Effect of interfaces on the melting of PEO confined in triblock PS-b-PEO-b-PS copolymers.

Block copolymers form nanostructures that have interesting physical properties because they combine, for a single compound, the complementary features brought by each block. However, in order to fully exploit these properties, the physical state of each kind of domain must be precisely controlled. In this work, triblock PS-b-PEO-b-PS copolymers consisting of a central poly(ethylene oxide) (PEO) block covalently bonded to polystyrene (PS) blocks were synthesized by Atom Transfer Radical Polymerization. Their morphology was investigated by X-ray scattering and TEM experiments whereas their thermodynamic behavior was characterized by DSC. A strong decrease of both the melting temperature and the degree of crystallinity of PEO, due to its confinement between the PS domains, was observed and analyzed with a modified Gibbs-Thomson equation, following the approaches used for fluids confined in porous media. The existence of an amorphous bound layer, a few nanometers thick, at the PEO/PS interface, that does not undergo any phase transition in the temperature range investigated, accounts for both the melting temperature depression and the decrease of crystallinity upon confinement. This interfacial layer may significantly affect the mechanical and transport properties of these block copolymers that find applications as solid polymer electrolytes in batteries for example. Moreover, the value obtained for the solid PEO/liquid PEO surface tension is lower than those previously published but is thermodynamically consistent with the surface tensions of polymers at the solid/vapor and liquid/vapor interfaces.

Sulphonic acid strong cation-exchange restricted access columns in sample cleanup for profiling of endogenous peptides in multidimensional liquid chromatography. Structure and function of strong cation-exchange restricted access materials.

In this work, the pore structural parameters and size exclusion properties of LiChrospher strong cation-exchange and reverse phase restricted access materials (RAM) are analysed. The molecular weight size exclusion limit for polystyrenes was found to be about 17.7 kDa, while for standard proteins, the molecular weight size exclusion limit was higher, at approximately 25 kDa. The average pore diameter on a volume basis calculated from the pore network model changes from 8.5 nm (native LiChrospher) to 8.6 nm (diol derivative) to 8.2 nm (sulphonic acid derivative) to 6.9 nm (n-octadecyl derivative). Additional characterisations were performed on restricted access materials with nitrogen sorption at 77 K, water adsorption at 25 degrees C, intrusion-extrusion of water (in order to evaluate the hydrophobic properties of the pores of the hydrophobic RAM), and zeta potential measurements by microelectrophoresis. For peptide analysis out of the biofluids, the strong cation-exchange functionality seems to be particularly suitable mainly because of the high loadability of the strong cation-exchange restricted access material (SCX-RAM) and the fact that one can work under non-denaturing conditions to perform effective chromatographic separations. For bacitracin, the dynamic capacity of the SCX-RAM columns does not reach its maximum value in the analysed range. For lysozyme, the dynamic capacity reaches a value of 0.08 mg/ml of column volume before column is overloaded. Additionally, the proper column operating conditions that lead to the total effective working time of the RAM column to be equal to approximately 500 injections (depending on the type of sample), is comprehensively described. The SCX-RAM column was used in the same system analysing urine samples for the period of 1 month (approximately 150 injections) with run-to-run reproducibility below 5% RSD and below 10% RSD for the relative fractions.

Wettability of calcite and mica modified by different long-chain fatty acids (C18 acids).

The effect of long-chain fatty acid adsorption on the wetting states of calcite and mica powders is investigated. The selected long-chain fatty acids are saturated or unsaturated aliphatic acids (stearic acid and oleic acid, respectively) and naphthenic acids with saturated or unsaturated aromatic rings (18-cyclohexyloctadecanoic acid and 18-phenoloctadecanoic acid, respectively). The amount of irreversibly adsorbed acid is determined by thermogravimetric analysis. The affinity of water and n-decane for these samples before and after modification is deduced from their adsorption isotherm and microcalorimetry. Thermodynamic analysis of surface pressure and spreading tension are performed based on adsorption isotherms. The enthalpy versus coverage curve for water adsorption and its comparison to liquefaction enthalpy is shown to be a meaningful method for characterizing the wettability of a surface. The naphthenic acid with unsaturated aromatic ring deeply modifies the calcite to an oil-wet state. The mica powder was not as strongly modified as calcite by these acid molecules.

