Observation and modelling of capillary flow occlusion resulting from the capture of superparamagnetic nanoparticles in a magnetic field

The magnetic field mediated capture of 10 nm diameter superparamagnetic nanoparticles, in the form of agglomerates of mean diameter 330 and 580 nm, from microcapillary flows has been observed and modelled. The steady state thickness of the captured layer in microcapillaries of diameter 400- could be predicted for both the 330 and the 580 nm diameter agglomerates at flow rates of between 0.1 and . The model provides insight into blockage formation at a constant flow rate as a precursor to the prediction of thrombotic embolism in magnetic directed therapies. Capillary constriction was particularly acute for the 580 nm agglomerates in large microcapillaries with flow rates of . From this model, agglomerates of diameter 330 nm or less offer the potential for minimal microcapillary occlusion in a range of flow rates.     

Sonocrystallisation of sodium chloride particles for inhalation

Fine sodium chloride particles are of pharmaceutical interest in aerosol delivery for diagnosis of asthma and bronchial related disorders. In this paper, stable NaCl particles with size ranging from approximately to sub-micron range were achieved by sonocrystallisation. The effects of sonocrystallisation temperature, ultrasonic power output and salt concentration were investigated in the ranges of , 22-60 W and 8-34 g/100 g water, respectively, under a fixed ultrasonic frequency of 20 kHz. Size and morphology characterisation of particles were undertaken using laser diffraction and scanning electron microscopy. Optimally prepared particles were spray dried followed by in vitro impaction test for inhalation efficiency determination using an Aeroliser^®. Optimal conditions of temperature ), ultrasonic power output and salt concentration water) exist that reduced the size of the crystals to the sub-micron scale. Spray drying increased the size of the prepared particles and altered the cubic shape to more rounded morphology. The fine particle fraction (based on recovery) was improved from approximately 12 to 34% when dispersion air flow rate was increased from 60 to 120 L/min. Sonocrystallisation represents an effective method for the preparation of NaCl particles suitable for pharmaceutical inhalation. The main advantage of this method is that it is rapid, simple and produces small crystal NaCl particles suitable for inhalation.     

The effect of magnetic fields on the electrodeposition of cobalt

The effect of a magnetic field on the electrodeposition of Co has been investigated with respect to the strength and the orientation of the magnetic field (B). Two different effects of the magnetic field B on the electrodeposition of cobalt have been observed. The first is the magnetohydrodynamic (MHD) effect caused by the Lorentz force (). The second is an effect due to the paramagnetic force (), caused by the concentration gradient () and therefore the gradient of the molar susceptibility (). The limiting current density and the deposition rate of Co increases if the B-field is oriented parallel to the electrode surface. This is mainly due to the expected convection induced by . Both, the Co deposition and the reduction of hydrogen ions, are affected by this. At high cathodic potentials the contribution of the hydrogen reduction to the process changed, which led to homogeneous deposits. A decreasing deposition rate was measured for B-fields oriented parallel or antiparallel to the flow of ions. These results are attributed to the effect of on the electrochemical processes close to the surface.     

Development and performance test of a thermo-denuder for separation of volatile matter from submicron aerosol particles

In this study we designed and evaluated a home-made thermo-denuder (TD) both experimentally and numerically. Sodium chloride (NaCl) particles, toluene gas, and carbon black particles were used for the performance evaluation of the TD. The TD was evaluated for various set-point air temperatures and particle sizes using the following three parameters: the temperature profile, penetration efficiency, and gas adsorption efficiency. At , the temperature was nearly uniform, remaining within of the set-point temperature, in the heating section and decreased to the temperature of ambient air in the cooling section. The particle penetration efficiencies were 93–96% at and 58–67% at for particle sizes of 20–60 nm. The gas adsorption efficiency was nearly unity until the breakthrough time of 65 h, and the total amount of toluene adsorbed by activated carbon particles was 72 mg-toluene/g-activated carbon particles. From size distribution measurements of dry carbon black and toluene enriched carbon black particles, the mode diameter measured at the set-point temperature of was found to be 48.6 nm, which agreed with the one obtained from the dry particle measurements. The overall number concentration obtained after particle losses were compensated was lower than that measured without using the TD by 35.6%, which was caused by gas adsorption in the TD.     

