Application of density functional theory to equilibrium adsorption of argon and nitrogen on amorphous silica surface

We present a new version of non-local density functional theory (NL-DFT) adapted to description of vapor adsorption isotherms on amorphous materials like non-porous silica. The novel feature of this approach is that it accounts for the roughness of adsorbent surface. The solid–fluid interaction is described in the same framework as in the case of fluid–fluid interactions, using the Weeks–Chandler–Andersen (WCA) scheme and the Carnahan–Starling (CS) equation for attractive and repulsive parts of the Helmholtz free energy, respectively. Application to nitrogen and argon adsorption isotherms on non-porous silica LiChrospher Si-1000 at their boiling points, recently published by Jaroniec and co-workers, has shown an excellent correlative ability of our approach over the complete range of pressures, which suggests that the surface roughness is mostly the reason for the observed behavior of adsorption isotherms. From the analysis of these data, we found that in the case of nitrogen adsorption short-range interactions between oxygen atoms on the silica surface and quadrupole of nitrogen molecules play an important role. The approach presented in this paper may be further used in quantitative analysis of adsorption and desorption isotherms in cylindrical pores such as MCM-41 and carbon nanotubes.

Capillary phenomena in the framework of the two-dimensional density functional theory

We present results of application of the density functional theory (DFT) to adsorption and desorption in finite and infinite cylindrical pores accounting for the density distribution in radial and axial directions. Capillary condensation via formation of bridges is considered using canonical and grand canonical versions of the 2D DFT. The potential barrier of nucleation is determined as a function of the bulk pressure and the pore diameter. In the framework of the conventional assumptions on intermolecular interactions both 1D and 2D DFT versions lead to the same results and confirm the classical scenario of condensation and evaporation: the condensation occurs at the vapor-like spinodal point, and the evaporation corresponds to the equilibrium transition pressure. The analysis of experimental data on argon and nitrogen adsorption on MCM-41 samples seems to not completely corroborate this scenario, with adsorption branch being better described by the equilibrium pressure - diameter dependence. This points to the necessity of the further development of basic representations on the hysteresis phenomena.

Modeling of adsorption in finite cylindrical pores by means of density functional theory

Adsorption of argon at its boiling point infinite cylindrical pores is considered by means of the non-local density functional theory (NLDFT) with a reference to MCM-41 silica. The NLDFT was adjusted to amorphous solids, which allowed us to quantitatively describe argon adsorption isotherm on nonporous reference silica in the entire bulk pressure range. In contrast to the conventional NLDFT technique, application of the model to cylindrical pores does not show any layering before the phase transition in conformity with experimental data. The finite pore is modeled as a cylindrical cavity bounded from its mouth by an infinite flat surface perpendicular to the pore axis. The adsorption of argon in pores of 4 and 5 nm diameters is analyzed in canonical and grand canonical ensembles using a two-dimensional version of NLDFT, which accounts for the radial and longitudinal fluid density distributions. The simulation results did not show any unusual features associated with accounting for the outer surface and support the conclusions obtained from the classical analysis of capillary condensation and evaporation. That is, the spontaneous condensation occurs at the vapor-like spinodal point, which is the upper limit of mechanical stability of the liquid-like film wetting the pore wall, while the evaporation occurs via a mechanism of receding of the semispherical meniscus from the pore mouth and the complete evaporation of the core occurs at the equilibrium transition pressure. Visualization of the pore filling and empting in the form of contour lines is presented.

Influence of nanowire density on the shape and optical properties of ternary InGaAs nanowires

We have synthesized ternary InGaAs nanowires on (111)B GaAs surfaces by metal-organic chemical vapor deposition. Au colloidal nanoparticles were employed to catalyze nanowire growth. We observed the strong influence of nanowire density on nanowire height, tapering, and base shape specific to the nanowires with high In composition. This dependency was attributed to the large difference of diffusion length on (111)B surfaces between In and Ga reaction species, with In being the more mobile species. Energy dispersive X-ray spectroscopy analysis together with high-resolution electron microscopy study of individual InGaAs nanowires shows large In/Ga compositional variation along the nanowire supporting the present diffusion model. Photoluminescence spectra exhibit a red shift with decreasing nanowire density due to the higher degree of In incorporation in more sparsely distributed InGaAs nanowires.

