Investigation of flow boiling in circulating three-phase fluidised bed: Part II: Theoretical correlation

The following part of this paper reviews existing theoretical correlations to predict the behaviour of two-phase (liquid-solid) and three-phase (liquid-solid-vapour) fluidised beds as well as models describing heat transfer coefficients. Moreover, a theoretical correlation is developed to describe heat transfer during boiling in a three-phase circulating fluidised bed. The approach uses earlier work on two-phase (liquid-vapour) flow boiling, two-phase (liquid-solid) fluidised beds and three-phase (liquid-vapour-solid) circulating fluidised beds. The correlation developed is validated against experimental data obtained in Part I of the presented paper. The model's ability to predict the experimental data has been successfully demonstrated. The developed expression for heat transfer coefficients is written as follows:

α_T.F.B.-[(α_nb)^t_R+(α_cb)^t_R]^1/t_R     

Electrosorption of hydrogen into palladium-rhodium alloys: Part 2. Pd-rich electrodes of various thickness

Hydrogen electrosorption into Pd-rich (≥80% Pd) Pd-Rh alloy layers of various thickness has been studied in acidic solutions (0.5 M H₂SO₄) using cyclic voltammetry and chronoamperometry. Pd-Rh electrodes were prepared as limited volume electrodes (LVEs) by electrochemical deposition. The influence of electrode potential and alloy thickness on the amount of electrosorbed hydrogen was investigated. For the thickness range examined (0.11-1.55 μm) no distinct effect on alloy absorption properties was found. The influence of scan rate on hydrogen oxidation charge was also studied. The results obtained suggest that the layer of subsurface hydrogen in Pd-Rh alloys is much less developed than in pure Pd and direct hydrogen absorption/desorption path is more probable.     

Two new siloxanic proton-conducting membranes: Part I. Synthesis and structural characterization

The development of stable polymer electrolytes having good proton conductivity, low cost and operating at medium temperatures represent a crucial step in the evolution of polymer electrolyte fuel cells. We describe two new siloxanic proton-conducting membranes that were synthesized through a two-stage protocol. In the first stage, a poly(methyl hydrosiloxane) precursor (P) bearing siloxane side chains with sulfonic acid groups was prepared. In the second step, the hydrolysis of pristine precursor or its derivative obtained by grafting siloxane chains on P yielded two types of membranes with the formulas {Si(CH₃)₃O[Si(CH₃)HO]_21.26[Si(CH₃)((CH₂)₃SO₃H)O]_1.8[Si(CH₃)((CH₂)₃Si(CH₃)₂O)O]₁₄Si(CH₃)₃}_n (A) and {Si(CH₃)₃O[Si(CH₃)HO]_21.26[Si(CH₃)((CH₂)₃SO₃H)O]_1.8[Si(CH₃)((CH₂)₃(Si(CH₃)₂O)_w)O]_v[Si(CH₃)((CH₂)₃Si(CH₃)₂O-)O]_14 − vSi(CH₃)₃}_n (B), with w = 20.31. Polymer membranes of A and B were prepared by means of a hot-pressing process at 80 °C and 10 t/cm². Scanning electron microscopy showed that A and B are rubbery materials with rough and transparent surfaces. Thermogravimetric investigations performed under air atmosphere disclosed that A and B are thermally stable up to at least 198 °C. DSC measurements yielded T_g(s) of −44 and −60 °C for A and B, respectively. The polymers exhibit ionic exchange capacities of 0.33 (A) and 0.15 meq/g (B). FT-IR and FT-Raman investigations revealed that the polymers consist of reticulated siloxane networks with pendant silicone chains having sulfonic acid groups.     

