems. It is found that dispersions of carbonaceous additive (excluding fullerenes) at intermediate surfactant concentrations (below the liquid-crystalline region of the native surfactant) induce demixing and macroscopic phase separation in otherwise homogeneous solutions of CTAB. Two coexisting liquid phases of similar CTAB concentrations are observed, with the carbonaceous species residing within the lower phase. At high CTAB concentrations (liquid-crystal region) the SWNTs are found to incorporate into the ordered lyotropic liquid-crystalline phase while preserving the native d-spacing. Investigation of nanometrically thin films at intermediate surfactant concentrations under external shear reveals shear-induced structure (SIS) in the presence of minute amounts of SWNTs. The effect is found to be exclusive to SWNT and does not occur in dispersions of other carbonaceous additives.

  18. Structure and phase behavior in five-component microemulsions

    SciTech Connect

    Billman, J.F. ); Kaler, E.W. )

    1990-03-01

    Droplet-to-bicontinuous structure transitions in a family of five-component microemulsions formed with sodium 4-(1{prime}-heptylnonyl)benzenesulfonate, isobutyl alcohol, D{sub 2}O, sodium chloride, and alkanes with even carbon numbers from octane to hexadecane are probed by using small-angle neutron scattering, electrical conductivity, and NMR self-diffusion measurements. The phase behavior and structure of these microemulsions are intimately linked and depend on salinity and the chain length of the alkane. Both the range of salt concentration in which the three-phase region is observed and the range of microemulsion water volume fraction within the three-phase region decrease with decreasing alkane chain length. Further, the appearance of the three-phase region is preceded by droplet-to-bicontinuous transitions. Microemulsions not exhibiting three-phase regions become bicontinuous only when they contain equal amounts of oil and water. The coincidence of the so-called percolation thresholds as determined by using electrical conductivity and self-diffusion measurements shows that electrical conduction in a dispersion of water droplets occurs with the exchange of material between the droplets.

  19. Adsorption Behavior of Rare Earth Metal Cations in the Interlayer Space of γ-ZrP.

    PubMed

    Takei, Takahiro; Iidzuka, Kiyoaki; Miura, Akira; Yanagida, Sayaka; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

    2016-10-04

    Adsorption competencies of rare earth metal cations in γ-zirconium phosphate were examined by ICP, synchrotron X-ray diffraction (SXRD), and ab initio simulation. The adsorption amounts are around 0.06-0.10 per zirconium phosphate. From the SXRD patterns of the adsorbed samples, the basal spacing estimated by c sin β increased linearly with an increasing ionic radius of rare earth metal cation, though a and b lattice constants show no change. These SXRD patterns can be classified into four groups that have different super lattices. The four superlattices have multiplicities of x131, x241, and x221 for the xabc axis, and the location of the rare earth metal cation in the original unit cell changes depending on the superlattice cell. In the x131 superlattice, Yb and Er occupied the site near the zirconium phosphate layer, though La and Ce in the x221 superlattice remained in the center position between the phosphate sheet. For the ab initio simulation of γ-ZrP with the typical rare earth metal cations (Tb, Eu, Dy, and La), the results of simulation show a similar tendency of the position estimated by SXRD refinements.

  20. Microstructure and phase behavior in colloids and liquid crystals

    NASA Astrophysics Data System (ADS)

    Lohr, Matthew Alan

    This thesis describes our investigation of microstructure and phase behavior in colloids and liquid crystals. The first set of experiments explores the phase behavior of helical packings of thermoresponsive microspheres inside glass capillaries as a function of volume fraction. Stable helical packings are observed with long-range orientational order. Some of these packings evolve abruptly to disordered states as the volume fraction is reduced. We quantify these transitions using correlation functions and susceptibilities of an orientational order parameter. The emergence of coexisting metastable packings, as well as coexisting ordered and disordered states, is also observed. These findings support the notion of phase-transition-like behavior in quasi-one-dimensional systems. The second set of experiments investigates cross-over behavior from glasses with attractive interactions to sparse gel-like states. In particular, the vibrational modes of quasi-two-dimensional disordered colloidal packings of hard colloidal spheres with short-range attractions are measured as a function of packing fraction. A crossover from glassy to sparse gel-like states is indicated by an excess of low-frequency phonon modes. This change in vibrational mode distribution appears to arise from highly localized vibrations that tend to involve individual and/or small clusters of particles with few local bonds. These mode behaviors and corresponding structural insights may serve as a useful signature for glass-gel transitions in wider classes of attractive packings. A third set of experiments explores the director structures of aqueous lyotropic chromonic liquid crystal (LCLC) films created on square lattice cylindrical-micropost substrates. The structures are manipulated by modulating of the concentration-dependent elastic properties of LCLC s via drying. Nematic LCLC films exhibit preferred bistable alignment along the diagonals of the micropost lattice. Columnar LCLC films form two distinct

  1. Mercury Phase II Study - Mercury Behavior in Salt Processing Flowsheet

    SciTech Connect

    Jain, V.; Shah, H.; Bannochie, C. J.; Wilmarth, W. R.

    2016-07-25

    Mercury (Hg) in the Savannah River Site Liquid Waste System (LWS) originated from decades of canyon processing where it was used as a catalyst for dissolving the aluminum cladding of reactor fuel. Approximately 60 metric tons of mercury is currently present throughout the LWS. Mercury has long been a consideration in the LWS, from both hazard and processing perspectives. In February 2015, a Mercury Program Team was established at the request of the Department of Energy to develop a comprehensive action plan for long-term management and removal of mercury. Evaluation was focused in two Phases. Phase I activities assessed the Liquid Waste inventory and chemical processing behavior using a system-by-system review methodology, and determined the speciation of the different mercury forms (Hg+, Hg++, elemental Hg, organomercury, and soluble versus insoluble mercury) within the LWS. Phase II activities are building on the Phase I activities, and results of the LWS flowsheet evaluations will be summarized in three reports: Mercury Behavior in the Salt Processing Flowsheet (i.e. this report); Mercury Behavior in the Defense Waste Processing Facility (DWPF) Flowsheet; and Mercury behavior in the Tank Farm Flowsheet (Evaporator Operations). The evaluation of the mercury behavior in the salt processing flowsheet indicates, inter alia, the following: (1) In the assembled Salt Batches 7, 8 and 9 in Tank 21, the total mercury is mostly soluble with methylmercury (MHg) contributing over 50% of the total mercury. Based on the analyses of samples from 2H Evaporator feed and drop tanks (Tanks 38/43), the source of MHg in Salt Batches 7, 8 and 9 can be attributed to the 2H evaporator concentrate used in assembling the salt batches. The 2H Evaporator is used to evaporate DWPF recycle water. (2) Comparison of data between Tank 21/49, Salt Solution Feed Tank (SSFT), Decontaminated Salt Solution Hold Tank (DSSHT), and Tank 50 samples suggests that the total mercury as well as speciated

  2. [Enantioseparation behavior of chiral stationary phases AD, AS and OD].

    PubMed

    Li, Liqun; Fan, Jun; Zhang, Jing; Chen, Xiaodong; Wang, Tai; He, Jianfeng; Zhang, Weiguang

    2016-01-01

    Over the past decades, HPLC enantioseparation with chiral stationary phases (CSPs) has been widely applied in chiral analysis and preparation of new pharmaceuticals, pesticides, food, etc. Herein, enantioseparation of 20 chiral compounds have been carried out on three polysaccharide-based CSPs (EnantioPak AD, AS and OD) with normal phases by HPLC, separately. The influences of skeletal structure and the kinds of derivative groups on separation behaviors of these CSPs have been studied in detail. As results indicated, except for compound 13, the other compounds were baseline separated on EnantioPak AD, with most of resolution over 2. 0; in addition, better separation for acidic or basic compounds was achieved through adding acidic/basic additives into the mobile phase of hexane-alcohol. For four aromatic alcohols (compounds 13-16), their retention in the EnantioPak AD column showed a weakening tendency with increase of carbon number in side chain group, and the reverse trend of their resolution was observed. Furthermore, EnantioPak AD showed much better separation performance for eight compounds (13-20) than the others. In short, these results have provided some references for further investigation of separation behavior and applications of polysaccharide-based CSPs.

  3. Phase Behavior of Pseudobinary Precious Metal-Carbide Systems

    SciTech Connect

    Gregoire, John M.; Tague, Michele E.; Smith, Eva H.; Dale, Darren; DiSalvo, Francis J.; Abruña, Héctor D.; Hennig, Richard G.; van Dover, R. Bruce

    2010-11-15

    Transition metal carbides exhibit a variety of interesting material properties, including electrochemical stability. When combined with precious metals, Ta and W carbides have shown promise as fuel cell electrode materials; yet, the phase behavior of these precious metal-carbide systems is largely unexplored. We investigated P-M-C phase behavior with P = Pt, Pd, and Ru and M = Ta and W using composition spread thin films. We attained limited control of the deposited carbide phase through variation of the sputter atmosphere and demonstrated decreased corrosion of W-C materials with increasing C content. A high-throughput X-ray diffraction and X-ray fluorescence experiment was employed for thin film characterization, which revealed solubility of Pt, Pd, and Ru in cubic WC. Density functional calculations of the lattice parameter dependence on carbon concentration enabled the determination of carbon concentration from the X-ray data as a function of transition metal stoichiometry. Our measurement of variations in the C stoichiometry and evolution of thin film texture with transition metal composition yielded surprising results. We detail how the combination of the composition spread technique, the high-throughput thin film characterization, and the density functional modeling of ternary carbide alloys provided a deep understanding of the chemical systems.

  4. Phase behavior, rheological and mechanical properties of hydrophilic polymer dispersions.

    PubMed

    Bhattarai, Sushila; Bunt, Craig; Rathbone, Michael; Alany, Raid G

    2011-06-01

    Liquid polymeric systems that can undergo phase change (sol to gel) upon administration into the teat canal of cow's mammary gland can serve as a physical barrier to invading pathogens and can also serve as a reservoir for controlled release of therapeutic agents. The aim of the study was to investigate the phase behavior, rheological and mechanical properties of selected in situ gelling systems. Six in situ gelling polymer formulations were identified using phase behavior studies. Rheological studies revealed pseudoplastic flow with thixotropy. All six formulations showed significantly different viscosity, pseudoplasticity and thixotropy values except for CMC1 and HPMC2 which where statistically similar. The gel strength was dependent on the solvent system used and amount of water in the system. These in situ gelling systems have the potential to serve as a platform for development of intramammary formulations intended for administration into the teat canal of the cow's mammary gland. They can serve as a physical barrier or a matrix for controlled drug release.

  5. Phase Behavior and Micellar Packing of Impurity-Free Pluronic Block Copolymers in Water

    NASA Astrophysics Data System (ADS)

    Ryu, Chang Yeol; Park, Hanjin

    We have investigated the impacts of the non-micellizable polymeric impurities on the micellar packing and solution phase behavior of Pluronic block copolymers in water. In particular, small angle x-ray scattering, rheology and dynamic light scattering techniques have been employed to elucidate how the low MW impurities affect the micellar packing and solution phase diagram in water, when ordered cubic structures of spherical micelles are formed. A silica slurry method has been developed using the competitive adsorption of the PEO-PPO-PEO triblock copolymers over the low MW polymeric impurities for a large scale purification of Pluronics and it purity of Pluronics has been assessed by interaction chromatography. Based on the comparative studies on micellar packing between As-Received (AR) and Purified (Pure) Pluronic F108 solutions, we found experimental evidence to support the hypothesis that the inter-micellar distance of Pluronic cubic structures in aqueous solution is governed by the effective polymer concentration in terms of PEO-PPO-PEO triblock copolymers. Removal of the impurities in AR F108 offers an important clue on window into the onset of BCC ordering via hydrodynamic contact between micelles in solution. NSF DMR Polymers.

  6. Distribution or adsorption: the major dilemma in reversed-phase HPLC

    NASA Astrophysics Data System (ADS)

    Deineka, V. I.

    2008-06-01

    A method is suggested for analyzing the dependences obtained for different compositions of mobile eluent system phases, their slopes and intercepts, log k( i, B) = a + b log k ( i, A), where a is the intercept for the A and B stationary phases and b is the proportionality factor. An analysis requires parallel investigation of sorbate retention on at least three stationary phases with different lengths of grafted hydrocarbon radicals. The dependence of correlation parameters on the sorbate retention mechanism is discussed. It is shown that the hypothetical dependences coincide with the experimental dependences for surface sorption of resveratrol and volume distribution of triglycerides.

  7. Effect of liquid phase on coarsening behavior in porous single-phase and duplex microstructures

    NASA Astrophysics Data System (ADS)

    Alves, Fernando Jorge Lino

    1997-11-01

    A systematic investigation of the influence of different glass volume fractions (Vsb{f}) on the grain growth behavior of single-phase alumina (Alsb2Osb3), c-zirconia (c-ZrOsb2) and duplex Alsb2Osb3+50 vol.% c-ZrOsb2 (AZ50), has been conducted. Grain growth was studied for porous single-phase alumina and c-zirconia for one glass (anorthite) composition and different Vsb{f}. Grain growth on dense single-phase alumina and c-zirconia was also studied and compared with the results obtained for porous samples. It was observed that glass additions to porous (≈1 vol.% porosity) single-phase alumina or c-zirconia increase the grain growth rate constant (K) up to a critical Vsb{f}, above which further glass additions decrease K. This behavior is contrary to that of dense single-phase materials, for which K decreases continuously with Vsb{f}. This can be explained by the fact that very small amounts of glass can coat pore surfaces with a very thin (nanometer scale) liquid film, which promotes a faster diffusion path for atoms, thereby increasing K. However, as Vsb{f} increases, glass pockets are continuously enlarged, the diffusion distances across these pockets thus increase as well, and hence K starts to decrease. The grain growth rate equation for the final stage of sintering was adapted to describe the kinetic behavior observed in porous single-phase materials, for small amounts of glass. Special emphasis was given to the residual porosity, the microstructural features of alumina and c-zirconia grains, and to the grain growth controlling mechanism(s). Grain growth was studied for AZ50 for two glass compositions and different Vsb{f}. Unlike dense single-phase materials, glass additions to AZ50 were shown to promote grain growth. K increases continuously with Vsb{f} because the grain growth rate in duplex systems is controlled by long range diffusion which is enhanced by the presence of the liquid phase. As Vsb{f} increases, glass pockets are continuously enlarged and K

  8. Adsorption behavior of pH-dependent phytic acid micelles at the copper surface observed by Raman and electrochemistry

    NASA Astrophysics Data System (ADS)

    Shen, Shu; Du, Juan; Guo, Xiao-yu; Wen, Ying; Yang, Hai-Feng

    2015-02-01

    As heated at 90 °C, phytic acid (PA) molecules in the solution self-organized to form the PA micelles. The size of PA micelles could be tuned by varying pH of the solutions. The adsorption behavior of the different micelles at the copper surface and their corrosion inhibition mechanisms in 0.5 M H2SO4 solution were studied by using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and surface-enhanced Raman scattering (SERS) spectroscopy. Raman studies showed that the bigger micelles anchoring on the copper surface via P27sbnd O28, P43sbnd O42 and P35sbnd O36 groups, while the smaller PA micelles formed at pH 9 adsorbed at the surface through P35sbnd O36 group. The electrochemical measurements demonstrated that the copper modified with the smaller micelles presented the best inhibition efficiency in 0.5 M H2SO4 solution.

  9. Phase-Amplitude Coupling in Spontaneous Mouse Behavior

    PubMed Central

    Thengone, Daniel; Gagnidze, Khatuna; Pfaff, Donald; Proekt, Alex

    2016-01-01

    The level of activity of many animals including humans rises and falls with a period of ~ 24 hours. The intrinsic biological oscillator that gives rise to this circadian oscillation is driven by a molecular feedback loop with an approximately 24 hour cycle period and is influenced by the environment, most notably the light:dark cycle. In addition to the circadian oscillations, behavior of many animals is influenced by multiple oscillations occurring at faster—ultradian—time scales. These ultradian oscillations are also thought to be driven by feedback loops. While many studies have focused on identifying such ultradian oscillations, less is known about how the ultradian behavioral oscillations interact with each other and with the circadian oscillation. Decoding the coupling among the various physiological oscillators may be important for understanding how they conspire together to regulate the normal activity levels, as well in disease states in which such rhythmic fluctuations in behavior may be disrupted. Here, we use a wavelet-based cross-frequency analysis to show that different oscillations identified in spontaneous mouse behavior are coupled such that the amplitude of oscillations occurring at higher frequencies are modulated by the phase of the slower oscillations. The patterns of these interactions are different among different individuals. Yet this variability is not random. Differences in the pattern of interactions are confined to a low dimensional subspace where different patterns of interactions form clusters. These clusters expose the differences among individuals—males and females are preferentially segregated into different clusters. These sex-specific features of spontaneous behavior were not apparent in the spectra. Thus, our methodology reveals novel aspects of the structure of spontaneous animal behavior that are not observable using conventional methodology. PMID:27631971

  10. Block voter model: Phase diagram and critical behavior

    NASA Astrophysics Data System (ADS)

    Sampaio-Filho, C. I. N.; Moreira, F. G. B.

    2011-11-01

    We introduce and study the block voter model with noise on two-dimensional square lattices using Monte Carlo simulations and finite-size scaling techniques. The model is defined by an outflow dynamics where a central set of NPCS spins, here denoted by persuasive cluster spins (PCS), tries to influence the opinion of their neighboring counterparts. We consider the collective behavior of the entire system with varying PCS size. When NPCS>2, the system exhibits an order-disorder phase transition at a critical noise parameter qc which is a monotonically increasing function of the size of the persuasive cluster. We conclude that a larger PCS has more power of persuasion, when compared to a smaller one. It also seems that the resulting critical behavior is Ising-like independent of the range of interaction.

  11. Adsorption geometry and interface states: Relaxed and compressed phases of NTCDA/Ag(111)

    NASA Astrophysics Data System (ADS)

    Jakob, P.; Zaitsev, N. L.; Namgalies, A.; Tonner, R.; Nechaev, I. A.; Tautz, F. S.; Höfer, U.; Sánchez-Portal, D.

    2016-09-01

    The theoretical modeling of metal-organic interfaces represents a formidable challenge, especially considering the delicate balance of various interaction mechanisms and the large size of the involved molecular species. In the present study, the energies of interface states, which are known to display a high sensitivity to the adsorption geometry and electronic structure of the deposited molecular species, have been used to test the suitability and reliability of current theoretical approaches. Two well-ordered overlayer structures (relaxed and compressed monolayers) of 1,4,5,8-naphthalene-tetracarboxylic acid dianhydride (NTCDA) on Ag(111) have been investigated using two-photon photoemission to derive precise interface-state energies for these closely related systems. The experimental values are reproduced by our density-functional theory (DFT) calculations with two approaches to treat dispersion interactions (semi-empirical correction DFT-D3 and parametrized functional optB88) and basis set approaches (localized numerical atomic orbitals, plane waves) with remarkable accuracy. Our results underline the trustworthiness and some of the limitations of current DFT-based methods regarding the description of geometric and electronic properties of metal-organic interfaces.

  12. Phase Behavior and Phase Structure of Protein-Surfactant-Water Systems.

    PubMed

    Morén; Khan

    1999-10-15

    Phase behavior of oppositely charged ovalbumin-DOTAC and BSA-DOTAC, and similarly charged ovalbumin-SDS, BSA-SDS, lysozyme-DOTAC, and BLG-SDS systems within the concentration range of 20 wt% of both protein and surfactant are examined in water. Aqueous solutions of ovalbumin yield, in succession, precipitation, gel, and solution with increased addition of the surfactant dodecyltrimethylammonium chloride (DOTAC). The stability range of each region is determined. Both isotropic and anisotropic gels are detected. Solutions of bovine serum albumin (BSA) form only a solution phase with oppositely charged DOTAC. One solution phase is also obtained with all similarly charged protein-surfactant systems except the BLG-SDS-water system, which produces a gel phase in addition to a large solution phase. (2)H NMR longitudinal (R(1)) and transverse (R(2)) relaxation rates are determined in solution and gel by following the behavior of selectively deuterated surfactant at the alpha-methylene group next to the surfactant head group for the oppositely charged systems ovalbumin-DOTAC and BSA-DOTAC. Large R(2)-values proved the existence of large protein-surfactant aggregates in both systems. Copyright 1999 Academic Press.

  13. Effect of Immobilized Thiolated Glycosaminoglycans on Fibronectin Adsorption and Behavior of Fibroblasts.

    PubMed

    Köwitsch, Alexander; Niepel, Marcus S; Michanetzis, Georgios P A; Missirlis, Yannis F; Groth, Thomas

    2016-03-01

    Glycosaminoglycans (GAGs) chondroitin sulfate, heparin, hyaluronan, and sulfated hyaluronan are lower and higher thiolated to enable a one-step covalent modification of gold or vinyl-terminated surfaces. Measurements of water contact angle and zeta potentials reveal that sulfated GAG-modified surfaces are more wettable and possess a negative surface potential. Additionally, higher thiolated GAGs (tGAGs) exhibit increased wettability and higher surface roughness. Fibronectin (FN) adsorption increases with sulfation degree of tGAGs. The tGAG-functionalized surfaces with higher degree of sulfation promote fibroblast adhesion most under serum-free conditions. The preadsorption of FN allows for more cell adhesion on tGAG surfaces. Metabolic activity measurements show that cell growth is enhanced for tGAGs up to a certain thiolation degree. Overall, thiolation of GAGs does not hamper their bioactivity toward proteins and cells, which make them highly interesting for biomimetic surface modification of implants and tissue engineering scaffolds.

  14. Surface behavior of malonic acid adsorption at the air/water interface.

    PubMed

    Blower, Patrick G; Shamay, Eric; Kringle, Loni; Ota, Stephanie T; Richmond, Geraldine L

    2013-03-28

    The presence of organic materials adsorbed to the surfaces of aerosol particles has been demonstrated to be a determining factor in relevant atmospheric processes. Malonic acid is a small, water-soluble organic acid that is common in aerosols and is surface-active. A comprehensive investigation of the adsorption of malonic acid to the air/water interface was accomplished using vibrational sum frequency spectroscopy (VSFS) and surface tension measurements as functions of concentration and pH. Malonic acid was found to be weakly solvated at the air/water interface, and its orientation as a function of concentration was explored through different VSFS polarization schemes. pH-dependent experiments revealed that the surface-active species is the fully protonated species. Computational analyses were used to obtain depth-specific geometries of malonic acid at the air/water interface that confirm and enrich the experimental results.

  15. Phase behavior of a binary fluid mixture of quadrupolar molecules

    NASA Astrophysics Data System (ADS)

    Toda, Masatoshi; Kajimoto, Shinji; Toyouchi, Shuichi; Kawakatsu, Toshihiro; Akama, Yohji; Kotani, Motoko; Fukumura, Hiroshi

    2016-11-01

    We propose a model molecule to investigate microscopic properties of a binary mixture with a closed-loop coexistence region. The molecule is comprised of a Lennard-Jones particle and a uniaxial quadrupole. Gibbs ensemble Monte Carlo simulations demonstrate that the high-density binary fluid of the molecules with the quadrupoles of the same magnitude but of the opposite signs can show closed-loop immiscibility. We find that an increase in the magnitude of the quadrupoles causes a shrinkage of the coexistence region. Molecular dynamics simulations also reveal that aggregates with two types of molecules arranged alternatively are formed in the stable one-phase region both above and below the coexistence region. String structures are dominant below the lower critical solution temperature, while branched aggregates are observed above the upper critical solution temperature. We conclude that the anisotropic interaction between the quadrupoles of the opposite signs plays a crucial role in controlling these properties of the phase behavior.

  16. Phase transitions in tumor growth: III vascular and metastasis behavior

    NASA Astrophysics Data System (ADS)

    Llanos-Pérez, J. A.; Betancourt-Mar, J. A.; Cocho, G.; Mansilla, R.; Nieto-Villar, José Manuel

    2016-11-01

    We propose a mechanism for avascular, vascular and metastasis tumor growth based on a chemical network model. Vascular growth and metastasis, appear as a hard phase transition type, as "first order", through a supercritical Andronov-Hopf bifurcation, emergence of limit cycle and then through a cascade of bifurcations type saddle-foci Shilnikov's bifurcation. Finally, the thermodynamics framework developed shows that the entropy production rate, as a Lyapunov function, indicates the directional character and stability of the dynamical behavior of tumor growth according to this model.

  17. Adsorption behavior of mercury on functionalized aspergillus versicolor mycelia: atomic force microscopic study.

    PubMed

    Das, Sujoy K; Das, Akhil R; Guha, Arun K

    2009-01-06

    The adsorption characteristics of mercury on Aspergillus versicolor mycelia have been studied under varied environments. The mycelia are functionalized by carbon disulfide (CS(2)) treatment under alkaline conditions to examine the enhance uptake capacity and explore its potentiality in pollution control management. The functionalized A. versicolor mycelia have been characterized by scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDXA), attenuated total reflection infrared (ATR-IR), and atomic force microscopy (AFM) probing. SEM and AFM images exhibit the formation of nanoparticles on the mycelial surface. ATR-IR profile confirms the functionalization of the mycelia following chemical treatment. ATR-IR and EDXA results demonstrate the binding of the sulfur groups of the functionalized mycelia to the mercury and consequent formation metal sulfide. AFM study reveals that the mycelial surface is covered by a layer of densely packed domain like structures. Sectional analysis yields significant increase in average roughness (R(rms)) value (20.5 +/- 1.82 nm) compared to that of the pristine mycelia (4.56 +/- 0.82 nm). Surface rigidity (0.88 +/- 0.06 N/m) and elasticity (92.6 +/- 10.2 MPa) obtained from a force distance curve using finite element modeling are found to increase significantly with respect to the corresponding values of (0.65 +/- 0.05 N/m and 32.8 +/- 4.5 MPa) of the nonfunctionalized mycelia. The maximum mercury adsorption capacity of the functionalized mycelia is observed to be 256.5 mg/g in comparison to 80.71 mg/g for the pristine mycelia.

  18. Phase Behavior of Neat Triblock Copolymers and Copolymer/Homopolymer Blends Near Network Phase Windows

    SciTech Connect

    M Tureau; L Rong; B Hsiao; T Epps

    2011-12-31

    The phase behavior of poly(isoprene-b-styrene-b-methyl methacrylate) (ISM) copolymers near the styrene-rich network phase window was examined through the use of neat triblock copolymers and copolymer/homopolymer blends. Both end-block and middle-block blending protocols were employed using poly(isoprene) (PI), poly(methyl methacrylate) (PMMA), and poly(styrene) (PS) homopolymers. Blended specimens exhibited phase transformations to well-ordered nanostructures (at homopolymer loadings up to 26 vol % of the total blend volume). Morphological consistency between neat and blended specimens was established at various locations in the ISM phase space. Copolymer/homopolymer blending permitted the refinement of lamellar, hexagonally packed cylinder, and disordered melt phase boundaries as well as the identification of double gyroid (Q{sup 230}), alternating gyroid (Q{sup 214}), and orthorhombic (O{sup 70}) network regimes. Additionally, the experimental phase diagram exhibited similar trends to those found in a theoretical ABC triblock copolymer phase diagram with symmetric interactions and statistical segments lengths generated by Tyler et al.

  19. Structural ordering and phase behavior of charged microgels.

    PubMed

    Mohanty, P S; Richtering, W

    2008-11-27

    Recent theoretical phase diagrams for loosely cross-linked ionic microgels with a low monomer volume fraction (Gottwald; et al. Phys. Rev. Lett. 2004, 92 , 068301 ) have predicted a re-entrant order-disorder transition (i.e., fluid-FCC-BCC-fluid) as a function of concentration and so far there has been no experimental verifications of these theoretical predictions. Here, we present experimental results on phase behavior of loosely cross-linked charged poly(N-isopropylacrylamide co acrylic acid) (PNIPAm-co-AAc) microgesls with a low monomer volume fraction (approximately 0.003) for a wide range of concentrations (0.02-0.6 wt %) using static and dynamic light scattering methods. These microgel dispersions exhibit a short-range liquid order at low concentration (<0.03 wt %), a FCC crystalline order at intermediate concentrations (0.03- 0.3 wt %). In addition, we suggested a possible coexistence of BCC and FCC phases at higher concentration crystalline suspension (approximately 0.34 wt %). These results clearly demonstrate the experimental verification of above theoretical prediction below the overlap concentration and also reveal that the interaction potential between the microgel particles is of screened Coulomb repulsive type within these concentration ranges. At further higher concentration (approximately 0.57 wt %), we once again observed a disordered state and this disordered state from dynamic light scattering was confirmed to be a glass. These initial results are discussed in the light of previously reported results on the phase behavior of ionic microgel colloidal dispersions.

  20. Two-Dimensional Phase Behavior of Colloidal Peanuts

    NASA Astrophysics Data System (ADS)

    Gerbode, Sharon; Wolfgang, Angie; Lee, Stephanie; John, Bettina; Liddell, Chekesha; Escobedo, Fernando; Cohen, Itai

    2007-03-01

    While the phase behavior of spherical colloidal suspensions has been well studied, the ordering of non-spherical colloidal particles remains a largely unexplored yet important problem. In this talk we will describe ongoing studies of one very simple extension of the spherical particle: the colloidal peanut. These peanuts have an aspect ratio that makes them comparable to dimer particles. Confining the colloidal peanuts to two dimensions, we find that the suspension can undergo a phase transition from a liquid to an ordered phase in which each individual peanut lobe resides on a triangular lattice site. The lobe packing is very similar to the hexagonally close packed crystalline arrangement formed by spheres in 2D. Unlike their spherical counterparts, however, the colloidal peanuts are not isotropic, and in particular, each peanut has a specific orientation, or director. In this talk we will describe the correlations between defects in the underlying triangular lattice and the local director field. We will also report on our measurements of long-range director correlations, and if time permits, we will describe ongoing work relating to phases formed by peanut particles with different aspect ratios.

  1. Ruthenium Behavior at Phase Separation of Borosilicate Glass-12259

    SciTech Connect

    Enokida, Youichi; Sawada, Kayo

    2012-07-01

    The Rokkasho reprocessing plant (RRP) located in Aomori, Japan, vitrifies high level waste (HLW) into a borosilicate glass. The HLW is generated from the reprocessing of spent fuel and contains ruthenium (Ru) and other platinum group metals (PGMs). Based on the recent consequences after a huge earthquake that occurred in Japan, a hypothetical blackout was postulated for the RRP to address additional safety analysis requirements. During a prolonged blackout, the borosilicate glass could phase separate due to cooling of the glass in the melter. The Ru present in the glass matrix could migrate into separate phases and impact the durability of the borosilicate glass. The durability of the glass is important for quality assurance and performance assessment of the vitrified HLW. A fundamental study was performed at an independent university to understand the impact of a prolonged blackout. Simulated HLW glasses were prepared for the RRP, and the Ru behavior in phase separated glasses was studied. The simulated HLW glasses contained nonradioactive elements and PGMs. The glass compositions were then altered to enhance the formation of the phase-separated glasses when subjected to thermal treatment at 700 deg. C for 24 hours. The synthesized simulated glasses contained 1.1 % Ru by weight as ruthenium dioxide (RuO{sub 2}). A portion of the RuO{sub 2} formed needle-shaped crystals in the glass specimens. After the thermal treatment, the glass specimen had separated into two phases. One of the two phases was a B{sub 2}O{sub 3} rich phase, and the other phase was a SiO{sub 2} rich phase. The majority of the chemical species in the B{sub 2}O{sub 3} rich phase was leached away with the Material Characterization Center-3 (MCC-3) protocol standardized by the Pacific Northwest National Laboratory using an aqueous low-concentrated nitric acid solution, but the leaching of the Ru fraction was very limited; less than 1% of the original Ru content. The Ru leaching was much less than

  2. Toward a Molecular-Scale Understanding of Chemical Adsorption and Frost Heaving: Phase II

    DTIC Science & Technology

    2007-11-02

    Management and Budget, Paperwork Reduction Project (0704-0188). Washington, DC 20503. 1. AGENCY USE ONLY ( Leave blank) 2. REPORT DATE 1/30/98 3. REPORT...induced liquifaction, chomatography and phase coexistence were presented. One book and 20 refereed papers wprp piihlichpH ha«;pH nn thPSP

  3. Dynamic observation of phase transformation behaviors in indium(III) selenide nanowire based phase change memory.

    PubMed

    Huang, Yu-Ting; Huang, Chun-Wei; Chen, Jui-Yuan; Ting, Yi-Hsin; Lu, Kuo-Chang; Chueh, Yu-Lun; Wu, Wen-Wei

    2014-09-23

    Phase change random access memory (PCRAM) has been extensively investigated for its potential applications in next-generation nonvolatile memory. In this study, indium(III) selenide (In2Se3) was selected due to its high resistivity ratio and lower programming current. Au/In2Se3-nanowire/Au phase change memory devices were fabricated and measured systematically in an in situ transmission electron microscope to perform a RESET/SET process under pulsed and dc voltage swept mode, respectively. During the switching, we observed the dynamic evolution of the phase transformation process. The switching behavior resulted from crystalline/amorphous change and revealed that a long pulse width would induce the amorphous or polycrystalline state by different pulse amplitudes, supporting the improvement of the writing speed, retention, and endurance of PCRAM.

  4. Freezing in porous media: Phase behavior, dynamics and transport phenomena

    SciTech Connect

    Wettlaufer, John S.

    2012-12-21

    This research was focused on developing the underlying framework for the mechanisms that control the nature of the solidification of a broad range of porous media. To encompass the scope of porous media under consideration we considered material ranging from a dilute colloidal suspension to a highly packed saturated host matrix with a known geometry. The basic physical processes that occur when the interstitial liquid phase solidifies revealed a host of surprises with a broad range of implications from geophysics to materials science and engineering. We now understand that ostensibly microscopic films of unfrozen liquid control both the equilibrium and transport properties of a highly packed saturated host matrix as well as a rather dilute colloidal suspension. However, our description of the effective medium behavior in these settings is rather different and this sets the stage for the future research based on our past results. Once the liquid phase of a saturated relatively densely packed material is frozen, there is a rich dynamical behavior of particles for example due to the directed motion driven by thermomolecular pressure gradients or the confined Brownian motion of the particles. In quite striking contrast, when one freezes a dilute suspension the behavior can be rather more like that of a binary alloy with the particles playing the role of a ``solute''. We probed such systems quantitatively by (i) using X ray photon correlation spectroscopy (XPCS) and Small Angle X-ray Scattering (SAXS) at the Advanced Photon Source at Argonne (ii) studying the Argonne cell in the laboratory using optical microscopy and imagery (because it is not directly visible while in the vacuum can). (3) analyzed the general transport phenomena within the framework of both irreversible thermodynamics and alloy solidification and (4) applied the results to the study of the redistribution of solid particles in a frozen interstitial material. This research has gone a long way towards

  5. Dimensionless Equation of State to Predict Microemulsion Phase Behavior.

    PubMed

    Ghosh, Soumyadeep; Johns, Russell T

    2016-09-06

    Prediction of microemulsion phase behavior for changing state variables is critical to formulation design of surfactant-oil-brine (SOB) systems. SOB systems find applications in various chemical and petroleum processes, including enhanced oil recovery. A dimensional equation-of-state (EoS) was recently presented by Ghosh and Johns1 that relied on estimation of the surfactant tail length and surface area. We give an algorithm for flash calculations for estimation of three-phase Winsor regions that is more robust, simpler, and noniterative by making the equations dimensionless so that estimates of tail length and surface area are no longer needed. We predict phase behavior as a function temperature, pressure, volume, salinity, oil type, oil-water ratio, and surfactant/alcohol concentration. The dimensionless EoS is based on coupling the HLD-NAC (Hydrophilic Lipophilic Difference-Net Average Curvature) equations with new relationships between optimum salinity and solubility. An updated HLD expression that includes pressure is also used to complete the state description. A significant advantage of the dimensionless form of the EoS over the dimensional version is that salinity scans are tuned based only on one parameter, the interfacial volume ratio. Further, stability conditions are developed in a simplified way to predict whether an overall compositions lies within the single, two-, or three-phase regions. Important new microemulsion relationships are also found, the most important of which is that optimum solubilization ratio is equal to the harmonic mean of the oil and water solubilization ratios in the type III region. Thus, only one experimental measurement is needed in the three-phase zone to estimate the optimum solubilization ratio, a result which can aid experimental design and improve estimates of optimum from noisy data. Predictions with changing state variables are illustrated by comparison to experimental data using standard diagrams including a new type

  6. Cesium adsorption/desorption behavior of clay minerals considering actual contamination conditions in Fukushima

    PubMed Central

    Mukai, Hiroki; Hirose, Atsushi; Motai, Satoko; Kikuchi, Ryosuke; Tanoi, Keitaro; Nakanishi, Tomoko M.; Yaita, Tsuyoshi; Kogure, Toshihiro

    2016-01-01

    Cesium adsorption/desorption experiments for various clay minerals, considering actual contamination conditions in Fukushima, were conducted using the 137Cs radioisotope and an autoradiography using imaging plates (IPs). A 50 μl solution containing 0.185 ~ 1.85 Bq of 137Cs (10−11 ~ 10−9 molL−1 of 137Cs) was dropped onto a substrate where various mineral particles were arranged. It was found that partially-vermiculitized biotite, which is termed “weathered biotite” (WB) in this study, from Fukushima sorbed 137Cs far more than the other clay minerals (fresh biotite, illite, smectite, kaolinite, halloysite, allophane, imogolite) on the same substrate. When WB was absent on the substrate, the amount of 137Cs sorbed to the other clay minerals was considerably increased, implying that selective sorption to WB caused depletion of radiocesium in the solution and less sorption to the coexisting minerals. Cs-sorption to WB continued for about one day, whereas that to ferruginous smectite was completed within one hour. The sorbed 137Cs in WB was hardly leached with hydrochloric acid at pH 1, particularly in samples with a longer sorption time. The presence/absence of WB sorbing radiocesium is a key factor affecting the dynamics and fate of radiocesium in Fukushima. PMID:26868138

  7. Facile synthesis of hydroxyapatite/yeast biomass composites and their adsorption behaviors for lead (II).

    PubMed

    Zhang, Wei; Wang, Feihu; Wang, Peilu; Lin, Li; Zhao, Yu; Zou, Ping; Zhao, Maojun; Chen, Hui; Liu, Yong; Zhang, Yunsong

    2016-09-01

    For the first time, the hydroxyapatite (HAp)/yeast biomass composites were successfully synthesized through a facile alkaline ultrasound cavitation method, and used as a novel sorbent for removal of Pb(2+) from aqueous solution. The obtained HAp/yeast biomass composites were characterized by various techniques, including SEM, EDX, XRD, TGA, FTIR, XPS and fluorescence detection, respectively. It was found that the yeast cells were wrapped by the well-dispersed HAp, and more functional groups (such as carboxyl, hydroxyl and amino) on yeast surface were exposed. Also, varying factors that may affect the adsorption efficiency of HAp/yeast biomass composites, such as solution pH, reaction temperature and time, have been carefully investigated respectively. Remarkably, more than 99% of Pb(2+) can be removed by the HAp/yeast biomass composites. Evidence from FTIR and XPS analysis revealed that the higher removal efficiency should be ascribed to the synergetic effect of synthesized HAp and more functional groups exposed on yeast surface.

