Comparative analysis of heterogeneous solid and soft materials by adsorption, NMR and thermally stimulated depolarisation current methods

Structural characterisation of such bio-objects as fibrinogen solution, yeast cells, wheat seeds and bone tissues has been done using two versions of cryoporometry based on the integral Gibbs-Thomson (IGT) equation for freezing point depression of pore liquids and the measurements by ¹H NMR spectroscopy (180-200 < T < 273 K) and the thermally stimulated depolarisation current (TSDC) method (90 < T < 273 K) of structured water. The IGT equation was solved using a self-consisting regularization procedure including the maximum entropy principle applied to the distribution function of pore size (PSD). Both methods give clear pictures of changes in the structural characteristics caused, e.g., by hydration and swelling of wheat seeds and yeast cells, coagulation and interaction of fibrinogen with solid nanoparticles in the aqueous media, and the human bone tissue disease.     

Study of the pore size distribution and fractal dimension of HNO3-treated activated carbons

In the present work, the effect of the oxidizing treatment with nitric acid on three activated carbon samples has been studied. The influence of the acid treatment on the surface groups of the different samples has been investigated by means of FT-IR spectroscopy. The pore size distributions of the different samples were determined by means of the HK and DFT methods. The HK method points out a moderate increment of the microporosity due to the action of the nitric acid, whereas the DFT method shows an increase in the microporosity range above 17 Å. Finally, the values of the fractal dimension reveal that the treatment of the samples with nitric acid leads to chemical reactions of a limited extent.     

Preparation of activated carbons from cherry stones by activation with potassium hydroxide

Using cherry stones, the preparation of activated carbon has been undertaken in the present study by chemical activation with potassium hydroxide. A series of KOH-activated products was prepared by varying the carbonisation temperature in the 400-900 °C range. Such products were characterised texturally by gas adsorption (N₂, −196 °C), mercury porosimetry, and helium and mercury density measurements. FT-IR spectroscopy was also applied. The carbons prepared as a rule are microporous and macroporous solids. The degree of development of surface area and porosity increases with increasing carbonisation temperature. For the carbon heated at 900 °C the specific surface area (BET) is 1624 m² g⁻¹, the micropore volume is 0.67 cm³ g⁻¹, the mesopore volume is 0.28 cm³ g⁻¹, and the macropore volume is 1.84 cm³ g⁻¹.     

Interactions of xanthines with activated carbon: II. The adsorption equilibrium

In the present work, we have studied the adsorption of xanthine derivatives by activated carbon sorbents in aqueous solutions. The study comprised both kinetic, equilibrium and thermodynamic aspects. The kinetic results were reported in a previous paper; the equilibrium-related results are discussed here. The two types of carbon used exhibit some differences but the equilibrium isotherms obtained are all of the H-3 type in the classification of Giles. This suggests a high affinity of the sorbents for the sorbates. We also found that the overall adsorption process comprises more than one individual adsorption-desorption process of which one leads to the formation of a “monolayer” and the other to the “precipitation” of the sorbate on the sorbent surface (multilayer adsorption); the amount of sorbate adsorbed in monolayer form was seemingly greater in C-A14.     

Vibrational studies in aqueous solutions: Part II. The acid oxalate ion and oxalic acid

Assignments for oxalic acid in solution are re-examined. A detailed assignment of the IR and Raman spectra of the acid oxalate ion is presented for the first time. Raman spectroscopy is used to study the first ionization of oxalic acid.     

Clathrate formation and dissociation in vapor/water/ice/hydrate systems in SBA-15, sol-gel and CPG porous media, as probed by NMR relaxation, novel protocol NMR cryoporometry, neutron scattering and ab initio quantum-mechanical molecular dynamics simulation

The Gibbs-Thomson effect modifies the pressure and temperature at which clathrates occur, hence altering the depth at which they occur in the seabed. Nuclear magnetic resonance (NMR) measurements as a function of temperature are being conducted for water/ice/hydrate systems in a range of pore geometries, including templated SBA-15 silicas, controlled pore glasses and sol-gel silicas. Rotator-phase plastic ice is shown to be present in confined geometry, and bulk tetrahydrofuran hydrate is also shown to probably have a rotator phase. A novel NMR cryoporometry protocol, which probes both melting and freezing events while avoiding the usual problem of supercooling for the freezing event, has been developed. This enables a detailed probing of the system for a given pore size and geometry and the exploration of differences between hydrate formation and dissociation processes inside pores. These process differences have an important effect on the environment, as they impact on the ability of a marine hydrate system to re-form once warmed above a critical temperature. Ab initio quantum-mechanical molecular dynamics calculations are also being employed to probe the dynamics of liquids in pores at nanometric dimensions.     

Impedance spectroscopic studies of planetary ball-milled lithium titanium phosphate material

The ac electrical conductivity properties of LiTi₂(PO₄)₃ (LTP) polycrystalline material in two different crystallite sizes are compared. Micrometer sized LTP is prepared by conventional solid-state reaction. LTP crystallites of 71 nm size are prepared by solid-state reaction of 40 h planetary milled stoichiometric mixture. The XRD and SEM are used as characterization techniques. Electrical properties are studied using impedance spectroscopic technique. Ball-milled LTP shows one order increase in grain-interior conduction compared to microcrystalline LTP at 388 K. The increase in conduction results from decreased crystallite size.     

Dielectric resonances in disordered media

Binary disordered systems are usually obtained by mixing two ingredients in variable proportions: conductor and insulator, or conductor and super-conductor. They present very specific properties, in particular the second-order percolation phase transition, with its fractal geometry and the multi-fractal properties of the current moments. These systems are naturally modeled by regular bi-dimensional or tri-dimensional lattices, on which sites or bonds are chosen randomly with given probabilities. The two significant parameters are the ratio h = σ ₁/σ of the complex conductances, σ and σ ₁, of the two components, and their relative abundances p (or, respectively, 1 - p). In this article, we calculate the impedance of the composite by two independent methods: the so-called spectral method, which diagonalises Kirchhoff's Laws via a Green function formalism, and the Exact Numerical Renormalization method (ENR). These methods are applied to mixtures of resistors and capacitors (R-C systems), simulating e.g. ionic conductor-insulator systems, and to composites constituted of resistive inductances and capacitors (LR-C systems), representing metal inclusions in a dielectric bulk. The frequency dependent impedances of the latter composites present very intricate structures in the vicinity of the percolation threshold. In this paper, we analyse the LR-C behavior of compounds formed by the inclusion of small conducting clusters (“n-legged animals”) in a dielectric medium. We investigate in particular their absorption spectra who present a pattern of sharp lines at very specific frequencies of the incident electromagnetic field, the goal being to identify the signature of each animal. This enables us to make suggestions of how to build compounds with specific absorption or transmission properties in a given frequency domain. Received 16 August 2002 Published online 14 February 2003 RID="a" ID="a"e-mail: laurent.raymond@l2mp.fr RID="b" ID="b"e-mail: steffen.schaefer@l2mp.fr RID="c" ID="c"UMR CNRS 6137     

Er‐ and Eu‐doped GaP‐oxide porous composites for optoelectronic applications

We demonstrate the controlled preparation of Er‐ and Eu‐doped GaP‐oxide porous composites. The fabrication procedure entails the use of porous semiconductor templates and the impregnation of rare earth ions from a rare earth salt solution in alcohol and thermal treatment. The composites exhibit strong green and red emission that comes from finely dispersed ErPO₄ and EuPO₄ oxide submicron phases in the composite. These materials may prove useful in future generations of optoelectronic and photonic devices. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)