CFD modelling of the fast pyrolysis of biomass in fluidised bed reactors. Part B: Heat, momentum and mass transport in bubbling fluidised beds

The fluid-particle interaction inside a 150 g/h fluidised bed reactor is modelled. The biomass particle is injected into the fluidised bed and the heat, momentum and mass transport from the fluidising gas and fluidised sand is modelled. The Eulerian approach is used to model the bubbling behaviour of the sand, which is treated as a continuum. Heat transfer from the bubbling bed to the discrete biomass particle, as well as biomass reaction kinetics are modelled according to the literature. The particle motion inside the reactor is computed using drag laws, dependent on the local volume fraction of each phase. FLUENT 6.2 has been used as the modelling framework of the simulations with the whole pyrolysis model incorporated in the form of user-defined function (UDF). The study completes the fast pyrolysis modelling in bubbling fluidised bed reactors.     

Silicone-containing polymer matrices as protective coatings: Properties and applications

The paper addresses the technologically important problem of porous building materials protection, e.g. sandstone, limestone, marble against soiling. Protective coatings applied to the surface of porous building material should be characterized by very efficient water vapour permeability and self-cleaning properties.     

Modelling of a gas flow measurement: Application to nuclear containment vessels

The objective of this work is to simulate the gas flow across a concrete wall of a nuclear power plant internal enclosure. In the laboratory, permeability measurements are generally made on cylindrical samples (15 cm diameter×5 cm height: ∅ 15×5 cm) with a steady-state experiment. To be able to predict structural behaviour, we studied size effect and steady-state time with a modified CEMBUREAU permeability test. A statistical approach showed that there is no size effect on concrete permeability. Laboratory results found on cylindrical samples can be applied to tests in situ, where concrete specimens are thicker. A model based on the mass balance relation provided times to reach steady state and reproduced experimental flow kinetics for uniform water content across specimens.     

Two new siloxanic proton conducting membranes: Part II. Proton conductivity mechanism and NMR study

The synthesis and structural characterization of two types of membranes with formulas {Si(CH₃)₃O[Si(CH₃)HO]_21.26-[Si(CH₃)((CH₂)₃SO₃H)O]_1.8-[Si(CH₃)((CH₂)₃Si(CH₃)₂O-)-O]₁₄-Si(CH₃)₃}_n (A) and {Si(CH₃)₃O[Si(CH₃)HO]_21.26-[Si(CH₃)((CH₂)₃SO₃H)O]_1.8-[Si(CH₃)((CH₂)₃(Si(CH₃)₂O-w₎)-Ov_][Si(CH₃)((CH₂)₃Si(CH₃)₂O-)-O_]14−vSi(CH₃)₃}_n (B), (w=20.31), were previously proposed.The ac electrical response of A and B was fully characterized in the 40 Hz-2 MHz frequency region by studying the impedance spectra in the medium and low frequency regions by equivalent circuits and complex dielectric spectra at high frequency in terms of dielectric relaxation modes. Results demonstrated that A and B conduct ionically by means of a proton exchange event which occurs via a vehicular mechanism between neighboring water clusters formed by water molecules aggregated around each sulfonic acid group of the siloxane side chains. The proton conductivities at 115 °C of ca. 1.9 × 10⁻³ and 1.8 × 10⁻⁴ S cm⁻¹ of fully hydrated membranes A and B, respectively, classify these silicone networks as good proton conductors.Membrane B was chosen for a closer investigation using NMR spectroscopy. Solid state ²⁹Si MAS NMR experiments gave further insight about the three-dimensional structure. Proton diffusion measurements provided some encouraging results about proton dynamics of this membrane signaling the great potential of siloxanic based proton conductors.     

Electrochemical study of polymethacrylonitrile electrolytes: Conductivity study of polymer/salt complexes and plasticized polymer electrolytes. Part I

In order to increase the stability in reduction with respect to polyacrylonitrile (PAN), polymethacrylonitrile (PMAN), is proposed as a matrix for plasticized polymer electrolytes, useable in lithium batteries. Highly concentrated complexes of lithium salt in PMAN homopolymer were prepared using lithium perchlorate, lithium triflate or lithium imide salts, ionic conductivities as well as spectroscopic data showing the solvating ability of PMAN. In order to prevent PMAN dissolution in usual liquid electrolytes, UV curing was carried out. Although, non-optimized, the resulting plasticized PMAN electrolytes exhibit appreciable conductivities.     