  8. Cesium adsorption/desorption behavior of clay minerals considering actual contamination conditions in Fukushima

    NASA Astrophysics Data System (ADS)

    Mukai, Hiroki; Hirose, Atsushi; Motai, Satoko; Kikuchi, Ryosuke; Tanoi, Keitaro; Nakanishi, Tomoko M.; Yaita, Tsuyoshi; Kogure, Toshihiro

    2016-02-01

    Cesium adsorption/desorption experiments for various clay minerals, considering actual contamination conditions in Fukushima, were conducted using the 137Cs radioisotope and an autoradiography using imaging plates (IPs). A 50 μl solution containing 0.185 ~ 1.85 Bq of 137Cs (10-11 ~ 10-9 molL-1 of 137Cs) was dropped onto a substrate where various mineral particles were arranged. It was found that partially-vermiculitized biotite, which is termed “weathered biotite” (WB) in this study, from Fukushima sorbed 137Cs far more than the other clay minerals (fresh biotite, illite, smectite, kaolinite, halloysite, allophane, imogolite) on the same substrate. When WB was absent on the substrate, the amount of 137Cs sorbed to the other clay minerals was considerably increased, implying that selective sorption to WB caused depletion of radiocesium in the solution and less sorption to the coexisting minerals. Cs-sorption to WB continued for about one day, whereas that to ferruginous smectite was completed within one hour. The sorbed 137Cs in WB was hardly leached with hydrochloric acid at pH 1, particularly in samples with a longer sorption time. The presence/absence of WB sorbing radiocesium is a key factor affecting the dynamics and fate of radiocesium in Fukushima.

  9. The Effect of Pitch Composition on the Adsorption Behavior of Pd-Doped ACF

    SciTech Connect

    Tekinalp, Halil; Cervo, Eduardo; Thies, Mark C; Contescu, Cristian I; Gallego, Nidia C; Edie, Dan

    2007-01-01

    Recent studies indicate that metal-containing activated carbon fibers (ACF) are promising adsorbents for hydrogen storage applications. In these studies, Pd compounds were added to a petroleum precursor and formed into ACFs. Results showed that the molecular composition of the pitch had a significant affect on critical characteristics of the ACFs, such as pore size and Pd particle size. In an ongoing Department of Energy project, we are testing pitch precursors with carefully controlled chemical compositions in order to develop an optimum precursor for hydrogen storage applications. A low softening point pitch made by Marathon Oil is being separated into narrow molecular weight fractions using a dense gas extraction (DGE) process. In the current series of tests the heavier portion of the extracted pitch was used to prepare both undoped and Pd-doped carbon fibers. These fibers were activated over a range of temperatures to determine the effect of temperature and pitch composition on ACF properties. Lower activation temperatures resulted in increased microporosity (desirable for hydrogen adsorption) for all Pd-doped pitch precursors. Comparing ACFs produced from various DGE-extracted pitches showed that even small quantities of mesophase-forming components inhibited activation and significantly reduced microporosity. Additional DGE pitch fractions are now being tested to further refine the optimum composition for hydrogen storage applications.

  10. Phase behavior of polymer/nanoparticle blends near a substrate

    NASA Astrophysics Data System (ADS)

    McGarrity, E. S.; Frischknecht, A. L.; Mackay, M. E.

    2008-04-01

    We use the recent fluids density functional theory of Tripathi and Chapman [Phys. Rev. Lett. 94, 087801 (2005); J. Chem. Phys. 122, 094506 (2005)] to investigate the phase behavior of athermal polymer/nanoparticle blends near a substrate. The blends are modeled as a mixture of hard spheres and freely jointed hard chains, near a hard wall. There is a first order phase transition present in these blends in which the nanoparticles expel the polymer from the surface to form a monolayer at a certain nanoparticle concentration. The nanoparticle transition density depends on the length of the polymer, the nanoparticle diameter, and the overall bulk density of the system. The phase transition is due to both packing entropy effects related to size asymmetry between the components and to the polymer configurational entropy, justifying the so-called "entropic push" observed in experiments. In addition, a layered state is found at higher densities which resembles that in colloidal crystals, in which the polymer and nanoparticles form alternating discrete layers. We show that this laminar state has nearly the same free energy as the homogeneously mixed fluid in the bulk and is nucleated by the surface.

  11. Deformation Behavior across the Zircon-Scheelite Phase Transition

    NASA Astrophysics Data System (ADS)

    Yue, Binbin; Hong, Fang; Merkel, Sébastien; Tan, Dayong; Yan, Jinyuan; Chen, Bin; Mao, Ho-Kwang

    2016-09-01

    The pressure effects on plastic deformation and phase transformation mechanisms of materials are of great importance to both Earth science and technological applications. Zircon-type materials are abundant in both nature and the industrial field; however, there is still no in situ study of their deformation behavior. Here, by employing radial x-ray diffraction in a diamond anvil cell, we investigate the dislocation-induced texture evolution of zircon-type gadolinium vanadate (GdVO4 ) in situ under pressure and across its phase transitions to its high-pressure polymorphs. Zircon-type GdVO4 develops a (001) compression texture associated with dominant slip along ⟨100 ⟩{001 } starting from 5 GPa. This (001) texture transforms into a (110) texture during the zircon-scheelite phase transition. Our observation demonstrates a martensitic mechanism for the zircon-scheelite transformation. This work will help us understand the local deformation history in the upper mantle and transition zone and provides fundamental guidance on material design and processing for zircon-type materials.

  12. Deformation Behavior across the Zircon-Scheelite Phase Transition.

    PubMed

    Yue, Binbin; Hong, Fang; Merkel, Sébastien; Tan, Dayong; Yan, Jinyuan; Chen, Bin; Mao, Ho-Kwang

    2016-09-23

    The pressure effects on plastic deformation and phase transformation mechanisms of materials are of great importance to both Earth science and technological applications. Zircon-type materials are abundant in both nature and the industrial field; however, there is still no in situ study of their deformation behavior. Here, by employing radial x-ray diffraction in a diamond anvil cell, we investigate the dislocation-induced texture evolution of zircon-type gadolinium vanadate (GdVO_{4}) in situ under pressure and across its phase transitions to its high-pressure polymorphs. Zircon-type GdVO_{4} develops a (001) compression texture associated with dominant slip along ⟨100⟩{001} starting from 5 GPa. This (001) texture transforms into a (110) texture during the zircon-scheelite phase transition. Our observation demonstrates a martensitic mechanism for the zircon-scheelite transformation. This work will help us understand the local deformation history in the upper mantle and transition zone and provides fundamental guidance on material design and processing for zircon-type materials.

  13. Impacts of relative permeability on CO2 phase behavior, phase distribution, and trapping mechanisms

    NASA Astrophysics Data System (ADS)

    Moodie, N.; McPherson, B. J. O. L.; Pan, F.

    2015-12-01

    A critical aspect of geologic carbon storage, a carbon-emissions reduction method under extensive review and testing, is effective multiphase CO2 flow and transport simulation. Relative permeability is a flow parameter particularly critical for accurate forecasting of multiphase behavior of CO2 in the subsurface. The relative per­meability relationship assumed and especially the irreducible saturation of the gas phase greatly impacts predicted CO2 trapping mechanisms and long-term plume migration behavior. A primary goal of this study was to evaluate the impact of relative permeability on efficacy of regional-scale CO2 sequestration models. To accomplish this we built a 2-D vertical cross-section of the San Rafael Swell area of East-central Utah. This model simulated injection of CO2 into a brine aquifer for 30 years. The well was then shut-in and the CO2 plume behavior monitored for another 970 years. We evaluated five different relative permeability relationships to quantify their relative impacts on forecasted flow results of the model, with all other parameters maintained uniform and constant. Results of this analysis suggest that CO2 plume movement and behavior are significantly dependent on the specific relative permeability formulation assigned, including the assumed irreducible saturation values of CO2 and brine. More specifically, different relative permea­bility relationships translate to significant differences in CO2 plume behavior and corresponding trapping mechanisms.

  14. 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.

  15. Influence of Inorganic Ions and Aggregation and Adsorption Behaviors of Human Adenovirus

    EPA Science Inventory

    In this study, influence of solution chemistries to the transport properties (aggregation and attachment behavior) of human adenovirus (HAdV) was investigated. Results showed isoelectric point (IEP) of HAdV in different salt conditions varied minimally, and it ranged from pH 3.5 ...

  16. Adsorption of CO on gas phase and zeolite supported gold monomers: A computational study

    NASA Astrophysics Data System (ADS)

    Deka, Ajanta; Deka, Ramesh Chandra; Choudhury, Amarjyoti

    2010-04-01

    We report for the first time the interaction of carbon monoxide with gold monomer in three oxidation states 0, +1 and +3 on FAU zeolite support using density functional theory. The gas phase structures of the gold carbonyls are retained on the zeolite support with only a slight change in the O-C-Au bond angle. For the supported cluster the CO vibrational frequency shows a blue shift on going to higher oxidation states. The CO binding energies on the supported gold monomers are 1.01, 1.15 and 1.12 eV in the oxidation states 0, +1 and +3, respectively.

  17. Management of agricultural waste for removal of heavy metals from aqueous solution: adsorption behaviors, adsorption mechanisms, environmental protection, and techno-economic analysis.

    PubMed

    Elhafez, S E Abd; Hamad, H A; Zaatout, A A; Malash, G F

    2017-01-01

    In the last decades, Egypt has been suffering from the phenomenon of black cloud resulting from burning rice husk and increasing the demand for water leading to the water crisis. An alternative, low-value and surplus agricultural byproduct (rice husk, RH) has an enormous potential for the removal of Cu(II) ions from water. The present study focuses on the chance of the use of rice husk as a bio-adsorbent without any chemical treatment instead of burning it and soiling the environment. The elemental, structural, morphological, surface functional, thermal, and textural characteristics of RH are determined by XRF, XRD, SEM, FT-IR, TGA, and BET surface area, respectively, and contributed to the understanding of the adsorption mechanism of Cu(II) ions in aqueous solution. Also, the performance analysis, adsorption mechanism, influencing factors, favorable conditions, etc. are discussed in this article. The results obtained from optimization by batch mode are achieved under the following conditions: initial concentration, 150 ppm; amount of rice husk, 1 g; average particle size, 0.25 mm; temperature, 25 °C; pH, 4; agitation rate, 180 rpm; and contact time, 60 min. RH exhibits a high degree of selectivity for Cu(II) adsorption. The adsorption isotherm is fitted well with Langmuir and Freundlich models with R (2) 0.998 and 0.997, respectively. The adsorption is well governed by the pseudo-second-order kinetics. It is observed that the rate of adsorption improves with decreasing temperature, and the process is exothermic and non-spontaneous. Particular attention has being paid to factors as production processes, fixed/operational cost, production cost, and profit. The techno-economical analysis is presented in this study that provides precise demands on capital for a fixed investment, provisions for operational capital, and finally provisions for revenue. The social, economical, and environmental benefits by industrial point of view using low-cost adsorbent are also

  18. Application of Statistical Thermodynamics To Predict the Adsorption Properties of Polypeptides in Reversed-Phase HPLC.

    PubMed

    Tarasova, Irina A; Goloborodko, Anton A; Perlova, Tatyana Y; Pridatchenko, Marina L; Gorshkov, Alexander V; Evreinov, Victor V; Ivanov, Alexander R; Gorshkov, Mikhail V

    2015-07-07

    The theory of critical chromatography for biomacromolecules (BioLCCC) describes polypeptide retention in reversed-phase HPLC using the basic principles of statistical thermodynamics. However, whether this theory correctly depicts a variety of empirical observations and laws introduced for peptide chromatography over the last decades remains to be determined. In this study, by comparing theoretical results with experimental data, we demonstrate that the BioLCCC: (1) fits the empirical dependence of the polypeptide retention on the amino acid sequence length with R(2) > 0.99 and allows in silico determination of the linear regression coefficients of the log-length correction in the additive model for arbitrary sequences and lengths and (2) predicts the distribution coefficients of polypeptides with an accuracy from 0.98 to 0.99 R(2). The latter enables direct calculation of the retention factors for given solvent compositions and modeling of the migration dynamics of polypeptides separated under isocratic or gradient conditions. The obtained results demonstrate that the suggested theory correctly relates the main aspects of polypeptide separation in reversed-phase HPLC.

  19. Densely-packed ZnTPPs Monolayer on the Rutile TiO2(110)-(1×1) Surface: Adsorption Behavior and Energy Level Alignment.

    PubMed

    Rangan, Sylvie; Ruggieri, Charles; Bartynski, Robert; Martínez, José Ignacio; Flores, Fernando; Ortega, José

    2016-03-03

    The adsorption of a densely packed Zinc(II) tetraphenylporphyrin monolayer on a rutile TiO2(110)-(1×1) surface has been studied using a combination of experimental and theoretical methods, aimed at analyzing the relation between adsorption behavior and barrier height formation. The adsorption configuration of ZnTPP was determined from scanning tunnel microscopy (STM) imaging, density functional theory (DFT) calculations and STM image simulation. The corresponding energy alignment was experimentally determined from X-ray and UV-photoemission spectroscopies and inverse photoemission spectroscopy. These results were found in good agreement with an appropriately corrected DFT model, pointing to the importance of local bonding and intermolecular interactions in the establishment of barrier heights.

  20. On the vibrational behavior of single- and double-walled carbon nanotubes under the physical adsorption of biomolecules in the aqueous environment: a molecular dynamics study.

    PubMed

    Ajori, S; Ansari, R; Darvizeh, M

    2016-03-01

    The adsorption of biomolecules on the walls of carbon nanotubes (CNTs) in an aqueous environment is of great importance in the field of nanobiotechnology. In this study, molecular dynamics (MD) simulations were performed to understand the mechanical vibrational behavior of single- and double-walled carbon nanotubes (SWCNTs and DWCNTs) under the physical adsorption of four important biomolecules (L-alanine, guanine, thymine, and uracil) in vacuum and an aqueous environment. It was observed that the natural frequencies of these CNTs in vacuum reduce under the physical adsorption of biomolecules. In the aqueous environment, the natural frequency of each pure CNT decreased as compared to its natural frequency in vacuum. It was also found that the frequency shift for functionalized CNTs as compared to pure CNTs in the aqueous environment was dependent on the radius and the number of walls of the CNT, and could be positive or negative.

  1. Densely-packed ZnTPPs Monolayer on the Rutile TiO2(110)-(1×1) Surface: Adsorption Behavior and Energy Level Alignment

    PubMed Central

    Rangan, Sylvie; Ruggieri, Charles; Bartynski, Robert; Martínez, José Ignacio; Flores, Fernando; Ortega, José

    2016-01-01

    The adsorption of a densely packed Zinc(II) tetraphenylporphyrin monolayer on a rutile TiO2(110)-(1×1) surface has been studied using a combination of experimental and theoretical methods, aimed at analyzing the relation between adsorption behavior and barrier height formation. The adsorption configuration of ZnTPP was determined from scanning tunnel microscopy (STM) imaging, density functional theory (DFT) calculations and STM image simulation. The corresponding energy alignment was experimentally determined from X-ray and UV-photoemission spectroscopies and inverse photoemission spectroscopy. These results were found in good agreement with an appropriately corrected DFT model, pointing to the importance of local bonding and intermolecular interactions in the establishment of barrier heights. PMID:26998188

  2. Phase behavior and microstructure of nonaqueous microemulsions. 2

    SciTech Connect

    Martino, A.; Kaler, E.W.

    1995-03-01

    The microstructure of nonaqueous microemulsions formed with propylene glycol, glycerol, three different alkanes, and pentaethylene glycol mono-n-dodecyl ether (C{sub 12}E{sub 6}) is probed with NMR self-diffusion measurements and small angle neutron scattering (SANS). At low oil concentrations, both NMR self-diffusion and SANS results can be modeled in terms of a microstructure of ellipsoidal oil-rich droplets with only excluded volume interactions. These droplet structures percolate to an oil-continuous structure as the volume fraction of oil in the microemulsions increases. Percolation thresholds measured as a function of alkane chain length are interpreted in terms of the phase behavior of the microemulsion and the strength of droplet interactions. 41 refs., 6 figs., 3 tabs.

  3. Probing the phase behavior of ABC triblock copolymers near network phase windows

    NASA Astrophysics Data System (ADS)

    Tureau, Maeva S.

    Block copolymers are one class of soft materials that consist of two or more covalently-bonded chains of chemically distinct monomers. Their ability to self-assemble into a variety of nanostructured materials with tailored chemical and physical properties has motivated extensive investigations for use in many emerging nanotechnologies such as nanotemplates, analytical separation membranes, and electrical and ionic conductors. Relative to cylindrical nanostructures that often require external alignment techniques to minimize structural defects, network structures possess co-continuous percolating domains in three-dimension and exhibit superior mechanical stability, short diffusion path lengths, and high internal interfacial areas, which can facilitate transport in applications such as water filtration and ion-conducting membranes. In this thesis project, the poly(ethylene-alt-propylene- b-styrene-b-methyl methacrylate) (EPSM) triblock copolymer system was produced from the selective poly(isoprene) hydrogenation of poly(isoprene-b-styrene-b-methyl methacrylate) (ISM) precursors. The EPSM system was selected due to the toughness given by the combined interactions of the glassy poly(styrene) (PS) and rubbery poly(ethylene-alt-propylene) (PEP) blocks, the mechanical strength provided by the PS block, and the ease of removal of the poly(methyl methacrylate) (PMMA) block. This dissertation first presents the phase behavioral exploration of anionically-synthesized ISM triblock copolymer precursors and associated ISM copolymer/homopolymer blends, which permitted the identification and refinement of network phase regions. The copolymer/homopolymer blending technique allowed for homopolymer-induced phase transformations to and from network structures where alternating gyroid (Q214), core-shell gyroid (Q230), and orthorhombic (O70) network phases were identified. The ISM phase behavior was found to qualitatively match the predicted self-consistent mean field theory (SCFT

  4. Dual-thermoresponsive phase behavior of blood compatible zwitterionic copolymers containing nonionic poly(N-isopropyl acrylamide).

    PubMed

    Chang, Yung; Chen, Wen-Yih; Yandi, Wetra; Shih, Yu-Ju; Chu, Wan-Ling; Liu, Ying-Ling; Chu, Chih-Wei; Ruaan, Ruoh-Chyu; Higuchi, Akon

    2009-08-10

    Thermoresponsive statistical copolymers of zwitterionic sulfobetaine methacrylate (SBMA) and nonionic N-isopropylacrylamide (NIPAAm) were prepared with an average molecular weight of about 6.0 kDa via homogeneous free radical copolymerization. The aqueous solution properties of poly(SBMA-co-NIPAAm) were measured using a UV--visible spectrophotometer. The copolymers exhibited controllable lower and upper critical solution temperatures in aqueous solution and showed stimuli-responsive phase transition in the presence of salts. Regulated zwitterionic and nonionic molar mass ratios led to poly(SBMA-co-NIPAAm) copolymers having double-critical solution temperatures, where the water-insoluble polymer microdomains are generated by the zwitterionic copolymer region of polySBMA or nonionic copolymer region of polyNIPAAm depending on temperature. A high content of the nonionic polyNIPAAm in poly(SBMA-co-NIPAAm) exhibits nonionic aggregation at high temperatures due to the desolvation of polyNIPAAm, whereas relatively low content of polyNIPAAm in poly(SBMA-co-NIPAAm) exhibits zwitterionic aggregation at low temperatures due to the desolvation of polySBMA. Plasma protein adsorption on the surface coated with poly(SBMA-co-NIPAAm) was measured with a surface plasmon resonance (SPR) sensor. The copolymers containing polySBMA above 29 mol % showed extremely low protein adsorption and high anticoagulant activity in human blood plasma. The tunable and switchable thermoresponsive phase behavior of poly(SBMA-co-NIPAAm), as well as its high plasma protein adsorption resistance and anticoagulant activity, suggests a potential for blood-contacting applications.

  5. Adsorption of polycations on clays: A comparative in situ study using {sup 133}Cs and {sup 23}Na solution phase NMR

    SciTech Connect

    Billingham, J.; Breen, C.; Rawson, J.O.; Yarwood, J.; Mann, B.E.

    1997-09-15

    {sup 23}Na solution phase NMR has been evaluated as an in situ probe to study the adsorption of tetramethylammonium (TMA{sup +}) and two polycations, FL17 and Magnafloc 1697, onto clays in aqueous suspensions containing 2.5 mass% low iron Texas bentonite. The NMR data shows the effectiveness of the organocations at displacing Na{sup +} from the bentonite surface. This information has been correlated with that obtained from particle-size and electrophoretic measurements in aqueous solution, together with information from adsorption isotherms. These results have been compared to those obtained in parallel studies using {sup 133}Cs solution phase NMR. FL17 and 1697 both exhibited high affinity adsorption isotherms on Na{sup +}- and Cs{sup +}-clay, whereas the adsorption of TMA{sup +}, which represents the cationic portion of the polymers was of lower affinity. Na{sup +}-bentonite adsorbed almost twice the amount of polycation required to fulfill the cation-exchange capacity (CEC) of the bentonite. The electrophoretic and particle size data indicated significant differences in the size of the polycation/clay flocs and the amount of polymer adsorbed on the external faces of the flocs in the presence of Na{sup +}- and Cs{sup +}-exchange ions. Correlation of this data with the NMR results suggests that the Na{sup +}-bentonite/polycation flocs are large, of low density, and that the polycation is concentrated in the interior while the Na{sup +}-ions occupy exchange sites on the external faces.

  6. Adsorption and separation behavior of yttrium and strontium in nitric acid solution by extraction chromatography using a macroporous silica-based adsorbent.

    PubMed

    Xu, Yuanlai; Kim, Seong-Yun; Ito, Tatsuya; Nakazawa, Kasane; Funaki, Yoshihito; Tada, Tsutomu; Hitomi, Keitaro; Ishii, Keizo

    2012-11-09

    To separate (90)Y from the fission product (90)Sr-(90)Y group, a silica-based TODGA/SiO(2)-P adsorbent was prepared by impregnating N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) extractant into the macroporous SiO(2)-P support with a mean diameter of 60 μm. The adsorption behavior of Sr(II) and Y(III) onto TODGA/SiO(2)-P adsorbent from HNO(3) solution and their mutual separation were investigated. Under the experimental conditions, this adsorbent showed high adsorption affinity to Y(III) and weak adsorption to Sr(II). It was found that the adsorption process of Y(III) could be expressed by both of Langmuir monomolecular layer adsorption mode and the pseudo-second order model. From the results of stability experiments, it became clear that TODGA/SiO(2)-P adsorbent is stable in 3M HNO(3) solution for 1 month contact time at 298 K. Using a column packed with TODGA/SiO(2)-P adsorbent, Sr(II) and Y(III) were eluted by distilled water and diethylenetriamine pentaacetic acid (DTPA) solution, respectively. The separation of Y(III) from Sr(II)-Y(III) group was achieved successfully.

  7. Spatiotemporal behavior and nonlinear dynamics in a phase conjugate resonator

    NASA Technical Reports Server (NTRS)

    Liu, Siuying Raymond

    1993-01-01

    The work described can be divided into two parts. The first part is an investigation of the transient behavior and stability property of a phase conjugate resonator (PCR) below threshold. The second part is an experimental and theoretical study of the PCR's spatiotemporal dynamics above threshold. The time-dependent coupled wave equations for four-wave mixing (FWM) in a photorefractive crystal, with two distinct interaction regions caused by feedback from an ordinary mirror, was used to model the transient dynamics of a PCR below threshold. The conditions for self-oscillation were determined and the solutions were used to define the PCR's transfer function and analyze its stability. Experimental results for the buildup and decay times confirmed qualitatively the predicted behavior. Experiments were carried out above threshold to study the spatiotemporal dynamics of the PCR as a function of Pragg detuning and the resonator's Fresnel number. The existence of optical vortices in the wavefront were identified by optical interferometry. It was possible to describe the transverse dynamics and the spatiotemporal instabilities by modeling the three-dimensional-coupled wave equations in photorefractive FWM using a truncated modal expansion approach.

  8. Spatiotemporal behavior and nonlinear dynamics in a phase conjugate resonator

    NASA Astrophysics Data System (ADS)

    Liu, Siuying Raymond

    1993-12-01

    The work described can be divided into two parts. The first part is an investigation of the transient behavior and stability property of a phase conjugate resonator (PCR) below threshold. The second part is an experimental and theoretical study of the PCR's spatiotemporal dynamics above threshold. The time-dependent coupled wave equations for four-wave mixing (FWM) in a photorefractive crystal, with two distinct interaction regions caused by feedback from an ordinary mirror, was used to model the transient dynamics of a PCR below threshold. The conditions for self-oscillation were determined and the solutions were used to define the PCR's transfer function and analyze its stability. Experimental results for the buildup and decay times confirmed qualitatively the predicted behavior. Experiments were carried out above threshold to study the spatiotemporal dynamics of the PCR as a function of Pragg detuning and the resonator's Fresnel number. The existence of optical vortices in the wavefront were identified by optical interferometry. It was possible to describe the transverse dynamics and the spatiotemporal instabilities by modeling the three-dimensional-coupled wave equations in photorefractive FWM using a truncated modal expansion approach.

  9. Tethered Nanoparticle -Polymer Composites: Phase behavior and rheology

    NASA Astrophysics Data System (ADS)

    Mangal, Rahul; Archer, Lynden A.

    2014-03-01

    Polymer nanocomposites with particle radius (a) approaching the radius of gyration (Rg) of entangled host polymer have been reported to exhibit an unusual negative reinforcement effect, which leads to an anomalous reduction in relative an anomalous reduction in relative viscosity at low particle loadings (φ) . This so-called Non-Einsteinian flow behavior is understood to be sensitive to the dispersion state of particles in host polymer. We studied suspensions of SiO2 nanoparticles tethered with polethylene glycol (PEG) in polymethylmethacralate (PMMA) with molecular weights (Mw) from 17 KDa to 280 KDa. Due to strong enthalpic interactions between PEG and PMMA (χ = -0.65), nanoparticles are expected to be well-dispersed, independent of Mw of PMMA. Using small angle x-ray scattering measurements we show that the phase stability of suspensions depends on Mw of the tethered PEG, host PMMA, and φ. Particles functionalized with low molecular weight PEG aggregate at low φ, but disperse at high φ. In contrast, nanoparticles functionalized with higher molecular weight PEG are well dispersed for host chain lengths (P) to tethered chain length (N), (P/N), is as high as 160. The stability boundary of these suspensions extends well beyond expectations for nanocomposites based on tethered PEG chains suspended in PEG. Through in-depth analysis of rheology and x-ray photon correlation spectra we explore the fundamental origins of non-Einsteinian flow behavior. King Abdullah University of Science and Technology (KAUST), Advanced Photon Source (APS).

  10. Adsorption behavior of a human monoclonal antibody at hydrophilic and hydrophobic surfaces

    PubMed Central

    Couston, Ruairidh G.; Skoda, Maximilian W.; Uddin, Shahid; van der Walle, Christopher F.

    2013-01-01

    One aspiration for the formulation of human monoclonal antibodies (mAb) is to reach high solution concentrations without compromising stability. Protein surface activity leading to instability is well known, but our understanding of mAb adsorption to the solid-liquid interface in relevant pH and surfactant conditions is incomplete. To investigate these conditions, we used total internal reflection fluorescence (TIRF) and neutron reflectometry (NR). The mAb tested (“mAb-1”) showed highest surface loading to silica at pH 7.4 (~12 mg/m2), with lower surface loading at pH 5.5 (~5.5 mg/m2, further from its pI of 8.99) and to hydrophobized silica (~2 mg/m2). The extent of desorption of mAb-1 from silica or hydrophobized silica was related to the relative affinity of polysorbate 20 or 80 for the same surface. mAb-1 adsorbed to silica on co-injection with polysorbate (above its critical micelle concentration) and also to silica pre-coated with polysorbate. A bilayer model was developed from NR data for mAb-1 at concentrations of 50–5000 mg/L, pH 5.5, and 50–2000 mg/L, pH 7.4. The inner mAb-1 layer was adsorbed to the SiO2 surface at near saturation with an end-on” orientation, while the outer mAb-1 layer was sparse and molecules had a “side-on” orientation. A non-uniform triple layer was observed at 5000 mg/L, pH 7.4, suggesting mAb-1 adsorbed to the SiO2 surface as oligomers at this concentration and pH. mAb-1 adsorbed as a sparse monolayer to hydrophobized silica, with a layer thickness increasing with bulk concentration - suggesting a near end-on orientation without observable relaxation-unfolding. PMID:23196810

  11. Evaluation of the adsorptive behavior of cesium and strontium on hydroxyapatite and zeolite for decontamination of radioactive substances.

    PubMed

    Ozeki, K; Aoki, H

    2016-08-12

    Removal of radioactive substances, such as cesium (Cs) and strontium (Sr), has become an emerging issue after the Fukushima Daiichi Nuclear Power Plant Disaster. To assess the possibility that hydroxyapatite (HA) and zeolites can be used for removal of radioactive substances, the adsorption capacities of Cs and Sr on the HA and a zeolite were investigated. The influence of Fe ions on Cs and Sr adsorption on the HA and the zeolite was also evaluated, because Fe ions are the most effective inhibitor of Cs adsorption on the zeolite.In the Cs adsorption process on the HA and the zeolite, the zeolite showed a higher adsorption ratio than the HA, and the maximum sorption capacity of the zeolite was calculated as 196 mg/g, whereas the HA showed a higher Sr adsorption ratio than the zeolite. The maximum sorption capacity of Sr on the HA was 123 mg/g. Under coexistence with Fe, Cs adsorption on the zeolite decreased with increasing Fe concentration, reaching 2.0 ± 0.8% at 0.1 M Fe concentration. In contrast, Cs adsorption on the zeolite was improved by adding the HA. In the case of coexistence of the HA, the Cs adsorption on the mixture of the HA and the zeolite was 52.4% ± 3.6 % at 0.1 M Fe concentration, although Cs adsorption on the HA alone was quite low. In the Fe adsorption processes of the HA and the zeolite, the HA exhibited a maximum sorption capacity of 256 mg/g, which was much higher than that of the zeolite (111 mg/g). The high affinity of Fe on the HA contributes to the improvement of the deteriorated Cs adsorption on the zeolite due to Fe ions.

  12. Metaphysics, science and the asphaltene phase behavior problem

    SciTech Connect

    Lockhart, T.P.

    1996-12-31

    Spontaneous phase separation and deposition of the asphaltenic component of crude oils is the source of costly problems in the petroleum industry. Over the past several decades so-called {open_quotes}colloid stabilization{close_quotes} model has dominated attempts to account for the phase behavior of the asphaltene fraction of the crude oil. We will argue that this model is not {open_quotes}scientific{close_quotes} in the sense that is has been applied only for the post-hoc rationalization of experimental results; absent have been serious attempts to experimentally test specific predictions deduced from the model. A critical examination of the colloid stabilization model brings to light several fundamental shortcomings. An alternative thermodynamic, or {open_quotes}solvation{close_quotes} model is shown to make predictions in far better agreement with experiment, and has been the key to developing an analytical model that accurately predicts the conditions under which crude oils become unstable to asphaltene deposition. This example will be used to argue that the defining elements of (good) scientific research - the formulation of explicit hypotheses of high predictive content and their critical evaluation, above all by experimental attempts at falsification - are also effective, indeed necessary, for analyzing the complex problems offered by the {open_quotes}real{close_quotes} world and for achieving technological advancement.

  13. Collective Behavior of Interacting Particles: Radius-Dependent Phase Transition

    NASA Astrophysics Data System (ADS)

    Tarras, I.; Moussa, N.; Mazroui, M.; Boughaleb, Y.; Hajjaji, A.

    2013-02-01

    The aim of this paper is to study and discuss the effect of three zones (repulsion zone, orientation zone and attraction zone) on the phase transition in 2D-collective moving particles. Our main motivation is to better understand the complex behavior of non-equilibrium multi-agent system by extending the earlier and original model proposed by Viscek et al. [T. Viscek et al., Phys. Rev. Lett.75 (1995) 1226] for one zone. The analysis is performed over different situations by using a numerical simulation method. It is found that the radius R2 of orientation zone plays an important role in the system. In effect, by varying the parameter R2 a phase transition can be achieved from disordered moving of individuals to a group to highly aligned collective motion. The results also show that, the critical value of R2 at which the transition emerges depends strongly on the size of the repulsion zone but not on the size of attraction one.

  14. Phase behavior, morphology, and polymorphism of surfactant systems

    NASA Astrophysics Data System (ADS)

    Liang, Jingmei

    Surfactants are amphiphilic molecules. They spontaneously form various microstructures in water to accommodate the hydrophilic-hydrophobic interactions. Soaps are the oldest kind of man-made surfactants that are commonly used as washing and cleaning agents. In spite of the long history of soap research, many aspects of soaps in nonaqueous solvents remain unclear. Unlike the aqueous soap systems, which have been studied extensively, investigations of nonaqueous, polar soap systems are rather limited. Motivated by the applications of nonaqueous, polar solvents in soap products, we investigated sodium stearate (NaSt)/water/propylene glycol (PG) systems. The effects of gradual substitution of PG for H 2O on the phase behavior, morphology and crystalline structure of NaSt systems were studied by a combination of characterization techniques. The techniques include direct visual observation, differential scanning calorimetry, wide-angle and small angle x-ray scattering, light and cryo-electron microscopy, and solid-state nuclear magnetic resonance. Anhydrous NaSt forms layered crystalline structures at 25°C. With increasing temperature, a distorted hexagonal phase and a hexagonal liquid crystalline phase form. Compared with aqueous soap systems, the regions of liquid crystalline phases in the phase diagrams are reduced as PG replaces or gradually substitutes for H2O. Fibrous and plate-like NaSt crystallites were investigated in the NaSt/PG/H 2O system containing 1-5 wt% NaSt. Despite of the morphological difference, NaSt fibers and platelets share the same layered crystalline structure at the molecular level. NaSt fibers consist of stacked thin ribbons of NaSt bilayers. NaSt platelets exhibit large basal planes {001} surrounded by other faster-growing lateral planes. Two lamellar crystalline structures, alpha-NaSt and beta-NaSt, which formed in the NaSt/PG/H2O system with 10 wt% NaSt, were characterized on the atomic, molecular and microscopic levels. In a PG

  15. Cancrinite: Crystal Structure, Phase Transitions, and Dehydration Behavior with Temperature

    SciTech Connect

    Hassan,I.; Antao, S.; Parise, J.