Thermodynamics of the structural transition in metal-organic frameworks.

A thermodynamic study of the structural large-pore (LP) to narrow pore (NP) transition in various Metal Organic Frameworks (MOFs) is presented. First, the pressure induced transition at a constant temperature is investigated using a Tian-Calvet microcalorimeter set-up equipped with a high pressure cell. This device permits simultaneous measurements of the mechanical work and heat associated with the LP → NP transition. It is shown that MIL-53(Al) and MIL-53(Cr) have similar thermodynamic and mechanical behaviour whilst the MIL-47(V) system is characterized by much higher transition energy and mechanical work. Second, the temperature induced transition at ambient pressure is studied by means of differential scanning calorimetry (DSC) combined with X-ray absorption spectroscopy. This set-up enables one to follow simultaneously the structural changes associated with the phase transition detected by DSC. The MIL-53(Cr)-Br functionalized MOF is chosen here as a case study where both energetics and structural changes are discussed.

Production of activated carbon from a new precursor molasses by activation with sulphuric acid.

Activated carbon has been prepared from molasses, a natural precursor of vegetable origin resulting from the sugar industry in Morocco. The preparation of the activated carbon from the molasses has been carried out by impregnation of the precursor with sulphuric acid, followed by carbonisation at varying conditions (temperature and gas coverage) in order to optimize preparation parameters. The influence of activation conditions was investigated by determination of adsorption capacity of methylene blue and iodine, the BET surface area, and the pore volume of the activated carbon were determined while the micropore volume was determined by the Dubinin-Radushkevich (DR) equation. The activated materials are mainly microporous and reveal the type I isotherm of the Brunauer classification for nitrogen adsorption. The activated carbons properties in this study were found for activation of the mixture (molasses/sulphuric acid) in steam at 750 degrees C. The samples obtained in this condition were highly microporous, with high surface area (> or =1200 m2/g) and the maximum adsorption capacity of methylene blue and iodine were 435 and 1430 mg/g, respectively.

Interactions of lysozyme with hydrophilic and hydrophobic polymethacrylate stationary phases in reversed phase chromatography (RPC).

Two silicas, one with a mean pore diameter of 30 nm and the other non-porous, were coated with polymethacrylates of increasing hydrophobicity in the sequence: poly-2-hydroxyethylmethacrylate (P2HEMA)1 polyethylmethacrylate (PEMA) and poly-n-octylmethacrylate (POMA). Association constants, Kass, between lysozyme and the coated silicas were determined by means of frontal analysis, and the apparent heats of adsorption, delta Happ, by means of microcalorimetry. Using Kass and delta Happ the changes in the apparent free energy, delta Gapp, and in the apparent entropy, delta Sapp, were calculated at a concentration of lysozyme < 10 mumol/l. The association between the lysozyme and the coated silica gave negative delta Happ and delta Sapp values. The delta Sapp values calculated from the experimental data in the absence of an added electrolyte and with 0.1 M sodium perchlorate present to be -12 (-96) J/mol deg on the P2HEMA silica, -27 (-51) J/mol deg on the PEMA silica, -98 (-186) J/mol deg on the POMA silica, respectively. The high delta Sapp value of the lysozyme on the POMA silica reflects a kind of stabilisation effect due to the conformational changes of lysozyme on the most hydrophobic POMA silica. As evidenced by RPC, lysozyme elutes on the POMA column in its totally unfolded form enabling a more disordered conformation with respect to entropy than in the native form.

Ionic surfactant adsorption onto activated carbons.

