A Multi-Scale Study of Water Dynamics under Confinement, Exploiting Numerical Simulations in Relation to NMR Relaxometry, PGSE and NMR Micro-Imaging Experiments: An Application to the Clay/Water Interface.

Water mobility within the porous network of dense clay sediments was investigated over a broad dynamical range by using 2H nuclear magnetic resonance spectroscopy. Multi-quanta 2H NMR spectroscopy and relaxation measurements were first performed to identify the contributions of the various relaxation mechanisms monitoring the time evolution of the nuclear magnetisation of the confined heavy water. Secondly, multi-quanta spin-locking NMR relaxation measurements were then performed over a broad frequency domain, probing the mobility of the confined water molecules on a time-scale varying between microseconds and milliseconds. Thirdly, 1H NMR pulsed-gradient spin-echo attenuation experiments were performed to quantify water mobility on a time-scale limited by the NMR transverse relaxation time of the confined NMR probe, typically a few milliseconds. Fourthly, the long living quantum state of the magnetisation of quadrupolar nuclei was exploited to probe a two-time correlation function at a time-scale reaching one second. Finally, magnetic resonance imaging measurements allow probing the same dynamical process on time-scales varying between seconds and several hours. In that context, multi-scale modelling is required to interpret these NMR measurements and extract information on the influences of the structural properties of the porous network on the apparent mobility of the diffusing water molecules. That dual experimental and numerical approach appears generalizable to a large variety of porous networks, including zeolites, micelles and synthetic or biological membranes.

Ionic association analysis of LiTDI, LiFSI and LiPF6 in EC/DMC for better Li-ion battery performances.

New lithium salts such as lithium bis(fluorosulfonyl)imide (LiFSI) and lithium 4,5-dicyano-2-(trifluoromethyl)imidazole-1-ide (LiTDI) are now challenging lithium hexafluorophosphate (LiPF6), the most used electrolyte salt in commercial Li-ion batteries. Thus it is now important to establish a comparison of these electrolyte components in a standard solvent mixture of ethylene carbonate and dimethyl carbonate (EC/DMC: 50/50 wt%). With this aim, transport properties, such as the ionic conductivity, viscosity and 7Li self-diffusion coefficient have been deeply investigated. Moreover, as these properties are directly linked to the nature of the interionic interactions and ion solvation, a better understanding of the structural properties of electrolytes can be obtained. The Li salt concentration has been varied over the range of 0.1 mol L-1 to 2 mol L-1 at 25 °C and the working temperature from 20 °C to 80 °C at the fixed concentration of 1 mol L-1. Experimental results were used to investigate the temperature dependence of the salt ion-pair (IP) dissociation coefficient (α D) with the help of the Walden rule and the Nernst-Einstein equation. The lithium cation effective solute radius (r Li) has been determined using the Jones-Dole-Kaminsky equation coupled to the Einstein relation for the viscosity of hard spheres in solution and the Stokes-Einstein equation. From the variations of α D and rLi with the temperature, it is inferred that in EC/DMC LiFSI forms solvent-shared ion-pairs (SIP) and that, LiTDI and LiPF6 are likely to form solvent separated ion-pairs (S2IP) or a mixture of SIP and S2IP. From the temperature dependence of α D, thermodynamic parameters such as the standard Gibbs free energy, enthalpy and entropy for the ion-pair formation are obtained. Besides being in agreement with the information provided by the variations of α D and rLi, it is concluded that the ion-pair formation process is exergonic and endothermic for the three salts in EC/DMC.

Water Mobility within Compacted Clay Samples: Multi-Scale Analysis Exploiting 1H NMR Pulsed Gradient Spin Echo and Magnetic Resonance Imaging of Water Density Profiles.

1H NMR pulsed gradient spin echo attenuation and water density profile analysis by magnetic resonance imaging are both used to determine the mobility of water molecules confined within a porous network of compacted kaolinite clay sample (total porosity of ∼50%). These two complementary experimental procedures efficiently probe molecular diffusion within time scales varying between milliseconds and few hours, filling the gap between the time scale of diffusion dynamics measured by traditional quasi elastic neutron scattering and through-diffusion methods. Furthermore, magnetic resonance imaging is a nondestructive investigation tool that is able to assess the effect of the local structure on the macroscopic mobility of the diffusing probe.

New approach for understanding experimental NMR relaxivity properties of magnetic nanoparticles: focus on cobalt ferrite.

Relaxivities r1 and r2 of cobalt ferrite magnetic nanoparticles (MNPs) have been investigated in the aim of improving the models of NMR relaxation induced by magnetic nanoparticles. On one hand a large set of relaxivity data has been collected for cobalt ferrite MNP dispersions. On the other hand the relaxivity has been calculated for dispersions of cobalt ferrite MNPs with size ranging from 5 to 13 nm, without using any fitting procedure. The model is based on the magnetic dipolar interaction between the magnetic moments of the MNPs and the 1H nuclei. It takes into account both the longitudinal and transversal contributions of the magnetic moments of MNPs leading to three contributions in the relaxation equations. The comparison of the experimental and theoretical data shows a good agreement of the NMR profiles as well as the temperature dependence.