Influence of carbon dioxide partial pressure and fluidization velocity on activated carbons prepared from scrap car tyre in a fluidized bed

The effect of carbon dioxide partial pressure and fluidization velocity on activated carbons produced by carbon dioxide activation of scrap car tyre rubber in a fluidized bed has been studied. The method consisted of carbonization at under nitrogen followed by activation at . Three types of activated carbons were produced using activated gas concentrations of 20, 60 and 100% carbon dioxide by volume, the rest nitrogen, at a constant fluidization velocity (0.0393 m/s) to investigate the influence of carbon dioxide partial pressure. Within the experimental setup and activation time of 4 h, it was observed that BET surface area and total pore volume increased with carbon dioxide partial pressure reaching and , respectively, for 100% activation with carbon dioxide. Three other types of activated carbons were produced using 100% carbon dioxide at two (0.0393 m/s), three (0.0589 m/s) and four (0.0786 m/s) times the minimum fluidization velocity (U_mf). The BET surface area and total pore volume were observed to increase with fluidization velocity (which can be viewed as an indicator of the intensity of mixing in the bed), reaching and , respectively, at four times the minimum fluidization velocity.     

Study of limestone particle impact attrition

Impact attrition of limestone particles was investigated at temperatures from 25 to and 1 atm pressure. Impacts changed the particle size distribution and mean particle diameter significantly for conveying gas velocities of 20-100 m/s. With increasing temperature less attrition occurred due to a decrease in particle impact velocity and an increase in the threshold particle impact velocity. The activation energy for impact attrition was . The mean limestone particle diameter decreased with increasing number of impacts and increasing impact velocity. Two empirical equations give good agreement with the experiments. Based on the experimental observations and correlations, an impact mechanism is suggested, where the area of new surface generated is proportional to the total kinetic energy consumed, to the number of impact cycles and an exponential decrease with temperature. When particles break, each particle generally splits into 2-3 daughter particles. The threshold particle velocities for breaking limestone particles were found to be at , similar to the reported literature values.     

Oxidation of FGD-CaSO3 and effect on soil chemical properties when applied to the soil surface

Use of high-sulfur coal for power generation in the United States requires the removal of sulfur dioxide (SO₂) produced during burning in order to meet clean air regulations. If SO₂ is removed from the flue gas using a wet scrubber without forced air oxidation, much of the S product created will be sulfite (). Plants take up S in the form of sulfate (). Sulfite may cause damage to plant roots, especially in acid soils. For agricultural uses, it is thought that in flue gas desulfurization (FGD) products must first oxidize to in soils before crops are planted. However, there is little information about the oxidation of in FGD product to under field conditions. An FGD-CaSO₃ was applied at rates of 0, 1.12, and 3.36 Mg ha⁻¹ to the surface of an agricultural soil (Wooster silt loam, Oxyaquic Fragiudalf). The in the surface soil (0-10 cm) was analyzed on days 3, 7, 17, 45, and 61. The distribution of and Ca in the 0-90 cm soil layer was also determined on day 61. Results indicated that in the FGD-CaSO₃ rapidly oxidized to on the field surface during the first week and much of the and Ca moved downward into the 0-50 cm soil layer during the experimental period of two months. It is safe to grow plants in soil treated with FGD-CaSO₃ if the application is made at least three days to several weeks before planting.     

Flow behavior and regime transition in a high-density circulating fluidized bed riser

Flow behavior and flow regime transitions were determined in a circulating fluidized bed riser (0.203 m i.d. × 5.9 m high) of FCC particles (, ). A momentum probe was used to measure radial profiles of solids momentum flux at several heights and to distinguish between local net upward and downward flow. In the experimental range covered (; ), the fast fluidization flow regime was observed to coexist with dense suspension upflow (DSU). At a constant gas velocity, net downflow of solids near the wall disappeared towards the bottom of the riser with increasing solids mass flux, with dense suspension upflow achieved where there was no refluxing of solids near the riser wall on a time-average basis. The transition to DSU conditions could be distinguished by means of variations of net solids flow direction at the wall, annulus thickness approaching zero and flattening of the solids holdup versus G_s trend. A new flow regime map is proposed distinguishing the fast fluidization, DSU and dilute pneumatic transport flow regimes.     