Growth of ultrananocrystalline diamond film by DC Arcjet plasma enhanced chemical vapor deposition

Self-standing diamond films were grown by DC Arcjet plasma enhanced chemical vapor deposition (CVD). The feed gasses were Ar/H 2/CH 4, in which the flow ratio of CH 4 to H 2 (FCH4/FH2) was varied from 5% to 20%. Two distinct morphologies were observed by scanning electron microscope (SEM), i.e. the pineapple-like morphology and the cauliflower-like morphology. It was found that the morphologies of the as-grown films are strongly dependent on the flow ratio of CH 4 to H 2 in the feed gasses. High resolution transmission electron microscope (HRTEM) survey results revealed that there were nanocrystalline grains within the pineapple-like films whilst there were ultrananocrystalline grains within cauliflower-like films. X-ray diffraction (XRD) results suggested that (110) crystalline plane was the dominant surface in the cauliflower-like films whilst (100) crystalline plane was the dominant surface in the pineapple-like films. Raman spectroscopy revealed that nanostructured carbon features could be observed in both types of films. Plasma diagnosis was carried out in order to understand the morphology dependent growth mechanism. It could be concluded that the film morphology was strongly influenced by the density of gas phases. The gradient of C2 radical was found to be different along the growth direction under the different growth conditions. © 2012 Elsevier B.V. All rights reserved.

Comprehensive process maps for synthesizing high density aluminum oxide-carbon nanotube coatings by plasma spraying for improved mechanical and wear properties

Plasma sprayed aluminum oxide ceramic coating is widely used due to its outstanding wear, corrosion, and thermal shock resistance. But porosity is the integral feature in the plasma sprayed coating which exponentially degrades its properties. In this study, process maps were developed to obtain Al2O3-CNT composite coatings with the highest density (i.e. lowest porosity) and improved mechanical and wear properties. Process map is defined as a set of relationships that correlates large number of plasma processing parameters to the coating properties. Carbon nanotubes (CNTs) were added as reinforcement to Al2O 3 coating to improve the fracture toughness and wear resistance. Two novel powder processing approaches viz spray drying and chemical vapor growth were adopted to disperse CNTs in Al2O3 powder. The degree of CNT dispersion via chemical vapor deposition (CVD) was superior to spray drying but CVD could not synthesize powder in large amount. Hence optimization of plasma processing parameters and process map development was limited to spray dried Al2O3 powder containing 0, 4 and 8 wt. % CNTs. An empirical model using Pareto diagram was developed to link plasma processing parameters with the porosity of coating. Splat morphology as a function of plasma processing parameter was also studied to understand its effect on mechanical properties. Addition of a mere 1.5 wt. % CNTs via CVD technique showed ∼27% and ∼24% increase in the elastic modulus and fracture toughness respectively. Improved toughness was attributed to combined effect of lower porosity and uniform dispersion of CNTs which promoted the toughening by CNT bridging, crack deflection and strong CNT/Al2O3 interface. Al2O 3-8 wt. % CNT coating synthesized using spray dried powder showed 73% improvement in the fracture toughness when porosity reduced from 4.7% to 3.0%. Wear resistance of all coatings at room and elevated temperatures (573 K, 873 K) showed improvement with CNT addition and decreased porosity. Such behavior was due to improved mechanical properties, protective film formation due to tribochemical reaction, and CNT bridging between the splats. Finally, process maps correlating porosity content, CNT content, mechanical properties, and wear properties were developed.

Atomic vapor deposition of bismuth titanate thin films

c-axis oriented ferroelectric bismuth titanate (Bi4Ti 3O12) thin films were grown on (001) strontium titanate (SrTiO3) substrates by an atomic vapor deposition technique. The ferroelectric properties of the thin films are greatly affected by the presence of various kinds of defects. Detailed x-ray diffraction data and transmission electron microscopy analysis demonstrated the presence of out-of-phase boundaries (OPBs). It is found that the OPB density changes appreciably with the amount of titanium injected during growth of the thin films. Piezo-responses of the thin films were measured by piezo-force microscopy. It is found that the in-plane piezoresponse is stronger than the out-of-plane response, due to the strong c-axis orientation of the films.

Gas Solubility and Vapor Pressure of Electrolytes Based on Alkylcarbonates Containing Litfsi, Lifap, and LiPF6 Lithium Salt: Measurement and Prediction

Most liquid electrolytes used in commercial lithium-ion batteries are composed by alkylcarbonate mixture containing lithium salt. The decomposition of these solvents by oxidation or reduction during cycling of the cell, induce generation of gases (CO2, CH4, C2H4, CO …) increasing of pressure in the sealed cell, which causes a safety problem [1]. The prior understanding of parameters, such as structure and nature of salt, temperature pressure, concentration, salting effects and solvation parameters, which influence gas solubility and vapor pressure of electrolytes is required to formulate safer and suitable electrolytes especially at high temperature.