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 (σ), viscosity (η), and self-diffusion coefficient (D) measurements of two pure protic ionic liquids--pyrrolidinium hydrogen sulfate, [Pyrr][HSO(4)], and pyrrolidinium trifluoroacetate, [Pyrr][CF(3)COO]--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 H(3)O(+). This water weight fraction appears to be the solvation limit of the H(+) ions by water molecules in these two PILs solutions. However, [Pyrr][HSO(4)] and [Pyrr][CF(3)COO] PILs present opposed comportment in aqueous solution. In the case of [Pyrr][CF(3)COO], η, σ, D, and the attractive potential, E(pot), 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][HSO(4)], the strong H-bond between the HSO(4)(-) 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.

Anisotropic porous structure of pharmaceutical compacts evaluated by PGSTE-NMR in relation to mechanical property anisotropy.

PURPOSE: The pore space anisotropy of pharmaceutical compacts was evaluated in relation to the mechanical property anisotropy. METHODS: The topology and the pore space anisotropy were characterized by PGSTE-NMR measurements. Parallelepipedical compacts of anhydrous calcium phosphate (aCP) and microcrystalline cellulose (MCC) were tested on top, bottom and side faces. A microindentation and three-point single beam tests were used to measure Brinell hardness, tensile strength and Young's modulus. All the data were submitted to a statistical analysis to test for significance. RESULTS: The porous structure of MCC compacts was anisotropic, contrary to those of aCP. The analysis of the pore space by PGSTE-NMR method showed that its structural anisotropy was controlled by the behaviour under compaction of the excipients. At the same time, the Young's modulus and the tensile strength were the same whatever the direction of testing. For the aCP compacts, all the faces had the same Brinell hardness. With MCC compacts, only the bottom face showed a lower Brinell hardness. CONCLUSIONS: Except for Brinell hardness measured on MCC compacts, the tested samples were characterized by anisotropic mechanical properties when its porous structures were sometimes anisotropic. Then, there is not a straight link between porosity anisotropy and mechanical properties.

Orientational microdynamics and magnetic-field-induced ordering of clay platelets detected by 2H NMR spectroscopy.

The orientation of montmorillonite clays induced by a static magnetic field is quantified by using (2)H NMR spectroscopy. Indeed, the residual quadrupolar splitting of the (2)H resonance line measured for heavy water is a direct consequence of the specific orientation of the clay platelets in the static magnetic field. In the dilute regime, this residual splitting increases linearly with clay concentration, which confirms that the clay/clay electrostatic repulsions remain negligible by comparison with the diamagnetic coupling of these anisotropic platelets. At higher concentration, the electrostatic repulsion between clay particles markedly enhances the detected splitting. Such enhancement is well predicted by numerical simulations. By varying the size of the clay platelets and the strength of the static magnetic field, it is possible to evaluate the order of magnitude of the diamagnetic susceptibility of these anisotropic colloids.

Application of PGSTE-NMR technique to characterize the porous structure of pharmaceutical tablets.

Direct compaction of pharmaceutical tablets is a complex process that results in a heterogeneous density distribution inside the compact. In the present study, we have used a non-invasive and non-destructive technique: the pulsed-gradient stimulated-echo (PGSTE) NMR method to access to topological information (connectivity, tortuosity) about the porous structure of the tablets obtained with three different pharmaceutical excipients: the microcrystalline cellulose, the lactose and the anhydrous calcium phosphate. These materials were chosen since their mechanical properties under pressure are highly differentiated. To probe the pore space with the PGSTE-NMR technique, the tablets were initially impregnated with silicone oil that is NMR sensitive (1H NMR). The time-dependent apparent self-diffusion coefficient was measured over a suitable range of diffusion time in the directions perpendicular and parallel to the compression axis, from which the tortuosity factor and the anisotropy of the porous structure can be studied. These results show that the porous structure varies with pressure and depends on the excipient behaviour under pressure. Then, this work demonstrates that PGSTE-NMR could be an alternative and a very interesting technique to obtain useful information on the structural properties of such compacted materials.

Anomalous diffusion of water in [BMIM][TFSI] room-temperature ionic liquid.

We have studied the self-diffusion properties of butyl-methyl-imidazolium bis(trifluoromethylsulfonyl)-imide ([BMIM][TFSI]) + water system. The self-diffusion coefficients of cations, anions, and water molecules were determined by pulsed field gradient NMR. These measures were performed with increased water quantity up to saturation (from 0.3 to 30 mol %). Unexpected variations have been observed. The self-diffusion coefficient of every species increases with the quantity of water but not in the same order of magnitude. Whereas very similar evolutions are observed for the anion and cation, the increase is 25 times greater for water molecules. We interpret our data by the existence of phase separation at microscopic scale.

