Thermoelectric characterization of NaxMx/2Ti1−x/2O2 (M=Co, Ni and Fe) polycrystalline materials

Layered -titanate materials, Na_xM_x/2Ti_1−x/2O₂ (M=Co, Ni and Fe, x=0.2–0.4), were synthesized by flux reactions, and electrical properties of polycrystalline products were measured at 300–800 °C. After sintering at 1250 °C in Ar, all products show n-type thermoelectric behavior. The values of both d.c. conductivity and Seebeck coefficient of polycrystalline Na_0.4Ni_0.2Ti_0.8O₂ were ca. 7×10³ S/m and ca. −193 μV/K around 700 °C, respectively. The measured thermal conductivity of layered -titanate materials has lower value than conductive oxide materials. It was ca. 1.5 Wm⁻¹ K⁻¹ at 800 °C. The estimated thermoelectric figure-of-merit, Z, of Na_0.4Ni_0.2Ti_0.8O₂ and Na_0.4Co_0.2Ti_0.8O₂ was about 1.9×10⁻⁴ and 1.2×10⁻⁴ K⁻¹ around 700 °C, respectively.     

Particle motion at the wall of a circulating fluidized bed

The motion of alumina particles of mean size 74.9 μm in the region near to the wall of the 305 mm diameter riser of a cold model circulating fluidized bed has been studied using a high-speed video camera employing normal and magnifying lenses. Particles in this region were found to move predominantly downwards, against the main gas flow. High density groups or swarms of particles typically arch-shaped were observed to descend in contact with the wall at velocities in the range 0.3–0.4 m s⁻¹. Tfie distribution of swarm descent velocities was shown to be little affected by changes in superficial gas velocity over the range 3–5 m s⁻¹ and imposed mean solids mass flux over the range 2 to 80 kg m⁻² s⁻¹. A region of steady bulk downflow of solids with a velocity of approximately 1.0 m s⁻¹ was observed to appear a few millimetres from the wall at mean suspension densities greater than 5.6 kg m⁻³. Motion of particles in contact with the riser was analysed by identification of three flow forms; dilute, dense and swarm flow. Results of the analysis are linked with the observations of other workers concerning the onset of the so-called ‘similar profiles’ regime. The relationship between the measured effective particle swarm length and the cross-sectional mean suspension density was established and the implications for modelling suspension-to-wall heat transfer discussed.     

Gel Casting of Alumina using Boehmite as a Binder

The process for alumina gel casting was developed using an inorganic binder The monohydroxy aluminium oxide (boehmite, AlOOH) was incorporated with ultrafine alumina of particles (0·5 μm) and the slurry rheology was studied and presented. The effect of boehmite in slurry viscosity was observed with respect to different amounts of boehmite and time. The alumina 54 vol% slurry with 10 wt% boehmite showed the viscosity of 880 mPa s at 93 s⁻¹. An external coagulating agent, HMTA, was incorporated with alumina–boehmite slurry and the effective change in slurry viscosity with respect to concentration and time was studied. The addition of HMTA results in faster gelation and the optimum concentration was determined as 0·21 mol L⁻¹. The alumina gelcast body was dried under humidity conditions at 40°C, RH 70%. The defect free dried green body was obtained and the total linear drying shrinkage was calculated as 3·2% and the green density observed was 59·3% of theoretical value. The sintered density of 98% (TD) was achieved at 1450°C in 2 h. The mechanical hardness of sintered alumina measured as 2286 kg mm⁻². The sintered ceramic showed an extremely fine grained microstructure with an average grain size <2 μm. The boehmite acts as an excellent binder and sintering aid for alumina ceramics.     

