Transport Properties of Self-Consolidating Concrete

The permeability of concrete is influenced by the porosity and the interconnectivity of the pores in the cement paste and the microcracks in concrete, especially in the interface of paste-aggregate. The movements of gases, liquids, and ions through concrete is important because of their interactions with concrete constituents, including pore water, which can alter the integrity of concrete directly and indirectly, leading to the deterioration of structures. This study reports the findings from an investigation carried out to study the effect of the mixture variations on the durability of medium- and high-strength self-consolidating concrete (SCC). The mixture variations studied include the type of mineral admixtures, such as limestone powder (LSP) and pulverized fuel ash (PFA), and viscositymodifying admixtures (VMA) for both medium- and high-strength SCC. Air permeability, water permeability, capillary absorption, and chloride diffusivity were used to assess the durability of SCC mixtures in comparison with normal, vibrated concretes. The results showed that SCC mixtures, for medium- and high-strength grades using PFA followed by LSP, have lower permeability properties compared with normal concretes. SCC made with VMA had a higher sorptivity, air permeability, and water permeability compared with other SCC mixtures, which can be attributed to higher watercement ratio (w/c) and lack of pore filling effect. An in-place migration coefficient was obtained using the in-place ion migration test. This was used to compare the potential diffusivity of different concretes. The results indicated that SCC, for both grades of strength, made with PFA showed much lower diffusivity values in comparison with other mixtures, whereas the SCC mixtures with VMA showed higher diffusivity.

Transport properties of protic ionic liquids, pure and in aqueous solutions: Effects of the anion and cation structure

Ionic conductivities of twelve protic ionic liquids (PILs) and their mixtures with water over the whole composition range are reported at 298.15 K and atmospheric pressure. The selected PILs are the pyrrolidinium-based PILs containing nitrate, acetate or formate anions; the formate-based PILs containing diisopropylethylammonium, amilaminium, quinolinium, lutidinium or collidinium cations; and the pyrrolidinium alkylcarboxylates, [Pyrr][CnH2n+1COO] with n = 5–8. This study was performed in order to investigate the influence of molecular structures of the ions on the ionic conductivities in aqueous solutions. The ionic conductivities of the aqueous solutions are 2–30 times higher than the conductivities of pure PILs. The maximum in conductivity varies from ww=0.41???to???0.74 and is related to the nature of cations and anions. The molar conductance and the molar conductance at infinite dilution for (PIL + water) solutions are then determined. Self-diffusion coefficients of the twelve protic ionic liquids in water at infinite dilution and at 298.15 K are calculated by using the Nernst–Haskell, the original and the modified Wilke–Chang equations. These calculations show that similar values are obtained using the modified Wilke–Chang and the Nernst–Haskell equations. Finally, the effective hydrodynamic (or Stokes) radius of the PILs was determined by using the Stokes–Einstein equation. A linear relationship was established in order to predict this radius as a function of the anion alkyl chain length in the case of the pyrrolidinium alkylcarboxylates PILs.

Transport Properties Investigation of Aqueous Protic Ionic Liquid Solutions through Conductivity, Viscosity, and NMR Self-Diffusion Measurements

We present a study on the transport properties through conductivity (s), viscosity (?), and self-diffusion coefficient (D) measurements of two pure protic ionic liquids—pyrrolidinium hydrogen sulfate, [Pyrr][HSO4], and pyrrolidinium trifluoroacetate, [Pyrr][CF3COO]—and their mixtures with water over the whole composition range at 298.15 K and atmospheric pressure. Based on these experimental results, transport mobilities of ions have been then investigated in each case through the Stokes–Einstein equation. From this, the proton conduction in these PILs follows a combination of Grotthuss and vehicle-type mechanisms, which depends also on the water composition in solution. In each case, the displacement of the NMR peak attributed to the labile proton on the pyrrolidinium cation with the PILs concentration in aqueous solution indicates that this proton is located between the cation and the anion for a water weight fraction lower than 8%. In other words, for such compositions, it appears that this labile proton is not solvated by water molecules. However, for higher water content, the labile protons are in solution as H3O+. This water weight fraction appears to be the solvation limit of the H+ ions by water molecules in these two PILs solutions. However, [Pyrr][HSO4] and [Pyrr][CF3COO] PILs present opposed comportment in aqueous solution. In the case of [Pyrr][CF3COO], ?, s, D, and the attractive potential, Epot, between ions indicate clearly that the diffusion of each ion is similar. In other words, these ions are tightly bound together as ion pairs, reflecting in fact the importance of the hydrophobicity of the trifluoroacetate anion, whereas, in the case of the [Pyrr][HSO4], the strong H-bond between the HSO4– anion and water promotes a drastic change in the viscosity of the aqueous solution, as well as on the conductivity which is up to 187 mS·cm–1 for water weight fraction close to 60% at 298 K.