    2006-01-01

    The structural behavior of a cancrinite, Na{sub 5.96}Ca{sub 1.52}[Al{sub 6}Si{sub 6}O{sub 24}](CO{sub 3}){sub 1.57}{center_dot}1.75H{sub 2}O, was determined by using in situ synchrotron X-ray powder diffraction data [{lambda} = 0.91806(5) {angstrom}] at room pressure and from 25 to 982 {sup o}C. The sample was heated at a rate of about 9.5 {sup o}C/min, and X-ray traces were collected at about 15 {sup o}C intervals. The satellite reflections in cancrinite were lost at about 504 {sup o}C, where a phase transition occurs. All the unit-cell parameters for cancrinite also show a discontinuity at 504 {sup o}C. Initially, the [Ca{center_dot}CO{sub 3}] clusters and their vacancies are ordered in the channels, and this ordering is destroyed on heating to give rise to the phase transition. Cancrinite loses water continuously until about 625 {sup o}C; thereafter an anhydrous cancrinite phase exists. From 25 to 952 {sup o}C, a minimal amount of CO{sub 2} is lost from the structure. Over this temperature range, the average bridging angle, which is an indication of the degree of rotation of the tetrahedra, increases from 143.7(4) to 147.7(5){sup o}. Rotations of the tetrahedra are caused by expansion of the Na1-O2 bond lengths.

  16. OPTIMIZED MONOSODIUM TITANATE PHASE II SUPPLEMENTAL TESTING REPORT URANIUM ADSORPTION AND SHELF-LIFE MEASUREMENTS

    SciTech Connect

    Hobbs, D

    2008-01-01

    The DOE Office of Waste Processing recently funded supplemental Phase II testing to further investigate the uranium affinity and shelf-life of modified monosodium titanate (mMST). Testing results confirmed earlier findings that the mMST exhibits much lower affinity for uranium than the baseline monosodium titanate (MST) material. The loading of uranium onto the mMST sample measured more than an order of magnitude lower than that of the MST. This finding indicates that the use of mMST provides a significant advantage over MST in that the mMST will not concentrate enriched uranium to the degree that MST does. The reduced affinity of mMST for uranium allows more operational flexibility in treating waste solutions from a nuclear criticality safety perspective. Testing results also indicate that the mMST exhibits good shelf-life with no measurable loss in plutonium and neptunium removal upon storage of samples at ambient laboratory temperatures for up to 30-months. Testing did exhibit a change in strontium removal performance for both the mMST and MST samples at the most recent testing event. However, the decrease in strontium removal performance proved lower for the mMST than the MST sample. Given these positive findings SRNL recommends continued development of mMST as a replacement for MST in pretreatment facilities at the Savannah River Site (SRS).

  17. Unique lead adsorption behavior of activated hydroxyl group in two-dimensional titanium carbide.

    PubMed

    Peng, Qiuming; Guo, Jianxin; Zhang, Qingrui; Xiang, Jianyong; Liu, Baozhong; Zhou, Aiguo; Liu, Riping; Tian, Yongjun

    2014-03-19

    The functional groups and site interactions on the surfaces of two-dimensional (2D) layered titanium carbide can be tailored to attain some extraordinary physical properties. Herein a 2D alk-MXene (Ti3C2(OH/ONa)(x)F(2-x)) material, prepared by chemical exfoliation followed by alkalization intercalation, exhibits preferential Pb(II) sorption behavior when competing cations (Ca(II)/Mg(II)) coexisted at high levels. Kinetic tests show that the sorption equilibrium is achieved in as short a time as 120 s. Attractively, the alk-MXene presents efficient Pb(II) uptake performance with the applied sorption capacities of 4500 kg water per alk-MXene, and the effluent Pb(II) contents are below the drinking water standard recommended by the World Health Organization (10 μg/L). Experimental and computational studies suggest that the sorption behavior is related to the hydroxyl groups in activated Ti sites, where Pb(II) ion exchange is facilitated by the formation of a hexagonal potential trap.

  18. Foaming and adsorption behavior of bovine and camel proteins mixed layers at the air/water interface.

    PubMed

    Lajnaf, Roua; Picart-Palmade, Laetitia; Attia, Hamadi; Marchesseau, Sylvie; Ayadi, M A

    2017-03-01

    The aim of this work was to examine foaming and interfacial behavior of three milk protein mixtures, bovine α-lactalbumin-β-casein (M1), camel α-lactalbumin-β-casein (M2) and β-lactoglobulin-β-casein (M3), alone and in binary mixtures, at the air/water interface in order to better understand the foaming properties of bovine and camel milks. Different mixture ratios (100:0; 75:25; 50:50; 25:75; 0:100) were used during foaming tests and interfacial protein interactions were studied with a pendant drop tensiometer. Experimental results evidenced that the greatest foam was obtained with a higher β-casein amount in all camel and bovine mixtures. Good correlation was observed with the adsorption and the interfacial rheological properties of camel and bovine protein mixtures. The proteins adsorbed layers are mainly affected by the presence of β-casein molecules, which are probably the most abundant protein at interface and the most efficient in reducing the interfacial properties. In contrast of, the globular proteins, α-lactalbumin and β-lactoglobulin that are involved in the protein layer composition, but could not compact well at the interface to ensure foams creation and stabilization because of their rigid molecular structure.

  19. Quality properties and adsorption behavior of freeze-dried beef meat from the Biceps femoris and Semimembranosus muscles.

    PubMed

    Aykın, Elif; Erbaş, Mustafa

    2016-11-01

    The aim of this research was to determine the quality properties and adsorption behavior of freeze-dried beef meat from the Biceps femoris and Semimembranosus muscles. Most quality properties of both muscles were similar apart from total fat content. Freeze-dried meat pieces were kept in ten different equilibrium levels of relative humidity (2.0-97.3%) at 5, 15, 25 and 30°C. The experimental data were evaluated using BET (Brunauer-Emmett-Teller) and GAB (Guggenheim, Anderson and deBoer) models. The equilibrium moisture contents of freeze-dried Biceps femoris were lower than those of Semimembranosus at all water activities and temperature. The constants m0 and C of BET and GAB equations were determined to be between 6.27 and 8.07g/100g dry matter and 9.32-13.73, respectively. Constant k was about 0.90 at all temperatures, and the GAB equation exhibited a better fit to the experimental data of both muscles as a result of all %E values being approximately equal to 10%.

  20. Continuous flow adsorption of methylene blue by cellulose nanocrystal-alginate hydrogel beads in fixed bed columns.

    PubMed

    Mohammed, Nishil; Grishkewich, Nathan; Waeijen, Herman Ambrose; Berry, Richard M; Tam, Kam Chiu

    2016-01-20

    The adsorption behavior of methylene blue by cellulose nanocrystal-alginate (CNC-ALG) hydrogel beads in a fixed bed column was studied by varying the initial dye concentrations, bed depths and flow rates. An unusual phenomenon was observed in the early phase of the adsorption, and the phenomenon was elucidated by varying other critical design parameters, such as the flow direction, diameter of column and composition of adsorbent. The swelling and shrinkage of hydrogel beads during the adsorption was responsible for the anomalous concentration versus time profile of the adsorption process. The maximum adsorption capacity of the column was 255.5mg/g, which is in agreement with the batch study determined from the Langmuir adsorption isotherm. A comprehensive understanding on the adsorption mechanism of CNC-ALG hydrogel beads during the early stages of adsorption was derived from this study.

  1. A study on the adsorption of heavy metals by using raw wheat bran bioadsorbent in aqueous solution phase.

    PubMed

    Ogata, Fumihiko; Kangawa, Moe; Iwata, Yuka; Ueda, Ayaka; Tanaka, Yuko; Kawasaki, Naohito

    2014-01-01

    Raw wheat bran (R-WB) was used as a biomass adsorbent. The properties of R-WB were investigated. Moreover, the adsorption of cadmium and lead ions onto R-WB was evaluated. Adsorption equilibrium of cadmium and lead ions onto R-WB was achieved within 10 h, indicating that the adsorption followed a pseudo-second-order model rather than a pseudo-first-order kinetic model. The adsorption amount increased with increasing temperature. Correlation coefficient of the Langmuir equation is 0.999 for cadmium and 0.996 for lead ions, and that of the Freundlich equation is 0.994 for cadmium and 0.993 for lead ions. The negative ΔG value implied that the adsorption of cadmium and lead ions onto R-WB is a spontaneous process. The positive ΔS value indicated an increase in randomness at the solid-liquid interface. The optimal conditions for the adsorption column experiment were investigated (space velocity (SV) 2.2 1/h, linear velocity (LV) 0.1 m/h for cadmium; SV 6.51 1/h, LV 0.23 m/h for lead ions). Further, repeated adsorption-desorption of the cadmium and lead ions could be effected by using 0.01 mol/L HCl or 0.01 mol/L HNO3 solution. Consequently, polluted water could be successfully purified by using a column filled with this bioadsorbent.

  2. 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.

  3. Adsorption at the solid-liquid interface as the source of contact angle dependence on the curvature of the three-phase line.

    PubMed

    Ward, C A; Sefiane, K

    2010-12-15

    We review the thermodynamic approach to determining the surface tension of solid-fluid interfaces. If the pressure is in the narrow range where the contact angle, θ, can exist, then for isothermal systems, adsorption at the solid-liquid interface affects γ(SL) or θ, but γ(SV) is very nearly equal γ(LV), the surface tension of the adsorbing fluid. For a liquid partially filling a cylinder, the pressure in the liquid phase at the three-phase line, x(3)(L), depends on the curvature of the three-phase line, C(cl), but the line tension can play no role, since it acts perpendicular to the cylinder wall. C(cl) is decreased as the cylinder diameter is increased; x(3)(L) is increased; and θ increases. For a given value of C(cl), x(3)(L) can be changed by rotating the cylinder or by changing the height of the three-phase line in a gravitational field. In all cases, for water in borosilicate glass cylinders, the value of θ is shown to increase as x(3)(L) is increased. This behaviour requires the Gibbsian adsorption at the solid-liquid interface to be negative, indicating the liquid concentration in the interphase is less than that in the bulk liquid. For sessile droplets, the value of θ depends on both x(3)(L) and C(cl). If the value of θ for spherical sessile droplets is measured as a function of C(cl), the adsorption at the solid-liquid interface that would give that dependence can be determined. It is unnecessary to introduce the line tension hypothesis to explain the dependence of θ on C(cl). Adsorption at the solid-liquid interface gives a full explanation.

  4. Adsorption Behavior of Black Carbon for Radioactive Iodine Species in Subsurface Environments

    NASA Astrophysics Data System (ADS)

    Choung, S.; Kim, M.; Um, W.

    2012-12-01

    Releases of radioactive iodines (125/129/131I) into subsurface environments occur during nuclear power plant operations, nuclear weapons tests, and nuclear accidents such as Chernobyl and Fukushima. Environmental concern is mostly for 129I due to high toxicity and long-half life, t1/2=1,600,000 years. The fate and transport of radioactive iodines depend on the speciation in the environments. Sorption of iodate (IO3-) is strongly affected by natural organic matter (NOM) in soil/sediments, while iodide (I-) sorption is less. Although there are numerous forms and compositions of NOM in soil/sediments, previous studies were mostly focused on general organic matter such as humic and fulvic acids. The objective of this study is addressed to evaluate the impact of black carbon as different NOM forms in subsurface environments. Laboratory-produced wood char was used as a representative of black carbon for sorption batch experiments. Commercial humic acid was added to experiments for comparison of iodine sorption behavior to black carbon material. Stable iodine isotope, 127I, was used as a surrogate of radioactive iodine. The 13C-NMR analyses indicated that the wood char consisted of dominantly aromatic chemical structures, while the humic acid exhibited relatively more aliphatic structures than aromaticity. The char and humic acid significantly increased iodide and iodate sorption, respectively. However, iodate sorption on char and iodide sorption on humic acid were negligible in this study. These observations implied different sorption mechanisms between black carbon and humic acid due to different pore structures and chemical compositions. Both of sorption isotherms are dependent on aqueous concentrations, following Freundlich isotherm with n~0.7. The sorption behavior and mechanism of iodine is significantly influenced by the NOM types in soils and sediments, which can enhance iodine retardation in the subsurface environment.

  5. Investigation of adsorption behavior of (-)-epigallocatechin gallate on bovine serum albumin surface using quartz crystal microbalance with dissipation monitoring.

    PubMed

    Wang, Xiaoyong; Ho, Chi-Tang; Huang, Qingrong

    2007-06-27

    Quartz crystal microbalance with dissipation monitoring (QCM-D) has been employed to study the interactions between (-)-epigallocatechin gallate (EGCG) and bovine serum albumin (BSA) surface. The adsorbed mass, thickness, and viscoelastic properties of EGCG adlayer on BSA surface at various EGCG concentrations, temperatures, sodium chloride concentrations, and pH values have been determined by QCM-D in combination with the Voigt model. The adsorption isotherm of EGCG on BSA surfaces can be better described by the Freundlich model than the Langmuir model, indicating that EGCG adsorption on BSA surfaces is dominated by nonspecific hydrophobic interactions, as supported by stronger EGCG adsorption at higher temperature. Shifts in the Fourier transform infrared spectra of the BSA surface with and without EGCG adsorption disclose that hydrogen bonding might also be involved in EGCG adsorption on BSA surfaces. The addition of salt and change of pH can also influence the EGCG adsorption on BSA surfaces. Usually, higher EGCG adsorption leads to higher values of viscosity and shear elastic modulus of EGCG adlayer, which can be explained by the aggregation of BSA through EGCG bridges. Compared with EGCG, nongalloylated (+)-catechin shows much lower adsorption capacity on BSA surfaces, suggesting the importance of the galloyl group in polyphenol/protein interactions.

  6. Preparation of a novel magnetic microporous adsorbent and its adsorption behavior of p-nitrophenol and chlorotetracycline.

    PubMed

    Ma, Yan; Zhou, Qing; Li, Aimin; Shuang, Chendong; Shi, Qianqian; Zhang, Mancheng

    2014-02-15

    A novel method for fabricating hypercrosslinked magnetic polymer beads with improved acid resistance was developed. Magnetite nanoparticles were covered with tetraethoxysilane and vinyltriethoxysilane, followed by co-polymerization and post-crosslinking. The resulting M150 beads were highly stable at pH ≥ 2 and were superparamagnetic, with a saturation magnetization of 3.1 emu/g. M150 exhibited a specific surface area of 1022.4m(2)/g and an average pore width of 2.6 nm. The adsorption of p-nitrophenol and chlorotetracycline (CTC) onto M150 and the commercial non-magnetic resins NDA 150 and XAD-4 followed both pseudo-first-order and pseudo-second-order equations. M150 displayed much faster kinetics than the other resins because of its small particle size and abundant macropores. The adsorption isotherm of p-nitrophenol onto the three resins fitted the Freundlich equation (R(2)>0.98), whereas CTC adsorption was better described by the Langmuir isotherm. p-Nitrophenol adsorption was optimal at pH ≤ 4, whereas CTC adsorption was optimal at pH 5-6. All three sorbents showed high reusability for p-nitrophenol adsorption. XAD-4 demonstrated the highest reusability for CTC. The CTC adsorption capacities of M150 and NDA150 decreased by 12.42% and 20% after 10 adsorption-desorption cycles, respectively.

  7. High-pressure behavior of fcc phase FeHx

    NASA Astrophysics Data System (ADS)

    Thompson, E. C.; Chidester, B.; Fischer, R. A.; Prakapenka, V.; Bi, W.; Alp, E. E.; Campbell, A. J.

    2015-12-01

    Earth's core is composed of iron with the inclusion of light elements to compensate for the difference between seismically obtained densities and the density of pure Fe at relevant pressure and temperature conditions. As the most abundant and lightest element in the solar system, hydrogen is a plausible contributor to this core density deficit. Nearly stoichiometric iron hydride (FeHx) has been shown to result from the reaction of Fe and hydrous silicates, and is stable up to at least 80 GPa [1]. Iron hydride formation at Earth's surface is unlikely because the equilibrium hydrogen solubility in iron at atmospheric conditions is prohibitively low, yet as hydrogen solubility increases with pressure, so does the likelihood of FeHx formation within the Earth's interior [2]. Recent experimental and ab initio attempts disagree on the equation of state parameters needed to describe the compressional behavior of FeHx [3-5]. The work presented here combines synchrotron x-ray diffraction of laser-heated diamond anvil cell compressed samples with high-pressure, ambient temperature nuclear resonant inelastic scattering (NRIXS) and synchrotron Mössbauer spectroscopy (SMS) to better constrain the behavior of the fcc phase of FeHx at elevated pressures and temperatures. By pairing P-V-T data for iron hydride with the sound velocity information available through high-pressure NRIXS studies, we can better understand the degree to which hydrogen may contribute to the density deficit of Earth's iron core. [1] Antonov et al. (1998) J. Alloys Compd. 264, 214-222 [2] Fukai and Akimoto (1983) Proc. Japan Acad. 59, 158-162 [3] Pépin et al. (2014) Phys. Rev. Lett. 265504, 1-5 [4] Hirao (2004) Geophys. Res. Lett. 31, L06616 [5] Badding et al. (1991) Science. 253, 421-424

  8. Prediction of multicomponent adsorption behavior in activated carbon adsorbers: kinetic aspects

    SciTech Connect

    Merk, W.

    1987-09-01

    Although the concentrations of solutes are very low in water treatment, it cannot be expected that the film-diffusion model predicts breakthrough behavior satisfactorily, for the following reasons: most of the solutes have less favorable isotherms than p-nitrophenol or p-chlorophenol; many solutes are much larger molecules and hence have a much higher internal diffusion resistance than p-nitrophenol or p-chlorophenol; and displacement effects cause a much higher internal resistance than expected from single-solute data. Therefore, internal diffusion resistance has to be incorporated into the film-homogeneous diffusion model. All parameters needed in this model can be obtained from batch reactor tests. Multi-solute systems may be regarded as a single-solute system or a bi-solute system, respectively, if all solutes except one or two are present in very different concentrations; and/or have a comparatively small affinity to activated carbon; and/or have a comparatively small internal diffusion coefficient.

  9. Phase behavior of inverse microemulsions for the polymerization of acrylamide in near-critical and supercritical continuous phases

    SciTech Connect

    Beckman, E.J.; Smith, R.D. )

    1990-01-11

    The inverse microemulsion polymerization of water-soluble acrylamide monomers within near-critical and supercritical alkane continuous phases provides a potential route for production of polymers with novel physical properties and at high reaction rates. In order to define conditions for a model polymerization process, the phase behavior of a nonionic surfactant/acrylamide/water system in near-critical and supercritical mixtures of ethane and propane was examined. Acrylamide was found to act as a cosurfactant due to its short chain length and hydrophilic character and this is probably coordinated about the surfactant's ethylene oxide units at the interface, rather than residing in the micelle core. The effects of temperature and composition on the phase behavior can be qualitatively explained from results on C{sub i}E{sub j}/water/alkane systems at atmospheric pressure by using either generalized ternary liquid-phase diagrams or a model that considers micelle-micelle and micelle-fluid interactions. Increasing pressure up to 550 bar acts to shrink the various two-component phase envelopes which govern the phase behavior of the multicomponent system and thus increases stability. At constant dispersed-phase composition and temperature, the clearing pressure of the system depends on the ethane/propane ratio only via the fluid density, possibly due to the nearly ideal mixing behavior of these two alkanes at high pressure. The ramifications of the phase behavior for the choice of polymerization conditions are discussed.

  10. PNIPAm(x)-PPO(36)-PNIPAm(x) thermo-sensitive triblock copolymers: chain conformation and adsorption behavior on a hydrophobic gold surface.

    PubMed

    Li, Jianyuan; Zhang, Zhijun; Zhou, Xianjing; Chen, Tongquan; Nie, Jingjing; Du, Binyang

    2016-01-07

    The chain conformations and adsorption behaviors of four thermo-sensitive poly(N-isopropylacrylamide)x-poly(propylene oxide)36-poly(N-isopropylacrylamide)x (PNIPAmx-PPO36-PNIPAmx) triblock copolymers with x values of 15, 33, 75, and 117 in dilute aqueous solutions were investigated by combined techniques of micro-differential scanning calorimetry (micro-DSC), static and dynamic light scattering (SLS & DLS), and the quartz crystal microbalance (QCM). PNIPAm15-PPO36-PNIPAm15 only exhibited the lower critical solution temperature (LCST) of the PPO block, i.e. 25 °C, because the PNIPAm block with x = 15 was too short to maintain its own LCST. With middle lengths x of 33 and 75, the LCSTs of PPO and PNIPAm blocks were observed, respectively. For the longest PNIPAm block with x = 117, only LCST of PNIPAm block dominated, i.e. 32.3 °C. DLS results revealed that the four PNIPAmx-PPO36-PNIPAmx triblock copolymers formed "associate" structures in their dilute aqueous solutions at 20 °C, which was well below the LCSTs of the PPO and PNIPAm blocks. QCM results indicated that the adsorption time constant decreased with increasing adsorption temperature but tended to increase with increasing length x of the PNIPAm block. A complex adsorption behavior with large adsorption amounts was only observed at the corresponding LCST of the PNIPAm block for PNIPAmx-PPO36-PNIPAmx with longer PNIPAm blocks with x = 33, 75, and 117. Furthermore, the adsorbed PNIPAmx-PPO36-PNIPAmx layers obtained at 20 °C were rigid with less energy dissipation.

  11. The adsorptive capacity of vapor-phase mercury chloride onto powdered activated carbon derived from waste tires.

    PubMed

    Lin, Hsun-Yu; Yuan, Chung-Shin; Wu, Chun-Hsin; Hung, Chung-Hsuang

    2006-11-01

    Injection of powdered activated carbon (PAC) upstream of particulate removal devices (such as electrostatic precipitator and baghouses) has been used effectively to remove hazardous air pollutants, particularly mercury-containing pollutants, emitted from combustors and incinerators. Compared with commercial PACs (CPACs), an alternative PAC derived from waste tires (WPAC) was prepared for this study. The equilibrium adsorptive capacity of mercury chloride (HgCl2) vapor onto the WPAC was further evaluated with a self-designed bench-scale adsorption column system. The adsorption temperatures investigated in the adsorption column were controlled at 25 and 150 degrees C. The superficial velocity and residence time of the flow were 0.01 m/sec and 4 sec, respectively. The adsorption column tests were run under nitrogen gas flow. Experimental results showed that WPAC with higher Brunauer-Emmett-Teller (BET) surface area could adsorb more HgCl2 at room temperature. The equilibrium adsorptive capacity of HgCl2 for WPAC measured in this study was 1.49 x 10(-1) mg HgCl2/g PAC at 25 degrees C with an initial HgCI2 concentration of 25 microg/m3. With the increase of adsorption temperature < or = 150 degrees C, the equilibrium adsorptive capacity of HgCl2 for WPAC was decreased to 1.34 x 10(-1) mg HgCl2/g PAC. Furthermore, WPAC with higher sulfur contents could adsorb even more HgCl2 because of the reactions between sulfur and Hg2+ at 150 degrees C. It was demonstrated that the mechanisms for adsorbing HgCl2 onto WPAC were physical adsorption and chemisorption at 25 and 150 degrees C, respectively. Experimental results also indicated that the apparent overall driving force model appeared to have the good correlation with correlation coefficients (r) > 0.998 for HgCl2 adsorption at 25 and 150 degrees C. Moreover, the equilibrium adsorptive capacity of HgCl2 for virgin WPAC was similar to that for CPAC at 25 degrees C, whereas it was slightly higher for sulfurized WPAC than for

  12. Investigation of diarrhetic shellfish toxins in Lingshan Bay, Yellow Sea, China, using solid-phase adsorption toxin tracking (SPATT).

    PubMed

    Li, Feng-Ling; Li, Zhao-Xin; Guo, Meng-Meng; Wu, Hai-Yan; Zhang, Ting-Ting; Song, Cai-Hu

    2016-08-01

    Early detection of toxin contamination in shellfish (i.e., prior to harvest) would be of considerable advantage to fish farmers, researchers and food safety administrators. In 2004, a solid-phase adsorption toxin tracking (SPATT) technique was developed to study algal toxins in New Zealand shellfish harvesting areas. In subsequent years, the basic idea have been further developed. Using a SPATT method, an investigation into diarrhetic shellfish toxins (DSTs) was conducted over a 10.5-month period in 2012 in shellfish farming areas in Lingshan Bay (Yellow Sea, China). This paper discusses the relationship among DSTs in toxic algae, seawater and contaminated shellfish. OA, DTX1 and PTX2 toxins were found in this shellfish farming area from summer to autumn. In shellfish the maximum concentrations of OA and DTX1 were 81 and 41 ng g(-1) respectively. PTX2 was very low. The maximum levels of OA and DTX1 in seawater were 165 and 56 ng g(-1) respectively, and were detected on June, separated by a 14-day period. Shellfish had accumulated the highest levels of OA and DTX1 recorded in this study. Comparison of the variations in DST levels in seawater showed there to be about 2 weeks for administrators to warn of the potential for toxin contamination in shellfish. Further research to explore the relationship between the variables of seawater temperature, sunlight and salinity, and DSTs in shellfish may help to establish a more suitable model for forecasting DST contamination in shellfish.

  13. Spatiotemporal Behavior and Nonlinear Dynamics in a Phase Conjugate Resonator

    NASA Astrophysics Data System (ADS)

    Liu, Siuying Raymond

    The work described in this dissertation can be divided into two parts. The first part is an investigation of the transient behavior and stability property of a phase conjugate resonator (PCR) below threshold. The second part is an experimental and theoretical study of the PCR's spatiotemporal dynamics above threshold. The time-dependent coupled wave equations for four-wave mixing (FWM) in a photorefractive crystal, with two distinct interaction regions caused by feedback from an ordinary mirror, was used to model the transient dynamics of a PCR below threshold. Analytical expressions of the steady state cavity's fields for the case of nondepleted pumps and an absorption free medium were derived and used to determine the self-oscillation conditions. The solutions, through simple frequency domain transformation techniques, were used to define the PCR's transfer function and analyse its stability. Taking into account pump depletion and medium absorption, the transient buildup and decay times of the cavity's fields as well as the specularly reflected and phase conjugate reflected intensities were numerically calculated as functions of a number of system parameters such as the coupling parameter and the pump and probe ratios. Experiments were carried out above threshold to study the spatiotemporal dynamics of the PCR as a function of the Bragg detuning achieved by misaligning one of the two pump beams and of the degree of transverse confinement controlled by varying the resonator's Fresnel number. The temporal aspects of the beam's complexity were studied by local intensity time series, power spectra, and reconstructed pseudo phase portraits. The transverse dynamics and the spatiotemporal instabilities were also described by modeling the three dimensional coupled wave equations in photorefractive FWM, using a truncated modal expansion approach. Numerical solutions of the model revealed the presence and motion of optical vortices in the wavefront. Simulations using the

  14. Theory of Gas Injection: Interaction of Phase Behavior and Flow

    NASA Astrophysics Data System (ADS)

    Dindoruk, B.

    2015-12-01

    The theory of gas injection processes is a central element required to understand how components move and partition in the reservoir as one fluid is displacing another (i.e., gas is displacing oil). There is significant amount of work done in the area of interaction of phase-behavior and flow in multiphase flow conditions. We would like to present how the theory of gas injection is used in the industry to understand/design reservoir processes in various ways. The tools that are developed for the theory of gas injection originates from the fractional flow theory, as the first solution proposed by Buckley-Leveret in 1940's, for water displacing oil in porous media. After 1960's more and more complex/coupled equations were solved using the initial concept(s) developed by Buckley-Leverett, and then Welge et al. and others. However, the systematic use of the fractional flow theory for coupled set of equations that involves phase relationships (EOS) and phase appearance and disappearance was mainly due to the theory developed by Helfferich in early 80's (in petroleum literature) using method of characteristics primarily for gas injection process and later on by the systematic work done by Orr and his co-researchers during the last two decades. In this talk, we will present various cases that use and extend the theory developed by Helfferich and others (Orr et al., Lake et al. etc.). The review of various injection systems reveals that displacement in porous media has commonalities that can be represented with a unified theory for a class of problems originating from the theory of gas injection (which is in a way generalized Buckley-Leverett problem). The outcome of these solutions can be used for (and are not limited to): 1) Benchmark solutions for reservoir simulators (to quantify numerical dispersion, test numerical algorithms) 2) Streamline simulators 3) Design of laboratory experiments and their use (to invert the results) 4) Conceptual learning and to investigate

  15. Swelling, Compressibility, and Phase Behavior of Soft Ionic Microgels

    NASA Astrophysics Data System (ADS)

    Denton, Alan

    Soft colloids have inspired great attention recently for their rich and tunable materials properties. Particular interest has focused on microgels - microscopic cross-linked polymer gel particles that, when dispersed in water, become swollen and can acquire charge through dissociation of counterions. Electrostatic interparticle interactions strongly influence the structure and thermodynamics of ionic microgel suspensions*. Permeability to solvent molecules and small ions creates a competition between elastic and electrostatic forces that determines equilibrium particle sizes. Swelling can be controlled by adjusting temperature, pH, and salt concentration, with applications to chemical/biosensing and targeted drug delivery. By combining molecular dynamics and Monte Carlo simulation with Poisson-Boltzmann theory of electrostatics and Flory-Rehner theory of swollen polymer networks, we investigate swelling and compressibility of ionic microgel particles and implications for thermodynamic phase behavior of bulk suspensions at concentrations approaching and exceeding hard-sphere close packing. Predictions for particle size and osmotic pressure are compared with available experimental data. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

  16. Fluorinated microemulsions: A study of the phase behavior and structure

    SciTech Connect

    LoNostro, P.; Choi, S.M.; Chen, S.H.; Ku, C.Y.

    1999-06-24

    Fluorinated surfactants have been studied for their peculiar property to form micellar aggregates in water and oils (hydrocarbons or fluorocarbons) and to produce stable microemulsions. Because of their capacity to dissolve large amounts of gases (such as oxygen and carbon dioxide) and for their characteristic physicochemical properties, fluorocarbons have been tested for specific medical purposes, and their microemulsions are among the most promising candidates for the production of suitable blood substitutes and other biocompatible fluids. The authors have synthesized a new partially fluorinated nonionic surfactant, namely, F(CF{sub 2}){sub 7}-CO-(OCH{sub 2}CH{sub 2}){sub 7.2}OCH{sub 3} (I), that forms stable microemulsions with water and perfluorocarbons such as perfluorooctane (PFO). In this paper the authors describe for the first time the phase behaviors of perfluorooctanoic acid (PFOA) in water/PFH and in water/PFO, and that of ester I in water/PFO. Small-angle neutron-scattering (SANS) experiments provide a detailed description of the microstructure of the H{sub 2}O/PFO/PFOA ternary system.

  17. Adsorption of toxic carbamate pesticide oxamyl from liquid phase by newly synthesized and characterized graphene quantum dots nanomaterials.

    PubMed

    Agarwal, Shilpi; Sadeghi, Nima; Tyagi, Inderjeet; Gupta, Vinod Kumar; Fakhri, Ali

    2016-09-15

    Graphene quantum dots have been synthesized using the microwave-assisted hydrothermal route. The surface textural and morphological structure of synthesized adsorbent i.e. graphene quantum dots was analyzed using various analytical techniques such as X-ray diffraction, Transmission electron Microscopy, Atomic Force Microscopy and N2 adsorption-desorption instrumental techniques. The application of graphene quantum dots as an adsorbent for the removal of noxious pesticide compound i.e. oxamyl from aqueous solutions was well investigated and elucidated. The impact of several effective parameters such as effect of agitation speed, pH, adsorbent dose, contact time, temperature and initial concentration on sorption efficiency was studied and optimized using batch adsorption experiments. The optimized pH for maximum oxamyl adsorption was found to be 8.0 and for the maximum adsorption rates the adsorbent dose of 0.6g was found to be optimum to carry out the adsorption with in less than 25min of contact time. From the results obtained, it is clear that for all contact times, an increase in oxamyl concentration resulted in increase in the percent oxamyl removal. The adsorption equilibrium and kinetic data were well fitted and found to be in good agreement with the Langmuir isotherm and pseudo-second-order kinetic model.

  18. Investigation of the adsorption mechanism of a peptide in reversed phase liquid chromatography, from pH controlled and uncontrolled solutions

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2009-01-01

    The single-component equilibrium adsorption of the tripeptide Leucyl-Leucyl-Leucine (LLL) on a high-efficiency Jupiter Proteo column (C{sub 12}) was investigated experimentally and modeled theoretically. The experimental equilibrium isotherms of LLL for adsorption on a C{sub 12} packing material from an aqueous solution of methanol (48%) and trifluoroacetic acid (0.1%) were measured by frontal analysis (FA). The FA measurements were done with two solutions, one in which the pH was controlled, the other in which it was not. Two solutions of LLL in the mobile phase were prepared (4.3 and 5.4 g/L) and their pH measured (2.94 and 2.88), respectively. The first solution was titrated with TFA to match the pH of the mobile phase (2.03), so its pH was controlled. The pH of the other solution was left uncontrolled. In both cases the isotherms could be modeled by a bi-Langmuir equation, a choice consistent with the bimodal affinity energy distribution (AED) obtained for LLL. The isotherm parameters derived from the inverse method (IM) of isotherm determination under controlled pH conditions (by fitting calculated profiles to experimental breakthrough profiles) are in a good agreement with those derived from the FA data. Under uncontrolled pH conditions, the application of IM suggests the coexistence of two different adsorption mechanisms. According to the isotherm parameters found by these three methods (FA, AED and IM), the C{sub 12}-bonded silica can adsorb around 500 and 70 g/L of LLL under controlled and uncontrolled pH conditions, respectively. The adsorption of LLL on the C{sub 12} material strongly depends on the pH of the mobile phase and on the quantity of TFA added, which plays the role of an ion-pairing agent.

  19. Anomalous bond length behavior and a new solid phase of bromine under pressure

    PubMed Central

    Wu, Min; Tse, John S.; Pan, Yuanming

    2016-01-01

    The behavior of diatomic molecular solids under pressure have attracted great interest and been extensively studied. Under ambient pressure, the structure of bromine is known to be a molecular phase (phase I). With increasing pressure, it transforms into an incommensurate phase (phase V) before eventually to a monoatomic phase (phase II). However, between phases I and V, the interatomic distance was found to first increase with pressure and then decreased abruptly. This anomalous bond length behavior is accompanied by the splitting of the Raman bands. These phenomena have not been resolved. Here we suggest a new solid phase that explains the Raman spectra. Furthermore, the anomalous bond length behavior is found to be the result of subtle second neighbor intermolecular interactions and is an intrinsic property of bromine in molecular phases. PMID:27156710

  20. Anomalous bond length behavior and a new solid phase of bromine under pressure

    NASA Astrophysics Data System (ADS)

    Wu, Min; Tse, John S.; Pan, Yuanming

    2016-05-01

    The behavior of diatomic molecular solids under pressure have attracted great interest and been extensively studied. Under ambient pressure, the structure of bromine is known to be a molecular phase (phase I). With increasing pressure, it transforms into an incommensurate phase (phase V) before eventually to a monoatomic phase (phase II). However, between phases I and V, the interatomic distance was found to first increase with pressure and then decreased abruptly. This anomalous bond length behavior is accompanied by the splitting of the Raman bands. These phenomena have not been resolved. Here we suggest a new solid phase that explains the Raman spectra. Furthermore, the anomalous bond length behavior is found to be the result of subtle second neighbor intermolecular interactions and is an intrinsic property of bromine in molecular phases.

  1. Effect of redox potential and pH status on degradation and adsorption behavior of tylosin in dairy lagoon sediment suspension.

    PubMed

    Ali, Muhammad; Wang, Jim J; DeLaune, Ronald D; Seo, Dong Cheol; Dodla, Syam K; Hernandez, Amy B

    2013-06-01

    Veterinary antibiotics are the most heavily used pharmaceuticals in intensive animal farming operation. Their presence in the environment through application of manure and lagoon water as fertilizer in agricultural fields has generated a growing concern in recent years due to potential threat to the ecosystem and the risk they pose to human and animal health. Among the antibiotics, tylosin, a macrolide class of antibiotics, has been widely used for disease prevention and growth promotion in swine, cattle/dairy, and poultry production. To understand degradation and sorption behavior of tylosin A, a laboratory microcosm incubation study was conducted on dairy lagoon sediments suspension under different pH (5.5, 7.0, 8.5) and redox potentials (Eh at -100 mV, 0 mV, +250 mV, +350 mV). Sorption and degradation of tylosin was strongly influenced by sediment pH and redox conditions. Under acidic (pH 5.5) and reduced (Eh -100 mV) condition, tylosin persisted in the solution phase of dairy lagoon sediment suspension much longer with resident time of 77 d. Under oxidized (Eh +350 mV) condition, microbial degradation was much greater causing 68-75% of tylosin loss from the solution at pH 5.5 and 32-75% at pH 7.0 during the 20 d incubation. At pH 8.5, abiotic transformation of tylosin A into unknown degradates rather than sediment adsorption and microbial degradation was the major mechanism controlling tylosin disappearance from the solution regardless of the status of redox potentials. Overall, the results suggested that under reduced condition with low pH, tylosin will be persisted in the lagoon effluents and residue of tylosin may enter agricultural fields through the application of lagoon slurry as fertilizer.