Pyrrole nanoscaled electropolymerization: Effect of the proton

Polypyrrole (Ppy) nanowires are electrochemically synthesized using the nanochannels of a proton-modified natural zeolite clinoptilolite (HNZ). The synthetic inorganic structures Y zeolite and clay montmorillonite (M) in acid form (HY and HM) are also employed for pyrrole polymerization. The generation of Ppy with electrochemical activity is favored in a strongly acidic nanoscaled environment, in comparison with the polymer synthesized in the hosts without previous proton modification. It is proposed that the reduction/oxidation responses are a consequence of the polymer protonation/deprotonation where the H⁺ ions possibly act as charge transfer promoters. The well defined redox signals of Ppy included in HNZ, compared to the HY and HM, suggest that the polymeric units are held more tightly to the channels walls due to its complex framework. The TEM image of HNZ-Ppy reveals the presence of the polymer nanowires inside the natural zeolite framework. It is also found that the one electron oxidation process do not depend on first order monomer concentration but lower (0.38) for Ppy growth in HNZ, which is related to the spatial restriction of the host.     

Water-entrained cement-based materials : II. Experimental observations

This paper concerns a new concept for the prevention of self-desiccation in hardening cement-based materials. The concept is based on using fine, superabsorbent polymer (hydrogel, SAP) particles as a concrete admixture. This permits a controlled formation of water-filled macropore inclusions—water entrainment—in the fresh concrete. Consequently, the pore structure is actively designed to control self-desiccation. In the paper, experimental observations in relation to this technique are described and discussed. The observations show that self-desiccation can be controlled by water entrainment. The paper forms the second part of a series. In the first part, the theoretical background was presented [Cem. Concr. Res. 31(4) (2001) 647].     

Cement composition and sulfate attack: Part I

Four cements were used to address the effect of tricalcium silicate content of cement on external sulfate attack in sodium sulfate solution. The selected cements had similar fineness and Bogue-calculated tricalcium aluminate content but variable tricalcium silicates. Durability was assessed using linear expansion and compressive strength. Phases associated with deterioration were examined using scanning electron microscopy and X-ray diffraction. Mineralogical phase content of the as-received cements was studied by X-ray diffraction using two methods: internal standard and Rietveld analysis.The results indicate that phase content of cements determined by X-ray mineralogical analysis correlates better with the mortar performance in sulfate environment than Bogue content. Additionally, it was found that in cements containing triclacium aluminate only in the cubic form, the observed deterioration is affected by tricalcium silicate content. Morphological similarities between hydration products of high tricalcium aluminate and high tricalcium silicate cements exposed to sodium sulfate environment were also observed.     

Electrochemical study of polymethacrylonitrile electrolytes: Comparative investigation of polynitriles electrochemical stability through model molecules. Part II

The replacement of polyacrylonitrile by polymethacrylonitrile is expected to provide an improvement of the electrochemical stability in reduction of the plasticized polymer electrolytes. In addition to the investigation on the polymer electrolyte, a comparative study of polymethacrylonitrile and polyacrylonitrile, performed through their respective model repeat unit, i.e. trimethylacetonitrile and isobutyronitrile confirms the stability improvement obtained by replacing polyacrylonitrile tertiary hydrogen by a methyl in polymethacrylonitrile.     

A novel scraped cooled wall crystallizer: Recovery of sodium carbonate and ice from an industrial aqueous solution by eutectic freeze crystallization

A novel scraped cooled wall crystallizer (SCWC-2) with 130 l capacity and total heat transfer area of 2.94 m² m⁻³ crystallizer volume was specifically designed for eutectic freeze crystallization (EFC). It has been successfully tested for the recovery of Na₂CO₃ from an industrial solution. Compared with earlier designs this new crystallizer shows a high improvement in gravitational separation and ice scaling removal. High heat transfer fluxes between the heat exchanger and the solution (up to 10.5 kW m⁻²) were obtained and as a consequence high production rates were achieved.     