Thermophysical properties of ammonium-based bis{(trifluoromethyl)sulfonyl} imide ionic liquids: Volumetric and transport properties

Density, rheological properties, and conductivity of a homologous series of ammonium-based ionic liquids N-alkyl-triethylammonium bis{(trifluoromethyl) sulfonyl}imide were studied at atmospheric pressure as a function of alkyl chain length on the cation, as well as of the temperature from (293.15 to 363.15) K. From these investigations, the effect of the cation structure was quantified on each studied properties, which demonstrated, as expected, a decrease of the density and conductivity, a contrario of an increase of the viscosity with the alkyl chain length on the ammonium cation. Furthermore, rheological properties were measured for both pure and water-saturated ionic liquids. The studied ionic liquids were found to be Newtonian and non-Arrhenius. Additionally, the effect of water content in the studied ionic liquids on their viscosity was investigated by adding water until they were saturated at 293.15 K. By comparing the viscosity of pure ionic liquids with the data measured in water-saturated samples, it appears that the presence of water decreases dramatically the viscosity of ionic liquids by up to three times. An analysis of involved transport properties leads us to a classification of the studied ionic liquids in terms of their ionicity using the Walden plot, from which it is evident that they can be classified as "good" ionic liquids. Finally, from measured density data, different volumetric properties, that is, molar volumes and thermal expansion coefficients were determined as a function of temperature and of cationic structure. Based on these volumetric properties, an extension of Jacquemin's group contribution model has been then established and tested for alkylammonium-based ionic liquids within a relatively good uncertainty close to 0.1 %. © 2012 American Chemical Society.

Comparative study on transport properties for LiFAP and LiPF6 in alkyl-carbonates as electrolytes through conductivity, viscosity and NMR self-diffusion measurements

We present in this work a comparative study on density and transport properties, such as the conductivity (sigma), viscosity (eta) and self-diffusion coefficients (D), for electrolytes based on the lithium hexafluorophosphate, LiPF6; or on the lithium tris(pentafluoroethane)-trifluorophosphate, LiFAP dissolved in a binary mixture of ethylene carbonate (EC) and dimethylcarbonate (DMC) (50:50 wt%). For each electrolyte, the temperature dependence on transport properties over a temperature range from 10 to 80 degrees C and 20 to 70 degrees C for viscosity and conductivity, respectively, exhibits a non-Arrhenius behavior. However, this dependence is correctly correlated by using the Vogel-Tamman-Fulcher (VTF) type fitting equation. In each case, the best-fit parameters, such as the pseudo activation energy and ideal glass transition temperature were then extracted. The self-diffusion coefficients (D) of the Li+ cation and PF6- or FAP(-) anions species, in each studied electrolyte, were then independently determined by observing Li-3, F-19 and P-31 nuclei with the pulsed-gradient spin-echo (PGSE) NMR technique over the same temperature range from 20 to 80 degrees C. Results show that even if the diffusion of the lithium cation is quite similar in both electrolytes, the anions diffusion differs notably. In the case of the LiPF6-based electrolyte, for example at T approximate to 75 degrees C (high temperature), the self-diffusion coefficients of Li+ cations in solution (D (Li+)approximate to 5 x 10(-19) m(2) s(-1)) is 1.6 times smaller than that of PF6- anions (D (PF6-) = 8.5 x 10(-19) m(2) s(-1)), whereas in the case of the LiFAP-based electrolyte, FAP(-) anions diffuse at same rate as the Li+ cations (D (FAP(-)) = 5 x 10(-1) m(2) s(-1)). Based on these experimental results, the transport mobility of ions were then investigated through Stokes-Einstein and Nernst-Einstein equations to determine the transport number of lithium t(Li)(+), effective radius of solvated Li+ and of PF6- and FAP(-) anions, and the degree of dissociation of these lithium salts in the selected EC/DMC (50:50 wt%) mixture over a the temperature range from 20 to 80 degrees C. This study demonstrates the conflicting nature of the requirements and the advantage of the well-balanced properties as ionic mobility and dissociation constant of the selected electrolytes. (C) 2013 Elsevier Ltd. All rights reserved.