  2. Surface self-segregation, wettability, and adsorption behavior of core-shell and pentablock fluorosilicone acrylate copolymers.

    PubMed

    Liang, Junyan; He, Ling; Dong, Xia; Zhou, Tie

    2012-03-01

    The surfaces of films cast from core-shell fluorosilicone acrylate copolymer (BA/MMA/DFHM and BA/MMA/DFHM/MPTMS/D(4)) latexes and linear pentablock fluorosilicone acrylate copolymer (PDMS-b-(PMMA-b-PDFHM)(2)) solutions are intensively investigated and compared by XPS, DCA, AFM, and QCM-D measurements. It is found that the molecular structures and in-solution aggregate structures of these well-defined copolymers have a dramatic influence on the surface structure formation, surface wetting, and adsorption behavior. The PDMS-b-(PMMA-b-PDFHM)(2) film cast from chloroform solution with high concentration of low-density unimers is able to perform as strong surface self-segregation of fluorine-containing groups as core-shell copolymer latex films. The BA/MMA/DFHM/MPTMS/D(4) in the core-shell latex particles exhibits the less pronounced surface self-segregation of silicon-containing groups than PDMS-b-(PMMA-b-PDFHM)(2) due to the occurrence of cross-linking reactions between polysiloxane chains. Indeed, such reactions induce the formation of silica network within the film material, which immobilizes tightly the fluorinated groups on the film surface and thus endows the film with higher surface structural stability for water compared to PDMS-b-(PMMA-b-PDFHM)(2) film with similar surface fluorine concentration and even higher silicon concentration. Still, the PDMS-b-(PMMA-b-PDFHM)(2) film definitely demonstrates higher advancing and receding contact angles for water than BA/MMA/DFHM/MPTMS/D(4) latex film in the case of synergism between surface enrichment of fluorine and silicon.

  3. Adsorption behavior of Hg2+ in aqueous solutions on a novel chelating cross-linked chitosan microsphere.

    PubMed

    Xiong, Chunhua; Pi, Leilei; Chen, Xinyi; Yang, Liqun; Ma, Chunan; Zheng, Xuming

    2013-10-15

    In this study, cross-linked chitosan microspheres (CCTS) was synthesized from chitosan and epichlorohydrin (ECH), then, 2-(chloromethyl) benzimidazole (CBM) was introduced to modify CCTS as the ligand. The resulting CBM-chitosan was characterized by EA, FTIR and TGA, and tested for metal adsorption. Results showed that CBM-chitosan has a relatively high selectivity toward Hg(2+). Equilibrium data were fitted well with Langmuir isotherms with the maximum adsorption capacity of 257.8 mg/g for Hg(2+). Both kinetics and thermodynamic parameters of the adsorption process were obtained. The data indicated that adsorption process was exothermic spontaneous reaction and kinetically proceeded according to Second-order kinetics model. CBM-chitosan can be eluted effectively using 1.0 mol/L HCl solution and it has a potential use for separation and preconcentration of Hg(2+) ions from contaminated natural waters.

  4. Bromide Adsorption by Reference Minerals and Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bromide, Br-, adsorption behavior was investigated on amorphous Al and Fe oxide, montmorillonite, kaolinite, and temperate and tropical soils. Bromide adsorption decreased with increasing solution pH with minimal adsorption occurring above pH 7. Bromide adsorption was higher for amorphous oxides t...

  5. Liquid phase adsorptions of Rhodamine B dye onto raw and chitosan supported mesoporous adsorbents: isotherms and kinetics studies

    NASA Astrophysics Data System (ADS)

    Inyinbor, A. A.; Adekola, F. A.; Olatunji, G. A.

    2016-04-01

    Irvingia gabonensis endocarp waste was charred (DNc) and subsequently coated with chitosan (CCDNc). Physicochemical characteristics of the two adsorbents were established, while Fourier transform infrared (FTIR), Scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) surface area methods were further employed for characterization. Efficiencies of the prepared adsorbents in the uptake of Rhodamine B (RhB) from aqueous effluent were investigated and adsorption data were tested using four isotherms and four kinetics models. The BET surface areas of the prepared adsorbent were 0.0092 and 4.99 m2/g for DNc and CCDNc, respectively, and maximum adsorption was recorded at pH between 3 and 4, respectively. While monolayer adsorption dominates the uptake of RhB onto DNc, uptake of RhB onto CCDNc was onto heterogeneous surface. The maximum monolayer adsorption capacities (q max) obtained from the Langmuir equation are 52.90 and 217.39 mg/g for DNc and CCDNc, respectively. Pseudo second order and Elovich kinetic models well described the kinetics of the two adsorption processes. The mean sorption energy (E) calculated from the D-R model and desorption efficiencies suggests that while the uptake of RhB onto DNc was physical in nature, for RhB-CCDNc system chemisorption dominates.

  6. Kinetics and isothermal modeling of liquid phase adsorption of rhodamine B onto urea modified Raphia hookerie epicarp

    NASA Astrophysics Data System (ADS)

    Inyinbor, A. A.; Adekola, F. A.; Olatunji, G. A.

    2016-09-01

    Epicarp of Raphia hookerie, a bioresource material, was modified with urea (UMRH) to adsorb Rhodamine B (RhB) from aqueous solution. Adsorbent morphology and surface chemistry were established by Brunauer-Emmett-Teller (BET) surface area determination, Fourier transform infrared spectroscopic (FTIR) analysis, scanning electron microscopy (SEM), as well as the pH point of zero charge (pHpzc) determination. Prepared material was subsequently utilized for the uptake of Rhodamine B (RhB). Operational parameters, such as adsorbent dosage, concentration, time, and temperature, were investigated. Evidence of effective urea modification was confirmed by vivid absorption bands at 1670 and 1472 cm-1 corresponding to C=O and C-N stretching vibrations, respectively. Optimum adsorption was obtained at pH 3. Freundlich adsorption isotherm best fits the equilibrium adsorption data, while evidence of adsorbate-adsorbate interaction was revealed by Temkin isotherm model. The maximum monolayer adsorption capacity (q max) was 434.78 mg/g. Kinetics of the adsorption process was best described by the pseudo-second-order kinetics model. Desorption efficiency was less than or equal to 25 % for all the eluents, and it follows the order HCl > H2O > CH3COOH.

  7. Adsorption and desorption behavior of copper ions on Na-montmorillonite: effect of rhamnolipids and pH.

    PubMed

    Ozdemir, Günseli; Yapar, Saadet

    2009-07-30

    In this work, the effects of an anionic biosurfactant, rhamnolipid (RL), and pH on the adsorption and desorption of Cu(2+) ions on Na-montmorillonite were investigated. Adsorption studies were conducted through the addition of Cu(2+) to the dispersions containing pristine- and/or RL-modified clay. In the case of pristine clay, RL was also added simultaneously with the Cu(2+). The effect of pH was studied in the range between 1.0 and 8.0. The highest adsorption capacity was obtained at the pH of 4.7-4.8. Among the models including the Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich isotherms; Langmuir isotherm gave a better fit to the experimental data. The most suitable fit for the adsorption kinetics of Cu(2+) was obtained with a pseudo-second-order model. It was determined that the adsorption capacity of the pristine clay is comparable with that of the activated carbon and the modification of clay with RL causes an increase in the adsorption rate due to the distribution of clay platelets in the solution.

  8. Measuring P-V-T Phase Behavior with a Variable Volume View Cell

    ERIC Educational Resources Information Center

    Hoffmann, Markus M.; Salter, Jason D.

    2004-01-01

    An experiment using a variable volume cell is presented where students actively control and directly observe the phase equilibrium inside the view cell. Measuring and exploring P-V-T phase behavior through dielectric constant measurements conveys the important concept that solvent behavior can be changed continuously in the sc fluid state.

  9. Self-healable and reversible liposome leakage by citrate-capped gold nanoparticles: probing the initial adsorption/desorption induced lipid phase transition

    NASA Astrophysics Data System (ADS)

    Wang, Feng; Liu, Juewen

    2015-09-01

    We herein report that the adsorption/desorption of citrate-capped gold nanoparticles (AuNPs) transiently causes leakage in fluid phase DOPC liposomes, while the liposomes do not leak with AuNPs capped with mercaptopropionic acid (MPA). Leakage also fails to occur for gel phase DPPC liposomes. Citrate-capped (but not MPA-capped) AuNPs raise the phase transition temperature of DPPC. We conclude that citrate-capped AuNPs interact with the PC liposomes very strongly, inducing a local fluid-to-gel lipid phase transition for DOPC. Leakage takes place during this transition, and the membrane integrity is resumed after the transition. Citrate-capped AuNPs allow stronger van der Waals forces than MPA-capped AuNPs with PC liposomes, since the latter are separated from the liposome surface by the ~0.3 nm MPA layer.We herein report that the adsorption/desorption of citrate-capped gold nanoparticles (AuNPs) transiently causes leakage in fluid phase DOPC liposomes, while the liposomes do not leak with AuNPs capped with mercaptopropionic acid (MPA). Leakage also fails to occur for gel phase DPPC liposomes. Citrate-capped (but not MPA-capped) AuNPs raise the phase transition temperature of DPPC. We conclude that citrate-capped AuNPs interact with the PC liposomes very strongly, inducing a local fluid-to-gel lipid phase transition for DOPC. Leakage takes place during this transition, and the membrane integrity is resumed after the transition. Citrate-capped AuNPs allow stronger van der Waals forces than MPA-capped AuNPs with PC liposomes, since the latter are separated from the liposome surface by the ~0.3 nm MPA layer. Electronic supplementary information (ESI) available: Methods, TEM, UV-vis and DLS data. See DOI: 10.1039/c5nr04805b

  10. Linear elasticity and phase behavior of block copolymer melts by self consistent field theory

    NASA Astrophysics Data System (ADS)

    Tyler, Christopher Austin

    Self Consistent Field Theory (SCFT) is a well established theory for describing the thermodynamics of block copolymer melts and blends. Although the theory is approximate, it has been quite successful in describing the phase behavior of diblock copolymers. We have applied SCFT to study the linear elastic behavior and the phase behavior of block copolymer melts. First, we calculate the linear elastic response of block copolymer melts ordered on a cubic lattice, with either body-centered or gyroid symmetry. We compare our results to experiments. A large, low-frequency plateau in the elastic storage modulus, corresponding to approximately 0.2kT per polymer chain, has been experimentally observed. By calculating the free energy of block copolymer melts on deformed lattices, we find that SOFT correctly predicts the elastic behavior of these three-dimensionally-ordered structures. We also investigate the phase behavior of triblock copolymer melts. Recent experimental work has identified a new, non-cubic, three-dimensional network phase, termed the O70 phase, in ABC triblock copolymers. We investigate the phase behavior of ABC triblock copolymer melts by calculating the free energy of several candidate phases, including the O70 phase. We find that O 70 is an equilibrium structure in triblock copolymer melts and that the SCFT and experimentally observed phase boundaries agree qualitatively. We also find that O70 is an equilibrium phase in diblock copolymer melts.

  11. Determination of trace levels of parabens in real matrices by bar adsorptive microextraction using selective sorbent phases.

    PubMed

    Almeida, C; Nogueira, J M F

    2014-06-27

    In the present work, the development of an analytical methodology which combines bar adsorptive microextraction with microliquid desorption followed by high performance liquid chromatography-diode array detection (BAμE-μLD/HPLC-DAD) is proposed for the determination of trace levels of four parabens (methyl, ethyl, propyl and buthyl paraben) in real matrices. By comparing six polymer (P1, P2, P3, P4, P5 and P6) and five activated carbon (AC1, AC2, AC3, AC4 and AC5) coatings through BAμE, AC2 exhibited much higher selectivity and efficiency from all the sorbent phases tested, even when compared with the commercial stir bar sorptive extraction with polydimethylsiloxane. Assays performed through BAμE(AC2, 1.7mg) on 25mL of ultrapure water samples spiked at the 8.0μg/L level, yielded recoveries ranging from 85.6±6.3% to 100.6±11.8%, under optimized experimental conditions. The analytical performance showed also convenient limits of detection (0.1μg/L) and quantification (0.3μg/L), as well as good linear dynamic ranges (0.5-28.0μg/L) with remarkable determination coefficients (r(2)>0.9982). Excellent repeatability was also achieved through intraday (RSD<10.2%) and interday (RSD<10.0%) assays. By downsizing the analytical device to half-length (BAμE(AC2, 0.9mg)), similar analytical data was also achieved for the four parabens, under optimized experimental conditions, showing that this analytical technology can be design to operate with lower volumes of sample and desorption solvent, thus increasing the sensitivity and effectiveness. The application of the proposed analytical approach using the standard addition methodology on tap, underground, estuarine, swimming pool and waste water samples, as well as on commercial cosmetic products and urine samples, revealed good sensitivity, absence of matrix effects and the occurrence of levels of some parabens. Moreover, the present methodology is easy to implement, reliable, sensitive, requiring low sample and minimized

  12. Monitoring Domoic Acid production by Solid Phase Adsorption Toxin Tracking off the Santa Cruz Municipal Warf, Santa Cruz, California

    NASA Astrophysics Data System (ADS)

    Nolan, M.; Ziccarelli, L.; Kudela, R. M.

    2013-12-01

    Certain species of the diatom genus Pseudo-nitzschia are producers of the neurotoxin, domoic acid (DA). DA is known to cause amnesic shellfish poisoning also known as domoic acid poisoning, which can lead to permanent brain damage in humans and marine mammals. DA accumulates at higher trophic levels, generally due to consumption of toxic cells or through trophic transfer, and can potentially cause death of both humans and marine wildlife. The Santa Cruz Municipal Warf experiences periodic rises in DA concentrations, which can reach toxic levels in shellfish, fish, and other marine organisms. While these increases in toxicity often occur during Pseudo-nitzschia blooms, several periods of elevated DA have occurred when diatom abundance is restricted and/or dominated by non-toxic species, and there is increasing evidence that DA dissolved in seawater may be prevalent. One theory suggests that senescent or dead Pseudo-nitzschia cells sink to the benthos while retaining their toxin and are buried in sediment following the death of a bloom. Therefore, DA may accumulate in the benthos, where it is eventually released during storms or wave and tide conditions that disturb the sediment. We sampled DA in situ using Solid Phase Adsorption Toxin Tracking (SPATT) bags SPATT uses a synthetic resin to capture dissolved DA, allowing for the determination of integrated DA concentrations at known time intervals. The alternative method is mussel biotoxin monitoring, but it is less accurate due to uncertainties in the time of DA accumulation within the mussel, and the lack of uptake of dissolved DA by the mussel. We deployed and collected SPATT off the Santa Cruz Municipal Wharf at multiple depths beginning in February 2013. We expect to see increasing DA following the death of a harmful algal bloom. Under pre-bloom conditions, little to no DA has been detected in mussels or surface SPATT, but DA from SPATT is frequently observed at depth, suggesting that the sediment is exposed to

  13. Phase behavior of reverse microemulsions based on Peceol(®).

    PubMed

    Mouri, Abdelkader; Diat, Olivier; El Ghzaoui, Abdeslam; Bauer, Caroline; Maurel, Jean Claude; Devoisselle, Jean-Marie; Dorandeu, Christophe; Legrand, Philippe

    2014-02-15

    The phase diagram of the four component system Peceol®/lecithin/ethanol/water was studied at 25°C and at a fixed fraction of ethanol. It shows an isotropic W/O microemulsion phase, biphasic liquid system and Liquid crystalline phases. The stabilizing effect of lecithin with the fluidifying effect of ethanol on the microemulsion based on long chain glycerides provides an effective combination to solubilize a large amount of water. Some structural transitions in the phase diagram were investigated as a function of water content using conductivity, rheology, Karl Fisher titration, optical microscopy and SAXS measurements. The results show no change in the microstructure of the isotropic liquid upon phase separation in the liquid biphasic area. However, in the water rich region, migration of ethanol to the external aqueous phase at the expense of the saturated microemulsion promotes the formation of liquid crystalline phases. As a function of water content, the structural change to the liquid crystalline phases follows: isotropic phase L2 → Inverted hexagonal phase H2 → Inverted hexagonal H2/lamellar Lα phases.

  14. Laboratory investigation of steam adsorption in geothermal reservoir rocks

    SciTech Connect

    Luetkehans, J.

    1988-02-01

    Some vapor-dominated geothermal reservoirs and low-permeability gas reservoirs exhibit anomalous behavior that may be caused by surface adsorption. For example, geothermal reservoirs in the Larderello are of Italy and reservoirs in the Geysers Geothermal Field, California produce little, if any, liquid. Yet to satisfy material balance constraints, another phase besides steam must be present. If steam adsorption occurring in significant amounts is not accounted for, the reserves will be grossly under-estimated. In addition, well tests may be misinterpreted because the pressure response is delayed owing to be adsorbed material leaving or entering the gaseous phase. In the present research the role of adsorption in geothermal reservoirs in investigated. Two sets of laboratory equipment were constructed to measure adsorption isotherms of cores from Berea sandstone, Larderello, and The Geysers. Seven experimental runs were completed using nitrogen on the low temperature apparatus at -196/sup 0/C. Eight runs were conducted using steam on the high temperature apparatus at temperatures ranging from 150 C to 207/sup 0/C. The largest specific surface area and the greatest nitrogen adsorption isotherm were measured on the Berea sandstone, followed by a core from Larderello and then The Geysers. Difficulties in determining whether a system had reached equilibrium at the end of each step lead to questions regarding the magnitude of adsorption measured by the steam runs. Nevertheless, adsorption was observed and the difficulties themselves were useful indicators of needed future research.

  15. Phase behavior, formation, and rheology of cubic phase and related gel emulsion in Tween 80/water/oil systems.

    PubMed

    Alam, Mohammad Mydul; Ushiyama, Kousuke; Aramaki, Kenji

    2009-01-01

    We investigated the phase behavior, formation, and rheology of the cubic phase (I(1)) and related O/I(1) gel emulsion in water/Tween 80/oil systems using squalane, liquid paraffin (LP), and decane as oil components. In the phase behavior study, the phase sequences were similar for squalane and LP systems, while a lamellar liquid crystal (L(alpha)) was observed for decane system. In all the systems the addition of oil to W(m) or H(1) phase induced the I(1) phase, which can solubilize some amounts of oil followed by the appearance of I(1)+O phase. The formation of the O/I(1) gel emulsion has been studied at a fixed w/s (50/50) and we found that 30 wt% decane, 70 wt% squalane, and 60 wt% LP can form the gel emulsion. The water/Tween 80/squalane system has been taken as a model system to study viscoelastic properties of the I(1) phase and O/I(1) gel emulsion. The I(1) phase shows a typical hard gel cubic structure under the frequency and the values of the complex viscosity, /eta*/ and the elastic modulus, G ' increase with the addition of squalane, which could be due to the neighboring micellar interaction. On the other hand, the decreasing values of the viscoelastic parameters in the O/I(1) gel emulsion simply relate to the volume fraction of the I(1) phase in the system.

  16. Complete Phase I Tests As Described in the Multi-lab Test Plan for the Evaluation of CH3I Adsorption on AgZ

    SciTech Connect

    Bruffey, S. H.; Jubin, R. T.

    2014-09-30

    Silver-exchanged mordenite (AgZ) has been identified as a potential sorbent for iodine present in the off-gas streams of a used nuclear fuel reprocessing facility. In such a facility, both elemental and organic forms of iodine are released from the dissolver in gaseous form. These species of iodine must be captured with high efficiency for a facility to avoid radioactive iodine release above regulatory limits in the gaseous effluent of the plant. Studies completed at Idaho National Laboratory (INL) examined the adsorption of organic iodine in the form of CH3I by AgZ. Upon breakthrough of the feed gas through the sorbent bed, elemental iodine was observed in the effluent stream, despite the fact that the only source of iodine in the system was the CH3I in the feed gas.1 This behavior does not appear to have been reported previously nor has it been independently confirmed. Thus, as a result of these prior studies, multiple knowledge gaps relating to the adsorption of CH3I by AgZ were identified, and a multi-lab test plan, including Oak Ridge National Laboratory (ORNL), INL, Pacific Northwest National Laboratory (PNNL), and Sandia National Laboratories, was formulated to address each in a systematic way.2 For this report, the scope of work for ORNL was further narrowed to three thin-bed experiments that would characterize CH3I adsorption onto AgZ in the presence of water, NO, and NO2. Completion of these three-thin bed experiments demonstrated that organic iodine in the form of CH3I was adsorbed by reduced silver mordenite (Ag0Z) to a 50% higher loading than that of I2 when adsorbed from a dry air stream. Adsorption curves suggest different adsorption mechanisms for I2 and CH3I. In the presence of NO and NO2 gas, the loading of CH3I onto Ag0Z is suppressed and may be reversible. Further, the presence of NO and NO2 gas appears to oxidize CH3I to I2; this is indicated by an adsorption curve similar to that of I2 on Ag0Z. Finally, the loss of organic iodine loading

  17. Research of CO2 and N2 Adsorption Behavior in K-Illite Slit Pores by GCMC Method

    PubMed Central

    Chen, Guohui; Lu, Shuangfang; Zhang, Junfang; Xue, Qingzhong; Han, Tongcheng; Xue, Haitao; Tian, Shansi; Li, Jinbu; Xu, Chenxi; Pervukhina, Marina; Clennell, Ben

    2016-01-01

    Understanding the adsorption mechanisms of CO2 and N2 in illite, one of the main components of clay in shale, is important to improve the precision of the shale gas exploration and development. We investigated the adsorption mechanisms of CO2 and N2 in K-illite with varying pore sizes at the temperature of 333, 363 and 393 K over a broad range of pressures up to 30 MPa using the grand canonical Monte Carlo (GCMC) simulation method. The simulation system is proved to be reasonable and suitable through the discussion of the impact of cation dynamics and pore wall thickness. The simulation results of the excess adsorption amount, expressed per unit surface area of illite, is in general consistency with published experimental results. It is found that the sorption potential overlaps in micropores, leading to a decreasing excess adsorption amount with the increase of pore size at low pressure, and a reverse trend at high pressure. The excess adsorption amount increases with increasing pressure to a maximum and then decreases with further increase in the pressure, and the decreasing amount is found to increase with the increasing pore size. For pores with size greater larger than 2 nm, the overlap effect disappears. PMID:27897232

  18. Effect of humic acid on the adsorption/desorption behavior of glyphosate on goethite. Isotherms and kinetics.

    PubMed

    Arroyave, Jeison Manuel; Waiman, Carolina C; Zanini, Graciela P; Avena, Marcelo J

    2016-02-01

    The effects of humic acid (HA) on the adsorption/desorption of glyphosate (Gly) on goethite were investigated under pseudo equilibrium conditions by adsorption isotherms and under kinetic conditions by ATR-FTIR spectroscopy. Isotherms reveal that the attachment of Gly is almost completely inhibited by HA molecules. The opposite effect is not observed: HA adsorption is not affected by the presence of Gly. ATR-FTIR allowed the simultaneous detection of adsorbed HA and Gly during kinetic runs, revealing that HA at the surface decreases markedly the adsorption rate of Gly likely as a result of a decreased availability of sites for Gly adsorption and because of electrostatic repulsion. In addition, HA in solution increases the desorption rate of Gly. The rate law for Gly desorption could be determined giving important insights on the desorption mechanism. The herbicide is desorbed by two parallel processes: i) a direct detachment from the surface, which is first order in adsorbed Gly; and ii) a ligand exchange with HA molecules, which is first order in adsorbed Gly and first order in dissolved HA. Rate constants for both processes were quantified, leading to half-lives of 3.7 h for the first process, and 1.4 h for the second process in a 400 mg L(-1) HA solution. These data are important for modeling the dynamics of glyphosate in environmentally relevant systems, such as soils and surface waters.

  19. Adsorption behavior of activated carbon derived from pyrolusite-modified sewage sludge: equilibrium modeling, kinetic and thermodynamic studies.

    PubMed

    Chen, Yao; Jiang, Wenju; Jiang, Li; Ji, Xiujuan

    2011-01-01

    Activated carbon was developed from sewage sludge using pyrolusite as an additive. It was demonstrated that the removal efficiency of two synthetic dyes (Tracid orange GS and Direct fast turquoise blue GL) by the produced adsorbent was up to 97.6%. The activated carbon with pyrolusite addition had 38.2% higher surface area, 43.8% larger micropore and 54.4% larger mesopore production than ordinary sludge-based activated carbons. Equilibrium adsorption isotherms and kinetics were also investigated based on dyes adsorption tests. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption, and the results fitted well to the Langmuir isotherm. The kinetic data have been analyzed using pseudo-first-order, pseudo-second-order and intraparticle diffusion equation. The experimental data fitted very well with pseudo-second-order kinetic model. Activation energies for the adsorption processes ranged between 8.7 and 19.1 kJ mol 1. Thermodynamic parameters such as standard free energy (deltaG0), standard enthalpy (deltaH0) and standard entropy (deltaS0) were evaluated. The adsorption of these two dyes on the activated carbon was found to be a spontaneous and endothermic process in nature.

  20. Adsorption behavior of direct red 80 and congo red onto activated carbon/surfactant: process optimization, kinetics and equilibrium.

    PubMed

    Cheng, Zhengjun; Zhang, Lei; Guo, Xiao; Jiang, Xiaohui; Li, Tian

    2015-02-25

    Adsorptions of congo red and direct red 80 onto activated carbon/surfactant from aqueous solution were optimized. The Box-Behnken design (BBD) has been employed to analyze the effects of concentration of surfactant, temperature, pH, and initial concentration of the dye in the adsorption capacity. Their corresponding experimental data could be evaluated excellently by second order polynomial regression models and the two models were also examined based on the analysis of variance and t test statistics, respectively. The optimum conditions were obtained as follows: Cs=34.10 μM, T=50°C, pH=3.5, and CCR=160 mg/L for the congo red system, and Cs=34.10 μM, T=50°C, pH=6.1, and CDR80=110 mg/L for the direct red 80 system. And in these conditions, the measured experimental maximum adsorption capacities for the congo red and direct red 80 removals were 769.48 mg/g and 519.90 mg/g, which were consistent with their corresponding predicted values, with small relative errors of -2.81% and -0.67%, respectively. The adsorption equilibrium and kinetics for the two dye adsorptions onto AC/DDAC were also investigated. The experimental data were fitted by four isotherm models, and Langmuir model presented the best fit. The kinetic studies indicated that the kinetic data followed the pseudo-second-order model.

  1. Research of CO2 and N2 Adsorption Behavior in K-Illite Slit Pores by GCMC Method

    NASA Astrophysics Data System (ADS)

    Chen, Guohui; Lu, Shuangfang; Zhang, Junfang; Xue, Qingzhong; Han, Tongcheng; Xue, Haitao; Tian, Shansi; Li, Jinbu; Xu, Chenxi; Pervukhina, Marina; Clennell, Ben

    2016-11-01

    Understanding the adsorption mechanisms of CO2 and N2 in illite, one of the main components of clay in shale, is important to improve the precision of the shale gas exploration and development. We investigated the adsorption mechanisms of CO2 and N2 in K-illite with varying pore sizes at the temperature of 333, 363 and 393 K over a broad range of pressures up to 30 MPa using the grand canonical Monte Carlo (GCMC) simulation method. The simulation system is proved to be reasonable and suitable through the discussion of the impact of cation dynamics and pore wall thickness. The simulation results of the excess adsorption amount, expressed per unit surface area of illite, is in general consistency with published experimental results. It is found that the sorption potential overlaps in micropores, leading to a decreasing excess adsorption amount with the increase of pore size at low pressure, and a reverse trend at high pressure. The excess adsorption amount increases with increasing pressure to a maximum and then decreases with further increase in the pressure, and the decreasing amount is found to increase with the increasing pore size. For pores with size greater larger than 2 nm, the overlap effect disappears.

  2. EFFECTS OF CARBOXYLIC ACIDS ON LIQUID-PHASE ADSORPTION OF ETHANOL AND WATER BY HIGH-SILICA ZSM-5

    EPA Science Inventory

    Adsorption isotherms were measured for each compound adsorbed on commercially available ZSM-5 (Si/Al = 140) powder from binary and ternary liquid mixtures of ethanol, carboxylic acids, and water at room temperature. The amounts adsorbed were measured using a recently developed t...

  3. Aqueous phase adsorption of cephalexin by walnut shell-based activated carbon: A fixed-bed column study

    NASA Astrophysics Data System (ADS)

    Nazari, Ghadir; Abolghasemi, Hossein; Esmaieli, Mohamad; Sadeghi Pouya, Ehsan

    2016-07-01

    The walnut shell was used as a low cost adsorbent to produce activated carbon (AC) for the removal of cephalexin (CFX) from aqueous solution. A fixed-bed column adsorption was carried out using the walnut shell AC. The effect of various parameters like bed height (1.5, 2 and 2.5 cm), flow rate (4.5, 6 and 7.5 mL/min) and initial CFX concentration (50, 100 and 150 mg/L) on the breakthrough characteristics of the adsorption system was investigated at optimum pH 6.5. The highest bed capacity of 211.78 mg/g was obtained using 100 mg/L inlet drug concentration, 2 cm bed height and 4.5 mL/min flow rate. Three kinetic models, namely Adam's-Bohart, Thomas and Yoon-Nelson were applied for analysis of experimental data. The Thomas and Yoon-Nelson models were appropriate for walnut shell AC column design under various conditions. The experimental adsorption capacity values were fitted to the Bangham and intra-particle diffusion models in order to propose adsorption mechanisms. The effect of temperature on the degradation of CFX was also studied.

  4. [Spectrum analysis methods of protein adsorption and design of biomedical materials].

    PubMed

    Xu, Dong; Zhou, Ning-Lin; Shen, Jian

    2010-12-01

    Protein absorption happens firstly when biological materials contact environment of organisms. The competitive adsorption behavior of different protein and the impact of biomaterial surfaces characteristics on protein adsorption are summarized. Materials with small surface free energy, high hydrophility, and a negative charge, or with the presence of micro-phase separation structure are able to reduce fibrinogen adsorption, showing good anti-clotting properties. FTIR, CD, NMR and FL are applied in protein adsorption analysis. XPS, Raman, AFM and other modern instruments have also emerged in this area. QCM appears to be more intuitive in the study of protein adsorption mechanism. The development of study on protein adsorption would guide the design of biomedical materials.

  5. Sonochemical decomposition of hydrazine in water: effects of coal ash and pH on the decomposition and adsorption behavior.

    PubMed

    Nakui, Hiroyuki; Okitsu, Kenji; Maeda, Yasuaki; Nishimura, Rokurou

    2009-07-01

    Sonochemical decomposition of hydrazine in aqueous suspension of coal ash particles was investigated in the different pH solutions. It was clearly found that the initial rate of hydrazine decomposition and adsorption is strongly dependent on the amount of coal ash and pH. At pH1, the amount of the hydrazine adsorption on coal ash was very small and hydrazine was mainly decomposed by ultrasonic irradiation. At pH4, hydrazine was mainly adsorbed on coal ash and not decomposed by ultrasonic irradiation. At pH8, the sonochemical decomposition and the adsorption on coal ash proceeded simultaneously. These results were due to the interactions between the degree of the protonation of hydrazine, the electric charge of coal ash and the amount of OH radicals formed in the sonolysis of water.

  6. pH dependence of tailing in reversed-phase chromatography of a cationic dye: measurement of the strong adsorption site surface density.

    PubMed

    Smith, Emily A; Wirth, Mary J

    2004-12-10

    A question that has interested Dr. J.J. Kirkland is addressed: what is the nature of the silanols that cause tailing to persist at low pH in reversed-phase chromatography? Chromatograms for a cationic dye, 1,1'-didodecyl-3,3,3'3'-tetramethylindocarbocyanine perchlorate (DiI), were studied at varying pH using an Agilent SB-C8 column and 80% ACN/water for six DiI concentrations ranging from 0.9 to 316 microM. The chromatograms showed increased retention and tailing from pH 1 to 5, as expected. Simulations of the chromatograms agreed well with experiment for a bi-Langmuir isotherm with weak (C8) and strong (silica) adsorption sites. The simulation parameters revealed that the number of strong adsorption sites decreases by 40% from pH 1 to 5, which indicates that the silanols causing tailing are in the SiOH, not the SiO-, form. This seems paradoxical because tailing increases with increasing pH. The simulation parameters reveal that this increased tailing from pH 1 to 5 owes to doubling of the partition coefficient for DiI to the strong adsorption site, which more than compensates for the decreasing number of sites. We attribute this increased partition coefficient to increased long-range coulombic interactions with the increasingly abundant SiO- groups at higher pH, which boosts DiI's partition coefficient for both the C8 and SiOH sites. The picture thus emerges that for DiI, higher pH causes increased tailing because the SiO- groups exacerbate tailing that actually originates from adsorption to SiOH groups.

  7. Petalite under pressure: Elastic behavior and phase stability

    DOE PAGES

    Ross, Nancy L.; Zhao, Jing; Slebodnick, Carla; ...

    2015-04-01

    The lithium aluminosilicate mineral petalite (LiAlSi4O10) has been studied using high-pressure single-crystal X-ray diffraction (HP-XRD) up to 5 GPa. Petalite undergoes two pressure-induced first-order phase transitions, never reported in the literature, at ca. 1.5 and 2.5 GPa. The first of these transforms the low-pressure α-phase of petalite (P2/c) to an intermediate β-phase that then fully converts to the high-pressure β-phase at ca. 2.5 GPa. The α→β transition is isomorphic and is associated with a commensurate modulation that triples the unit cell volume. Analysis of the HP-XRD data show that although the fundamental features of the petalite structure are retained throughmore » this transition, there are subtle alterations in the internal structure of the silicate double-layers in the β-phase relative to the α-phase. Measurement of the unit cell parameters of petalite as a function of pressure, and fitting of the data with 3rd order Birch-Murnaghan equations of state, has provided revised elastic constants for petalite. The bulk moduli of the α and β-phases are 49(1) and 35(3) GPa, respectively. These values indicate that the compressibility of the- phase of petalite lies between the alkali feldpsars and alkali feldspathoids, whereas the β-phase has a compressibility more comparable with layered silicates. Structure analysis has shown that the compression of the -phase is facilitated by the rigid body movement of the Si2O7 units from which the silicate double-layers are constructed.« less

  8. Petalite under pressure: Elastic behavior and phase stability

    SciTech Connect

    Ross, Nancy L.; Zhao, Jing; Slebodnick, Carla; Spencer, Elinor C.; Chakoumakos, Bryan C.

    2015-04-01

    The lithium aluminosilicate mineral petalite (LiAlSi4O10) has been studied using high-pressure single-crystal X-ray diffraction (HP-XRD) up to 5 GPa. Petalite undergoes two pressure-induced first-order phase transitions, never reported in the literature, at ca. 1.5 and 2.5 GPa. The first of these transforms the low-pressure α-phase of petalite (P2/c) to an intermediate β-phase that then fully converts to the high-pressure β-phase at ca. 2.5 GPa. The α→β transition is isomorphic and is associated with a commensurate modulation that triples the unit cell volume. Analysis of the HP-XRD data show that although the fundamental features of the petalite structure are retained through this transition, there are subtle alterations in the internal structure of the silicate double-layers in the β-phase relative to the α-phase. Measurement of the unit cell parameters of petalite as a function of pressure, and fitting of the data with 3rd order Birch-Murnaghan equations of state, has provided revised elastic constants for petalite. The bulk moduli of the α and β-phases are 49(1) and 35(3) GPa, respectively. These values indicate that the compressibility of the- phase of petalite lies between the alkali feldpsars and alkali feldspathoids, whereas the β-phase has a compressibility more comparable with layered silicates. Structure analysis has shown that the compression of the -phase is facilitated by the rigid body movement of the Si2O7 units from which the silicate double-layers are constructed.

  9. Gate-opening gas adsorption and host-guest interacting gas trapping behavior of porous coordination polymers under applied AC electric fields.

    PubMed

    Kosaka, Wataru; Yamagishi, Kayo; Zhang, Jun; Miyasaka, Hitoshi

    2014-09-03

    The gate-opening adsorption behavior of the one-dimensional chain compound [Ru2(4-Cl-2-OMePhCO2)4(phz)] (1; 4-Cl-2-OMePhCO2(-) = 4-chloro-o-anisate; phz = phenazine) for various gases (O2, NO, and CO2) was electronically monitored in situ by applying ac electric fields to pelletized samples attached to a cryostat, which was used to accurately control the temperature and gas pressure. The gate-opening and -closing transitions induced by gas adsorption/desorption, respectively, were accurately monitored by a sudden change in the real part of permittivity (ε'). The transition temperature (TGO) was also found to be dependent on the applied temperature and gas pressure according to the Clausius-Clapeyron equation. This behavior was also observed in the isostructural compound [Rh2(4-Cl-2-OMePhCO2)4(phz)] (2), which exhibited similar gate-opening adsorption properties, but was not detected in the nonporous gate-inactive compound [Ru2(o-OMePhCO2)4(phz)] (3). Furthermore, the imaginary part of permittivity (ε″) effectively captured the electronic perturbations of the samples induced by the introduced guest molecules. Only the introduction of NO resulted in the increase of the sample's electronic conductivity for 1 and 3, but not for 2. This behavior indicates that electronic host-guest interactions were present, albeit very weak, at the surface of sample 1 and 3, i.e., through grain boundaries of the sample, which resulted in perturbation of the conduction band of this material's framework. This technique involving the in situ application of ac electric fields is useful not only for rapidly monitoring gas sorption responses accompanied by gate-opening/-closing structural transitions but also potentially for the development of molecular framework materials as chemically driven electronic devices.