The adsorption of sodium dodecyl sulfate onto a set of activated carbons from aqueous solutions has been studied in the low concentration range. The adsorption isotherms are reasonably well fitted by a double Langmuir equation but the calorimetry of adsorption enthalpies shows a rather wide distribution of energies. This distribution is related to direct adsorbate-adsorbent interactions in pores of different size, without noticeable contributions from the chemical nature of the surface. The adsorbate-adsorbent interaction free energy through water is evaluated using the model proposed by van Oss and co-workers for the interfacial free energy. The obtained results indicate that the calculated free energy is in good agreement with that found from application of the double Langmuir equation to the adsorption isotherms.

Characterisation of porous materials for bioseparation.

A set of chromatographic materials for bioseparation were characterised by various methods. Both commercial materials and new supports presenting various levels of rigidity were analysed. The methods included size-exclusion and capillary phenomena based techniques. Both batch exclusion and inverse size-exclusion chromatography were used. Gas adsorption, mercury porosimetry and thermoporometry were applied as well as a new method based on water desorption starting from the saturated state. When the rigidity of adsorbents is high enough, the agreement is reasonable between the values of the structural parameters that were determined (surface area, porosity, and pore size) by various methods. Nevertheless, a part of macroporosity may not be evidenced by inverse size-exclusion chromatography whereas it is visible by batch exclusion and the other methods. When the rigidity decreases, for example with soft swelling gels, where standard nitrogen adsorption or mercury porosimetry are no more reliable, two main situations are encountered: either the methods based on capillary phenomena (thermoporometry or water desorption) overestimate the pore size with an amplitude that depends on the method, or in some cases it is possible to distinguish water involved in the swelling of pore walls from that involved in pore filling by capillary condensation.

Melting mechanism of monolayers adsorbed in cylindrical pores: the influence of the pore wall roughness.

We have analyzed the mechanism of melting of molecular layers adsorbed in porous materials with cylindrical pores and rough pore walls. The working example studied here is a monolayer of methane molecules adsorbed in MCM-41 pore of diameter 2R=4 nm. Both experimental (neutron scattering) and simulation (Monte Carlo) results demonstrate the strong influence of the wall roughness on the melting mechanism. In particular, the transformation between solidlike and liquidlike monolayer phases adsorbed on a rough surface is observed over a broad temperature range, and solidlike properties persist even above the bulk methane melting temperature.

Tortuosity of porous particles.

Tortuosity is often used as an adjustable parameter in models of transfer properties through porous media. This parameter, not reducible to classical measured microstructural parameters like specific surface area, porosity, or pore size distribution, reflects the efficiency of percolation paths, which is linked to the topology of the material. The measurement of the effective conductivity of a bed of particles saturated with an electrolyte is a simple way to evaluate tortuosity. Nevertheless, it received only little attention because of the real difficulties in both getting reliable results and interpreting data. Notably, the discrimination between the contribution of interparticle and intraparticle porosities to the tortuosity is not resolved. To our knowledge, there is no model able to fit the experimental data of the tortuosity of a suspension, and a fortiori of a particle bed, in the whole porosity range. Only empirical expressions have been proposed, but they do not allow deriving intratortuosity of a porous particle. For a dilute system, Maxwell's equation predicts the effective conductivity of suspensions of spherical particles as a function of the bulk electrolyte conductivity and of particle conductivity. The intraparticle tortuosity can be derived from the particle conductivity obtained from the Maxwell equation applied to data at infinite dilution of particles. Then, by assuming that the Maxwell equation is a first-order approximation of the conductivity as a function of porosity, we propose an explicit relation of the tortuosity tau of a suspension of porous particles, obtained by conductivity measurement, as tau = tau(epsilon, epsilon(p), tau(p)), where epsilon is the total porosity of the suspension, tau(p) is the intraparticle tortuosity, and epsilon(p) is the particle porosity. This relationship fits the experimental data in the whole porosity range and can be used to determine tau(p) from an experiment at only one porosity. Finally, the obtained values of tau(p) for a set of porous particles used in chromatography are discussed and compared to the data available in the literature.

Comparative study of morphometric properties characterizing the complexity of silicate pore networks probed by adsorption of nitrogen and methanol.