Nonlinear transport and localization in single-walled carbon nanotubes

We have measured the electrical transport properties of mats of single-walled carbon nanotubes (SWNT) as a function of applied electric and magnetic fields. We find that at low temperatures the resistance as a function of temperature R(T) follows the Mott variable range hopping (VRH) formula for hopping in three dimensions. Measurement of the electric field dependence of the resistance R(E) allows for the determination of the Bohr radius of a localized state a = 700nm. The magnetoresistance (MR) of SWNT mat samples is large and negative at all temperatures and fields studied. The low field negative MR is proportional to H2, in agreement with variable range hopping in two or three dimensions. 3D VRH indicates good intertube contacts, implying that the localization is due to the disorder experienced by the individual tubes. The 3D localization radius gives a measure of the ID localization length on the individual tubes, which we estimate to be >700 nm. Implications for the electron-phonon mean free path are discussed.

Theoretical and experimental correlations of gas dissolution, diffusion, and thermodynamic properties in determination of gas permeability and selectivity in supported ionic liquid membranes

Supported ionic liquid membranes (SILMs) has the potential to be a new technological platform for gas/organic vapour separation because of the unique non-volatile nature and discriminating gas dissolution properties of room temperature ionic liquids (ILs). This work starts with an examination of gas dissolution and transport properties in bulk imidazulium cation based ionic liquids [C_nmim][NTf2] (n = 2.4, 6, 8.10) from simple gas H₂, N₂, to polar CO₂, and C₂H₆, leading to a further analysis of how gas dissolution and diffusion are influenced by molecular specific gas-SILMs interactions, reflected by differences in gas dissolution enthalpy and entropy. These effects were elucidated again during gas permeation studies by examining how changes in these properties and molecular specific interactions work together to cause deviations from conventional solution–diffusion theory and their impact on some remarkably contrasting gas perm-selectivity performance. The experimental perm-selectivity for all tested gases showed varied and contrasting deviation from the solution–diffusion, depending on specific gas-IL combinations. It transpires permeation for simpler non-polar gases (H₂, N₂) is diffusion controlled, but strong molecular specific gas-ILs interactions led to a different permeation and selectivity performance for C₂H₆ and CO₂. With exothermic dissolution enthalpy and large order disruptive entropy, C₂H₆ displayed the fastest permeation rate at increased gas phase pressure in spite of its smallest diffusivity among the tested gases. The C₂H₆ gas molecules “peg” on the side alkyl chain on the imidazulium cation at low concentration, and are well dispersed in the ionic liquids phase at high concentration. On the other hand strong CO₂-ILs affinity resulted in a more prolonged “residence time” for the gas molecule, typified by reversed CO₂/N₂ selectivity and slowest CO₂ transport despite CO₂ possess the highest solubility and comparable diffusivity in the ionic liquids. The unique transport and dissolution behaviour of CO₂ are further exploited by examining the residing state of CO₂ molecules in the ionic liquid phase, which leads to a hypothesis of a condensing and holding capacity of ILs towards CO₂, which provide an explanation to slower CO₂ transport through the SILMs. The pressure related exponential increase in permeations rate is also analysed which suggests a typical concentration dependent diffusion rate at high gas concentration under increased gas feed pressure. Finally the strong influence of discriminating and molecular specific gas-ILs interactions on gas perm-selectivity performance points to future specific design of ionic liquids for targeted gas separations.

Adsorption and aggregation properties of norovirus GI and GII virus-like particles demonstrate differing responses to solution chemistry

The transport properties (adsorption and aggregation behavior) of virus-like particles (VLPs) of two strains of norovirus ("Norwalk" GI.1 and "Houston" GII.4) were studied in a variety of solution chemistries. GI.1 and GII.4 VLPs were found to be stable against aggregation at pH 4.0-8.0. At pH 9.0, GI.1 VLPs rapidly disintegrated. The attachment efficiencies (a) of GI.1 and GII.4 VLPs to silica increased with increasing ionic strength in NaCl solutions at pH 8.0. The attachment efficiency of GI.1 VLPs decreased as pH was increased above the isoelectric point (pH 5.0), whereas at and below the isoelectric point, the attachment efficiency was erratic. Ca(2+) and Mg(2+) dramatically increased the attachment efficiencies of GI.1 and GII.4 VLPs, which may be due to specific interactions with the VLP capsids. Bicarbonate decreased attachment efficiencies for both GI.1 and GII.4 VLPs, whereas phosphate decreased the attachment efficiency of GI.1, while increasing GII.4 attachment efficiency. The observed differences in GI.1 and GII.4 VLP attachment efficiencies in response to solution chemistry may be attributed to differential responses of the unique arrangement of exposed amino acid residues on the capsid surface of each VLP strain.

