Calcium Carbonate Deposition on Cellulose

Cellulose powder was found to be a substrate favoring the deposition of calcite crystals from stable supersaturated solutions at pH 8.50 and at 25 degrees C. Kinetic analysis of the initial rates showed that they were proportional with the relative supersaturation with respect to calcite. Analysis of the dependence of the induction periods on the initial solution conditions showed that the number of ions forming the critical nucleus was 5. The second-order dependence of the rate of precipitation of calcite on cellulose on the solution supersaturation suggested a surface controlled mechanism. The surface energy of the calcite nuclei growing on cellulose was calculated to be 46 mJ m(-2) from the dependence of the induction time on the solution supersaturation. The overgrowth of calcite on cellulose was done selectively on the macromolecules possibly through active sites formation at ionizable functional groups (-OH). The nucleating capability of cellulose was found to be comparable with that of sulfonated polystyrene and significantly lower in comparison with sulfonated polystyrene divinyl benzene copolymer on which vaterite was formed. This fact together with the selective growth of the most stable calcite suggested that stereochemical factors are very important in determining both the kinetics and the nature of the polymorph formed. Copyright 2000 Academic Press.     

Fluorinated hydrotreatment catalysts: Promotion of the catalytic activity of unsupported MoS2 by doping with F? ions

Influence of fluorination on the HDS activity of unsupported MoS₂ phase has been studied and correlated with the influence of fluoride on the CoMo and NiMo catalysts supported on -Al₂O₃.

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MoS₂ . CoMo NiMo, -Al₂O₃.

     

Primary solid state batteries

Low - cost, easily fabricated dry cells were constructed by gluing a composite conducting material or a metal sulphide on magnesium or aluminium foils, using a solid electrolyte made from polyvinyl - pyrolidone. Composite conducting materials consisted of polypyrrole and polyaniline incorporated into an inorganic or polymer matrix or cupric oxide incorporated into a styrene - butadiene copolymer matrix. The efficiency, energy densities and voltage values of the cells were in the range 0.5 – 18.3 mWh cm⁻³, 9 – 339 wh kg⁻¹ and 0.5 – 2.0 V, respectively. The energy densities of the cells were up to seventeen times more than the energy density of the PbO₂ -H₂SO₄ - Pb multiple charge / discharge system and up to ten times more than the energy density of the nickel / cadmium rechargeable cell. A dry cell composed solely from polymers was constructed with cell voltage 0.25 – 0.50 V and efficiency ranging from 0.07 to 0.13 mWh cm⁻³ ten times lower than other commercial cells. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11–18 Sept. 1994     

Hydroxyapatite crystallization in the presence of acetaminophen

The effect of acetaminophen; a widely used analgesic and fever reducing medicine; in supersaturated solutions of calcium phosphate was investigated under plethostatic conditions, at 37 °C, 0.15 M NaCl, pH 7.40. The rates of crystal growth measured in the presence of acetaminophen 1.654×10⁻⁴ mol dm⁻³ to 6.616×10⁻⁴ mol dm⁻³ were reduced by 43% to 79%, respectively. The inhibition effect on the crystal growth rate may be explained through adsorption onto the active growth sites. Kinetic analysis suggested Langmuir-type adsorption of acetaminophen on the HAP surface with a affinity value of 2.4×10⁻⁴ dm³ mol⁻¹, for the substrate in the concentration range investigated. The electrophoretic mobility measurements showed that in the presence of acetaminophen the charge of the acetaminophen covered HAP particles was shifted to more negative values as compared to bare HAP. In the presence of acetaminophen no changes observed in the HAP overgrown morphology or in the apparent order of crystallization.     

The inhibition of calcium carbonate crystal growth by the cysteine-rich Mdm2 peptide

The crystal growth of calcite, the most stable calcium carbonate polymorph, in the presence of the cysteine-rich Mdm2 peptide (containing 48 amino acids in the ring finger configuration), has been investigated by the constant composition technique. Crystallization took place exclusively on well-characterized calcite crystals in solutions supersaturated only with respect to this calcium carbonate salt. The kinetic results indicated a surface diffusion spiral growth mechanism. The presence of the Mdm2 peptide inhibited the crystal growth of calcite by 22-58% in the concentration range tested, through adsorption onto the active growth sites of the calcite crystal surface. The kinetic results favored a Langmuir-type adsorption model, and the value of the calculated affinity constant was k(aff)=147x10(4) dm(3)mol(-1), a(ads)=0.29.     