We present in this work the CO2, CH4, C2H4, CO solubility in different pure alkyl-carbonate solvents (PC, DMC, EMC, DEC) and their binary or ternary mixtures as well as the effect of temperature and lithium salt LiX (X = LiPF6, LiTFSI or LiFAP) structure and concentration on these properties. Furthermore, in order to understand parameters that influence the choice of the structure of the solvents and their ability to dissolve gas through the addition of a salt, we firstly analyzed experimentally the transport properties (Self diffusion coefficient (D), fluidity (h-1), and conductivity (s) and lithium transport number (tLi) using the Stock-Einstein, and extended Jones-Dole equations [2]. Furthermore, measured data for the of CO2, C2H4, CH4 and CO solubility in pure alkylcarbonates and their mixtures containing LiPF6; LiFAP; LiTFSI salt, are reported as a function of temperature and concentration in salt. Based on experimental solubility data, the Henry’s law constant of gases in these solvents and electrolytes was then deduced and compared with values predicted by using COSMO-RS methodology within COSMOthermX software. From these results, the molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvents and electrolytes with the gases in its hypothetical liquid state were calculated and discussed [3]. Finally, the analysis of the CO2 solubility variations with the salt addition was then evaluated by determining specific ion parameters Hi by using the Setchenov coefficients in solution. This study showed that the gas solubility is entropy driven and can been influenced by the shape, charge density, and size of the anions in lithium salt.

References

[1] S.A. Freunberger, Y. Chen, Z. Peng, J.M. Griffin, L.J. Hardwick, F. Bardé, P. Novák, P.G. Bruce, Journal of the American Chemical Society 133 (2011) 8040-8047.

[2] P. Porion, Y.R. Dougassa, C. Tessier, L. El Ouatani, J. Jacquemin, M. Anouti, Electrochimica Acta 114 (2013) 95-104.

[3] Y.R. Dougassa, C. Tessier, L. El Ouatani, M. Anouti, J. Jacquemin, The Journal of Chemical Thermodynamics 61 (2013) 32-44.

Estudo da segregação gravitacional do processo de injeção de vapor em reservátórios heterogêneos

Due to reservoirs complexity and significantly large reserves, heavy oil recovery has become one of the major oil industry challenges. Thus, thermal methods have been widely used as a strategic method to improve heavy oil recovery. These methods improve oil displacement through viscosity reduction, enabling oil production in fields which are not considered commercial by conventional recovery methods. Among the thermal processes, steam flooding is the most used today. One consequence in this process is gravity segregation, given by difference between reservoir and injected fluids density. This phenomenon may be influenced by the presence of reservoir heterogeneities. Since most of the studies are carried out in homogeneous reservoirs, more detailed studies of heterogeneities effects in the reservoirs during steam flooding are necessary, since most oil reservoirs are heterogeneous. This paper presents a study of reservoir heterogeneities and their influence in gravity segregation during steam flooding process. In this study some heterogeneous reservoirs with physical characteristics similar those found in the Brazilian Northeast Basin were analyzed. To carry out the simulations, it was used the commercial simulator STARS by CMG (Computer Modeling Group) - version 2007.11. Heterogeneities were modeled with lower permeability layers. Results showed that the presence of low permeability barriers can improve the oil recovery, and reduce the effects of gravity segregation, depending on the location of heterogeneities. The presence of these barriers have also increased the recovered fraction even with the reduction of injected steam rate

Pastas compósitas cimento/sílica/polímero para cimentação de poços de baixa profundidade sujeitas à injeção de vapor

The production of heavy oil fields, typical in the Northeastern region, is commonly stimulated by steam injection. High bottom hole temperatures are responsible not only for the development of deleterious stresses of the cement sheath but also for cement strength retrogression. To overcome this unfavorable scenario, polymeric admixtures can be added to cement slurries to improve its fracture energy and silica flour to prevent strength retrogression. Therefore, the objective of the present study was to investigate the effect of the addition of different concentrations of polyurethane (5-25%) to cement slurries containing 40% BWOC silica flour. The resulting slurries were characterized using standard API (American Petroleum Institute) laboratory tests. In addition to them, the mechanical properties of the slurries, including elastic modulus and microhardness were also evaluated. The results revealed that density, free water and stability of the composite cement/silica/polyurethane slurries were within acceptable limits. The rheological behavior of the slurries, including plastic viscosity, yield strength and gel strength increased with the addition of 10% BWOC polyurethane. The presence of polyurethane reduced the fluid loss of the slurries as well as their elastic modulus. Composite slurries also depicted longer setting times due to the presence of the polymer. As expected, both the mechanical strength and microhardness of the slurries decreased with the addition of polyurethane. However, at high bottom hole temperatures, the strength of the slurries containing silica and polyurethane was far superior than that of plain cement slurries. In summary, the use of polyurethane combined with silica is an interesting solution to better adequate the mechanical behavior of cement slurries to heavy oil fields subjected to steam injection

Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.