Improved sliding wear-resistance of alumina with sub-micron grain size: A comparison with coarser grained material

Un-lubricated sliding wear behaviour of sub-micron grained (average grain size, G = 0.45 μm), self-mated alumina was studied using conformal-contact with a unidirectional pin-on-disc wear testing machine. The wear characteristics of higher grained alumina samples (G = 0.95 and 4 μm) are also studied under self mating condition for comparative analysis by using similar test parameters and identical test configuration. Sub-micron grained alumina exhibits substantially higher wear resistance compared to the alumina of larger grain size. Scanning electron microscopy of the worn out test samples reveals that in un-lubricated condition, compaction of wear debris on sliding surface governs the wear characteristics of the present set of alumina. In many cases, partly revealed intergranular fracture was noticed. The strength of adhesion of the compacted wear debris with sliding surface increases with decreasing grain size. In case of alumina of larger grain size, the stability of the compacted layer decreases due to cracking. For sub-micron grained alumina, compacted layer of debris with increased adherence efficiently protects the virgin material resulting substantial decrease in wear loss.     

A new tantalum sulfur compound as electrode material for non-aqueous alkali metal batteries

Polycrystalline (PbS)_1.14(TaS₂)₂, a misfit layer sulfide, was used as cathodic material for lithium secondary battery. One molar LiClO₄ in propylene carbonate (PC) was used as electrolyte. The cell could be galvanostatic discharged down to x = 4.6 [Li_x(PbS)_1.14(TaS₂)₂] when the current density was 65 μA cm⁻² and the cell was cycled more than 100 times between 3.5 and 1.5 V at a current density of 260 μA cm⁻². Lattice expansion increased linearly with lithium content and was less than that reported for the Li/TaS₂ system. Chemical diffusion coefficients were determined by a modified version of the galvanostatic intermittent titration technique and they were fairly constant in the composition range 0.2 < x < 1, and an average value of 8.1 × 10⁻¹¹ cm² s⁻¹ was calculated. Sodium intercalation was also accomplished, but the uptake of this ion resulting in a significant lattice expansion compared with that observed for lithium ions. Moreover, a similar dependence of the sodium chemical diffusion coefficient on the composition was observed with an average value of 1.4 × 10⁻¹⁰ cm² s⁻¹, somewhat higher than that of lithium ion. We believe that differences in lattice expansion may be responsible for the differences found in the chemical diffusivity values.     

Variation of the aerosol charge neutralization coefficient in the entire particle size range

The rate at which the mean charge on aerosol particles relaxes to its steady-state value under bipolar charging is characterized by the neutralization rate constant, β (s⁻¹). It is an important parameter for fixing the nt product in charge neutralizers as well as in the theory of charging-induced diffusion. Here we compute the neutralization coefficient, β/n (where n is the mean ion density), as a function of particle size through the use of ion-particle combination coefficients provided by the recent theories. The results indicate that β/n decreases from a continuum limit value of 3.1 × 10⁻⁶ cm³ s⁻¹, to a free molecular limit value of 1.4 × 10⁻⁶ cm³ s⁻¹. The changeover occurs rapidly in the transitional regime (10–100 nm). This clearly indicates that the nt product required to attain steady state is higher for nano particles than for larger ones. The paper also presents the variations of the mean square variance of charge, the coefficients of charging-induced drift and diffusion, as a function of particle size.     

Effect of physical parameters on the microfiltration of wine on a flat polymeric membrane

This paper investigates the microfiltration of unfiltered red and white wines through organic polyvinylidene difluoride membranes in plate and frame systems. Various pore sizes between 0.1 and 3 μm were first tested using a small laboratory unit and it was found that 0.4 μm pores gave the best comprise between turbidity and flux requirements. Tests with membrane areas between 1 and 2 m² were carried out i a modular plate and frame system in which both gasket thickness and parallel vs. series arangements of compartments can be modified. With red wine the permeate flux is almost independent of fluid velocity but increases linearly with transmembrane pressure, reaching 50 1 h⁻¹ m⁻² at 3 bar. The permeate flux is larger in a turbulent regime than in a laminar one at the same velocity. With white wine, the permeate flux is higher and increases almost linearly with velocity reaching 170 1h⁻¹ m⁻² at 2 bar and 3.6 m s⁻¹. The turbidity of the permeate was generally below 0.5 NTU for both white and red wines while initial turbidity was above 150 NTU for red and above 50 NTU for white. When several membrane compartments are placed in series, the output of the downstream compartment is reduced by 10%–15% compared with that of the upstream one owing to the drop in transmembrane pressure.     