In this work, we compare the surface and morphometric properties of the pore networks in four silicas (code names Fr1428, Fr474, Fr1386, and MM1164) with different random porosities using the adsorption isotherms of two different probe adsorbents, nitrogen and methanol. The parent material Fr1428 was a pure silica 25 microm sample. The Fr474 sample was the same one with bonded electroneutral diol groups on its outer surface. Fr1386 was the parent material with bonded electroneutral diol groups on its outer surface and sulfonic groups on its inner surface, and the MM1164 sample was the original sample with external electroneutral diol groups and internal n-octadecyl groups. The properties examined were the specific surface area S(p) and the specific pore volume V(p), the pore connectivity c, the pore anisotropy b, the tortuosity tau, and the lacunarity lambda of the pore network as well as the percentage microporosity. These properties provide a complete characterization of complexity of the porous network. The surface areas of the solids were estimated via the traditional BET plots (S(BET)) and the I-point method (S(I)). The two sets of values S(BET) and S(I) were practically identical and they decrease as the size of the functional group increases. The values of percentage microporosity were also determined by the same I-point method using the variation of the C parameter of the BET equation. The total pore volume V(p) was found to be higher in the case of methanol adsorption, compared to nitrogen, which might be related to increase condensation. The networks of the pores were simulated using a dual site bond model (DSBM) and Monte Carlo (MC) techniques for achieving their proper arrangement into the solids. From the resulting simulating networks, the pore connectivity distributions (PCD) and their mean values c(mean) were estimated and favorably compared to the values of connectivity c(Seaton) determined according to the method of Seaton. Both values decrease with the size of the functional groups and are weakly affected by the adsorbent employed. From the simulation pore network, the mean values of tortuosity tau(mean) were also estimated and found to be lower when N2 was used as adsorbate compared to MeOH. The values of lacunarity lambda, estimated according to the method by Allain and Cloitre using the moving box technique in the DSBM/MC simulation matrix of the pore network, indicate that the distribution of the poreless mass into the matrix increases with the size of the functional group. Finally, the internal relationships observed between the pore anisotropy b and the percentage microporosity as well as between the tortuosity tau and the pore connectivity c are discussed.

Porous texture evolution in Nomex-derived activated carbon fibers.

In the present work, the textural evolution of a series of activated carbon fibers with increasing burn-off degree, prepared by the pyrolysis and steam activation of Nomex aramid fibers, is followed by measurements of physical adsorption of N(2) (77 K) and CO(2) (273 K) and immersion calorimetry into different liquids (dichloromethane, benzene, cyclohexane). The immersion calorimetry results are discussed in depth, paying special attention to the choice of the reference material. The activated carbon fibers studied possess an essentially homogeneous microporous texture, which suggests that these materials may be applied in gas separation, either directly or with additional CVD treatment.

Sorption of hydrophobic molecules by organic/inorganic mesostructures.

During the synthesis of micelle-templated silica an intermediate inorganic/organic mesostructure is obtained with an hexagonal arrangement of channels filled by surfactant molecules. The ability of such a mesostructure to solubilize organic molecules from an aqueous solution was investigated. To that end, silica/cationic surfactant mesostructures were prepared under various conditions and their stability toward surfactant release in water was first compared in order to select materials as stable as possible. Swelled mesostructures were also used. The sorption from solution of hydrophobic molecules was then studied. The affinity of the molecules for the mesostructures is directly related to their hydrophobic character as it is derived from their octanol/water partition coefficient. A cooperative effect between hydrophobic molecules and the cationic surfactant that stabilizes the surfactant inside the mesostructure was observed. Interaction energies between the solutes and the mesostructures were determined by microcalorimetry. They varied in accordance with the hydrophobic character of the molecule and, at low sorption amounts, they were of the same order of magnitude as the solubilization enthalpies in bulk micelles. When the sorption increases, the surfactant layer in the mesostructure is not allowed to swell as the free micelle does, and steric limitations in the headgroup area render sorption less favorable.