Catalytic filamentous carbon: Structural and textural properties

Catalytic filamentous carbon (CFC) synthesized by the decomposition of methane over iron subgroup metal catalysts (Ni, Co, Fe or their alloys) is a new family of mesoporous carbon materials possessing the unique structural and textural properties. Microstructural properties of CFC (arrangement of the graphite planes in filaments) are shown to depend on the nature of catalyst for methane decomposition. These properties widely vary for different catalysts: the angle between graphite planes and the filament axis can be 0° (Fe-Co-Al₂O₃), 15° (Co-Al₂O₃), 45° (Ni-Al₂O₃), 90° (Ni-Cu-Al₂O₃). The textural properties of CFC depend both on the catalyst nature and the conditions of methane decomposition (T, °C). The micropore volume in CFC is very low, 0.001-0.022 cm³ g⁻¹ at the total pore volume of 0.26-0.59 cm³ g⁻¹. Nevertheless, the BET surface area may reach 318 m² g⁻¹. Results of the TEM (HRTEM), XRD, Raman spectroscopic, SEM and adsorption studies of the structural and textural properties of CFC are discussed.     

Electrodeposition of Ni-Co-Cu/Cu multilayers: 2. Calculations of the element distribution and experimental depth profile analysis

It has long been known that a concentration gradient can develop in electrodeposits along the growth direction as a result of the combined impact of anomalous codeposition and mass trasnport limitation of the reactants. It is shown in the present paper that this composition change in electrodeposited Co-Ni-Cu/Cu multilayers can be verified by secondary neutral mass spectrometry (SNMS). Various electrodeposited samples have been analyzed and the resulting composition profiles have been compared to the calculation based on the non-destructive analysis of the overall composition. The change of the Co:Ni ratio in the magnetic layer along the growth direction has been verified. A calculation method has been proposed by which the local composition of the magnetic layer can be estimated from the thickness dependence of the overall multilayer composition. It has also been shown that the deviation of the experimental depth profile data from the estimation based on the variation of the total composition with the Co-Ni-Cu layer thickness can be ascribed to the roughness increase during the sputtering in the SNMS instrument.     

Direct numerical simulation (DNS) modeling of PEFC electrodes: Part II. Random microstructure

The direct numerical simulation (DNS) method, developed for modeling the cathode catalyst layer (CL) of a polymer electrolyte fuel cell (PEFC) in Part I, is further extended wherein the catalyst layer is described as a random three-dimensional porous structure. A random CL microstructure is obtained using a computer-generated random number with specified porosity and pore size as the input structural parameters. Some statistical features of the CL and their dependence on the porosity are identified and demonstrated. The charge and species conservation equations are solved directly on this microscopically complex structure. The results from the DNS calculation are compared with the one-dimensional macrohomogeneous predictions and the Bruggeman factor for transport property correction is evaluated, which can be used as direct input into the macroscopic fuel cell models.     

Photocurrents and degradation rates on particulate TiO2 layers: Effect of layer thickness, concentration of oxidizable substance and illumination direction

Different routes for immobilization of TiO₂ on conducting substrates were compared to find active and stable photocatalysts, which could either be operated in open circuit (photocatalysis) or with applied electric potential (photoelectrocatalysis). The advantage of applying an electric potential was investigated. Polarization curves and photoelectrochemical degradation reactions served to characterize catalysts and to find a way of predicting the optimum synthesis conditions. The difference between front side (EE) and back side (SE) illumination is discussed as a function of layer thickness, as well as the influence of oxidizable substance concentration on photocurrents. Stability of catalysts was investigated in repetitive degradation experiments.