Solvation of ions—XX. The ferrocene—ferricinium couple and its role in the estimation of free energies of transfer of single ions

The ferrocene-ferricinium electrode (Pt/Foc, Fic⁺) was investigated in water, acetonitrile, ethanol, DMSO and DMF using single scan cyclic voltammetry and phase sensitive ac polarography. The oxidation-reduction is pseudo-reversible in all five solvents with an electrochemical rate constant of approximately 10⁻² cm/s. In all solvents a slow irreversible chemical step involving the ferricinium cation follows electron transfer, so that slow cyclic voltammetry or polarography rather than potentiometry is preferred if ferrocene is to be used as a reference electrode in non-aqueous solvents.

The Strehlow assumption, ΔG_tr(Foc) = ΔG_tr(Fic⁺ gives very different free energies of transfer of single ions from non-aqueous solvents to water when compared with the TATB assumption that ΔG_tr(Ph₄As⁺) = ΔG_tr(Ph₄B⁻). This discrepancy is likely to be because ferricinium is only a moderately large cation, so that ΔG_tr(Fic⁺) is less positive than ΔG_tr(Foc) for transfer to water. The discrepancy is not because of abnormal electrochemical behavior of the Pt/Foc, Fic⁺ electrode in water or other solvents. Values of E° vs nhe, H₂O in a variety of solvents based on the TATB assumption are presented.     

H4SiW12O40-catalyzed oxidation of nitrobenzene in supercritical water: kinetic and mechanistic aspects

The catalytic effect of a heteropolyacid, H₄SiW₁₂O_40, on nitrobenzene (20 and 30 μM) oxidation in supercritical water was investigated. A capillary flow-through reactor was operated at varying temperatures (T=400–500 °C; P=30.7 MPa) and H₄SiW₁₂O₄₀ concentrations (3.5–34.8 μM) in an attempt to establish global power-law rate expressions for homogenous H₄SiW₁₂O₄₀-catalyzed and uncatalyzed supercritical water oxidation. Oxidation pathways and reaction mechanisms were further examined via primary oxidation product identification and the addition of various hydroxyl radical scavengers (2-propanol, acetone, acetone-d₆, bromide and iodide) to the reaction medium. Under our experimental conditions, nitrobenzene degradation rates were significantly enhanced in the presence of H₄SiW₁₂O₄₀. The major differences in temperature dependence observed between catalyzed and uncatalyzed nitrobenzene oxidation kinetics strongly suggest that the reaction path of H₄SiW₁₂O₄₀-catalyzed supercritical water oxidation (average activation E_a=218 kJ/mol; k=0.015–0.806 s⁻¹ energy for T=440–500 °C; E_a=134 kJ/mol for the temperature range T=470–490 °C) apparently differs from that of uncatalyzed supercritical water oxidation (E_a=212 kJ/mol; k=0.37–6.6 μM s⁻¹). Similar primary oxidation products (i.e. phenol and 2-, 3-, and 4-nitrophenol) were identified for both treatment systems. H₄SiW₁₂O₄₀-catalyzed homogenous nitrobenzene oxidation kinetics was not sensitive to the presence of OH√ scavengers.     