Physical properties of a new Deep Eutectic Solvent based on lithium bis[(trifluoromethyl)sulfonyl]imide and N-methylacetamide as superionic suitable electrolyte for lithium ion batteries and electric double layer capacitors

Herein we present a study on the physical/chemical properties of a new Deep Eutectic Solvent (DES) based on N-methylacetamide (MAc) and lithium bis[(trifluoromethyl)sulfonyl]imide (LiTFSI). Due to its interesting properties, such as wide liquid-phase range from -60°C to 280°C, low vapor pressure, and high ionic conductivity up to 28.4mScm at 150°C and at x=1/4, this solution can be practically used as electrolyte for electrochemical storage systems such as electric double-layer capacitors (EDLCs) and/or lithium ion batteries (LiBs). Firstly, relationships between its transport properties (conductivity and viscosity) as a function of composition and temperature were discussed through Arrhenius' Law and Vogel-Tamman-Fulcher (VTF) equations, as well as by using the Walden classification. From this investigation, it appears that this complex electrolyte possesses a number of excellent transport properties, like a superionic character for example. Based on which, we then evaluated its electrochemical performances as electrolyte for EDLCs and LiBs applications by using activated carbon (AC) and lithium iron phosphate (LiFePO) electrodes, respectively. These results demonstrate that this electrolyte has a good compatibility with both electrodes (AC and LiFePO) in each testing cell driven also by excellent electrochemical properties in specific capacitance, rate and cycling performances, indicating that the LiTFSI/MAc DES can be a promising electrolyte for EDLCs and LiBs applications especially for those requiring high safety and stability. © 2013 Elsevier Ltd.

A comparative study on the thermophysical properties for two bis[(trifluoromethyl)sulfonyl]imide-based ionic liquids containing the trimethyl-sulfonium or the trimethyl-ammonium cation in molecular solvents

Herein, we present a comparative study of the thermophysical properties of two homologous ionic liquids, namely, trimethyl-sulfonium bis[(trifluoromethyl) sulfonyl]imide, [S₁₁₁][TFSI], and trimethyl-ammonium bis[(trifluoromethyl)sulfonyl]imide, [HN₁₁₁][TFSI], and their mixtures with propylene carbonate, acetonitrile, or gamma butyrolactone as a function of temperature and composition. The influence of solvent addition on the viscosity, conductivity, and thermal properties of IL solutions was studied as a function of the solvent mole fraction from the maximum solubility of IL, x_s, in each solvent to the pure solvent. In this case, x_s is the composition corresponding to the maximum salt solubility in each liquid solvent at a given temperature from 258.15 to 353.15 K. The effect of temperature on the transport properties of each binary mixture was then investigated by fitting the experimental data using Arrhenius' law and the Vogel-Tamman-Fulcher (VTF) equation. The experimental data shows that the residual conductivity at low temperature, e.g., 263.15 K, of each binary mixture is exceptionally high. For example, conductivity values up to 35 and 42 mS·cm^-1 were observed in the case of the [S ₁₁₁][TFSI] + ACN and [HN₁₁₁][TFSI] + ACN binary mixtures, respectively. Subsequently, a theoretical approach based on the conductivity and on the viscosity of electrolytes was formulated by treating the migration of ions as a dynamical process governed by ion-ion and solvent-ion interactions. Within this model, viscosity data sets were first analyzed using the Jones-Dole equation. Using this theoretical approach, excellent agreement was obtained between the experimental and calculated conductivities for the binary mixtures investigated at 298.15 K as a function of the composition up to the maximum solubility of the IL. Finally, the thermal characterization of the IL solutions, using DSC measurements, showed a number of features corresponding to different solid-solid phase transitions, T_S-S, with extremely low melting entropies, indicating a strong organizational structure by easy rotation of methyl group. These ILs can be classified as plastic crystal materials and are promising as ambient-temperature solid electrolytes. © 2013 American Chemical Society.

Microplasma Processed Ultrathin Boron Nitride Nanosheets for Polymer Nanocomposites with Enhanced Thermal Transport Performance

This paper reports on the enhancement of the thermal transport properties of nanocomposite materials containing hexagonal boron nitride in poly (vinyl alcohol)through room-temperature atmospheric pressure direct-current microplasma processing. Results show that the microplasma treatment leads to exfoliation of the hexagonal boron nitride in isopropyl alcohol, reducing the number of stacks from >30to a few or single layers. The thermal diffusivity of the resulting nanocomposites reaches 8.5 mm2 s-1, 50 times greater than blank poly (vinyl alcohol) and twice that ofnanocomposites containing non-plasma treated boron nitride nanosheets. From TEM analysis, we observe much less aggregation of the nanosheets after plasma processing along with indications of an amorphous carbon interfacial layer which may contribute to stable dispersion of boron nitride nanosheets in the resulting plasma treated colloids.