An insight into the localization of charge carriers in conducting polyaniline by analyzing thermally stimulated depolarization signals

A dielectric relaxation mechanism, which is attributed to the localized motion of trapped polarons, has been recorded in conducting polyaniline by employing the thermally stimulated depolarization current technique. The signal was analyzed within the frame of the normal distribution in the activation energy value. The experimental dielectric relaxation results were manipulated in order to evaluate the length of the jump distance that the trapped polarons transfer along and the concentration of trap centers. The concentration of trapped carriers is calculated from two different viewpoints: the pair approximation that assumes phonon-assisted tunneling through the barrier separating two adjacent sites and the pinning model that considers the trapped polaron oscillating around its pinning point. Both models provide compatible results.     

Localized and long-distance charge hopping in fresh and thermally aged conductive copolymers of polypyrrole and polyaniline studied by combined TSDC and dc conductivity

The charge trapping centers in fresh and thermally aged conductive polyaniline-polypyrrole copolymers (starting from pure polyaniline and ending in pure polypyrrole by steps of 10 wt%) were studied by thermally stimulated depolarization current (TSDC) spectroscopy and dc conductivity measurements. One low temperature (115-135 K) relaxation mechanism appears in polyaniline-rich copolymers and disappears after thermal anneal. It is attributed to polaron trapping in the vicinity of chlorine anion dopants. Another relaxation mechanism operates close to room temperature and is related to conformational relaxation, which corresponds to the influence of the annihilation of the conformons on the conduction mechanism. The relaxation is sensitive to thermal aging as a result of the thermal annealing on the conductivity. The temperature derivative of the dc conductivity supports the latter assertion. The activation energy values were obtained as a function of composition for both fresh and heated samples. The TSDC spectroscopy is a sensitive tool which is an alternative to the standard conductivity studies for the characterization of polypyrrole-polyaniline conductive copolymers and the study of the thermal degradation.     

Calcite crystallization on oxadiazole-terpyridine copolymer

The nucleation and further crystallization of calcite on oxadiazole-terpyridine copolymer were investigated by the constant composition method. The apparent order of the crystallization process was found to be 2.3±0.2 indicative of a surface diffusion-controlled spiral growth mechanism. The number of ions forming the critical nucleus was found experimentally to be (n^*=) 3 in accordance with the simulation by the PM3 method included in the MOPAC program package. The surface energy of the growing phase was found to be 29.5 mJ m⁻².     

The effect of carrier solution on the particle size distribution of inorganic colloids measured by steric field-flow fractionation

The number average and the weight average particle diameters for suspended inorganic colloids found by the new technique of steric field-flow fractionation may be successfully used provided that the most suitable carrier solution is selected, in order to minimize the coagulation and adhesion phenomena.In the present work polydisperse, irregular colloidal particles of FePO₄·2H₂O (strengite) were studied. The average particle diameters were found to vary with the electrolyte concentration in the suspending medium. A strong variation of the number and weight average particle diameters was also observed with the quantity of the surfactant added to aquatic medium in order to increase colloidal stability. The influence of the electrokinetic charge of the FePO₄·2H₂O particles in relation to the surface charge of the material of the column employed, on the particle size measured was investigated. The proper carrier solution for minimizing coagulation and adhesion phenomena in the FePO₄·2H₂O colloidal particles was found to contain either 1.5% (v/v) detergent FL-70 and 0.1 MKNO₃ or 0.5% (v/v) detergent FL-70 and 0.033 MNa₂SO₄.     

Simultaneous determination of particle size and density in polydisperse colloidal samples by sedimentation field-flow fractionation

Sedimentation Field-Flow Fractionation (SFFF), which is a one-phase chromatographic system, is shown to be a rapid and convenient method for the simultaneous determination of particle size and density in polydisperse colloidal samples. This can be done by a methodology based on the variation of the carrier solution density using various aqueous glycerol solutions having different concentrations. A polydisperse polyvinyl chloride (PVC) latex sample was used as a model colloid. The average diameters and densities found by the proposed methodology are in good agreement with those obtained from the normal. SFFF procedure using a carrier of constant density or given by the manufacturer. Number average, d_N, and weight average, d_w, particle diameters were determined for the PVC sample at various carrier solutions containing glycerol up to 40 % (w/w) in order to show whether sample aggregation has occurred or not in the presence of glycerol. In all cases, the ratio d_w/d_N was found to be constant, showing that PVC aggregation has not occurred. Therefore our results, obtained by the proposed methodology in SFFF, are accurate, showing that this approach has considerable promise for characterizing complex colloidal materials.