  10. Polymerization behavior of hydrophilic-rich phase of dentin adhesive.

    PubMed

    Abedin, F; Ye, Q; Parthasarathy, R; Misra, A; Spencer, P

    2015-03-01

    The 2-fold objectives of this study were 1) to understand whether model hydrophobic- and hydrophilic-rich phase mimics of dentin adhesive polymerize similarly and 2) to determine which factor, the dimethacrylate component, bisphenol A glycerolate dimethacrylate (BisGMA) or photoinitiator concentration, has greater influence on the polymerization of the hydrophilic-rich phase mimic. Current dentin adhesives are sensitive to moisture, as evidenced by nanoleakage in the hybrid layer and phase separation into hydrophobic- and hydrophilic-rich phases. Phase separation leads to limited availability of the cross-linkable dimethacrylate monomer and hydrophobic photoinitiators within the hydrophilic-rich phase. Model hydrophobic-rich phase was prepared as a single-phase solution by adding maximum wt% deuterium oxide (D2O) to HEMA/BisGMA neat resins containing 45 wt% 2-hydroxyethyl methacrylate (HEMA). Mimics of the hydrophilic-rich phase were prepared similarly but using HEMA/BisGMA neat resins containing 95, 99, 99.5, and 100 wt% HEMA. The hydrophilic-rich mimics were prepared with standard or reduced photoinitiator content. The photoinitiator systems were camphorquinone (CQ)/ethyl 4-(dimethylamino)benzoate (EDMAB) with or without [3-(3, 4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-2-hydroxypropyl]trimethylammonium chloride (QTX). The polymerization kinetics was monitored using a Fourier transform infrared spectrophotometer with a time-resolved collection mode. The hydrophobic-rich phase exhibited a significantly higher polymerization rate compared with the hydrophilic-rich phase. Postpolymerization resulting in the secondary rate maxima was observed for the hydrophilic-rich mimic. The hydrophilic-rich mimics with standard photoinitiator concentration but varying cross-linker (BisGMA) content showed postpolymerization and a substantial degree of conversion. In contrast, the corresponding formulations with reduced photoinitiator concentrations exhibited lower polymerization and

  11. Dependence on sphere size of the phase behavior of mixtures of rods and spheres

    NASA Astrophysics Data System (ADS)

    Urakami, Naohito; Imai, Masayuki

    2003-07-01

    By the addition of chondroitin sulfate (Chs) to the aqueous suspension of tobacco mosaic virus (TMV), the aggregation of TMV occurs at very dilute TMV concentration compared with the addition of polyethylene oxide (PEO). The difference of physical behavior between Chs and PEO is the chain conformation in solution. The Chs chain has a semirigid nature, whereas the PEO chain has a flexible nature. In this study, the Chs and PEO chains are simplified to spherical particles having different size, and we use the spherocylinder model for TMV particle. The effect of the sphere size on the phase behaviors in the mixtures of rods and spheres is investigated by Monte Carlo simulations. By the addition of small spheres, the system transforms from the miscible isotropic phase to the miscible nematic phase. On the other hand, by the addition of large spheres, the system changes from the miscible isotropic phase to the immiscible nematic phase through the immiscible isotropic phase. The different phase behaviors between the small and the large spheres originate from the difference of overlapping volume of the depletion zone. In addition, we perform the Monte Carlo simulations in the case that semirigid chains are used as the Chs chain models. The same phase behaviors are observed as the mixtures of rods and large spheres. Thus the sphere model captures the phase behaviors of rod and polymer mixture systems.

  12. A first-principles study on the adsorption behavior of amphetamine on pristine, P- and Al-doped B12N12 nano-cages

    NASA Astrophysics Data System (ADS)

    Bahrami, Aidin; Seidi, Shahram; Baheri, Tahmineh; Aghamohammadi, Mohammad

    2013-12-01

    The first-principles computations using density functional theory (DFT) calculations at the M062X/6-311++G** level have been applied to scrutinize the adsorption behavior of amphetamine (AMP) molecule on the external surface of pristine, P- and Al-doped B12N12 nano-cages. In order to gain insight into the binding features of pristine and doped B12N12 complexes as adsorbent with AMP, the structural and electronic parameters as well as the Atoms in Molecules (AIM) properties were examined. The results showed that AMP prefers to adsorb via its nitrogen atom on the Lewis acid sites of B and Al atoms of the nano-cages. On the basis of calculated density of states, the interaction of AMP with the external wall of B12N12 leads to the remarkable differences in their conductivities. Presence of polar solvent increases the AMP adsorption on the nano-cage. In addition, AIM based analyses indicated an electrostatic nature for N-B interaction in Amph-B12N12 and partial covalent for N-Al in AMP-B11AlN12. Based on calculated results, the B12N12 and B11AlN12 nano-cages are expected to be a potential efficient adsorbent as well as sensors for adsorption of AMP in environmental systems.

  13. Effect of OH content on phase separation behavior of soda-silica glasses

    NASA Technical Reports Server (NTRS)

    Neilson, G. F.; Weinberg, M. C.; Smith, G. L.

    1986-01-01

    The kinetics of phase separation in a gel and ordinary soda-silica glass are followed by use of small angle X-ray scattering. Also, the influence of OH on the phase separation behavior is studied. It is found that OH accelerates the growth of the secondary phase, and that gel and ordinary glasses of similar composition and OH concentration exhibit similar phase separation characteristics.

  14. Nonequilibrium Phase Behavior from Minimization of Free Power Dissipation

    NASA Astrophysics Data System (ADS)

    Krinninger, Philip; Schmidt, Matthias; Brader, Joseph M.

    2016-11-01

    We develop a general theory for describing phase coexistence between nonequilibrium steady states in Brownian systems, based on power functional theory [M. Schmidt and J. M. Brader, J. Chem. Phys. 138, 214101 (2013)]. We apply the framework to the special case of fluid-fluid phase separation of active soft sphere swimmers. The central object of the theory, the dissipated free power, is calculated via computer simulations and compared to a simple analytical approximation. The theory describes well the simulation data and predicts motility-induced phase separation due to avoidance of dissipative clusters.

  15. Synthesis and phase behavior of end-functionalized associating polymers

    NASA Astrophysics Data System (ADS)

    Wrue, Michelle H.

    We have explored polymer blend phase behavior in the presence of multiple hydrogen bonding end-groups. This work details the synthesis of functionalized polymers and their subsequent use in miscibility studies. The synthesis of end-functionalized hydrogen bonding polymers and the investigation of their physical properties and miscibility is presented. Mono-functional and telechelic ureidopyrimidinone (UPy) functionalized polymers were prepared by two main routes: post-polymerization functionalization (of commercially available or synthesized polymers); and polymerization of monomers using a functionalized initiator. UPy-functionalized polymers were prepared with a variety of polymer backbones including poly(ethylene oxide)s; poly(butadiene)s, poly(dimethyl siloxanxe)s; poly(styrene)s and poly(methyl methacrylate)s. The most successful route to polymers with UPy end-groups was atom transfer radical polymerization (ATRP) using a UPy-functionalized initiator, followed by atom transfer radical coupling (ATRC). The incorporation of ureidopyrimidinone end-groups was shown to affect the physical properties of the polymer backbone. Parent polymers that were liquids became viscous liquids or waxy solids upon UPy-functionalization of chain end. UPy-functionalization of a hydroxyl-terminated polybutadiene (HO-PB-OH) resulted in a waxy solid while the HO-PB-OH precursor was a viscous liquid. The thermal properties of functionalized polymers also differed from those of the unfunctionalized parent polymers. Hot-stage optical microscopy revealed that UPy-functionalized PEO displayed a depressed melting point relative to the analogous unfunctionalized precursor. Differential scanning calorimetry was also used to investigate the synthesized UPy-polymers. UPy-functionalized polystyrenes and poly(methyl methacrylate)s showed an increased T g compared to the equivalent homopolymer standards. This increased Tg was determined to be dependent upon the fraction of UPy groups present and

  16. Effect of many-body interactions on the bulk and interfacial phase behavior of a model colloid-polymer mixture.

    PubMed

    Dijkstra, Marjolein; van Roij, René; Roth, Roland; Fortini, Andrea

    2006-04-01

    We study a model suspension of sterically stabilized colloidal particles and nonadsorbing ideal polymer coils, both in bulk and adsorbed against a planar hard wall. By integrating out the degrees of freedom of the polymer coils, we derive a formal expression for the effective one-component Hamiltonian of the colloids. We employ an efficient Monte Carlo simulation scheme for this mixture based on the exact effective colloid Hamiltonian; i.e., it incorporates all many-body interactions. The many-body character of the polymer-mediated effective interactions between the colloids yields bulk phase behavior and adsorption phenomena that differ substantially from those found for pairwise simple fluids. We determine the phase behavior for size ratios q=sigma(p)/sigma(c)=1, 0.6, and 0.1, where sigma(c) and sigma(p) denote the diameters of the colloids and polymer coils, respectively. For q=1 and 0.6, we find both a fluid-solid and a stable colloidal gas-liquid transition with an anomalously large bulk liquid regime caused by the many-body interactions. We compare the phase diagrams obtained from simulations with the results of the free-volume approach and with direct simulations of the true binary mixture. Although we did not simulate the polymer coils explicitly, we are able to obtain the three partial structure factors and radial distribution functions. We compare our results with those obtained from density functional theory and the Percus-Yevick approximation. We find good agreement between all results for the structure. We also study the mixture in contact with a single hard wall for q=1. Upon approach of the gas-liquid binodal, we find far from the triple point, three layering transitions in the partial wetting regime.

  17. Adsorption behavior of light green anionic dye using cationic surfactant-modified wheat straw in batch and column mode.

    PubMed

    Su, Yinyin; Zhao, Binglu; Xiao, Wei; Han, Runping

    2013-08-01

    An agricultural by-product, natural wheat straw (NWS), was soaked in 1 % cationic surfactant (hexadecylpyridinium bromide, CPB) solution for 24 h (at 293 K), and modified wheat straw (MWS) was obtained. Analysis of FTIR, XFR, and nitrogen element showed that CPB was adsorbed onto surface of NWS. Then, MWS was used as adsorbent for the removal of light green dye (LG, anionic dye) from aqueous solution. The experiment was performed in batch and column mode at room temperature (293 K). Sodium chloride (up to 0.1 mol/L) existed in solution was not favor of LG dye adsorption. The equilibrium data were better described by Langmuir isotherm, and adsorption capacity of q m from Langmuir model was 70.01 ± 3.39 mg/g. In fixed-bed column adsorption mode, the effects of initial LG concentration (30, 50, 70 mg/L) and flow rate (6.5, 9.0, 14.5 mL/min) on adsorption were presented. Thomas and modified dose-response models were used to predict the breakthrough curves using nonlinear analysis method, and both models can fit the breakthrough curves. Theoretical and experimental breakthrough curves were drawn and compared. The results implied that MWS can be used as adsorbent material to remove LG from aqueous solution.

  18. The adsorption behavior and mechanism investigation of Pb(II) removal by flocculation using microbial flocculant GA1.

    PubMed

    Feng, Jing; Yang, Zhaohui; Zeng, Guangming; Huang, Jing; Xu, Haiyin; Zhang, Yuanyuan; Wei, Shumei; Wang, Like

    2013-11-01

    In this work, microbial flocculant GA1 (MBFGA1) was used to remove Pb(II) ions from aqueous solution. A series of experimental parameters including initial pH, MBFGA1 dose, temperature and initial calcium ions concentration on Pb(II) uptake was evaluated. Meanwhile, the flocculation mechanism of MBFGA1 was investigated. The removal efficiency of Pb(II) reached up to 99.85% when MBFGA1 was added in two stages, separately. The results indicated that Pb(II) adsorption could be described by the Langmuir adsorption model, and being the monolayer capacity negatively affected with an increase in temperature. The adsorption process could be described by pseudo-second-order kinetic model. Fourier transform-infrared spectra and environmental scanning electron microscope analysis indicated that MBFGA1 had a large number of functional groups, which had strong capacity for removing Pb(II). The main mechanisms of Pb(II) removal by MBFGA1 could be charge neutralization and adsorption bridging.

  19. Effect of pyrolysis temperature on characteristics and aromatic contaminants adsorption behavior of magnetic biochar derived from pyrolysis oil distillation residue.

    PubMed

    Li, Hao; Mahyoub, Samah Awadh Ali; Liao, Wenjie; Xia, Shuqian; Zhao, Hechuan; Guo, Mengya; Ma, Peisheng

    2017-01-01

    The magnetic biochars were easily fabricated by thermal pyrolysis of Fe(NO3)3 and distillation residue derived from rice straw pyrolysis oil at 400, 600 and 800°C. The effects of pyrolysis temperature on characteristics of magnetic biochars as well as adsorption capacity for aromatic contaminants (i.e., anisole, phenol and guaiacol) were investigated carefully. The degree of carbonization of magnetic biochars become higher as pyrolysis temperature increasing. The magnetic biochar reached the largest surface area and pore volume at the pyrolysis temperature of 600°C due to pores blocking in biochar during pyrolysis at 800°C. Based on batch adsorption experiments, the used adsorbent could be magnetically separated and the adsorption capacity of anisole on magnetic biochars was stronger than that of phenol and guaiacol. The properties of magnetic biochar, including surface area, pore volume, aromaticity, grapheme-like-structure and iron oxide (γ-Fe2O3) particles, showed pronounced effects on the adsorption performance of aromatic contaminants.

  20. Phase behavior and dynamics of a cholesteric liquid crystal

    SciTech Connect

    Roy, D.; Fragiadakis, D.; Roland, C. M.; Dabrowski, R.; Dziaduszek, J.; Urban, S.

    2014-02-21

    The synthesis, equation of state, phase diagram, and dielectric relaxation properties are reported for a new liquid crystal, 4{sup ′}-butyl-4-(2-methylbutoxy)azoxybenzene (4ABO5*), which exhibits a cholesteric phase at ambient temperature. The steepness of the intermolecular potential was characterized from the thermodynamic potential parameter, Γ = 4.3 ± 0.1 and the dynamic scaling exponent, γ = 3.5 ± 0.2. The difference between them is similar to that seen previously for nematic and smectic liquid crystals, with the near equivalence of Γ and γ consistent with the near constancy of the relaxation time of 4ABO5* at the cholesteric to isotropic phase transition (i.e., the clearing line). Thus, chirality does not cause deviations from the general relationship between thermodynamics and dynamics in the ordered phase of liquid crystals. The ionic conductivity of 4ABO5* shows strong coupling to the reorientational dynamics.

  1. Re-entrant phase behavior of a concentrated anionic surfactant system with strongly binding counterions.

    PubMed

    Ghosh, Sajal Kumar; Rathee, Vikram; Krishnaswamy, Rema; Raghunathan, V A; Sood, A K

    2009-08-04

    The phase behavior of the anionic surfactant sodium dodecyl sulfate (SDS) in the presence of the strongly binding counterion p-toluidine hydrochloride (PTHC) has been examined using small-angle X-ray diffraction and polarizing microscopy. A hexagonal-to-lamellar transition on varying the PTHC to SDS molar ratio (alpha) occurs through a nematic phase of rodlike micelles (Nc) --> isotropic (I) --> nematic of disklike micelles (N(D)) at a fixed surfactant concentration (phi). The lamellar phase is found to coexist with an isotropic phase (I') over a large region of the phase diagram. Deuterium nuclear magnetic resonance investigations of the phase behavior at phi = 0.4 confirm the transition from N(C) to N(D) on varying alpha. The viscoelastic and flow behaviors of the different phases were examined. A decrease in the steady shear viscosity across the different phases with increasing alpha suggests a decrease in the aspect ratio of the micellar aggregates. From the transient shear stress response of the N() and N(D) nematic phases in step shear experiments, they were characterized to be tumbling and flow aligning, respectively. Our studies reveal that by tuning the morphology of the surfactant micelles strongly binding counterions modify the phase behavior and rheological properties of concentrated surfactant solutions.

  2. Association of menstrual phase with smoking behavior, mood and menstrual phase-associated symptoms among young Japanese women smokers

    PubMed Central

    2013-01-01

    Background Previous studies of the relationship between the menstrual phases and smoking behavior have been problematic, so the association of menstrual phases with smoking behavior and correlations among smoking, psychological and physical conditions in each phase of the menstrual cycle are unclear. Methods To accurately examine the association between menstrual phases and the amount of smoking (number of cigarettes smoked and breath CO concentration), craving of smoking on visual analogue scale (VAS), depression in the Center for Epidemiologic Studies Depression (CES-D) Scale, and menstrual phase-associated symptoms in the Menstrual Distress Questionnaire (MDQ), we improved various methodological issues, specifically, 1) Ovulation was confirmed by measuring the basal body temperature and identifying a urinary luteinizing hormone (LH) surge in two cycles; 2) The menstrual, follicular, and luteal phases were clearly defined for subjects with different menstrual cycles; 3) The breath CO concentration was measured every day. A notice was posted on public bulletin boards to recruit research subjects and twenty-nine young Japanese women smokers aged 19 to 25 years old were analyzed. Results The number of cigarettes smoked was greater and the CO concentration was higher in the luteal phase than in the follicular phase. The levels of craving for smoking (VAS), depressiveness (CES-D), and menstrual phase-associated symptoms (MDQ) in the menstrual and luteal phases were higher than those in the follicular phase. The mean score for CES-D was 16 points (the cut-off value in screening for depression) or higher in the menstrual (16.9 ± 8.2) and luteal phases (17.2 ± 8.4). The number of cigarettes smoked and CO concentration were significantly correlated with the levels of craving for smoking, depressiveness, and menstrual phase-associated symptoms in all phases except for MDQ scores in follicular phase. The amount of smoking in the luteal phase was most strongly

  3. Effects of Blockiness on the phase behavior of random copolymers

    NASA Astrophysics Data System (ADS)

    Vanderwoude, Gordon; Shi, An-Chang

    Theoretical study of random block copolymers remains a challenging topic due in part to the sheer enormity of their phase space. In this study we use the self-consistent field theory to investigate the phase behaviour of linear (AB)n-type and (AB)n-C-type multiblock copolymers with randomly distributed A and B blocks. In particular, we examine the effect of ``blockiness'' of the random copolymers on the formation of ordered phases. The blockiness can be quantified by the average length of individual A or B blocks, which can be taken as a measure of the heterogeneity of the random copolymers. We observed that the critical value of the χ parameter, at which the order-disorder transition occurs, decreases with increasing blockiness in the (AB)n copolymers. We also observed that the phase behaviour of the (AB)n-C copolymers depends strongly on the blockiness of the random chain. In particular, the blockiness governs whether or not the A/B blocks can phase separate within the A/B domains, thus dictating whether the (AB)n-C behaves as A/B-C diblock copolymers or as ABC terpolymers. The theoretical phase diagrams will be compared with available experiments.

  4. Modeling Interfacial Adsorption of Polymer-Grafted Nanoparticles

    NASA Astrophysics Data System (ADS)

    Yong, Xin

    2014-11-01

    Numerous natural and industrial processes demand advances in our fundamental understanding of colloidal adsorption at liquid interfaces. Using dissipative particle dynamics (DPD), we model the interfacial adsorption of core-shell nanoparticles at the water-oil interface. The solid core of the nanoparticle encompasses beads arranged in an fcc lattice structure and its surface is uniformly grafted with polymer chains. The nanoparticles bind to the interface from either phase to minimize total surface energy. With a single nanoparticle, we demonstrate detailed kinetics of different stages in the adsorption process. Prominent effect of grafted polymer chains is characterized by varying molecular weight and polydispersity of the chains. We also preload nanoparticles straddling the interface to reveal the influence of nanoparticle surface density on further adsorption. Importantly, these studies show how surface-grafted polymer chains can alter the interfacial behavior of colloidal particles and provide guidelines for designing on-demand Pickering emulsion.

  5. The Influence of Disorder on Thermotropic Nematic Liquid Crystals Phase Behavior

    PubMed Central

    Popa-Nita, Vlad; Gerlič, Ivan; Kralj, Samo

    2009-01-01

    We review the theoretical research on the influence of disorder on structure and phase behavior of condensed matter system exhibiting continuous symmetry breaking focusing on liquid crystal phase transitions. We discuss the main properties of liquid crystals as adequate systems in which several open questions with respect to the impact of disorder on universal phase and structural behavior could be explored. Main advantages of liquid crystalline materials and different experimental realizations of random field-type disorder imposed on liquid crystal phases are described. PMID:19865529

  6. Introduction of an ionic liquid into the micropores of a metal-organic framework and its anomalous phase behavior.

    PubMed

    Fujie, Kazuyuki; Yamada, Teppei; Ikeda, Ryuichi; Kitagawa, Hiroshi

    2014-10-13

    Controlling the dynamics of ionic liquids (ILs) is a significant issue for widespread use. Metal-organic frameworks (MOFs) are ideal host materials for ILs because of their small micropores and tunable host-guest interactions. Herein, we demonstrate the first example of an IL incorporated within the micropores of a MOF. The system studied consisted of EMI-TFSA (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide) and ZIF-8 (composed of Zn(MeIM)2 ; H(MeIM)=2-methylimidazole) as the IL and MOF, respectively. Construction of the EMI-TFSA in ZIF-8 was confirmed by X-ray powder diffraction, nitrogen gas adsorption, and infrared absorption spectroscopy. Differential scanning calorimetry and solid-state NMR measurements showed that the EMI-TFSA inside the micropores demonstrated no freezing transition down to 123 K, whereas bulk EMI-TFSA froze at 231 K. Such anomalous phase behavior originates from the nanosize effect of the MOF on the IL. This result provides a novel strategy for stabilizing the liquid phase of the ILs down to a lower temperature region.

  7. Definition of two-phase flow behaviors for spacecraft design

    NASA Technical Reports Server (NTRS)

    Reinarts, Thomas R.; Best, Frederick R.; Miller, Katherine M.; Hill, Wayne S.

    1991-01-01

    Data for complete models of two-phase flow in microgravity are taken from in-flight experiments and applied to an adiabatic flow-regime analysis to study the feasibility of two-phase systems for spacecraft. The data are taken from five in-flight experiments by Hill et al. (1990) in which a two-phase pump circulates a freon mixture and vapor and liquid flow streams are measured. Adiabatic flow regimes are analyzed based on the experimental superficial velocities of liquid and vapor, and comparisons are made with the results of two-phase flow regimes at 1 g. A motion analyzer records the flow characteristics at a rate of 1000 frames/sec, and stratified flow regimes are reported at 1 g. The flow regimes observed under microgravitational conditions are primarily annular and include slug and bubbly-slug regimes. The present data are of interest to the design and analysis of two-phase thermal-management systems for use in space missions.

  8. Np Behavior in Synthesized Uranyl Phases: Results of Initial Tests

    SciTech Connect

    Friese, Judah I.; Douglas, Matthew; McNamara, Bruce K.; Clark, Sue B.; Hanson, Brady D.

    2004-09-28

    Initial tests were completed at Pacific Northwest National Laboratory for developing a potential mechanism to retard the mobility of neptunium at the Yucca Mountain repository. Neptunium is of concern because of its mobility in the environment and long half life, contributing a large percentage of the potential dose over extended times at the perimeter of the site. The mobility of neptunium could be retarded by associating with uranium mineral phases. The following four uranium mineral phases were examined and are potential secondary phases expected to form as a result of interactions of spent nuclear fuel with the local environment: meta-schoepite, studtite, uranophane, and sodium boltwoodite. The fate of the neptunium was examined in these synthetic experiments.

  9. On phase transformation behavior of porous Shape Memory Alloys.

    PubMed

    Liu, Bingfei; Dui, Guansuo; Zhu, Yuping

    2012-01-01

    This paper is concerned on the phase transformation mechanism of porous Shape Memory Alloys (SMAs). A unit-cell model is adopted to establish the constitutive relation for porous SMAs, the stress distributions, the phase distributions and the martensitic volume fractions for the model are then derived under both pure hydrostatic stress and uniaxial compression. Further, an example for the uniaxial response under compression for a porous Ni-Ti SMA material considering hydrostatic stress is supplied. Good agreement between the theoretical prediction of the proposed model and published experimental data is observed.

  10. Adhesion-induced phase behavior of two-component membranes and vesicles.

    PubMed

    Rouhiparkouhi, Tahereh; Weikl, Thomas R; Discher, Dennis E; Lipowsky, Reinhard

    2013-01-22

    The interplay of adhesion and phase separation is studied theoretically for two-component membranes that can phase separate into two fluid phases such as liquid-ordered and liquid-disordered phases. Many adhesion geometries provide two different environments for these membranes and then partition the membranes into two segments that differ in their composition. Examples are provided by adhering vesicles, by hole- or pore-spanning membranes, and by membranes supported by chemically patterned surfaces. Generalizing a lattice model for binary mixtures to these adhesion geometries, we show that the phase behavior of the adhering membranes depends, apart from composition and temperature, on two additional parameters, the area fraction of one membrane segment and the affinity contrast between the two segments. For the generic case of non-vanishing affinity contrast, the adhering membranes undergo two distinct phase transitions and the phase diagrams in the composition/temperature plane have a generic topology that consists of two two-phase coexistence regions separated by an intermediate one-phase region. As a consequence, phase separation and domain formation is predicted to occur separately in each of the two membrane segments but not in both segments simultaneously. Furthermore, adhesion is also predicted to suppress the phase separation process for certain regions of the phase diagrams. These generic features of the adhesion-induced phase behavior are accessible to experiment.

  11. Americium(III) capture using phosphonic acid-functionalized silicas with different mesoporous morphologies: adsorption behavior study and mechanism investigation by EXAFS/XPS.

    PubMed

    Zhang, Wen; He, Xihong; Ye, Gang; Yi, Rong; Chen, Jing

    2014-06-17

    Efficient capture of highly toxic radionuclides with long half-lives such as Americium-241 is crucial to prevent radionuclides from diffusing into the biosphere. To reach this purpose, three different types of mesoporous silicas functionalized with phosphonic acid ligands (SBA-POH, MCM-POH, and BPMO-POH) were synthesized via a facile procedure. The structure, surface chemistry, and micromorphology of the materials were fully characterized by (31)P/(13)C/(29)Si MAS NMR, XPS, and XRD analysis. Efficient adsorption of Am(III) was realized with a fast rate to reach equilibrium (within 10 min). Influences including structural parameters and functionalization degree on the adsorption behavior were investigated. Slope analysis of the equilibrium data suggested that the coordination with Am(III) involved the exchange of three protons. Moreover, extended X-ray absorption fine structure (EXAFS) analysis, in combination with XPS survey, was employed for an in-depth probe into the binding mechanism by using Eu(III) as a simulant due to its similar coordination behavior and benign property. The results showed three phosphonic acid ligands were coordinated to Eu(III) in bidentate fashion, and Eu(P(O)O)3(H2O) species were formed with the Eu-O coordination number of 7. These phosphonic acid-functionalized mesoporous silicas should be promising for the treatment of Am-containing radioactive liquid waste.

  12. PHASE BEHAVIOR OF WATER/PERCHLOROETHYLENE/ANIONIC SURFACTANT SYSTEMS

    EPA Science Inventory

    Winsor Type I (o/w), Type II (w/o), and Type III (middle phase) microemulsions have been generated for water and perchloroethylene (PCE) in combination with anionic surfactants and the appropriate electrolyte concentration. The surfactant formulation was a combination of sodium d...

  13. Retention behavior of proton pump inhibitors using immobilized polysaccharide-derived chiral stationary phases with organic-aqueous mobile phases.

    PubMed

    Cirilli, Roberto; Ferretti, Rosella; Gallinella, Bruno; Zanitti, Leo

    2013-08-23

    In the present study, the chromatographic behavior of two immobilized polysaccharide-derived chiral stationary phases (CSPs), the Chiralpak ID-3 and Chiralpak IE-3, under aqueous mobile phases conditions is presented. Four proton pump inhibitors (PPIs) (omeprazole, lansoprazole, pentaprazole and rabeprazole) were selected as test compounds. The effect of the concentration of water in the mobile phase was investigated with respect to its contribution to enantioselectivity and retention. Under acetonitrile-water mobile phase conditions, retention behavior evidenced an interesting pattern. At lower water content, the retention factors decreased with increasing water and at higher water content a reversed trend was observed. These findings support the hypothesis that two retention mechanisms operated successively on the same CSP: the HILIC (with water-poor eluents) and RPLC (with water-rich eluents) modes. The retention factors were minimum in the intermediate region, corresponding to a water concentration of about 20%. Interestingly, the baseline separation of all PPIs investigated was optimized under organic-aqueous mobile phases containing a high water content (from about 50 to 65%). Thus, the dual retention behavior of the PPIs on the Chiralpak ID-3 and Chiralpak IE-3 made it possible to reach greener and harmless enantioselective conditions in a short analysis time.

  14. Adsorption of the anionic surfactant sodium dodecyl sulfate on a C18 column under micellar and high submicellar conditions in reversed-phase liquid chromatography.

    PubMed

    Ortiz-Bolsico, C; Ruiz-Angel, M J; García-Alvarez-Coque, M C

    2015-02-01

    Micellar liquid chromatography makes use of aqueous solutions or aqueous-organic solutions containing a surfactant, at a concentration above its critical micelle concentration. In the mobile phase, the surfactant monomers aggregate to form micelles, whereas on the surface of the nonpolar alkyl-bonded stationary phases they are significantly adsorbed. If the mobile phase contains a high concentration of organic solvent, micelles break down, and the amount of surfactant adsorbed on the stationary phase is reduced, giving rise to another chromatographic mode named high submicellar liquid chromatography. The presence of a thinner coating of surfactant enhances the selectivity and peak shape, especially for basic compounds. However, the risk of full desorption of surfactant is the main limitation in the high submicellar mode. This study examines the adsorption of the anionic surfactant sodium dodecyl sulfate under micellar and high submicellar conditions on a C18 column, applying two methods. One of them uses a refractive index detector to obtain direct measurements of the adsorbed amount of sodium dodecyl sulfate, whereas the second method is based on the retention and peak shape for a set of cationic basic compounds that indirectly reveal the presence of adsorbed monomers of surfactant on the stationary phase.

  15. Corrosion inhibition and adsorption behavior of methionine on mild steel in sulfuric acid and synergistic effect of iodide ion.

    PubMed

    Oguzie, E E; Li, Y; Wang, F H

    2007-06-01

    The corrosion inhibition of mild steel in sulfuric acid by methionine (MTI) was investigated using electrochemical techniques. The effect of KI additives on corrosion inhibition efficiency was also studied. The results reveal that MTI inhibited the corrosion reaction by adsorption onto the metal/solution interface. Inhibition efficiency increased with MTI concentration and synergistically increased in the presence of KI, with an optimum [KI]/[MTI] ratio of 5/5, due to stabilization of adsorbed MTI cations as revealed by AFM surface morphological images. Potentiodynamic polarization data suggest that the compound functioned via a mixed-inhibition mechanism. This observation was further corroborated by the fit of the experimental adsorption data to the Temkin and Langmuir isotherms. The inhibition mechanism has been discussed vis-à-vis the presence of both nitrogen and sulfur atoms in the MTI molecule.

  16. Adsorption behavior and electronic properties of Pdn (n ≤ 10) clusters on silicon carbide nanotubes: a first-principles study.

    PubMed

    Wang, Jianguang; Ma, Li; Wang, Guanghou

    2013-02-27

    First-principles calculations have been carried out to investigate the adsorption of Pd(n) (n ≤ 10) clusters on the single-walled (8, 0) and (5, 5) SiC nanotubes (SiCNTs). We find that the Pd(n) clusters can be stably adsorbed on the outer surfaces of both SiCNTs through an exothermic adsorption process. The adsorption energies of the Pd(n) clusters on the (8, 0) SiCNT are generally larger than those of clusters on the (5, 5) SiCNT. The number of bonds between the Pd(n) clusters and the SiCNTs increases with increasing cluster size. The Pd atoms adjacent to the SiCNTs adsorb preferentially on the bridge sites over an axial Si-C bond. The adsorption leads to elongation of the Pd-Pd bond lengths and structural reconstruction for the Pd(n) clusters. Moreover, the adsorbed Pd(n) clusters show two-layered structures at the cluster size n ≥ 4. We also find that the adsorbed Pd(n) clusters induce some impurity states within the band gap of the pristine SiCNTs and the strong pd hybridization near the Fermi level, thereby reducing the band gap. The charge transfer from the SiCNTs to the Pd atoms that occurs is observed for all the systems considered. Due to the strong interactions between the Pd(n) clusters and the SiCNTs, most adsorbed Pd(n) clusters exhibit zero magnetic moment.

  17. Adsorption hysteresis in nanopores

    PubMed

    Neimark; Ravikovitch; Vishnyakov

    2000-08-01

    Capillary condensation hysteresis in nanopores is studied by Monte Carlo simulations and the nonlocal density functional theory. Comparing the theoretical results with the experimental data on low temperature sorption of nitrogen and argon in cylindrical channels of mesoporous siliceous molecular sieves of MCM-41 type, we have revealed four qualitatively different sorption regimes depending on the temperature and pore size. As the pore size increases at a given temperature, or as the temperature decreases at a given pore size, the following regimes are consequently observed: volume filling without phase separation, reversible stepwise capillary condensation, irreversible capillary condensation with developing hysteresis, and capillary condensation with developed hysteresis. We show that, in the regime of developed hysteresis (pores wider than 5 nm in the case of nitrogen sorption at 77 K), condensation occurs spontaneously at the vaporlike spinodal while desorption takes place at the equilibrium. A quantitative agreement is found between the modeling results and the experimental hysteresis loops formed by the adsorption-desorption isotherms. The results obtained provide a better understanding of the general behavior of confined fluids and the specifics of sorption and phase transitions in nanomaterials.

  18. Adsorption behavior of ferritin and buffer components, buffer agents and salts, onto silane-coupled silicon substrate.

    PubMed

    Fukuta, Megumi; Yamashita, Ichiro

    2010-01-01

    Fixation of ferritin using amino-silane modified substrates is effective, but salt and alkali ions of the buffer can contaminate substrates, inhibiting the sensing and fabrication of nano-electronic devices. To avoid adsorption of salts and alkali ions, buffer solutions have been replaced by pure water or alkali-metal-ion-free buffer. However, proteins in such solutions are sometimes denatured. Therefore, we developed a substrate which adsorbs ferritin but does not adsorb contaminants such as salts and alkali metal-ions contained in the buffer. Adsorption of ferritin was achieved by using a buffer with a high ion strength, such as PBS buffer, because the Debye length becomes shorter with increased ion strength due to intermolecular force even when the substrate has no positive charge. The combination of high coverage methyltrimethoxysilane (MTMS)-coupled silicon substrate and PBS buffer solution is effective for adsorption of ferritin while not adsorbing buffer components such as contaminants and/or salts on the silicon substrate.

  19. Adsorption and corrosion inhibition behavior of hydroxyethyl cellulose and synergistic surfactants additives for carbon steel in 1M HCl.

    PubMed

    Mobin, Mohammad; Rizvi, Marziya

    2017-01-20

    The inhibitory effect of hydroxyethylcellulose (HEC) on A1020 carbon steel corrosion in 1M HCl solution was evaluated at different concentrations and temperatures using weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), UV-vis spectrophotometry, scanning electron microscopy (SEM), energy dispersive x-ray analysis (EDX), atomic force microscopy (AFM) and quantum chemical analysis. Inhibition efficiency was found to increase with increase in concentration of HEC but decreased with increasing temperature. Inhibitory effect of HEC mixed with minimal concentration of surfactants, triton X 100 (TX), cetyl pyridinium chloride (CPC) and sodium dodecyl sulfate (SDS) was also evaluated. HEC gets adsorbed onto the mild steel surface via mixed type adsorption. Ea, ΔH, ΔS and ΔG⁰ads, the thermodynamic and activation parameters, were calculated and discussed. Adsorption of inhibitor on the steel/solution interface follows Langmuir adsorption isotherm. EIS suggests formation of protective layer over the carbon steel surface. Results of different experimental techniques pertaining to the inhibitory effect of HEC and HEC mixed with surfactants are in good agreement with theoretical quantum chemical investigation.

  20. Designing stable finite state machine behaviors using phase plane analysis and variable structure control

    SciTech Connect

    Feddema, J.T.; Robinett, R.D.; Driessen, B.J.