Inlet characteristics of bioaerosol samplers

The inlet sampling characteristics of several commercial bioaerosol samplers operating in indoor and outdoor environments have been analyzed by use of available and newly developed equations for sampling efficiency. With a focus on the physical aspects of sampling efficiency, the aspiration and transmission efficiencies have been calculated for the bioaerosol particle size range 1–30 μm, which represents single bacteria, bacteria aggregates, bacteria carrying particles, fungal spores, yeast, and pollen. Under certain sampling conditions, the bioaerosol concentration was found to be significantly over- or underestimated. At wind velocities between 0 and 500 cm s⁻¹, calculations show that the AGI-30 would sample 1–10 μm particles with an inlet sampling efficiency of 20–100%. The entrance efficiency of the 6-stage Andersen viable sampler is 90–150% when sampling isoaxially with respect to horizontal aerosol flows, and 8–100% when oriented vertically at a right angle to the horizontal aerosol flow. For the Burkard portable air sampler, an even wider range of deviation may occur. The bioaerosol samplers used for large particles such as pollen are even less accurate: e.g. 10 times the ambient concentration of Lycopodium spores has been calculated to be aspirated by the Lanzoni sampler when operated at 0.5 1 min⁻¹ facing the wind at wind velocity of about 500 cm s⁻¹.

The actual bioaerosol concentration can be calculated from the measured data by use of the indicated procedures. The sampling efficiency graphs presented can be used to bracket the sampling conditions that enable the investigator to avoid or minimize significant sampling biases for each sampler. The findings can also be used for the design of new samplers or for improving commercially available samplers.     

Hydrodynamic studies of an advanced fluidized-bed bioreactor for direct interaction with coal

Fine coal particles fluidized by the upflow of a liquid medium containing a dissolved biocatalyst undergo size reduction as the reaction progresses. Three aspects of the design of such a reactor were examined:

1. (1)the use of force balances to describe pressure drop for the segregated bed;

2. (2) measurement of liquid-phase dispersion coefficients; and

3. (3) fluorescent tagging of particles to track size distribution.

Hydrodynamic data were obtained for a liquid-solid fluidized bed of coal particles in the size range 30–150 μm. Illinois No. 6 coal was ball-milled, sieved into four fractions, and suspended in a 0.1% aqueous solution of Tween 80. A sample with a bimodal particle size distribution centred on 49 and 63 μm was placed in a glass column and fluidization and pressure-drop data were compared with a new model developed to describe particle segregation. Measured liquid-phase dispersion coefficients varied from 0.034 to 0.283 cm² s⁻¹ as the flow varied from 0.005 to 0.0159 cm s⁻¹. A technique was also developed for coating coal particles with a fluorescent paint which may allow direct measurement of the change in the fraction of marked particles of known size along the axis of a fluidized bed.     

Dilute solution properties of carboxymethylchitins in high ionic-strength solvent

The hydrodynamic characteristics in aqueous solution at ionic strength I=0.2  of carboxymethylchitins of different degrees of chemical substitution have been determined. Experimental values varied over the following ranges: the translational diffusion coefficient (at 25.0°C), 1.1<10⁷×D<2.9 cm² s⁻¹; the sedimentation coefficient, 2.4<s<5.0 S; the Gralen coefficient (sedimentation concentration-dependence parameter), 130<k_s<680 mL g⁻¹; the intrinsic viscosity, 130<[η]<550 mL g⁻¹. Combination of s with D using the Svedberg equation yielded ‘sedimentation–diffusion' molecular weights in the range 40 000<M<240 000 g mol⁻¹. The corresponding Mark–Houwink–Kuhn–Sakurada (MHKS) relationships between the molecular weight and s, D and [η] were: [η]=5.58×10⁻³ M^0.94; D=1.87×10⁻⁴ M^−0.60; s=4.10×10⁻¹⁵ M^0.39. The equilibrium rigidity and hydrodynamic diameter of the carboxymethylchitin polymer chain is also investigated on the basis of wormlike coil theory without excluded volume effects. The significance of the Gralen k_s values for these substances is discussed.     