Application of percolation model to the tensile strength and the reduced modulus of elasticity of three compacted pharmaceutical excipients.

Percolation theory has been applied to several mechanical properties of pharmaceutical tablets. This power law describes the change of tablet's properties with the relative density. It defines critical tablet densities from which the mechanical properties start to change. The exponent in the law is expected to be universal for a mechanical property and numerical values are proposed in the literature. In this work, the percolation model was applied to the tensile strength and the reduced modulus of elasticity (obtained from surface indentation test) of three compacted pharmaceutical excipients (a microcrystalline cellulose, a lactose and an anhydrous calcium phosphate). Two approaches were proposed. First, the exponent was kept constant and equal to the values used in the literature (2.7 for the tensile strength and 3.9 for the reduced modulus of elasticity). Secondly, the critical tablet density (i.e. the percolation threshold) and the exponent were determined from the model. In the first approach, the percolation thresholds were higher than the relative tapped density. Using the second approach, the experimentally determined exponents were not close to the values of the literature and the critical relative densities were higher than the relative tapped density or equal to zero. Then, this study showed that the exponent seems not universal and that the model must be used carefully.

Quantitative measurements of localized density variations in cylindrical tablets using X-ray microtomography.

Direct compaction is a complex process that results in a density distribution inside the tablets which is often heterogeneous. Therefore, the density variations may affect the compact properties. A quantitative analysis of this phenomenon is still lacking. Recently, X-ray microtomography has been successfully used in pharmaceutical development to study qualitatively the impact of tablet shape and break-line in the density of pharmaceutical tablets. In this study, we evaluate the density profile in microcrystalline cellulose (Vivapur 12) compacts obtained at different mean porosity (ranging from 7.7% to 33.5%) using X-ray tomography technique. First, the validity of the Beer-Lambert law is studied. Then, density calibration is performed and density maps of cylindrical tablets are obtained and visualized using a process with colour-scale calibration plot which is explained. As expected, important heterogeneity in density is observed and quantified. The higher densities in peripheral region were particularly investigated and appraised in regard to the lower densities observed in the middle of the tablet. The results also underlined that in the case of pharmaceutical tablets, it is important to differentiate the mechanical properties representative of the total volume tablet and the mechanical properties that only characterize the tablet surface like the Brinell hardness measurements.

Quadrupolar interaction study of various cations confined in porous charged polymer film of sPI ionomers.

The structure of a sulfonated polyimide (sPI) ionomer membranes was investigated via the transport properties of various confined cations (7Li+, 23Na+, 87Rb+, 133Cs+). Their NMR spectra show large residual quadrupolar splitting depending on the orientation of the film in the static magnetic field B0. This behavior is the fingerprint of a macroscopic nematic ordering of charged interfaces. This is also confirmed by the anisotropy of the self-diffusion tensor measured by 1H and 7Li PGSE experiments on N(CH3)4+ and Li+ cations, respectively.

Study of the casting of sulfonated polyimide ionomer membranes: structural evolution and influence on transport properties.

A casting process has been studied for charged polymers: the sulfonated polyimide ionomer membrane. The formation of the membrane has been followed by X-ray reflectivity as a function of temperature. The effect of equivalent weight has been also investigated. The thickness loss presents two regimes: the first one is linear vs time indicating that the models developed for noncharged polymer may be suitable for ionomers in the early period of drying. The second one corresponds to the loss of X-ray reflectivity signal. Moreover, the X-ray reflectivity signal seems to be correlated to the characteristic time of the sample drying. In complement, we have studied the influence of casting on the properties of the dried ionomer membranes. The transport coefficients of N(CH(3))(4)(+) ions confined in two kinds of membranes that were differently cast were measured. The results show that shearing the ionomer solution during casting may lead to an enhancement of the anisotropy of structure and of transport. Moreover, we have studied the effect of both interfaces on the ion transport properties through the dried membranes.

Analysis of the degree of nematic ordering within dense aqueous dispersions of charged anisotropic colloids by 23Na NMR spectroscopy.

Aqueous dispersions of Laponite, a synthetic clay neutralized by sodium counterions, are used as a model of charged anisotropic colloids to probe the influence of the shape of the particle on their organization within a macroscopic nematic phase. Because of the large fraction of condensed sodium counterions in the vicinity of the clay particle, (23)Na NMR is a sensitive probe of the nematic ordering of the clay dispersions. We used line shape analysis of the (23)Na NMR spectra and measurements of the Hahn echo attenuation to quantify the degree of alignment of the individual clay particles along a single nematic director. As justified by simple dynamical simulations of the interplay between the sodium quadrupolar relaxation and its diffusion through the porous network limited by the surface of the clay particles, we probe the degree of ordering within these clay nematic dispersions by measuring the variation of the apparent (23)Na NMR relaxation rates as a function of the macroscopic orientation of the clay dispersion within the magnetic field.