    1998-03-10

    This paper discusses how phase plane analysis can be used to describe the overall behavior of single and multiple autonomous robotic vehicles with finite state machine rules. The importance of this result is that one can begin to design provably asymptotically stable group behaviors from a set of simple control laws and appropriate switching points with decentralized variable structure control. The ability to prove asymptotically stable group behavior is especially important for applications such as locating military targets or land mines.

  1. Pharmaceuticals in nanopores - A strategy to manipulate the phase behavior

    NASA Astrophysics Data System (ADS)

    Beiner, M.; Rengarajan, G. T.; Pankaj, S.; Enke, D.

    2007-03-01

    The manipulation of the crystalline state of substances existing in different polymorphic forms is an important issue in many fields of application. In case of pharmaceuticals the stabilization of unstable forms is interesting since solubility and bioavailability are improved. We will show in this presentation that it is possible to manipulate the crystallization behavior of pharmaceuticals and to stabilize unstable crystalline forms by confining the substance in pores with diameters in the range 20-400 nanometers. The crystallization behavior of a pharmaceutical model system in two different types of nanostructured inorganic host systems is studied by DSC and x-ray scattering. The results clearly show that the most unstable crystalline form of this pharmaceutical melts and is stable for long times under confinement which was never observed for bulk samples. This allows to extract the thermodynamic parameters of this crystalline form which have not been reported so far and shows that this is an interesting field of application for nanostructured host-guest systems. The influences of pore geometry and surface interaction are studied and possible explanations for the differences between the crystallization behavior in the bulk and under confinement are discussed. G.T. Rengarajan et al. J. Am. Chem. Soc., to be published.

  2. A comparative study of monoclonal antibodies. 1. Phase behavior and protein-protein interactions.

    PubMed

    Lewus, Rachael A; Levy, Nicholas E; Lenhoff, Abraham M; Sandler, Stanley I

    2015-01-01

    Protein phase behavior is involved in numerous aspects of downstream processing, either by design as in crystallization or precipitation processes, or as an undesired effect, such as aggregation. This work explores the phase behavior of eight monoclonal antibodies (mAbs) that exhibit liquid-liquid separation, aggregation, gelation, and crystallization. The phase behavior has been studied systematically as a function of a number of factors, including solution composition and pH, in order to explore the degree of variability among different antibodies. Comparisons of the locations of phase boundaries show consistent trends as a function of solution composition; however, changing the solution pH has different effects on each of the antibodies studied. Furthermore, the types of dense phases formed varied among the antibodies. Protein-protein interactions, as reflected by values of the osmotic second virial coefficient, are used to correlate the phase behavior. The primary findings are that values of the osmotic second virial coefficient are useful for correlating phase boundary locations, though there is appreciable variability among the antibodies in the apparent strengths of the intrinsic protein-protein attraction manifested. However, the osmotic second virial coefficient does not provide a clear basis to predict the type of dense phase likely to result under a given set of solution conditions.

  3. Phase behavior of self-associating fluids with weaker dispersion interactions between bonded particles.

    PubMed

    Talanquer, V

    2005-04-15

    In this study, we explore the global phase behavior of a simple model for self-associating fluids where association reduces the strength of the dispersion interactions between bonded particles. Recent research shows that this type of behavior likely explains the thermodynamic properties of strongly polar fluids and certain micellar solutions. Based on Wertheim's theory of associating liquids [M. S. Wertheim, J. Stat. Phys. 42, 459 (1986); 42, 477 (1986)], our model takes into account the effect that dissimilar particle interactions have on the equilibrium constant for self-association in the system. We find that weaker interactions between bonded molecules tend to favor the dissociation of chains at any temperature and density. This effect stabilizes a monomeric liquid phase at high densities, enriching the global phase behavior of the system. In particular, for systems in which the energy of mixing between bonded and unbonded species is positive, we find a triple point involving a vapor, a dense phase of chain aggregates, and a monomeric liquid. Phase coexistence between the vapor and the monomeric fluid is always more stable at temperatures above the triple point, but a highly associated fluid may exist as a metastable phase under these conditions. The presence of this metastable phase may explain the characteristic nucleation behavior of the liquid phase in strongly dipolar fluids.

  4. Peculiarities of laser phase behavior associated with the accelerated electron in a chirped laser pulse

    SciTech Connect

    Song, Q.; Wu, X. Y.; Wang, J. X.; Kawata, S.; Wang, P. X.

    2014-05-15

    In this paper, we qualitatively analyzed peculiarities of laser phase behavior associated with the accelerated electron in a chirped laser pulse. We unveiled the relationship between the changes in the orientation of the electron trajectory and the cusps in magnitude of the phase velocity of the optical field along the electron trajectory in a chirped laser pulse. We also explained how the chirp effect induced the singular point of the phase velocity. Finally, we discussed the phase velocity and phase witnessed by the electron in the particle's moving instantaneous frame.

  5. Low amplitude entrainment of mice and the impact of circadian phase on behavior tests.

    PubMed

    Beeler, Jeff A; Prendergast, Brian; Zhuang, Xiaoxi

    2006-05-30

    A tremendous increase in the use of genetically engineered mice as experimental animals has led to increased scrutiny of mouse models generally and mouse behavioral paradigms specifically. Although mice are nocturnal, for practical reasons, most experimental procedures, including behavioral studies, are conducted during their inactive, sleep phase. Accumulating evidence indicates that myriad behavioral, cellular and biochemical processes fluctuate with circadian rhythmicity; however, time of day at which experiments are conducted is rarely controlled. The impact of circadian phase on the reliability of experimental results has received little attention and the present data are conflicting. This study addressed two questions. First, will laboratory mice in a typical animal care facility entrain to a low amplitude light cycle using bright/dim rather than light/dark cycles? A positive answer will make reversing photocycle easy to implement in any facility as dim light suitable for animal husbandry and behavioral testing can substitute for darkness during work hours. By monitoring home cage wheel running, we examined the effectiveness of a dim/bright photocycle as a zeitgeiber. We found that mice subjected to dim/bright photocycles effectively entrained such that their subjective night and activity onset coincided with the beginning of the dim light period, suggesting a potential strategy for standardization and management of circadian phase in nocturnal animals. In a second experiment, we asked what effect circadian phase has on behavioral performance in commonly used mouse behavioral tests. We found no main effect of circadian phase on outcome in open field activity, elevated plus maze emotionality, water maze spatial memory, novel object exploration and hyperactivity in response to amphetamine; however, we observed occasional interactions between circadian phase and both strain and sex that were neither consistent nor systematic. These data suggest that the tests

  6. Behavior of universal critical parameters in the QCD phase diagram

    NASA Astrophysics Data System (ADS)

    Bluhm, Marcus; Nahrgang, Marlene; Bass, Steffen A.; Schäfer, Thomas

    2017-01-01

    We determine the dependence of important parameters for critical fluctuations on temperature and baryon chemical potential in the QCD phase diagram. The analysis is based on an identification of the fluctuations of the order parameter obtained from the Ising model equation of state and the Ginzburg-Landau effective potential approach. The impact of the mapping from Ising model variables to QCD thermodynamics is discussed.

  7. Novel Resistive Switching Behavior in Phase Separated Manganites

    NASA Astrophysics Data System (ADS)

    Guo, Hangwen; Ward, T. Zac; Sun, Dali; Snijders, Paul C.; Gai, Zheng; Shen, Jian

    2011-03-01

    Electronic phase separation plays a key role in many novel phenomena in complex materials. Manganites are a prime example of this class of materials and have recently come under increase scrutiny for possible application in resistive random-access memory (RRAM) technology. Here, we will discuss our recent work on spatially confined La5/8-xPrxCa3/8MnO3. We have discovered that it is possible to drive single electronic domain formation/annihilation through electric field pulsing. By measuring the I-V curve, we find such resistive switching is different from normal RRAM mechanisms in manganites and is closely related to the nature of electronic phase separation. These findings open these systems to a new understanding of the nature of electronic phase separation and begin the development of manganites for future applications in RRAM devices. Research sponsored by the Division of Materials Sciences and Engineering, Office of Basic Energy Sciences, U.S. Department of Energy.

  8. Chemical systems for improved oil recovery: Phase behavior, oil recovery, and mobility control studies

    SciTech Connect

    Llave, F.; Gall, B.; Gao, H., Scott, L., Cook, I.

    1995-09-01

    Selected surfactant systems containing a series of ethoxylated nonionic surfactants in combination with an anionic surfactant system have been studied to evaluate phase behavior as well as oil recovery potential. These experiments were conducted to evaluate possible improved phase behavior and overall oil recovery potential of mixed surfactant systems over a broad range of conditions. Both polyacrylamide polymers and Xanthan biopolymers were evaluated. Studies were initiated to use a chemical flooding simulation program, UTCHEM, to simulate oil recovery for laboratory and field applications and evaluate its use to simulate oil saturation distributions obtained in CT-monitoring of oil recovery experiments. The phase behavior studies focused on evaluating the effect of anionic-nonionic surfactant proportion on overall phase behavior. Two distinct transition behaviors were observed, depending on the dominant surfactant in the overall system. The first type of transition corresponded to more conventional behavior attributed to nonionic-dominant surfactant systems. This behavior is manifested by an oil-water-surfactant system that inverts from a water-external (highly conducting) microemulsion to an oil-external (nonconducting) one, as a function of temperature. The latter type which inverts in an opposite manner can be attributed to the separation of the anionic-nonionic mixtures into water- and oil-soluble surfactants. Both types of transition behavior can still be used to identify relative proximity to optimal areas. Determining these transition ranges provided more insight on how the behavior of these surfactant mixtures was affected by altering component proportions. Efforts to optimize the chemical system for oil displacement experiments were also undertaken. Phase behavior studies with systems formulated with biopolymer in solution were conducted.

  9. Ageneral approach to first order phase transitions and the anomalous behavior of coexisting phases in the magnetic case.

    SciTech Connect

    Gama, S.; de Campos, A.; Coelho, A. A.; Alves, C. S.; Ren, Y.; Garcia, F.; Brown, D. E.; da Silva, L. M.; Magnus, A.; Carvalho, G.; Gandra, G. C.; dos Santos, A. O.; Cardoso, L. P.; von Ranke, P. J.; X-Ray Science Division; Univ. Federal de Sao Paulo; Unv. Estadual de Champinas; Univ. Estadual de Maringa Lab. Nacional de Luz Sincrotron; Northern Univ.; Univ. de Estado do Rio de Janerio

    2009-01-01

    First order phase transitions for materials with exotic properties are usually believed to happen at fixed values of the intensive parameters (such as pressure, temperature, etc.) characterizing their properties. It is also considered that the extensive properties of the phases (such as entropy, volume, etc.) have discontinuities at the transition point, but that for each phase the intensive parameters remain constant during the transition. These features are a hallmark for systems described by two thermodynamic degrees of freedom. In this work it is shown that first order phase transitions must be understood in the broader framework of thermodynamic systems described by three or more degrees of freedom. This means that the transitions occur along intervals of the intensive parameters, that the properties of the phases coexisting during the transition may show peculiar behaviors characteristic of each system, and that a generalized Clausius-Clapeyron equation must be obeyed. These features for the magnetic case are confirmed, and it is shown that experimental calorimetric data agree well with the magnetic Clausius-Clapeyron equation for MnAs. An estimate for the point in the temperature-field plane where the first order magnetic transition turns to a second order one is obtained (the critical parameters) for MnAs and Gd{sub 5}Ge{sub 2}Si{sub 2} compounds. Anomalous behavior of the volumes of the coexisting phases during the magnetic first order transition is measured, and it is shown that the anomalies for the individual phases are hidden in the behavior of the global properties as the volume.

  10. Effects of attractive colloids on the phase separation behaviors of binary polymer blends

    NASA Astrophysics Data System (ADS)

    Zhang, Xinghua; Chen, Yunlin; Qu, Lijian; Yan, Dadong

    2013-08-01

    The attractive colloids are added as fillers to control the phase behaviors of binary polymer blends. Because the colloids attract both components in the blends, aggregates are formed by the colloids coated with both kinds of polymer brushes. The aggregation results in two contradictory effects on the phase separation. First, the formation of aggregate decreases the translational entropy, which promotes the phase separation. On the other hand, the phase separation causes the extra free energy penalty due to the stretch of the chains attaching on the colloids, which prevents the phase separation. Furthermore, as the concentration or adsorbability of the colloids increases the local fluctuations within the aggregates become important. This results in a transition from the macro-phase separation to the micro-phase separation and the existence of the Lifshitz point. All of these effects lead to diverse phase behaviors in the polymer nanocomposites system. In present work, these behaviors are studied theoretically by the random phase approximation in a model system.

  11. Phase behavior of chromonic liquid crystal mixtures of Sunset Yellow and Disodium Cromoglycate

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Akihiro; Smith, Gregory; Yi, Youngwoo; Xu, Charles; Biffi, Silvia; Serra, Francesca; Bellini, Tommaso; Clark, Noel

    2014-03-01

    Chromonic liquid crystals (CLCs) are formed when planar molecules dissolved in water stack into rod-like aggregates that can order as liquid crystals. Isotropic, nematic, and M-phases can be observed depending on the degree of molecular orientational and positional order by variation of the CLC concentration. We focused on mixtures of two well-known CLCs, Sunset Yellow, a food dye, and disodium cromoglycate (DSCG), an asthma medication. In order to study the phase behaviors of these mixtures, we observed their textures in glass cells and capillaries using polarized light microscopy. We report here a ternary phase diagram describing the complete phase behavior of the CLC mixtures. We observed a variety of phase behaviors depending on species ratio and concentration. In the isotropic phase, no clear phase separation of the two dyes was observed, while separation did occur in many nematic and M-phase combinations. We will also describe phase observations made using a light spectroscopy and bulk centrifugal partitioning. Grant support: NSF DMR 1207606 and NSF MRSEC DMR-0820579.

  12. Magnetic hysteresis, compensation behaviors, and phase diagrams of bilayer honeycomb lattices

    NASA Astrophysics Data System (ADS)

    Ersin, Kantar

    2015-10-01

    Magnetic behaviors of the Ising system with bilayer honeycomb lattice (BHL) structure are studied by using the effective-field theory (EFT) with correlations. The effects of the interaction parameters on the magnetic properties of the system such as the hysteresis and compensation behaviors as well as phase diagrams are investigated. Moreover, when the hysteresis behaviors of the system are examined, single and double hysteresis loops are observed for various values of the interaction parameters. We obtain the L-, Q-, P-, and S-type compensation behaviors in the system. We also observe that the phase diagrams only exhibit the second-order phase transition. Hence, the system does not show the tricritical point (TCP).

  13. Structural Properties and Phase Behavior of Crosslinked Networks in Polymer Solutions

    PubMed Central

    Benmouna, Farida; Zemmour, Samira; Benmouna, Mustapha

    2016-01-01

    ABSTRACT Structural properties and phase behavior of crosslinked networks embedded in polymer solutions are theoretically investigated. The partial structure factor of the network is calculated using a matrix formulation of the random phase approximation and the forward scattering limit is correlated with the phase behavior. Swelling and deswelling processes are analyzed in terms of the polymer concentration, the mismatch of solvent quality with respect to polymer and network, the polymers incompatibility and their characteristic sizes. Most studies reported so far in the literature have focussed on the swelling of crosslinked networks and gels in pure solvents but the correlation of the structural properties with the phase behavior in the presence of high molecular weight polymers in solution has not been given sufficient attention. The present work is intended to fill this gap in view of the current efforts to develop novel drug encapsulating and targeted delivery devices. PMID:27134310

  14. Predicting phase behavior of mixtures of reservoir fluids with carbon dioxide

    SciTech Connect

    Grigg, R.B.; Lingane, P.J.

    1983-01-01

    The use of an equation of state to predict phase behavior during carbon dioxide flooding is well established. The characterization of the C/sub 7/ fraction and the selection of interaction parameters are the most important variables. Single-contact phase behavior is presented for mixtures of Ford Geraldine (Delaware), Maljamar (Grayburg), West Sussex (Shannon), and Reservoir D reservoir fluids, and of a synthetic oil with carbon dioxide. The phase behavior of these mixtures can be reproduced using 3 to 5 pseudo components and common interaction parameters. The critical properties of the pseudo components are calculated from detailed oil characterizations. Because the parameters are not further adjusted, this approach reduces the empiricism in fitting phase data and may result in a more accurate representation of the system as the composition of the oil changes during the approach to miscibility. 21 references.

  15. Structural Properties and Phase Behavior of Crosslinked Networks in Polymer Solutions.

    PubMed

    Benmouna, Farida; Zemmour, Samira; Benmouna, Mustapha

    2016-03-03

    Structural properties and phase behavior of crosslinked networks embedded in polymer solutions are theoretically investigated. The partial structure factor of the network is calculated using a matrix formulation of the random phase approximation and the forward scattering limit is correlated with the phase behavior. Swelling and deswelling processes are analyzed in terms of the polymer concentration, the mismatch of solvent quality with respect to polymer and network, the polymers incompatibility and their characteristic sizes. Most studies reported so far in the literature have focussed on the swelling of crosslinked networks and gels in pure solvents but the correlation of the structural properties with the phase behavior in the presence of high molecular weight polymers in solution has not been given sufficient attention. The present work is intended to fill this gap in view of the current efforts to develop novel drug encapsulating and targeted delivery devices.

  16. Tuning of electrostatic vs. depletion interaction in deciding the phase behavior of nanoparticle-polymer system

    SciTech Connect

    Kumar, Sugam Aswal, V. K.; Kohlbrecher, J.

    2015-06-24

    Nanoparticle-polymer system interestingly show a re-entrant phase behavior where charge stabilized silica nanoparticles (phase I) undergo particle clustering (phase II) and then back to individual particles (phase I) as a function of polymer concentration. Such phase behavior arises as a result of dominance of various interactions (i) nanoparticle-nanoparticle electrostatic repulsion (ii) polymer induced attractive depletion between nanoparticles and (iii) polymer-polymer repulsion, at different concentration regimes. Small-angle neutron scattering (SANS) has been used to study the evolution of interaction during this re-entrant phase behavior of nanoparticles by contrast-marching the polymer. The SANS data have been modeled using a two-Yukawa potential accounting for both attractive and repulsive parts of the interaction between nanoparticles. The degree of both of these parts has been separately tuned by varying the polymer concentration and ionic strength of the solution. Both of these parts are found to have long-range nature. At low polymer concentrations, the electrostatic repulsion dominates over the depletion attraction. The magnitude and the range of the depletion interaction increase with the polymer concentration leading to nanoparticle clustering. At higher polymer concentrations, the increased polymer-polymer repulsion reduces the strength of depletion leading to re-entrant phase behavior. The clusters formed under depletion attraction are found to have surface fractal morphology.

  17. Effects of geometrical and energetic nonadditivity on the phase behavior of two-component symmetric mixtures

    NASA Astrophysics Data System (ADS)

    Patrykiejew, A.

    2017-01-01

    Using Monte Carlo simulation methods in the grand-canonical ensemble, we have studied the phase behavior of three-dimensional symmetric binary mixtures of Lennard-Jones particles. We have also elucidated the effects of geometric and energetic nonadditivity on the phase behavior. Phase diagrams for several systems have been evaluated. We have demonstrated that in completely miscible mixtures the geometrical nonadditivity (negative as well as positive) stabilizes a liquid phase leading to a gradual increase of the critical temperature. The mechanism leading to such behavior is different when the system shows negative and positive geometrical nonadditivity. In the case of systems with negative energetic nonadditivity, which may exhibit demixing transition in the liquid phase, their phase behavior is also strongly affected by the geometric non-additivity. The systems with negative geometric nonadditivity have been demonstrated to show reentrant miscibility, while those with positive geometric nonadditivity show enhanced tendency toward mixing at sufficiently high temperatures. We have evaluated phase diagrams for several systems.

  18. Structure and phase behavior of aqueous methylcellulose solutions

    NASA Astrophysics Data System (ADS)

    McAllister, John; Schmidt, Peter; Lodge, Timothy; Bates, Frank

    2015-03-01

    Cellulose ethers (CE) constitute a multi-billion dollar industry, and have found end uses in a broad array of applications from construction materials, food products, personal care products, and pharmaceuticals for more than 80 years. Methylcellulose (MC, with the trade name METHOCEL™) is a CE in which there is a partial substitution of -OH groups with -OCH3 groups. This results in a polymer that is water-soluble at low temperatures, and aqueous solutions of MC display gelation and phase separation at higher temperatures. The nature of MC gelation has been debated for many years, and this project has made significant advances in the understanding of the solution properties of CEs. We have characterized a fibrillar structure of MC gels by cryogenic transmission electron microscopy (cryo-TEM) and small angle neutron scattering (SANS). Using light scattering, turbidity measurements, and dynamic mechanical spectroscopy (DMS) we report that MC microphase separates by nucleation and growth of fibril aggregates, and is a different process from LCST phase separation.

  19. The effect of specific chloride adsorption on the electrochemical behavior of ultrathin Pd films deposited on Pt( 1 1 1 ) in acid solution

    NASA Astrophysics Data System (ADS)

    Arenz, M.; Stamenkovic, V.; Schmidt, T. J.; Wandelt, K.; Ross, P. N.; Markovic, N. M.

    2003-01-01

    The electrochemical behavior of thin Pd films supported on a Pt(1 1 1) electrode is investigated by cyclic voltammetry and in situ Fourier transform infrared (FTIR) spectroscopy. It is demonstrated that in perchloric acid solution underpotential deposition of hydrogen (H upd) and hydroxyl adsorption (OH ad) is in strong competition with the adsorption of Cl - anions, the latter being present as a trace impurity in HClO 4. The interaction of Cl - with Pd is rather strong, controlling the adsorption of H upd and OH ad as well as the kinetic rate of CO oxidation. The microscopic insight (the binding sites) of the adsorbed CO (CO ad) and the rate of CO oxidation (established from CO 2 production) on Pt(1 1 1) modified with a (sub)monolayer of Pd is elucidated by means of Fourier infrared (FTIR) spectroscopy. The appearance of both the characteristic Pt(1 1 1)-CO ad and Pt(1 1 1)-1 ML Pd-CO ad stretching bands on a Pt(1 1 1) surface covered by 0.5 ML Pd confirms previous findings that the Pd atoms agglomerate into islands and that the bare Pt areas and the Pd islands behave according to their own surface chemistry. The systematic increase of the Pd surface coverage results in a gradual change in the catalytic properties of Pt(1 1 1)- xPd electrodes towards CO oxidation, from those characteristic of bare Pt(1 1 1) to those which are characteristic for Pt(1 1 1) covered with 1 ML of Pd.

  20. Enhanced super-hydrophobic and switching behavior of ZnO nanostructured surfaces prepared by simple solution--immersion successive ionic layer adsorption and reaction process.

    PubMed

    Suresh Kumar, P; Sundaramurthy, J; Mangalaraj, D; Nataraj, D; Rajarathnam, D; Srinivasan, M P

    2011-11-01

    A simple and cost-effective successive ionic layer adsorption and reaction (SILAR) method was adopted to fabricate hydrophobic ZnO nanostructured surfaces on transparent indium-tin oxide (ITO), glass and polyethylene terephthalate (PET) substrates. ZnO films deposited on different substrates show hierarchical structures like spindle, flower and spherical shape with diameters ranging from 30 to 300 nm. The photo-induced switching behaviors of ZnO film surfaces between hydrophobic and hydrophilic states were examined by water contact angle and X-ray photoelectron spectroscopy (XPS) analysis. ZnO nanostructured films had contact angles of ~140° and 160°±2 on glass and PET substrates, respectively, exhibiting hydrophobic behavior without any surface modification or treatment. Upon exposure to ultraviolet (UV) illumination, the films showed hydrophilic behavior (contact angle: 15°±2), which upon low thermal stimuli revert back to its original hydrophobic nature. Such reversible and repeatable switching behaviors were observed upon cyclical exposure to ultraviolet radiation. These biomimetic ZnO surfaces exhibit good anti-reflective properties with lower reflectance of 9% for PET substrates. Thus, the present work is significant in terms of its potential application in switching devices, solar coatings and self-cleaning smart windows.

  1. Solid phase extraction and spectrophotometric determination of mercury by adsorption of its diphenylthiocarbazone complex on an alumina column.

    PubMed

    Rajesh, N; Gurulakshmanan, G

    2008-02-01

    A simple method has been developed for the preconcentration of mercury based on the adsorption of its diphenylthiocarbazone complex on a neutral alumina column. The influence of acidity, eluting agents, stability of the column, sample volume and interfering ions has been investigated in detail. The adsorbed complex could be eluted using environmentally benign polyethylene glycol (PEG 400) and the concentration of mercury was determined by visible spectrophotometry at a wavelength maximum of 520nm. A detection limit of 4microgL(-1) could be achieved and the developed procedure was successfully applied for the determination of mercury in spiked water samples and city waste incineration ash (CRM176). The preconcentration factor attainable for quantitative recovery (>95%) of mercury(II) was 100 for a 1000mL sample volume.

  2. Modeling phase behavior for quantifying micro-pervaporation experiments

    NASA Astrophysics Data System (ADS)

    Schindler, M.; Ajdari, A.

    2009-01-01

    We present a theoretical model for the evolution of mixture concentrations in a micro-pervaporation device, similar to those recently presented experimentally. The described device makes use of the pervaporation of water through a thin PDMS membrane to build up a solute concentration profile inside a long microfluidic channel. We simplify the evolution of this profile in binary mixtures to a one-dimensional model which comprises two concentration-dependent coefficients. The model then provides a link between directly accessible experimental observations, such as the widths of dense phases or their growth velocity, and the underlying chemical potentials and phenomenological coefficients. It shall thus be useful for quantifying the thermodynamic and dynamic properties of dilute and dense binary mixtures.

  3. Modeling phase behavior for quantifying micro-pervaporation experiments.

    PubMed

    Schindler, M; Ajdari, A

    2009-01-01

    We present a theoretical model for the evolution of mixture concentrations in a micro-pervaporation device, similar to those recently presented experimentally. The described device makes use of the pervaporation of water through a thin PDMS membrane to build up a solute concentration profile inside a long microfluidic channel. We simplify the evolution of this profile in binary mixtures to a one-dimensional model which comprises two concentration-dependent coefficients. The model then provides a link between directly accessible experimental observations, such as the widths of dense phases or their growth velocity, and the underlying chemical potentials and phenomenological coefficients. It shall thus be useful for quantifying the thermodynamic and dynamic properties of dilute and dense binary mixtures.

  4. Phase behavior of a lattice hydrophobic oligomer in explicit water.

    PubMed

    Romero-Vargas Castrillón, Santiago; Matysiak, Silvina; Stillinger, Frank H; Rossky, Peter J; Debenedetti, Pablo G

    2012-08-09

    We investigate the thermodynamics of hydrophobic oligomer collapse using a water-explicit, three-dimensional lattice model. The model captures several aspects of protein thermodynamics, including the emergence of cold- and thermal-unfolding, as well as unfolding at high solvent density (a phenomenon akin to pressure-induced denaturation). We show that over a range of conditions spanning a ≈14% increase in solvent density, the oligomer transforms into a compact, strongly water-penetrated conformation at low temperature. This contrasts with thermal unfolding at high temperature, where the system "denatures" into an extended random coil conformation. We report a phase diagram for hydrophobic collapse that correctly captures qualitative aspects of cold and thermal unfolding at low to intermediate solvent densities.

  5. Chaotic behavior on in-phase vibratory conveyors

    SciTech Connect

    Raski, J.Z.

    1998-07-01

    One of the basic building blocks of IBM's computer technology is the thin-film interstitial metallized ceramic (IMC) substrate. The packaging of these substrates employs small input/output (IO) pins to provide both mechanical and electrical connection to the printed circuit board. In the automated manufacturing of the substrate, the input and output pins are individually conveyed by in-line vibratory conveyors. However, a nonperiodic motion of these pins is observed at certain angles of conveyor table tilt that cannot be explained by classical models of friction. This paper models the motion of a single I/O pin on an in-phase, linearly oscillating conveyor using the classical model of friction and compares that result with experimental observations. It is shown here, analytically and experimentally, that when the vibratory conveyor table amplitude and the coefficient of friction between the pin and the table are sufficiently large, the pin is conveyed forward with some velocity. If the conveyor table's angle of tilt is sufficiently large and the coefficient of friction is sufficiently low, the pin may slip backwards just as fast as the conveyor table drives it forward, resulting in a net pin velocity of zero. Surrounding the condition at which the net velocity of the pin is zero is a chaotic basin of attraction in which the pin motion is non-periodic. This basin of attraction was experimentally determined to be bracketed within a range of values of the coefficient of friction. The implications of these theoretical and experimental results are discussed in terms of the practical application of in-phase vibratory conveyors in manufacturing.

  6. Investigation of the relationships between the thermodynamic phase behavior and gelation behavior of a series of tripodal trisamide compounds

    NASA Astrophysics Data System (ADS)

    Feng, Li

    Low molecular weight organic gelators(LMOGs) are important due to potential applications in many fields. Currently, most of the major studies focus on the empirical explanation of the crystallization for gelator assembly formation and morphologies, few efforts have been devoted to the thermodynamic phase behaviors and the effect of the non-ideal solution behavior on the structure of the resultant gels. In this research, tripodal trisamide compounds, synthesized from tris(2-aminoethyl)amine (TREN) by condensation with different acid chlorides, were studied as model LMOGs due to the simple one-step reaction and the commercially available chemical reactants. Gelation of organic solvents was investigated as a function of concentration and solvent solubility parameter.It has been found that the introduction of branches or cyclic units have dramatically improves the gelation ability compared to linear alkyl peripheral units. Fitting the liquidus lines using the regular solution model and calculation of the trisamide solubility parameter using solubility parameter theory gave good agreement with the trisamide solubility parameter calculated by group contribution methods. These results demonstrate that non-ideal solution behavior is an important factor in the gelation behavior of low molecular mass organic gelators. Understanding and controlling the thermodynamics and phase behaviors of the gel systems will provide effective ways to produce new efficient LMOGs in the future.

  7. Use of absorbent materials in on-line coupled reversed-phase liquid chromatography-gas chromatography via the through oven transfer adsorption desorption interface.

    PubMed

    Flores, Gema; Díaz-Plaza, Eva María; Cortés, Jose Manuel; Villén, Jesús; Herraiz, Marta

    2008-11-21

    The use of absorbents as retaining materials in the through oven transfer adsorption desorption interface (TOTAD) of an on-line coupled reversed-phase liquid chromatography-gas chromatography system (RPLC-GC) is proposed for the first time. A comparative study of an adsorbent (Tenax TA) and two absorbents, namely polydimethylsiloxane and poly(50% phenyl/50% methylsiloxane) is performed to establish the best experimental conditions for the automated and simultaneous determination of 15 organophosphorus and organochlorine pesticide residues in olive oil. The proposed method provides satisfactory repeatability (RSDs lower, in general, than 8.5%) and sensitivity (limits of detection ranging from 0.6 to 81.9 microg/L) for the investigated compounds.

  8. Molecular dynamics investigation on the adsorption behaviors of H2O, CO2, CH4 and N2 gases on calcite (1 1 bar 0) surface

    NASA Astrophysics Data System (ADS)

    Wang, Shimeng; Zhou, Guanggang; Ma, Yue; Gao, Lei; Song, Ranran; Jiang, Guancheng; Lu, Guiwu

    2016-11-01

    Molecular dynamics simulations (MD) were carried out to investigate the adsorption behaviors of H2O, CO2, CH4 and N2 gases, which are the main and important components in gas wells, on the calcite surface at reservoir conditions. By analyzing the binding energy and Helmholtz free energy, we found that the preferential adsorption order of these four gases is: H2O > CO2 > CH4 > N2. Moreover, we have also calculated the radial distribution function profiles of the system. It shows that the H2O molecules will form two compact adsorbed layers on the surface, which denotes the calcite (1 1 bar 0) surface is hydrophilic. The CO2 molecules can also form a adsorbed layer on the surface, while there are no significant features indicating that the CH4 and N2 molecules were apparently adsorbed on calcite (1 1 bar 0) surface. Our calculations results can not only give a microscopic insight into the wettability of gas reservoirs but also provide theoretical instructions for hydrate risk evaluation of enhanced gas recovery.

  9. Evolutionary screening and adsorption behavior of engineered M13 bacteriophage and derived dodecapeptide for selective decoration of gold interfaces.

    PubMed

    Causa, F; Della Moglie, R; Iaccino, E; Mimmi, S; Marasco, D; Scognamiglio, P L; Battista, E; Palmieri, C; Cosenza, C; Sanguigno, L; Quinto, I; Scala, G; Netti, P A

    2013-01-01

    There is a growing interest in identifying biomacromolecules such as proteins and peptides to functionalize metallic surfaces through noncovalent binding. One method for functionalizing materials without fundamentally changing their inherent structure is using biorecognition moieties. Here, we proved a general route to select a biomolecule adhesive motif for surface functionalization by comprehensively screening phage displayed peptides. In particular, we selected a genetically engineered M13 bacteriophage and a linear dodecapeptide derived from its pIII domain for recognizing gold surfaces in a specific and selective manner. In the phage context, we demonstrated the adhesive motif was capable to adsorb on gold in a preferential way with a morphological and viscoelastic signature of the adsorbed layer as evidenced by QCM-D and AFM investigations. Out of the phage context, the linear dodecapeptide is reproducibly found to adhere to the gold surface, and by quantitative SPR measurements, high affinity constants (K(eq)~10(6)M(-1), binding energy ~-8 kcal/mol) were determined. We proved that the interactions occurring at gold interface were mainly hydrophobic as a consequence of high frequency of hydrophobic residues in the peptide sequence. Moreover, by CD, molecular dynamics and steered molecular dynamics, we demonstrated that the molecular flexibility only played a minor role in the peptide adsorption. Such noncovalent but specific modification of inorganic surfaces through high affinity biomolecule adsorption represents a general strategy to modulate the functionality of multipurpose metallic surfaces.

  10. Adsorption-desorption behavior of magnetic amine/Fe3O4 functionalized biopolymer resin towards anionic dyes from wastewater.

    PubMed

    Song, Wen; Gao, Baoyu; Xu, Xing; Xing, Lulu; Han, Shuang; Duan, Pijun; Song, Wuchang; Jia, Ruibao

    2016-06-01

    In this work, a new kind of magnetic amine/Fe3O4 functionalized biopolymer resin (amine/Fe3O4-resin) was prepared and applied to remove various anionic dyes from water. Methyl Orange (MO), Reactive Brilliant Red K-2BP (RBR) and Acid Red 18 (AR) were selected as the typical anionic dye for this research. Meanwhile, amine/Fe3O4-resin was characterized by VSM, XRD, FT-IR, SEM, TEM and XPS. Three anionic dyes removed by amine/Fe3O4-resin were investigated using batch adsorption technique, and the parameters including adsorbent dosage, pH, contact time and temperature were considered. Due to a large number of amine groups and high surface areas, amine/Fe3O4-resin exhibited a remarkably high adsorption capacity for all three dyes, reaching 101.0mg/g, 222.2mg/g and 99.4mg/g for RBR, MO and AR at 25°C, respectively. The pseudo second order model and Langmuir model agreed well with the experimental data, and regeneration experiments indicated its merit of separability and reusability.

  11. Studies on adsorptions of metallic ions in water by zirconium glyphosate (ZrGP): Behaviors and mechanisms

    NASA Astrophysics Data System (ADS)

    Jia, Yunjie; Zhang, Yuejuan; Wang, Runwei; Fan, Faying; Xu, Qinghong

    2012-01-01

    A new adsorbent named zirconium glyphosate [Zr(O3PCH2NHCH2COOH)2·0.5H2O, denoted as ZrGP] and its selective adsorptions to Pb2+, Cd2+, Mg2+ and Ca2+ ions in water were reported in this paper. Compared to other zirconium adsorbents, such as zirconium phosphate [Zr(HPO4)2], ZrGP exhibited highly selective adsorption to Pb2+ in solution which contained Pb2+, Cd2+, Mg2+ and Ca2+ ions. The loaded ZrGP with metallic ions can be efficaciously regenerated by aqueous solution of HCl (1.0 M) without any noticeable capacity loss, and almost all of it can be reused and recycled. The memory effect on structural regeneration of ZrGP was also found when Mg2+ and Ca2+ were adsorbed. To be specific, the structure of ZrGP was destroyed due to adsorbing these two ions, but it could be regenerated after the loaded materials were dipped in HCl solution (1.0 M) for several minutes to remove metallic ions.

  12. Extracting Constitutive Stress-Strain Behavior of Microscopic Phases by Micropillar Compression

    NASA Astrophysics Data System (ADS)

    Williams, J. J.; Walters, J. L.; Wang, M. Y.; Chawla, N.; Rohatgi, A.