Selective permeation and separation of steam from water–methanol–hydrogen gas mixtures through mordenite membrane

Separation properties of a mordenite membrane for water–methanol–hydrogen mixtures were studied in the temperature range from 423 to 523 K under pressurized conditions. The mordenite membrane was prepared on the outer surface of a porous alumina tubular support by a secondary-growth method. It was found that water was selectively permeated through the membrane. The separation factor of water/hydrogen and water/methanol were 49–156 and 73–101, respectively. Even when only hydrogen was fed at 0.5 MPa, its permeance was as low as 10⁻⁹ mol m⁻² s⁻¹ Pa⁻¹ up to 493 K, possibly suggesting that water pre-adsorbed in the micropores of mordenite hindered the permeation of hydrogen. The hydrogen permeance dramatically increased to 6.5 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 503 K and reached to 1.4 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ at 523 K because of the formation of cracks in the membrane. However, the membrane was thermally stabilized in the presence of steam and/or methanol.     

Low-temperature H2 and N2 transport through thin Pd66Cu34Hx layers

The single gas H₂ and N₂ permeability of a 4 μm thick dense fcc-Pd₆₆Cu₃₄ layer has been studied between room temperature and 510 °C and at pressure differences up to 400 kPa. Above 50 °C the H₂ flux exhibits an Arrhenius-type temperature dependence with J_H2=(5.2±0.3) mol m⁻² s⁻¹ exp[(−21.3 ± 0.2) kJ mol⁻¹/(R·T)]. The hydrogen transport rate is controlled by the bulk diffusion although the pressure dependence of the H₂ flux deviates slightly from Sieverts’ law. A sudden increase of the H₂ flux below 50 °C is attributed to embrittlement.     

Chlorination kinetics of pyrite mineral in two Turkish lignites

The kinetics of the chlorination of pyrite in two Turkish lignites in water and water-carbon tetrachloride media at ambient pressure ( 610 mm Hg) are investigated. The effects of speed of stirring (5–20 s⁻¹), particle size (74–88, 150–180 and 250–425 μm), temperature (13–70°C) and reaction time (0–18 000 s) were studied. The experimental data were analyzed on the basis of the unreacted shrinking core model. The fine pyrite particles are assumed to be embedded inside the coal particles. The rate-controlling step was found to be diffusion of chlorine through the ash (the coal matrix). The activation energies were calculated as 25.1 kJ mol⁻¹ for Dada i coal in water medium and 25.0 kJ mol⁻¹ for Mengen coal in water-carbon tetrachloride medium.     

Mechanism of gas flow through coal

Coals are fossilized plant material plus inorganic silt deposited in irregular layers and containing 1–20% void space which provides a medium which is porous to gas flow. Gas flows have been measured using discs of coal cut from several coal seams. Observed flow phenomena include molecular diffusion (low gas pressure, small pores) and bulk diffusion (higher gas pressure, larger pores). In the examples investigated, methane flows ranged from 1.2 × 10⁻¹⁰ cm² s⁻¹ atm⁻¹ for Pittsburgh-seam attrital coal to 2.0 cm² s⁻¹ atm⁻¹ for Oklahoma Hartshorne coal. Flow characteristics have been compared with gas flows observed by Knudsen through glass capillaries. This information can be applied to mine safety and to coal utilization studies.     

Ionic conductivity of PEO9: Cu(CF3SO3)2: Al2O3 nano-composite solid polymer electrolyte

Cu⁺⁺ ion containing solid polymer electrolytes exhibit interesting electrochemical properties. In particular, the polymer electrolyte PEO₉:Cu(CF₃SO₃)₂ made by complexing copper triflate (CuTf₂) with PEO appears to show scientifically intriguing transport properties. Although some copper ion transport in these systems has been seen from plating stripping processes, the detailed mechanism of ionic transport and the species involved are yet to be established. In order to obtain enhanced ionic conductivities and also to contribute towards understanding the ionic transport process in Cu⁺⁺ ion containing, PEO based composite polymer electrolytes, we have studied the system PEO₉: CuTf₂: Al₂O₃ incorporating 10 wt.% of alumina filler particles of grain size 10 μm, 37 nm, 10–20 nm and also particles of pore size 5.8 nm. Thermal and electrical measurements show that the system remains amorphous down to room temperature. The composite electrolyte is predominantly an ionic conductor with electronic conductivity less than 2%. The triflate (CF₃SO₃⁻) anions appear to be the dominant carriers. The presence of alumina grains has enhanced the conductivity significantly from room temperature up to 100 °C. The nano-porous grains with 5.8 nm pore size and 150 m²/g specific surface area exhibited the maximum conductivity enhancement. This enhancement has been attributed to Lewis acid–base type surface interactions of ionic species with O²⁻ and OH⁻ groups on the filler grain surface.     