    2013-02-01

    The macroscopic behavior of metallic materials is a complex function of microstructure. The size, morphology, volume fraction, crystallography, and distribution of a 2nd phase within a surrounding matrix all control the mechanical properties. Understanding the contributions of the individual microconstituents to the mechanical behavior of multiphase materials has proven difficult due to the inability to obtain accurate constitutive relationships of each individual constituent. In dual-phase steels, for example, the properties of martensite or ferrite in bulk form are not representative of their behavior at the microscale. In this study, micropillar compression was employed to determine the mechanical properties of individual microconstituents in metallic materials with "composite" microstructures, consisting of two distinct microconstituents: (I) a Mg-Al alloy with pure Mg dendrites and eutectic regions and (II) a powder metallurgy steel with ferrite and martensite constituents. The approach is first demonstrated in a Mg-Al directionally solidified alloy where the representative stress-strain behavior of the matrix and eutectic phases was obtained. The work is then extended to a dual-phase steel where the constitutive behavior of the ferrite and martensite were obtained. Here, the results were also incorporated into a modified rule-of-mixtures approach to predict the composite behavior of the steel. The constitutive behavior of the ferrite and martensite phases developed from micropillar compression was coupled with existing strength-porosity models from the literature to predict the ultimate tensile strength of the steel. Direct comparisons of the predictions with tensile tests of the bulk dual-phase steel were conducted and the correlations were quite good.

  13. 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.

  14. Phase transformation and deformation behavior of NiTi-Nb eutectic joined NiTi wires

    PubMed Central

    Wang, Liqiang; Wang, Cong; Zhang, Lai-Chang; Chen, Liangyu; Lu, Weijie; Zhang, Di

    2016-01-01

    NiTi wires were brazed together via eutectic reaction between NiTi and Nb powder deposited at the wire contact region. Phase transformation and deformation behavior of the NiTi-Nb eutectic microstructure were investigated using transmission electron microscopy (TEM) and cyclic loading-unloading tests. Results show that R phase and B19′ martensite transformation are induced by plastic deformation. R phase transformation, which significantly contributes to superelasticity, preferentially occurs at the interfaces between NiTi and eutectic region. Round-shaped Nb-rich phase with rod-like and lamellar-type eutectics are observed in eutectic regions. These phases appear to affect the deformation behavior of the brazed NiTi-Nb region via five distinct stages in stress-strain curves: (I) R phase reorientation, (II) R phase transformation from parent phase, (III) elastic deformation of reoriented martensite accompanied by the plastic deformation of Nb-rich phase and lamellar NiTi-Nb eutectic, (IV) B19′ martensitic transformation, and (V) plastic deformation of the specimen. PMID:27049025

  15. Phase transformation and deformation behavior of NiTi-Nb eutectic joined NiTi wires.

    PubMed

    Wang, Liqiang; Wang, Cong; Zhang, Lai-Chang; Chen, Liangyu; Lu, Weijie; Zhang, Di

    2016-04-06

    NiTi wires were brazed together via eutectic reaction between NiTi and Nb powder deposited at the wire contact region. Phase transformation and deformation behavior of the NiTi-Nb eutectic microstructure were investigated using transmission electron microscopy (TEM) and cyclic loading-unloading tests. Results show that R phase and B19' martensite transformation are induced by plastic deformation. R phase transformation, which significantly contributes to superelasticity, preferentially occurs at the interfaces between NiTi and eutectic region. Round-shaped Nb-rich phase with rod-like and lamellar-type eutectics are observed in eutectic regions. These phases appear to affect the deformation behavior of the brazed NiTi-Nb region via five distinct stages in stress-strain curves: (I) R phase reorientation, (II) R phase transformation from parent phase, (III) elastic deformation of reoriented martensite accompanied by the plastic deformation of Nb-rich phase and lamellar NiTi-Nb eutectic, (IV) B19' martensitic transformation, and (V) plastic deformation of the specimen.

  16. The study of Xe adsorption behavior in meso-size pores of carbon black materials using laser-polarized 129Xe NMR spectroscopy.

    PubMed

    Saito, Koji; Kimura, Atsuomi; Fujiwara, Hideaki

    2003-01-01

    The meso size pores of carbon black materials with Pt critically affect catalysts which play an important role for fuel cells of electric vehicles. Time-consuming BET methods are usually used to measure the physisorption enthalpy which determines the characteristics of catalysts. The laser polarized method enhances 129Xe polarization by 4 orders of magnitude, overcoming a low sensitivity, making this measurement technique faster than conventional experiments. In this paper, we first demonstrate Laser-Polarized 129Xe NMR Spectroscopy for studying carbon black materials with Pt of fuel cells of electric vehicles in order to determine the physisorption enthalpy. At the same time, T1 experiments using Laser-Polarized 129Xe will be discussed in order to clarify the surface condition and adsorption behavior.

  17. Adsorption behavior of poly(dimethyl-diallylammonium chloride) on pulp fiber studied by cryo-time-of-flight secondary ion mass spectrometry and cryo-scanning electron microscopy

    NASA Astrophysics Data System (ADS)

    Masumi, Takashi; Matsushita, Yasuyuki; Aoki, Dan; Takama, Ruka; Saito, Kaori; Kuroda, Katsushi; Fukushima, Kazuhiko

    2014-01-01

    In this study, the adsorption behavior of poly(dimethyl-diallylammonium chloride) (PDADMAC), a retention agent used in papermaking, in a dual polymer system with anionic poly(acrylamide) (A-PAM) was investigated by time-of-flight secondary ion mass spectrometry (TOF-SIMS). Initially, fragment structures and cleavage patterns were identified via TOF-SIMS experiments with deuterium-labeled PDADMAC and the unlabeled analogue. Visualization of PDADMAC on a dry handsheet surface using traditional TOF-SIMS analysis indicated that the electrostatic interaction between coagulated PDADMAC and A-PAM was relatively weak. A novel cryo-TOF-SIMS/SEM system enabled the evaluation of a wet handsheet containing PDADMAC. Analysis of this sample indicated that PDADMAC adsorbs onto the fiber surface and collects preferentially on the tangled fibrils located between fibers.

  18. Influence of surfactant amphiphilicity on the phase behavior of IL-based microemulsions.

    PubMed

    Harrar, Agnes; Zech, Oliver; Klaus, Angelika; Bauduin, Pierre; Kunz, Werner

    2011-10-15

    In this work, we report on the phase behavior of 1-ethyl-3-methyl-imidazolium-ethylsulfate ([emim][etSO(4)])/limonene/polyethylene glycol tert-octylphenyl ether (Triton X-114 or TX-114) microemulsions as a function of ionic liquid (IL) content and temperature. Phase diagrams, conductivity measurements, and small angle X-ray scattering (SAXS) experiments will be presented. A hydrophilic IL, instead of water is used with the goal to enlarge the temperature range on which stable microemulsions can be formed. Indeed, the system shows remarkably large temperature stability, in particular down to -35 °C. We will emphasize on a comparison with a recently published work about microemulsions composed of [emim][etSO(4)], limonene, and Triton X-100 that to some extent are stable at temperatures well below the freezing point of water. The key parameter responsible for the difference in phase behavior, microstructure, and temperature stability is the average repeating number of ethylene oxide units in the surfactant head group, which is smaller for Triton X-114 compared to Triton X-100. Among the fundamental interest, how the amphiphilicity of the surfactant influences the phase diagram and phase behavior of IL-based microemulsions, the exchange of Triton X-100 by Triton X-114 results in one main advantage: along the experimental path the temperature where phase segregation occurs is significantly lowered leading to single phase microemulsions that exist at temperatures beneath 0 °C.

  19. Nonlinear magnitude and linear phase behaviors of T2* imaging: theoretical approximation and Monte Carlo simulation.

    PubMed

    Chen, Zikuan; Calhoun, Vince

    2015-05-01

    The underlying source of brain imaging by T2*-weighted magnetic resonance imaging (T2*MRI) is the intracranial inhomogeneous tissue magnetic susceptibility (denoted by χ) that causes an inhomogeneous field map (via magnetization) in a main field. By decomposing T2*MRI into two steps, we understand that the 1st step from a χ source to a field map is a linear but non-isomorphic spatial mapping, and the 2nd step from the field map to a T2* image is a nonlinear mapping due to the trigonometric behavior of spin precession signals. The magnitude and phase calculations from a complex T2* image introduce additional nonlinearities. In this report, we look into the magnitude and phase behaviors of a T2* image (signal) by theoretical approximation and Monte Carlo simulation. We perform the 1st-order Taylor expansion on intravoxel dephasing formula of a T2* signal and show that the T2* magnitude is a quadratic mapping of the field map and T2* phase is a linear isomorphic mapping. By Monte Carlo simulation of T2*MRI for a span of echo times (with B0=3T and TE=[0,120] ms), we first confirm the quadratic magnitude and linear phase behaviors in small phase angle regime (via TE <30ms), and then provide more general magnitude and phase nonlinear behaviors in large phase angle scenarios (via TE >30ms). By solving the inverse problem of T2*MRI, we demonstrate χ tomography and conclude that the χ source can be reliably reconstructed from a T2* phase image in a small phase angle regime.

  20. Structure and interaction in the polymer-dependent reentrant phase behavior of a charged nanoparticle solution.

    PubMed

    Kumar, Sugam; Ray, D; Aswal, V K; Kohlbrecher, J

    2014-10-01

    Small-angle neutron scattering (SANS) studies have been carried out to examine the evolution of interaction and structure in a nanoparticle (silica)-polymer (polyethylene glycol) system. The nanoparticle-polymer solution interestingly shows a reentrant phase behavior where the one-phase charged stabilized nanoparticles go through a two-phase system (nanoparticle aggregation) and back to one-phase as a function of polymer concentration. Such phase behavior arises because of the nonadsorption of polymer on nanoparticles and is governed by the interplay of polymer-induced attractive depletion with repulsive nanoparticle-nanoparticle electrostatic and polymer-polymer interactions in different polymer concentration regimes. At low polymer concentrations, the electrostatic repulsion dominates over the depletion attraction. However, the increase in polymer concentration enhances the depletion attraction to give rise to the nanoparticle aggregation in the two-phase system. Further, the polymer-polymer repulsion at high polymer concentrations is believed to be responsible for the reentrance to one-phase behavior. The SANS data in polymer contrast-matched conditions have been modeled by a two-Yukawa potential accounting for both repulsive and attractive parts of total interaction potential between nanoparticles. Both of these interactions (repulsive and attractive) are found to be long range. The magnitude and the range of the depletion interaction increase with the polymer concentration leading to nanoparticle clustering. At higher polymer concentrations, the increased polymer-polymer repulsion reduces the depletion interaction leading to reentrant phase behavior. The nanoparticle clusters in the two-phase system are characterized by the surface fractal with simple cubic packing of nanoparticles within the clusters. The effect of varying ionic strength and polymer size in tuning the interaction has also been examined.

  1. Phase behavior and microstructure of microemulsions with a room-temperature ionic liquid as the polar phase.

    PubMed

    Atkin, Rob; Warr, Gregory G

    2007-08-09

    Microemulsions of nonionic alkyl oligoethyleneoxide (CiEj) surfactants, alkanes, and ethylammonium nitrate (EAN), a room-temperature ionic liquid, have been prepared and characterized. Studies of phase behavior reveal that EAN microemulsions have many features in common with corresponding aqueous systems, the primary difference being that higher surfactant concentrations and longer surfactant tailgroups are required to offset the decreased solvophobicity the surfactant molecules in EAN compared with water. The response of the EAN microemulsions to variation in the length of the alkane, surfactant headgroup, and surfactant tailgroup has been found to parallel that observed in aqueous systems in most instances. EAN microemulsions exhibit a single broad small-angle X-ray scattering peak, like aqueous systems. These are well described by the Teubner-Strey model. A lamellar phase was also observed for surfactants with longer tails at lower temperatures. The scattering peaks of both microemulsion and lamellar phases move to lower wave vector on increasing temperature. This is ascribed to a decrease in the interfacial area of the surfactant layer. Phase behavior, small-angle X-ray scattering, and conductivity experiments have allowed the weakly to strongly structured transition to be identified for EAN systems.

  2. Multilayer adsorption on fractal surfaces.

    PubMed

    Vajda, Péter; Felinger, Attila

    2014-01-10

    Multilayer adsorption is often observed in liquid chromatography. The most frequently employed model for multilayer adsorption is the BET isotherm equation. In this study we introduce an interpretation of multilayer adsorption measured on liquid chromatographic stationary phases based on the fractal theory. The fractal BET isotherm model was successfully used to determine the apparent fractal dimension of the adsorbent surface. The nonlinear fitting of the fractal BET equation gives us the estimation of the adsorption equilibrium constants and the monolayer saturation capacity of the adsorbent as well. In our experiments, aniline and proline were used as test molecules on reversed phase and normal phase columns, respectively. Our results suggest an apparent fractal dimension 2.88-2.99 in the case of reversed phase adsorbents, in the contrast with a bare silica column with a fractal dimension of 2.54.

  3. Adsorption and co-precipitation behavior of arsenate, chromate, selenate and boric acid with synthetic allophane-like materials.

    PubMed

    Opiso, Einstine; Sato, Tsutomu; Yoneda, Tetsuro

    2009-10-15

    Pollution caused by boric acid and toxic anions such as As(V), Cr(VI) and Se(VI) is hazardous to human health and environment. The sorption characteristics of these environmentally significant ionic species on allophane-like nanoparticles were investigated in order to determine whether allophane can reduce their mobility in the subsurface environment at circum-neutral pH condition. Solutions containing 100 or 150 mmol of AlCl(3)x6H(2)O were mixed to 100 mmol of Na(4)SiO(4) and the pH were adjusted to 6.4+/-0.3. The mineral suspensions were shaken for 1h and incubated at 80 degrees C for 5 days. Appropriate amounts of As, B, Cr and Se solutions were added separately during and after allophane precipitation. The results showed that As(V) and boric acid can be irreversibly fixed during co-precipitation in addition to surface adsorption. However, Cr(VI) and Se(VI) retention during and after allophane precipitation is mainly controlled by surface adsorption. The structurally fixed As(V) and boric acid were more resistant to release than those bound on the surface. The sorption characteristics of oxyanions and boric acid were also influenced by the final Si/Al molar ratio of allophane in which Al-rich allophane tend to have higher uptake capacity. The overall results of this study have demonstrated the role of allophane-like nanoparticles and the effect of its Si/Al ratio on As, B, Cr and Se transport processes in the subsurface environment.

  4. {CdTe(111) B}/{Si(100) } structure grown by metalorganic vapor phase epitaxy with Te adsorption and annealing

    NASA Astrophysics Data System (ADS)

    Nishino, Hironori; Nishijima, Yoshito

    1996-10-01

    We studied the crystal structure of CdTe(111)B layers directly grown on Si(100) by MOVPE using a new pre-growth process, which includes a metalorganic Te adsorption and an annealing process. In this paper, we discussed the CdTe structure from the three aspects of antiphase, twinning and tilt. We investigated the dependence of the antiphase content in CdTe(111)B on the anneal temperature and the Si misorientation angle. From the results, we assume that the origin of the antiphase formation is the difference in the arrangement of adsorbed Te atoms. Te arrangement leading to antiphase formation occurs on Si terraces away from steps at relatively low temperatures. We reduced most of the twinning in epilayers by optimizing the {VI}/{II} ratio. We think the remaining twinning was confined to near the interface and it nucleated from the Te arrangement on terraces. We found that the Si(100)-CdTe(111) tilt was much smaller than that expected from the well-known Nagai model. We propose that a negative tilt is induced to reduce the lateral mismatch. To adjust the lateral distance of unit cells, 30 CdTe lattices match to 31 Si lattices. CdTe(111)B planes are inclined to reduce the remaining mismatch between two lattices. This initial tilt also causes wider CdTe terraces. We modified Nagai's tilting model for this reconstructed CdTe surface. The total tilt angle is defined by these two tilting mechanisms.

  5. Experimental data showing the thermal behavior of a flat roof with phase change material.

    PubMed

    Tokuç, Ayça; Başaran, Tahsin; Yesügey, S Cengiz

    2015-12-01

    The selection and configuration of building materials for optimal energy efficiency in a building require some assumptions and models for the thermal behavior of the utilized materials. Although the models for many materials can be considered acceptable for simulation and calculation purposes, the work for modeling the real time behavior of phase change materials is still under development. The data given in this article shows the thermal behavior of a flat roof element with a phase change material (PCM) layer. The temperature and energy given to and taken from the building element are reported. In addition the solid-liquid behavior of the PCM is tracked through images. The resulting thermal behavior of the phase change material is discussed and simulated in [1] A. Tokuç, T. Başaran, S.C. Yesügey, An experimental and numerical investigation on the use of phase change materials in building elements: the case of a flat roof in Istanbul, Build. Energy, vol. 102, 2015, pp. 91-104.

  6. Aqueous phase behavior of polyelectrolytes with amphiphilic counterions modulated by cyclodextrin: the role of polyion flexibility.

    PubMed

    Carlstedt, Jonas; Bilalov, Azat; Olsson, Ulf

    2012-07-21

    Polyelectrolytes with amphiphilic counterions, PEACs, are water insoluble because the amphiphiles self-assemble into highly charged micelles that strongly associate with the equally highly charged polyions. However, in the presence of water soluble cyclodextrins (CDs) that form inclusion complexes with the amphiphiles and prevent micellization, PEACs become soluble as the dispersed amphiphiles behave essentially as simple monovalent counterions. In this paper, we illustrate, by example, how strongly the ternary phase behavior of PEAC:CD:water depends on the polyion flexibility; for a highly flexible polyion (polyacrylate) the amphiphilic aggregates dictate the phase behavior, whereas a much stiffer polyion (DNA) itself dictates liquid crystalline ordering.

  7. Effect of Charge Patterning on the Phase Behavior of Polymer Coacervates for Charge Driven Self Assembly

    NASA Astrophysics Data System (ADS)

    Radhakrishna, Mithun; Sing, Charles E.

    Oppositely charged polymers can undergo associative liquid-liquid phase separation when mixed under suitable conditions of ionic strength, temperature and pH to form what are known as `polymeric complex coacervates'. Polymer coacervates find use in diverse array of applications like microencapsulation, drug delivery, membrane filtration and underwater adhesives. The similarity between complex coacervate environments and those in biological systems has also found relevance in areas of bio-mimicry. Our previous works have demonstrated how local charge correlations and molecular connectivity can drastically affect the phase behavior of coacervates. The precise location of charges along the chain therefore dramatically influences the local charge correlations, which consequently influences the phase behavior of coacervates. We investigate the effect of charge patterning along the polymer chain on the phase behavior of coacervates in the framework of the Restricted Primitive Model using Gibbs Ensemble Monte Carlo simulations. Our results show that charge patterning dramatically changes the phase behavior of polymer coacervates, which contrasts with the predictions of the classical Voorn-Overbeek theory. This provides the basis for designing new materials through charge driven self assembly by controlling the positioning of the charged monomers along the chain.

  8. Theoretical Analysis of the Longitudinal Behavior of an Automatically Controlled Supersonic Interceptor During the Attack Phase

    NASA Technical Reports Server (NTRS)

    Gates, Ordway B., Jr.; Woodling, C. H.

    1959-01-01

    Theoretical analysis of the longitudinal behavior of an automatically controlled supersonic interceptor during the attack phase against a nonmaneuvering target is presented. Control of the interceptor's flight path is obtained by use of a pitch rate command system. Topics lift, and pitching moment, effects of initial tracking errors, discussion of normal acceleration limited, limitations of control surface rate and deflection, and effects of neglecting forward velocity changes of interceptor during attack phase.

  9. Short-Cycle Adsorption Refrigerator

    NASA Technical Reports Server (NTRS)

    Chan, C. K.

    1988-01-01

    Modular adsorption/Joule-Thomson-effect refrigerator offers fast regeneration; adsorption/desorption cycle time expected to be 1 minute. Pressurized hydrogen generated by bank of compressor modules during heating phase passes through system of check valves and expands in Joule-Thomson junction as it enters refrigeration chamber. Hydrogen absorbs heat from load before it is sucked out by another bank of compressor modules in cooling phase.

  10. Social and Behavioral Sciences: Report of the Project 2061 Phase I Social and Behavioral Sciences Panel.

    ERIC Educational Resources Information Center

    Appley, Mortimer H.; Maher, Winifred B.

    This is one of five panel reports that have been prepared as part of the first phase of Project 2061, a long-term, multipurpose undertaking of the American Association for the Advancement of Science designed to help reform science, mathematics, and technology education in the United States. Major sections included are: (1) "Orienting…

  11. Adsorption of As(III), As(V) and Cu(II) on zirconium oxide immobilized alginate beads in aqueous phase.

    PubMed

    Kwon, Oh-Hun; Kim, Jong-Oh; Cho, Dong-Wan; Kumar, Rahul; Baek, Seung Han; Kurade, Mayur B; Jeon, Byong-Hun

    2016-10-01

    A composite adsorbent to remove arsenite [As(III)], arsenate [As(V)], and copper [Cu(II)] from aqueous phase was synthesized by immobilizing zirconium oxide on alginate beads (ZOAB). The composition (wt%) of ZOAB (Zr-34.0; O-32.7; C-21.3; Ca-1.0) was confirmed by energy dispersive X-ray (EDX) analysis. Sorption studies were conducted on single and binary sorbate systems, and the effects of contact time, initial adsorbate concentration, and pH on the adsorption performance of ZOAB (pHPZC = 4.3) were monitored. The sorption process for As(III)/As(V) and Cu(II) reached an equilibrium state within 240 h and 24 h, respectively, with maximum sorption capacities of 32.3, 28.5, and 69.9 mg g(-1), respectively. The addition of Cu(II) was favorable for As(V) sorption in contrast to As(III). In the presence of 48.6 mg L(-1) Cu(II), the sorption capacity of As(V) increased from 1.5 to 3.8 mg g(-1) after 240 h. The sorption data for As(III)/As(V) and Cu(II) conformed the Freundlich and Langmuir isotherm models, respectively. The adsorption of As(III), As(V), and Cu(II) followed pseudo second order kinetics. The effect of arsenic species on Cu(II) sorption was insignificant. The results of present study demonstrated that the synthesized sorbent could be useful for the simultaneous removal of both anionic and cationic contaminants from wastewaters.

  12. Nature of the Adsorption of Zwitterionic Surfactants at Hydrophilic Surfaces

    PubMed

    Harwigsson; Tiberg; Chevalier

    1996-11-10

    This paper describes the adsorption of zwitterionic dodecyl-N,N-dimethylammonio alkanoates with polymethylene intercharge arms of different lengths on silica. The data presented were obtained by in situ ellipsometry, allowing time-resolved studies of the surface excess, the mean thickness, and the refractive index of thin interfacial films. It is shown that the mode of adsorption of zwitterionic surfactants is similar to that observed for ethylene-oxide-based nonionic surfactants. The interaction energy between single zwitterionic surfactants and silica is relatively weak and the adsorption process is best described in terms of surfactant self-assembly, promoted by the presence of the solid surface. The mode of adsorption is only weakly affected by increasing the number of intercharge methylene units. The surface aggregation behavior observed at the silica surface displays many parallels with the corresponding solution phase behavior. Finally, the adsorption of zwitterionic surfactants is relatively independent of the pH. However, as the pH is lowered to the pKa values of the terminal carboxyl group (i.e., as the surfactants become increasingly positively charged) desorption is observed.

  13. Adsorptive potential of cationic Basic Yellow 2 (BY2) dye onto natural untreated clay (NUC) from aqueous phase: Mass transfer analysis, kinetic and equilibrium profile

    NASA Astrophysics Data System (ADS)

    Öztürk, A.; Malkoc, E.

    2014-04-01

    In this work, natural untreated clay (NUC) was studied for the removal of Basic Yellow 2 (BY2) from aqueous solution in batch system. The effects of initial BY2 concentration, contact time, solution temperature and solution pH on BY2 adsorption were investigated. Nitrogen sorption measurements were employed to investigate the variation in surface and pore properties after dye adsorption. The adsorbent was characterized by means of FTIR, PSD, TEM, XRD and BET analysis. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin and Scatchard isotherm models. The maximum monolayer adsorption capacity was found to be 833.33 mg/g at 25 °C (at room temperature). The pseudo-second-order kinetic model provided the best fit to the experimental datas compared with pseudo-first-order kinetic adsorption models. To explain mass transfer mechanism of BY2 adsorption, obtained experimental datas were applied Weber and Morris model, Body and Frusawa and Smith models. The results show that the adsorption process is controlled by film diffusion. The thermodynamic parameters such as, Gibbs free energy changes (ΔG°), standard enthalpy change (ΔH°) and standard entropy change (ΔS°) were determined. Adsorption of BY2 on NUC is exothermic and spontaneous in nature. The calculated activation energy of adsorption was found to be 5.24 kJ/mol for BY2. This value indicates that the adsorption process is a physisorption.

  14. Anion adsorption induced surface reconstructions

    NASA Astrophysics Data System (ADS)

    Tang, Lei

    2005-11-01

    Surface stress plays an important role in the behavior of solid surfaces. Potential-controlled anion adsorption in electrolytes alters the surface stress of the electrode and results in morphology changes to the surfaces. With a combination of potential-induced surface stress measurement and in situ electrochemical scanning tunneling microscopy (STM), it is demonstrated that anion adsorption induces changes in structure of thin films and modifies the growth morphology and stress evolution in epitaxially grown films. Surface structural transitions in the heteroepitaxial system consisting of one to two gold monolayers on platinum substrates were observed. By increasing the potential, structural transitions, from (1 x 1), to a striped phase, to a hexagonal structure, occurred in the gold bilayer. This hexagonal structure was related to the formation of an ordered sulfate adlayer with a ( 3x7 ) structure. Such transitions were repeatable by cycling the potential. Furthermore, the transitions between various dislocation structures were affected by anion adsorption. The surface composition of the gold bilayer on Pt was measured by underpotential deposition of copper. By subtracting the contribution of a pure Pt surface from the gold bi-layer on Pt, a stress change of -2.4 N/m was observed, which agrees with the stress change of -2.46 N/m predicted to accompany formation of 1.5 MLs of coherent Au on Pt(111) from epitaxy theory. The Cu monolayer deposited on Au(111) from an acid sulfate electrolyte was found to be pseudomorphic while the Cu monolayer formed on Au(111) in vacuum was incoherent. The stress-thickness change associated with the coherent monolayer of copper on Au(111) in electrolyte was -0.6 N/m, while conventional epitaxy theories predict a value of +7.76 N/m. STM results elucidated the sulfate adsorption on the copper monolayer caused an expansion of the layer as evidenced by a Moire Structure. For the Cu monolayer on Au(111), the sulfate-induced expansion

  15. Phase Transition Behavior of Novel Soybean Oil-based Thermosensitive Polymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The thermal phase transition behavior of novel soybean oil-based polymers was studied. The effect of polymer concentration on the cloud points was investigated. The light transmittance increased sharply with increasing temperature suggesting dissociation of polymer aggregates. The cloud points we...

  16. Interactive Augmentation of Computer Generated Force Behavior Based on Cooperative and Reinforcement Learning. Phase 1.

    DTIC Science & Technology

    1995-09-01

    produced a design methodology for augmenting computer generated force behavior with the NeurRule Technology concepts of cooperative and reinforcement ... learning . The Phase I results indicate that (1) Intelligent CGFs can improve task performance through on-line learning, utilizing information from

  17. Effect of shrinkage on isothermal drying behavior of 2-phase olive mill waste

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The objective of this study was to determine the drying behavior of 2-phase olive mill waste (2POMW) under isothermal microwave-convection drying conditions. 2POMW samples were dried in a thin layer in a variable-power pilot microwave oven with impinging air, using a feedback controller to maintain...

  18. Level dependence in behavioral measurements of auditory-filter phase characteristics.

    PubMed

    Shen, Yi; Lentz, Jennifer J

    2009-11-01

    Two masking experiments were conducted to behaviorally estimate auditory-filter phase curvatures at different stimulus levels. Maskers were harmonic complexes consisting of equal-amplitude tones and phase spectra with varied curvatures. In Experiment 1, sinusoidal signal thresholds were measured at 2 and 4 kHz at fixed masker levels ranging from 50 to 90 dB sound pressure level (SPL). In Experiment 2, the masker level that just masked a sinusoidal signal at 2 and 4 kHz was measured at fixed signal levels of 25, 38, and 50 dB SPL. For both experiments, the estimated phase curvature approached zero (became less negative) with increasing stimulus level. This shift could suggest that the off-frequency phase characteristic of the auditory filter has an increasingly greater role on the estimated auditory-filter phase curvature at higher stimulus levels. This explanation is supported through the use of psychophysical modeling.

  19. Effects of pressure on the thermal decomposition kinetics, chemical reactivity and phase behavior of RDX

    SciTech Connect

    Miller, P.J. ); Block, S.; Piermarini, G.J. )

    1991-01-01

    The effects of pressure on the thermal decomposition kinetics, chemical reactivity, and phase behavior of RDX have been studied by a combination of measurement techniques in conjunction with a high-pressure diamond anvil cell. These techniques include Fourier transform infrared (FTIR) spectroscopy for kinetic measurements and phase identification, energy dispersive x-ray powder diffraction for identification of the observed polymorphic forms and also compression measurements, and optical polarizing microscopy for visual detection and confirmation of phase transformations and determinations of transition pressures. The ruby method of pressure measurement was used in all methods employed. Studies were generally limited to the region where decomposition rates could be measured within reasonable laboratory time, i.e., below 10 GPa and 573 K. The P-T phase diagram for RDX was determined to 573 K and 7.0/GPa, delineating the stability fields of three solid phases, and the liquidus.

  20. Phase behavior, self-assembly, and emulsification of Tween 80/water mixtures with limonene and perfluoromethyldecalin.

    PubMed

    Sharma, Suraj Chandra; Warr, Gregory G

    2012-08-14

    The phase behavior, microstructure, and emulsification of polyoxyethylene (20) sorbitan monooleate (Tween 80), water, and d-limonene (LM) or perfluoromethyldecalin (PFMD) has been studied by small-angle X-ray scattering and polarizing optical microscopy. In the Tween 80/water binary system, a micellar solution (L(1)), a hexagonal (H(1)) phase, and a water-swellable isotropic surfactant liquid (L(2)) phase are successively formed at 25 °C. LM can be solubilized into all of the phases formed by Tween 80/water mixtures, whereas no solubilization of PFMD occurs. The L(2) phase was found by small-angle neutron scattering to be bicontinuous with low interfacial curvature. Added water swells and amplifies the pre-existing amphiphilic structure. The stability of oil-in-H(1) complex emulsions is found to be sensitive to changes in structure that accompany solubilization.

  1. Computational study of trimer self-assembly and fluid phase behavior

    SciTech Connect

    Hatch, Harold W. Shen, Vincent K.; Mittal, Jeetain

    2015-04-28

    The fluid phase diagram of trimer particles composed of one central attractive bead and two repulsive beads was determined as a function of simple geometric parameters using flat-histogram Monte Carlo methods. A variety of self-assembled structures were obtained including spherical micelle-like clusters, elongated clusters, and densely packed cylinders, depending on both the state conditions and shape of the trimer. Advanced simulation techniques were employed to determine transitions between self-assembled structures and macroscopic phases using thermodynamic and structural definitions. Simple changes in particle geometry yield dramatic changes in phase behavior, ranging from macroscopic fluid phase separation to molecular-scale self-assembly. In special cases, both self-assembled, elongated clusters and bulk fluid phase separation occur simultaneously. Our work suggests that tuning particle shape and interactions can yield superstructures with controlled architecture.

  2. Characterization and protein-adsorption behavior of deposited organic thin film onto titanium by plasma polymerization with hexamethyldisiloxane.

    PubMed

    Hayakawa, Tohru; Yoshinari, Masao; Nemoto, Kimiya

    2004-01-01

    Plasma polymerized hexamethyldisiloxane (HMDSO) thin film was deposited onto titanium using a radio-frequency apparatus for the surface modification of titanium. A titanium disk was first polished using colloidal silica at pH=9.8. Plasma-polymerized HMDSO films were firmly attached to the titanium by heating the titanium to a temperature of approximately 250 degrees C. The thickness of the deposited film was 0.07-0.35mum after 10-60min of plasma polymerization. The contact angle with respect to double distilled water significantly increased after HMDSO coating. X-ray photoelectron spectroscopy revealed that the deposited thin film consisted of Si, C, and O atoms. No Ti peaks were observed on the deposited surface. The deposited HMDSO film was stable during 2-weeks immersion in phosphate buffer saline solution. Fourier transform reflection-absorption spectroscopy showed the formation of Si-H, Si-C, C-H, and Cz.dbnd6;O bonds in addition to Si-O-Si bonds. Quartz crystal microbalance-dissipation measurement demonstrated that the deposition of HMDSO thin films on titanium has a benefit for fibronectin adsorption at the early stage. In conclusion, plasma polymerization is a promising technique for the surface modification of titanium. HMDSO-coated titanium has potential application as a dental implant material.

  3. Behavioral indicators to detect ovarian phase in the dromedary she-camel.

    PubMed

    Padalino, B; Rateb, S A; Ibrahim, N B; Monaco, D; Lacalandra, G M; El-Bahrawy, K A

    2016-06-01

    This pilot study was conducted to test the hypothesis that female camels behave differently in various ovarian phases in the presence of a restrained male camel. The aim was to identify behavioral patterns which could be used as indicators to detect ovulatory phase by visual observation in the presence of a restrained virile bull. Twenty-four healthy, nonpregnant, and nonlactating adult females were used. Transrectal ultrasonography was performed for each animal once a week over a 3-week period to determine the phase of the ovarian cycle. Females were considered to be in the ovulatory phase (O) when there was at least one preovulatory follicle (12<Ø<19 mm) protruding from the ovarian surface, and in the nonovulatory phase (NO), when growing follicles, regressing follicles, or corpora lutea were detected. Immediately after examination, each female was freely exposed to a restrained bull for 15 minutes, and her behaviors were filmed. The videos were analyzed through a focal animal-sampling ethogram (states: looking at the male; looking outside; standing close to the male; searching; and lying down; events: interaction with the male; urination; defecation; sound emission; and steps). A score for tail position (tail score: 1 = close to the vulva, 2 = horizontal, 3 = vertical) and for interest in the bull (male time score: from 1 to 5; 1 = <20% of observation period spent near the bull; 5 = more than 80%) were recorded. Ovulatory phase camels showed higher interest in the male than nonovulatory phases: they stood close to the male for longer periods (P = 0.0159), interacted with the male more frequently (P = 0.0004), and tended to lie down in front of him (P = 0.1202). Moreover, ovulatory phase had a significant effect on male time score (P < 0.01), mature follicular ovarian phase being associated with higher scores. Seeking the male has already been proposed as a behavioral indicator of estrus in camels, this has now been confirmed using a

  4. Influence of particle phase state on the hygroscopic behavior of mixed organic-inorganic aerosols

    NASA Astrophysics Data System (ADS)

    Hodas, N.; Zuend, A.; Mui, W.; Flagan, R. C.; Seinfeld, J. H.

    2014-12-01

    Recent work has demonstrated that organic and mixed organic-inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic-inorganic aerosol systems with physical states ranging from well-mixed liquids, to phase-separated particles, to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40-90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids, (2) forcing a single phase, but accounting for non-ideal interactions through activity coefficient calculations, and (3) a Zdanovskii-Stokes-Robinson-like calculation in which complete separation between the inorganic and organic components is assumed at all RH values, with water-uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid-liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF

  5. Influence of particle-phase state on the hygroscopic behavior of mixed organic-inorganic aerosols

    NASA Astrophysics Data System (ADS)

    Hodas, N.; Zuend, A.; Mui, W.; Flagan, R. C.; Seinfeld, J. H.

    2015-05-01

    Recent work has demonstrated that organic and mixed organic-inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle-phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic-inorganic aerosol systems with physical states ranging from well-mixed liquids to phase-separated particles to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40 to 90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids; (2) forcing a single phase but accounting for non-ideal interactions through activity coefficient calculations; and (3) a Zdanovskii-Stokes-Robinson-like calculation in which complete separation of the inorganic and organic components is assumed at all RH values, with water uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid-liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF

  6. Congruent qualitative behavior of complete and reconstructed phase space trajectories from biomolecular dynamics simulation.

    PubMed

    Caves, Leo S D; Verma, Chandra S

    2002-04-01

    Central to the study of a complex dynamical system is knowledge of its phase space behavior. Experimentally, it is rarely possible to record a system's (multidimensional) phase space variables. Rather, the system is observed via one (or few) scalar-valued signal(s) of emission or response. In dynamical systems analysis, the multidimensional phase space of a system can be reconstructed by manipulation of a one-dimensional signal. The trick is in the construction of a (higher-dimensional) space through the use of a time lag (or delay) on the signal time series. The trajectory in this embedding space can then be examined using phase portraits generated in selected subspaces. By contrast, in computer simulation, one has an embarrassment of riches: direct access to the complete multidimensional phase space variables, at arbitrary time resolution and precision. Here, the problem is one of reducing the dimensionality to make analysis tractable. This can be achieved through linear or nonlinear projection of the trajectory into subspaces containing high information content. This study considers trajectories of the small protein crambin from molecular dynamics simulations. The phase space behavior is examined using principal component analysis on the Cartesian coordinate covariance matrix of 138 dimensions. In addition, the phase space is reconstructed from a one dimensional signal, representing the radius of gyration of the structure along the trajectory. Comparison of low-dimensional phase portraits obtained from the two methods shows that the complete phase space distribution is well represented by the reconstruction. The study suggests that it may be possible to develop a deeper connection between the experimental and simulated dynamics of biomolecules via phase space reconstruction using data emerging from recent advances in single-molecule time-resolved biophysical techniques.