Wet Erosive Wear of Alumina Densified with Magnesium Silicate Additions

A study was made of the wet erosive wear of polycrystalline alumina of mean grain size >1 μm, containing up to 10 wt% of magnesium silicate sintering aid. For pure polycrystalline alumina, the dominant wear mechanism was grain-boundary microfracture, leading to partial or complete grain removal. In the case of the liquid-phase-sintered materials, wear rates could be as low as 25% of those of pure alumina of the same mean grain size, and the main material removal mechanism was transgranular fracture combined with tribochemical wear. The use of Cr³⁺ photoluminescence line broadening showed much higher levels of local stress in the magnesium silicate-sintered materials (∼450 MPa) than in the pure-alumina materials (∼200 MPa). Grain-boundary compressive hoop stresses, caused by the thermal expansion mismatch between a continuous magnesium silicate film and the alumina grains, provided an explanation for the improved wear resistance of the alumina sintered with magnesium silicate.     

Grain growth in TiO2-added ZnO–Bi2O3–CoO–MnO ceramics prepared by chemical processing

The effect of TiO₂ on the grain growth of the ZnO–Bi₂O₃–CoO–MnO ceramic system prepared by chemical coprecipitation, was studied between 1150 and 1300 °C in air. Bi₂O₃ melts during firing, and then TiO₂ dissolves into Bi₂O₃-rich liquid. TiO₂ initially reacts with Bi₂O₃ to form Bi₄Ti₃O₁₂. Above ≈1050 °C, Bi₄Ti₃O₁₂ reacts with ZnO to form Zn₂TiO₄ spinel phase. The kinetic study of grain growth carried out using the expression Gⁿ–G_oⁿ=K_o·t·exp(−Q/RT) gave grain exponent (n) value as 6 and the apparent activation energy (Q) as 226.46 kJ/mol. 1.00 mol% TiO₂ addition increased the grain growth exponent value from 6 to 7 and apparent activation energy with 1.00 mol% TiO₂ addition was found to be 197.10 kJ/mol. The ZnO grain size gradually increases with increasing TiO₂ content. Addition of TiO₂ may increase the reactivity of the Bi₂O₃-rich liquid towards the ZnO grain, thus affecting the ZnO grain growth.     

A comparison of the attachment of the decay products of radon-220 and radon-222 to monodispersed aerosols

The adsorption of radioactive aerosols is of prime importance when assessing the hazard of inhalation of radioactive materials, especially in the uranium mining industry. In previous studies of the attachment rate, contradicting results on the dependence on particle size have been found. The attachment rate for the attachment of the decay products of Rn-222 to monodispersed polystyrene aerosols (of a diameter from 1.2 to 5.3 μm) in the concentration range 1–67 particles cm⁻³ was measured directly. This is compared with the attachment rate of radon-220 decay products which was measured in a previous experiment. As before, the attachment between the radioactive atoms and the aerosols was found to be directly proportional to the particle concentration N, as well as to the square of the particle radius R.

The attachment coefficient of 4.1 × 10⁵ R² cm³ min⁻¹ and the sticking probability of 0.13 for Rn-222 decay products were found to be larger than that for the decay products of Rn-220 (2.4 × 10⁵ R² cm³ min⁻¹ and 0.08, respectively). The mechanism for the attachment, however, is the same.