  7. Thermodynamics and Phase Behavior of Phosphonated Block Copolymers Containing Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Jung, Ha Young; Park, Moon Jeong

    Charge-containing copolymers have drawn intensive attention in recent years for their uses in wide range of electrochemical devices such as fuel cells, lithium batteries and actuators. Particularly, the creation of microphase-separated morphologies in such materials by designing them in block and graft configurations has been the subject of extensive studies, in order to establish a synergistic means of optimizing ion transport properties and mechanical integrity. Interest in this topic has been further stimulated by intriguing phase behavior from charge-containing polymers, which was not projected from conventional phase diagrams of non-ionic polymers. Herein, we investigate thermodynamics and phase behavior of a set of phosphonated block copolymers. By synthesizing low-molecular weight samples with degree of polymerization (N) <35, we observed order-disorder transition that enabled us to estimate effective Flory-Huggins interaction parameters (χ) by using random phase approximation. We further examined the systems by adding various ionic liquids, where noticeable increases in χ values and modulated microphase separation behavior were observed. The morphology-conductivity relationship has been elucidated by taking into account the segmental motion of polymer chains, volume of conducting phases, and the molecular interactions between phosphonated polymer chains and cations of ionic liquids.

  8. High-pressure phase behavior of binary mixtures of octacosane and carbon dioxide

    SciTech Connect

    McHugh, M.A.; Seckner, A.J.; Yogan, T.J.

    1984-11-01

    The high-pressure fluid phase behavior of binary mixtures of octacosane and CO/sub 2/ is experimentally investigated. Solubilities of octacosane in supercritical CO/sub 2/ and mixture molar volumes are determined for isotherms of 34.7, 45.4, 50.2, and 52.0/sup 0/C over a range of pressures from 80 to 325 atm. The solubility data are obtained by two different experimental techniques. The pressure-temperature projection of the two branches of the three-phase solid-liquid-gas freezing point depression curve is also determined. The octacosane-CO/sub 2/ LCEP is determined as 32.2/sup 0/ C and 72.6 atm. The UCEP, which is at a pressure greater than 650 atm, could not be determined due to the pressure limitation of the experimental apparatus. Phase diagram constructions are used qualitatively to explain the observed phase behavior and to provide information on the expected phase behavior of the octacosane-CO/sub 2/ system at pressures higher than those experimentally investigated.

  9. Phase behavior of AOT microemulsions in compressible liquids. [AOT = bis(2-ethylhexyl) sodium sulfosuccinate

    SciTech Connect

    McFann, G.J.; Johnston, K.P. )

    1991-06-13

    The phase behavior of bis(2-ethylhexyl) sodium sulfosuccinate (AOT)-alkane-brine systems is described over a wide range of pressure, temperature, and salinity for alkanes from ethane to dodecane. The partitioning of AOT between the oil, middle, and brine phases is reported for propane in order to determine the natural curvature. This is important for understanding separation processes with water-in-oil microemulsions. For the lighter, more compressible alkanes, the pressure effect on the hydrophilicity of the surfactant is much larger and in the opposite direction as for the heavier, less compressible ones. In propane at constant temperature and salinity, water-in-oil (w/o) microemulsions have been converted to middle phase microemulsions and then to oil-in-water (o/w) microemulsions by decreasing the pressure. These phase inversions are described in terms of the immiscibilities in the binary systems, and the molecular interactions at the surfactant interface. Although temperature and salinity are used commonly to manipulate interactions primarily on the water side of the interface, these results show it is possible to control interactions on the oil side by adjusting the pressure. The well-established trends in the phase behavior and size of microemulsion drops for dodecane through hexane are not observed for the lighter alkanes. For butane through ethane, a new unusual behavior is identified and attributed to a significant decrease in the strength of the attractive interactions between the surfactant tails and the alkane.

  10. Effect of phase behavior on the ethenolysis of ethyl oleate in compressed CO2.

    PubMed

    Song, Jiyuan; Hou, Minqiang; Lin, Gang; Zhang, Jianling; Han, Buxing; Yang, Guanying

    2009-03-05

    How to enhance the reaction efficiency using greener methods is an important topic. In this work, the phase behavior of the reaction system of metathesis of ethyl oleate with ethene in compressed CO2 was studied at 308.15 and 323.15 K using the Peng-Robinson equation of state. The effect of the phase behavior on the reaction rate and equilibrium conversion was studied. It was demonstrated that addition of CO2 in the reaction system could increase the reaction rate and equilibrium conversion considerably at suitable conditions where the solubility of the reactant in the vapor phase was low, while the solubility of the products was very high. However, at the condition where the solubility of the reactant and products were all high, the reaction rate was much slower. The mechanism for this interesting phenomenon was discussed in detail.

  11. Thermal behavior of glassy phase stabilized ammonium nitrate (PSAN) thin films

    DOE PAGES

    Yeager, J. D.; Chellappa, R.; Singh, S.; ...

    2015-06-01

    Ammonium nitrate (AN) is a high interest material because of its wide usage in propellants and explosives but can be difficult to handle from a formulation standpoint. It is soluble in many common solvents and has complex phase behavior. Here, we formulate phase stabilized AN (PSAN) films in a polymer matrix and characterize thermal and phase behavior using neutron reflectometry and ellipsometry. Our PSAN films are generally stable up to 160 °C, though we observe small material loss between 60 and 100 °C, which we attribute to solvent interactions with the PSAN. Crystallization of AN from supersaturated polymer is mostmore » common at thicker regions of the film, suggesting a critical nucleation thickness for the AN which can be avoided by making very thin films.« less

  12. Thermal behavior of glassy phase stabilized ammonium nitrate (PSAN) thin films

    SciTech Connect

    Yeager, J. D.; Chellappa, R.; Singh, S.; Majewski, J.

    2015-06-01

    Ammonium nitrate (AN) is a high interest material because of its wide usage in propellants and explosives but can be difficult to handle from a formulation standpoint. It is soluble in many common solvents and has complex phase behavior. Here, we formulate phase stabilized AN (PSAN) films in a polymer matrix and characterize thermal and phase behavior using neutron reflectometry and ellipsometry. Our PSAN films are generally stable up to 160 °C, though we observe small material loss between 60 and 100 °C, which we attribute to solvent interactions with the PSAN. Crystallization of AN from supersaturated polymer is most common at thicker regions of the film, suggesting a critical nucleation thickness for the AN which can be avoided by making very thin films.

  13. Phase behavior and microstructure of microemulsions containing the hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate.

    PubMed

    Anjum, Nishat; Guedeau-Boudeville, Marie-Alice; Stubenrauch, Cosima; Mourchid, Ahmed

    2009-01-08

    The phase behavior and microstructure of the ternary system water/1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF(6))/Triton X-100 was studied as a function of temperature and ionic liquid (IL) mass fraction alpha. In the present study, a hydrophobic IL instead of commonly used organic solvents such as n-alkanes is used. The fish-shaped region is distorted at low and high values of alpha, whereas it is symmetric at intermediate alpha. With increasing alpha, the extension of the three-phase region decreases regarding the surfactant concentration range, whereas it increases regarding the temperature range. For comparison the phase behavior of two ternary water/bmimPF(6)/alkyl oligoethyleneoxide (C(i)E(j)) systems has been investigated. Our results are compared with those obtained for water/n-alkane/C(i)E(j) and IL/n-alkane/C(i)E(j) systems, respectively.

  14. Structure and phase transition behavior of strontium modified barium zirconium titanate

    SciTech Connect

    Badapanda, T.; Sarangi, S.; Behera, B.; Saha, S.; Sinha, T. P.

    2015-06-24

    Pervoskite ceramics with composition Ba{sub 1-x}Sr{sub x}Zr{sub 0.05}Ti{sub 0.95}O{sub 3} (x= 0.1, 0.2, 0.3, 0.4 and 0.5) have been prepared by high energy ball milling. X-ray diffraction (XRD) patterns confirm that the all the compositions are in single phase. The composition shows tetragonal symmetry upto x=0.3 and with further increase in Sr content the structure changes to cubic. The temperature dependent dielectric behavior shows three phase transition in the parent material which merges with increase in Sr content. The transition temperature and dielectric constant decreases with increase in Sr concentration. The phase transition becomes more diffused with increment in doping concentration. The ferroelectric behavior of the ceramics is studied by the hysteresis loop.

  15. Effects of pentanol isomers on the phase behavior of phospholipid bilayer membranes.

    PubMed

    Griffin, Kathryn L; Cheng, Chih-Yin; Smith, Eric A; Dea, Phoebe K

    2010-11-01

    Differential scanning calorimetry (DSC) was used to analyze the thermotropic phase behavior of dipalmitoylphosphatidylcholine (DPPC) bilayers in the presence of pentanol isomers. The concentration of each pentanol isomer needed to induce the interdigitated phase was determined by the appearance of a biphasic effect in the main transition temperatures, the onset of a hysteresis associated with the main transition from the gel-to-liquid crystalline phase, and the disappearance of the pretransition. Lower threshold concentrations were found to correlate with isomers of greater alkyl chain length while branching of the alkyl chain was found to increase biphasic behavior. The addition of a methyl group to butanol systems drastically decreased threshold concentrations. However, as demonstrated in the DPPC/neopentanol system, branching of the alkyl chain away from the -OH group lowers the threshold concentration while maintaining a biphasic effect.

  16. Behavior of embedded phase in shock-driven two-phase flow

    NASA Astrophysics Data System (ADS)

    Kuehner, Garrett; Wayne, Patrick; Olmstead, Dell; Corbin, Clint; Bernard, Tennille; Vorobieff, Peter; Truman, C. Randall

    2013-11-01

    We present an experimental study of droplet acceleration in a shock-driven two-phase flow (air with embedded liquid droplets). The droplets (propylene glycol, diameter 0.5-3 μm) were pre-mixed with the air in the test section of a shock tube, then impulsively accelerated with planar shock wave with a Mach number of 1.7. A cross-section of the flow is illuminated with multiple pulses from Nd:YAG lasers, producing time-resolved visualizations of the seeded volume. The images are then analyzed to quantify droplet velocity and acceleration from the shock passage to about 1.5 ms after the shock. Based on the velocity measurements, we can resolve the droplet lag after the shock, when the massive droplets ``catch up'' with the flow of the surrounding air, as well as validate our earlier estimates of boundary layer growth. This research is supported by NNSA (US National Nuclear Security Agency).

  17. First principles calculations of the site substitution behavior in gamma prime phase in nickel based superalloys

    NASA Astrophysics Data System (ADS)

    Chaudhari, Mrunalkumar

    Nickel based superalloys have superior high temperature mechanical strength, corrosion and creep resistance in harsh environments and found applications in the hot sections as turbine blades and turbine discs in jet engines and gas generator turbines in the aerospace and energy industries. The efficiency of these turbine engines depends on the turbine inlet temperature, which is determined by the high temperature strength and behavior of these superalloys. The microstructure of nickel based superalloys usually contains coherently precipitated gamma prime (gamma') Ni3Al phase within the random solid solution of the gamma (gamma) matrix, with the gamma' phase being the strengthening phase of the superalloys. How the alloying elements partition into the gamma and gamma' phases and especially in the site occupancy behaviors in the strengthening gamma' phases play a critical role in their high temperature mechanical behaviors. The goal of this dissertation is to study the site substitution behavior of the major alloying elements including Cr, Co and Ti through first principles based calculations. Site substitution energies have been calculated using the anti-site formation, the standard defect formation formalism, and the vacancy formation based formalism. Elements such as Cr and Ti were found to show strong preference for Al sublattice, whereas Co was found to have a compositionally dependent site preference. In addition, the interaction energies between Cr-Cr, Co-Co, Ti-Ti and Cr-Co atoms have also been determined. Along with the charge transfer, chemical bonding and alloy chemistry associated with the substitutions has been investigated by examining the charge density distributions and electronic density of states to explain the chemical nature of the site substitution. Results show that Cr and Co atoms prefer to be close by on either Al sublattice or on a Ni-Al mixed lattice, suggesting a potential tendency of Cr and Co segregation in the gamma' phase.

  18. Liquid crystalline phase behavior of protein fibers in water: experiments versus theory.

    PubMed

    Jung, Jin-Mi; Mezzenga, Raffaele

    2010-01-05

    We have developed a new method allowing the study of the thermodynamic phase behavior of mesoscopic colloidal systems consisting of amyloid protein fibers in water, obtained by heat denaturation and aggregation of beta-lactoglobulin, a dairy protein. The fibers have a cross section of about 5.2 nm and two groups of polydisperse contour lengths: (i) long fibers of 1-20 microm, showing semiflexible behavior, and (ii) short rods of 100-200 nm long, obtained by cutting the long fibers via high-pressure homogenization. At pH 2 without salt, these fibers are highly charged and stable in water. We have studied the isotropic-nematic phase transition for both systems and compared our results with the theoretical values predicted by Onsager's theory. The experimentally measured isotropic-nematic phase transition was found to occur at 0.4% and at 3% for the long and short fibers, respectively. For both systems, this phase transition occurs at concentrations more than 1 order of magnitude lower than what is expected based on Onsager's theory. Moreover, at low enough pH, no intermediate biphasic region was observed between the isotropic phase and the nematic phase. The phase diagrams of both systems (pH vs concentration) showed similar, yet complex and rich, phase behavior. We discuss the possible physical fundamentals ruling the phase diagram as well as the discrepancy we observe for the isotropic-nematic phase transition between our experimental results and the predicted theoretical results. Our work highlights that systems formed by water-amyloid protein fibers are way too complex to be understood based solely on Onsager's theories. Experimental results are revisited in terms of the Flory's theory (1956) for suspensions of rods, which allows accounting for rod-solvent hydrophobic interactions. This theoretical approach allows explaining, on a semiquantitative basis, most of the discrepancies observed between the experimental results and Onsager's predictions. The sources of

  19. Prediction of salt effects on protein phase behavior by HIC retention and thermal stability.

    PubMed

    Baumgartner, Kai; Großhans, Steffen; Schütz, Juliane; Suhm, Susanna; Hubbuch, Jürgen

    2016-09-05

    In the biopharmaceutical industry it is mandatory to know and ensure the correct protein phase state as a critical quality attribute in every process step. Unwanted protein precipitation or crystallization can lead to column, pipe or filter blocking. In formulation, the formation of aggregates can even be lethal when injected into the patient. The typical methodology to illustrate protein phase states is the generation of protein phase diagrams. Commonly, protein phase behavior is shown in dependence of protein and precipitant concentration. Despite using high-throughput methods for the generation of phase diagrams, the time necessary to reach equilibrium is the bottleneck. Faster methods to predict protein phase behavior are desirable. In this study, hydrophobic interaction chromatography retention times were correlated to crystal size and form. High-throughput thermal stability measurements (melting and aggregation temperatures), using an Optim(®)2 system, were successfully correlated to glucose isomerase stability. By using hydrophobic interaction chromatography and thermal stability determinations, glucose isomerase conformational and colloidal stability were successfully predicted for different salts in a specific pH range.

  20. Phase Behavior of Block Copolymer directed Nanostructured Organic/Inorganic Hybrids

    NASA Astrophysics Data System (ADS)

    Wiesner, Ulrich

    2002-03-01

    The study of amphiphilic polymer based polymer-ceramic hybrid materials is an exciting emerging research area offering enormous scientific and technological promise. By choice of the appropriate block copolymer system (PI-b-PEO) as well as ceramic precursors (organically modified ceramic precursors, ormocers) unprecedented morphology control on the nanoscale is obtained. It is based on a unique polymer-ceramic interface that can be characterized in detail by solid-state NMR measurements. The hydrophilic parts of the block copolymers are completely integrated into the ceramic phase, analogous to what is often found in biological hybrid materials. The resulting composites can be described as a 'quasi two-phase system' allowing for a more rational hybrid morphology design based on the current understanding of the phase behavior of block copolymers and copolymer-homopolymer mixtures. The structures generated on the nanoscale are a result of a fine balance of competing interactions, another feature of complex biological systems. In the present contribution the synthesis and characterization of nanostructured hybrids based on aluminosilicates will be described. Besides morphologies known from other polymer studies the existence of a 'Plumber's Nightmare' phase is suggested. This indicates subtle, not yet understood differences of the ternary 'pseudo' phase diagram (morphology diagram) of these systems to behavior of conventional block copolymers. Implications of these findings for further explorations of the complex phase space of the present novel nanostructured organic-inorganic hybrid systems will be discussed.

  1. The adsorption of HCl on volcanic ash

    NASA Astrophysics Data System (ADS)

    Gutiérrez, Xochilt; Schiavi, Federica; Keppler, Hans

    2016-03-01

    Understanding the interaction between volcanic gases and ash is important to derive gas compositions from ash leachates and to constrain the environmental impact of eruptions. Volcanic HCl could potentially damage the ozone layer, but it is unclear what fraction of HCl actually reaches the stratosphere. The adsorption of HCl on volcanic ash was therefore studied from -76 to +150 °C to simulate the behavior of HCl in the dilute parts of a volcanic plume. Finely ground synthetic glasses of andesitic, dacitic, and rhyolitic composition as well as a natural obsidian from Vulcano (Italy) served as proxies for fresh natural ash. HCl adsorption is an irreversible process and appears to increase with the total alkali content of the glass. Adsorption kinetics follow a first order law with rate constants of 2.13 ṡ10-6 s-1 to 1.80 ṡ10-4 s-1 in the temperature range investigated. For dacitic composition, the temperature and pressure dependence of adsorption can be described by the equation ln ⁡ c = 1.26 + 0.27 ln ⁡ p - 715.3 / T, where c is the surface concentration of adsorbed HCl in mg/m2, T is temperature in Kelvin, and p is the partial pressure of HCl in mbar. A comparison of this model with a large data set for the composition of volcanic ash suggests that adsorption of HCl from the gas phase at relatively low temperatures can quantitatively account for the majority of the observed Cl concentrations. The model implies that adsorption of HCl on ash increases with temperature, probably because of the increasing number of accessible adsorption sites. This temperature dependence is opposite to that observed for SO2, so that HCl and SO2 are fractionated by the adsorption process and the fractionation factor changes by four orders of magnitude over a temperature range of 250 K. The assumption of equal adsorption of different species is therefore not appropriate for deriving volcanic gas compositions from analyses of adsorbates on ash. However, with the experimental

  2. Thermodynamic modeling of solute adsorption equilibrium from near-critical carbon dioxide.

    PubMed

    Yang, Xiaoning

    2004-05-15

    Modeling of adsorption equilibrium for supercritical fluid mixtures, with as few parameters as possible, is important in applications of the technology of supercritical fluid adsorption. In this paper, a correlative model has been developed to represent the adsorption equilibria of solutes from the near-critical CO(2) fluid. A two-dimensional van der Waals equation of state and the three-dimensional P - R equation of state were used to describe the adsorbed and bulk phases, respectively. This model contains five parameters for adsorption equilibrium isotherms at finite concentrations and two parameters for adsorption equilibrium constants at infinite dilution. All the parameters are independent of temperature and pressure. By applying the model to the experimental data from the literature, it was shown that this model is capable of describing the adsorption behavior of solutes from supercritical carbon dioxide over relatively wide temperature and pressure ranges. In addition, the adsorption behavior of supercritical fluid mixtures was investigated at finite and infinite dilution conditions.

  3. Exploring the correlated phase behavior and electronic properties of parent and doped spin-orbit Mott phases

    NASA Astrophysics Data System (ADS)

    Wilson, Stephen

    2014-03-01

    An unusual manifestation of Mott physics dependent on strong spin-orbit interactions has recently been identified in a growing number of classes of 5d transition metal oxides built from Ir4+ ions. Instead of the naively expected increased itinerancy of these iridates due to the larger orbital extent of their 5d valence electrons, the interplay between the amplified relativistic spin-orbit interaction (intrinsic to large Z iridium cations) and their residual on-site Coulomb interaction U, conspires to stabilize a novel class of spin-orbit assisted Mott insulators with a proposed Jeff = 1/2 ground state wavefunction. The identification of this novel spin-orbit Mott state has been the focus of recent interest due to its potential of hosting a variety of new phases driven by correlated electron phenomena (such as high temperature superconductivity or enhanced ferroic behavior) in a strongly spin-orbit coupled setting. Currently, however, there remains very little understanding of how spin-orbit Mott phases respond to carrier doping and, more specifically, how relevant U remains for the charge carriers of a spin-orbit Mott phase once the bandwidth is increased. Here I will present our group's recent experimental work exploring carrier doping and the resulting electronic phase behavior in one such spin-orbit driven Mott material, Sr3Ir2O7, with the ultimate goal of determining the relevance of U and electron correlation effects within the doped system's ground state. Our results reveal the stabilization of an electronically phase separated ground state in B-site doped Sr3Ir2O7, suggestive of an extended regime of localization of in-plane doped carriers within the spin-orbit Mott phase. This results in a percolative metal-to-insulator transition with a novel, global, antiferromagnetic order. The electronic response of B-site doping in Sr3Ir2O7will then be compared with recent results exploring A-site doping if time permits. Supported by NSF CAREER Award DMR-1056625.

  4. Unfolding and aggregation of a glycosylated monoclonal antibody on a cation exchange column. Part I. Chromatographic elution and batch adsorption behavior.

    PubMed

    Guo, Jing; Zhang, Shaojie; Carta, Giorgio

    2014-08-22

    A glycosylated IgG2 monoclonal antibody exhibits a two-peak elution behavior when loaded on a strong cation exchange column and eluted with either a linear salt gradient or two salt steps at increasing salt concentrations. The two-peak behavior is more pronounced for conditions where the initial antibody binding is stronger, i.e. at lower pH and buffer concentration, where the hold time prior to elution is longer, where the protein mass load is lower, and where the load flow rate is higher. The effect is also dependent on the resin type, being prominent for the polymer-functionalized resin Fractogel EMD SO₃(-) and virtually absent for a macroporous resin with similar backbone but no grafted polymers. Size exclusion chromatography and dynamic light scattering show that the early eluting peak consists exclusively of the native monomeric species while the late eluting peak is a mixture of monomeric and aggregated species. Batch adsorption/desorption experiments show that the bound protein can be desorbed in two steps, with a fraction desorbed in 0.33 M NaCl, corresponding to native monomer, and a second fraction desorbed in 1M NaCl. The latter fraction decreases with protein mass load and becomes almost negligible when the resin is initially completely saturated with protein. Confocal laser scanning microscopy showed that the two-peak elution/desorption behavior is related to the unique kinetics of protein binding in the Fractogel resin. Following partial loading of the resin, the bound protein migrates toward the center of the particles during a hold step and is redistributed across the particle volume attaining low local bound protein concentrations. For these conditions the protein is apparently destabilized forming a strongly-bound unfolded intermediate that, in turn, generates aggregates upon elution in high salt.

  5. Phase transformation induced resistive switching behavior in Al/Cu2Se/Pt

    NASA Astrophysics Data System (ADS)

    Rehman, Shania; Kim, Kihwan; Hur, Ji-Hyun; Kim, Deok-kee

    2017-04-01

    The phase transformation induced resistive switching behavior of an Al/Cu2Se/Pt device was studied. While the device did not demonstrate any resistive switching behavior at room temperature, it exhibited resistive switching behavior at 125 °C, near the transition temperature of copper(I) selenide (Cu2Se) (137 °C), where Cu2Se is known to transform from the monoclinic to superionic phase. The increase in ionic conductivity and structural variations (from ordered to disordered structure) associated with phase transformation were observed to be responsible for the origin of the switching behavior and increase in the on/off resistance ratio near the transition temperature. Thermodynamic calculations showed that a reduction in Gibb’s free energy of nucleation and an increase in the migration speed of the Cu ion associated with the ionic conductivity and order to disorder the transition of the Cu2Se at the transition temperature were the important factors responsible for the reduction in the SET voltages at 155 °C.

  6. Elemental Solubility Tendency for the Phases of Uranium by Classical Models Used to Predict Alloy Behavior

    SciTech Connect

    Van Blackwood; Travis Koenig; Saleem Drera; Brajenda Mishra; Davis Olson; Doug Porter; Robert Mariani

    2012-03-01

    Traditional alloy theory models, specifically Darken-Gurry and Miedema’s analyses, that characterize solutes in solid solvents relative to physical properties of the elements have been used to assist in predicting alloy behavior. These models will be applied relative to the three solid phases of uranium: alpha (orthorhombic), beta (tetragonal), and gamma (bcc). These phases have different solubilities for specific alloy additions as a function of temperature. The Darken-Gurry and Miedema models, with modifications based on concepts of Waber, Gschneider, and Brewer will be used to predict the behavior of four types of solutes: 1) Transition metals that are used for various purposes associated with the containment as alloy additions in the uranium fuel 2) Transuranic elements in the uranium 3) Rare earth fission products (lanthanides) 4) Transition metals and other fission products Using these solute map criteria, elemental behavior will be predicted as highly soluble, marginally soluble, or immiscible (compound formers) and will be used to compare solute effects during uranium phase transformations. The overlapping of these solute maps are convenient first approximation tools for predicting alloy behavior.

  7. Characterization of partitioning behaviors of immunoglobulin G in polymer-salt aqueous two-phase systems.

    PubMed

    Chow, Yin Hui; Yap, Yee Jiun; Show, Pau Loke; Juan, Joon Ching; Anuar, Mohd Shamsul; Ng, Eng-Poh; Ooi, Chien-Wei; Ling, Tau Chuan

    2016-11-01

    The partitioning behavior of immunoglobulin G (IgG) in the aqueous two-phase system (ATPS) composed of poly(ethylene glycol) (PEG) and phosphate was studied. The parameters of ATPS exhibiting the pronounced effects on the partitioning behavior of IgG include phase composition, PEG molecular weight, and the addition of sodium chloride (NaCl). The accumulation of IgG at the interface of the ATPS increased drastically as the tie-line length (TLL) was increased. This trend was correlated with a linear relationship relating the natural logarithm of interfacial partition coefficient (ln G) to the difference of PEG concentration between the top phase and the bottom phase (Δ[PEG]), and a good fit was obtained. An attempt was made to correlate the natural logarithm of partition coefficient (ln K) to the presence of NaCl with the proposed linear relationship, ln K = α″ ln [Cl(-)] + β″. The proposed relationship, which serves as a better description of the underlying mechanics of the protein partitioning behavior in the polymer-salt ATPS, provides a good fit (r(2) > 0.95) for the data of IgG partitioning. An optimum recovery of 99.97% was achieved in an ATPS (pH 7.5) composed of 14.0% (w/w) PEG 1450, 12.5% (w/w) phosphate and 5.0% (w/w) NaCl.

  8. Predicting phase behavior of mixtures of reservoir fluids with carbon dioxide

    SciTech Connect

    Grigg, R.B.; Lingane, P.J.

    1983-10-01

    The use of an equation of state to predict phase behavior during carbon dioxide flooding is well established. There is consensus that the characterization of the C fraction, the grouping of this fraction into ''pseudo components'', and the selection of interaction parameters are the most important variables. However, the literature is vague as to how to best select the pseudo components, especially when aiming for a few-component representation as for a field scale compositional simulation. Single-contact phase behavior is presented for mixtures of Ford Geraldine (Delaware), Maljamar (Grayburg), West Sussex (Shannon), and Reservoir D reservoir fluids, and of a synthetic oil C/C/C, with carbon dioxide. One can reproduce the phase behavior of these mixtures using 3-5 pseudo components and common interaction parameters. The critical properties of the pseudo components are calculated from detailed oil characterizations. Because the parameters are not further adjusted, this approach reduces the empiricism in fitting phase data and may result in a more accurate representation of the system as the composition of the oil changes during the approach to miscibility.

  9. Numerical study of light-induced phase behavior of smectic solids

    NASA Astrophysics Data System (ADS)

    Chung, Hayoung; Park, Jaesung; Cho, Maenghyo

    2016-10-01

    By the chemical cross-linking of rigid molecules, liquid crystal polymer (LCP) has been envisaged as a novel heterogeneous material due to the fact that various optical and geometric states of the liquid crystalline (LC) phases are projected onto the polymeric constituents. The phase behavior, which refers to the macroscopic shape change of LCP under thermotropic phase change, is a compelling example of such optical-mechanical coupling. In this study, the photomechanical behavior, which broadly refers to the thermal- or light-induced actuation of smectic solids, is investigated using three-dimensional nonlinear finite element analysis (FEA). First, the various phases of LC are considered as well as their relation to polymeric conformation defined by the strain energy of the smectic polymer; a comprehensive constitutive equation that bridges the strong, optomechanical coupling is then derived. Such photomechanical coupling is incorporated in the FEA considering geometric nonlinearity, which is vital to understanding the large-scale light-induced bending behavior of the smectic solid.To demonstrate the simulation capability of the present model, numerous examples of photomechanical deformations are investigated parametrically, either by changing the operating conditions such as stimuli (postsynthesis) or the intrinsic properties (presynthesis). When compared to nematic solids, distinguished behaviors due to smectic substances are found herein and discussed through experiments. The quasisoftness that bidirectionally couples microscopic variables to mechanical behavior is also explained, while considering the effect of nonlinearity. In addition to providing a comprehensive measure that could deepen the knowledge of photomechanical coupling, the use of the proposed finite element framework offers an insight into the design of light-responsive actuating systems made of smectic solids.

  10. Phase behavior of the lecithin/water/isooctane and lecithin/water/decane systems.

    PubMed

    Angelico, Ruggero; Ceglie, Andrea; Colafemmina, Giuseppe; Delfine, Fabio; Olsson, Ulf; Palazzo, Gerardo

    2004-02-03

    The isothermal pseudo-ternary-phase diagram was determined at 25 degrees C for systems composed oflecithin, water, and, as oil, either isooctane or decane. This was accomplished by a combination of polarizing microscopy, small-angle X-ray scattering, and NMR techniques. The lecithin-rich region of the phase diagram is dominated by a lamellar liquid-crystalline phase (Lalpha). For lecithin contents less than 60% and low hydration (mole ratio water/lecithin = W0 < 5.5), the system forms a viscous gel of branched cylindrical reverse micelles. With increase in the water content, the system phase separates into two phases, which is either gel in equilibrium with essentially pure isooctane (for lecithin < 25%) or a gel in equilibrium with Lalpha (for lecithin > 25%). These two-phase regions are very thin with respect to water dilution. For 8 < W0 < 54 very stable water-in-oil emulsions form. It is only after ripening for more than 1 year that the large region occupied by the emulsion reveals a complex pattern of stable phases. Moving along water dilution lines, one finds (i) the coexistence of gel, isooctane and Lalpha, (ii) equilibrium between reverse micelles and spherulites, and, finally, (iii) disconnected reverse micelles that fail to solubilize water for W0 > 54. This results in a Winsor II phase equilibrium at low lecithin content, while for lecithin > 20% the neat water is in equilibrium with a reverse hexagonal phase and an isotropic liquid-crystalline phase. The use of the decane as oil does not change the main features of the phase behavior.

  11. The influence of particle size and structure on the sorption and oxidation behavior of birnessite: I. Adsorption of As(V) and oxidation of As(III)

    NASA Astrophysics Data System (ADS)

    Villalobos, Mario; Escobar-Quiroz, Ingrid N.; Salazar-Camacho, Carlos

    2014-01-01

    Sorption and oxidation reactions in the environment may affect substantially the mobility of redox-sensitive toxic trace elements and compounds. Investigating the environmental factors that influence these reactions is crucial in understanding and predicting the geochemical fate of these environmental species, as well as to design appropriate engineered remediation schemes. Arsenic is a widespread contaminant of concern, especially in its oxidized forms, and Mn oxide minerals are some of the major contributors to its oxidation. The goal of this work was to investigate the influence of particle size and structural differences of environmentally-relevant Mn(IV) birnessites on the adsorption of As(V) and on the oxidation of As(III). An acid birnessite of 39 m2/g and a δ-MnO2 of 114 m2/g were used. Both birnessites sorbed a maximum Pb(II) of 0.3 Pb/Mn, indicating a significantly larger layer cationic vacancy content for acid birnessite, and a density of reactive edge sites for both of 12 sites/nm2. As(V) forms a bidentate bridging complex on singly-coordinated surface sites at the birnessite particle edges regardless of loading, pH, birnessite type, and presence of pre-sorbed metals(II). Maximum As(V) adsorption, under repulsive electrostatic pH conditions did not yield adsorption congruency behavior between both birnessites at constant pH, presumably because the increase in internal vacancy content causes negative electrostatic repulsion towards external As(V) oxyanion binding. At pH 4.5 As(III) oxidation on birnessites was fast and quantitative at As/Mn ratios of 0.3-0.33, the reaction being largely driven by the proton concentration. At pH 6 δ-MnO2 oxidized As(III) faster and to a higher extent than acid birnessite, at equal masses; but the reverse at equal total surface areas. The oxidation driving force (independently from protons) was higher at pH 6 than at pH 4.5 because of Mn(II) product removal by sorption to interlayer vacancies, which overcomes reactive

  12. Effect of Enantiomeric Excess on the Phase Behavior of Antiferroelectric Liquid Crystals

    SciTech Connect

    L Pan; B McCoy; S Wang; Z Liu; S Wang; R Pindak; C Huang

    2011-12-31

    Null transmission ellipsometry and resonant x-ray diffraction are employed to study the effect of enantiomeric excess (EE) on the phase behavior of antiferroelectric liquid crystal 10OTBBB1M7. Phase sequence, layer spacing, and pitch of the helical structures of the smectic-C*{sub {alpha}} and smectic-C* phases are studied as a function of temperature and EE. Upon reducing EE, a liquid-gas-type critical point of the smectic-C*{sub {alpha}} to smectic-C* transition is observed, as well as the disappearance of the smectic-C*{sub d4} and the smectic-C*{sub d3} phases. Results are analyzed in a mean-field model.

  13. Nonlinear light behaviors near phase transition in non-parity-time-symmetric complex waveguides.

    PubMed

    Nixon, Sean; Yang, Jianke

    2016-06-15

    Many classes of non-parity-time (PT)-symmetric waveguides with arbitrary gain and loss distributions still possess all-real linear spectrum or exhibit phase transition. In this Letter, nonlinear light behaviors in these complex waveguides are probed analytically near a phase transition. Using multi-scale perturbation methods, a nonlinear ordinary differential equation (ODE) is derived for the light's amplitude evolution. This ODE predicts that a single class of these non-PT-symmetric waveguides supports soliton families and amplitude-oscillating solutions both above and below linear phase transition, in close analogy with PT-symmetric systems. For the other classes of waveguides, the light's intensity always amplifies under the effect of nonlinearity, even if the waveguide is below the linear phase transition. These analytical predictions are confirmed by direct computations of the full system.

  14. Macroscopic behavior of a bar undergoing the paraelectric-ferroelectric phase transformation

    NASA Astrophysics Data System (ADS)

    Jiang, Qing

    1993-10-01

    R ECENT WORK of the author has developed a continuum model for the paraelectric—ferroelectric phase transformation. The present paper describes the detailed implications of this model when it has been supplemented with constitutive information pertaining to the phase transformation. An explicit Helmholtz potential has been constructed to characterize a hypothetical crystal capable of undergoing the paraelectric-ferroelectric phase transformation under the influence of applied electric fields or thermomechanical loads. The hysteretic macroscopic behavior associated with the phase transformation, induced by variation of temperature, application of electric fields and mechanical loads, has been studied. Some of the predictions have been compared qualitatively with experimental observations. The entire analysis is carried out within a one-dimensional setting.

  15. Factors affecting the phase behavior and antimicrobial activity of carvacrol microemulsions.

    PubMed

    Shaaban, Hamdy A; Edris, Amr E

    2015-01-01

    The aim of this study was to investigate some factors that can contribute to the formulation of aqueous-based carvacrol microemulsion that can potentially be used in food preservation or disinfection. For this purpose the capacity of formation of carvacrol microemulsion was first revealed by studying the phase behavior of that compound in five different non-ionic microemulsion systems. Factors affecting that phase behavior like the type of non-ionic surfactant and presence of solubilization enhancers were also studied. The fully dilutable microemulsion system that can incorporate high carvacrol amount, as revealed from the phase diagrams, was chosen for the antibacterial evaluation study. The same microemulsion system was re-formulated in a cationic form by substituting the non-ionic surfactant, Tween 20 (T20) with the cationic cetylpyridinium chloride (CPC). The disc diffusion method was used to evaluate the activity of these microemulsion systems against different pathogenic bacteria. Results of the phase behavior study showed that carvacrol is a c