Anomalous IR optical properties of aggregates of Pd nanoparticles induced through electrochemical cyclic voltammetry

IR optical properties of Pd nanoparticles with different size and aggregation state were studied in the current paper. The dispersed Pd nanoparticles () stabilized with poly(N-vinylpyrrolidone) (PVP) were synthesized by the seeding growth method, in which the seeds were formed step by step through reducing H₂PdCl₄ with ethanol. The dispersed Pd nanoparticles of much large size () were grown from the by keeping the colloid of undisturbed for 150 days at room temperature around 20 °C. The aggregates of () were prepared through an agglomeration process induced during a potential cyclic scanning between −0.25 V and 1.25 V for 20 min at a scan rate of 50 mV s⁻¹. Scanning electron microscope (SEM) patterns confirmed such aggregation of . Fourier transform infrared (FTIR) spectroscopy together with CO adsorption as probe reaction was employed in studies of IR optical properties of the prepared Pd nanoparticles. The results demonstrated that CO adsorbed on films substrated on CaF₂ IR window or glassy carbon (GC) electrode yielded two strong IR absorption bands around 1970 cm⁻¹ and 1910 cm⁻¹, which were assigned to IR absorption of CO bonded on asymmetric and symmetric bridge sites, respectively. Similar IR bands were observed in spectra of CO adsorbed on films, except the IR bands were much weak, whereas CO adsorbed on film produced an IR absorption band near 1906 cm⁻¹, and an anomalous IR absorption band whose direction has been completely inverted around 1956 cm⁻¹. The direction inversion of the IR band of CO bonded to asymmetric bridge sites on was ascribed to the interaction between Pd nanoparticles inside the aggregates. Based on FTIR spectroscopic and cyclic voltammetric results, the aggregation mechanism of Pd nanoparticles from to has been suggested that the agglomeration of Pd nanoparticles was driven by the alteration of electric field across electrode-electrolyte interface, when the PVP stabilizer was stripped via oxidation during cyclic voltammetry.     

Estimate of solid flow rate from pressure measurement in circulating fluidized bed

A method is described to estimate solid mass flow rate based on measurement of pressure drop in horizontal section of circulating fluid bed (CFB). A theoretical model was derived based on momentum balance equation and used to predict the solids flow rate. Several approaches for formulating such models are compared and contrasted. A correlation was developed that predicts the solids flow rate as a function of pressure drop measured in the horizontal section of piping leading from the top of the riser to the cyclone, often referred to as the cross-over. Model validation data was taken from literature data and from steady state, cold flow, CFB tests results of five granular materials with various sizes and densities in which the riser was operated in core-annular and dilute flow regimes. Experimental data were taken from a 0.20 m ID cross-over piping and compared to literature data generated in a 0.10 m ID cross-over pipe. The solids mass flow rate data were taken from statistically designed experiments over a wide range of Froude number , load ratio , Euler number , density ratio , Reynolds number , and Archimedes number . Several correlations were developed and tested to predict the solids mass flux based on measuring pressure drop in the horizontal section of CFB. It was found that load ratio is a linear function of the Euler number and that each of these expressions all worked quite well (R² > 95%) for the data within the range of conditions from which the coefficients were estimated.     

Structure and thermal expansion of natural gas clathrate hydrates

We report on the structural properties of natural gas hydrate crystals from the Sea of Okhotsk. Using powder X-ray diffraction (PXRD), it was determined that sediments from four locations contained type I gas hydrate, which encage mostly methane (96-98%) and a small amount of carbon dioxide. For all hydrates, the lattice constant was estimated to be at 113 K, which approximately equals that of pure methane hydrate. The result is in good agreement with the structure of artificially synthesized methane + carbon dioxide mixed-gas hydrates. These results suggest that the lattice constant of the natural gas hydrate does not change due to a change of CO₂ gas content. In addition, the thermal expansion of the sampled hydrate was measured for the temperature range of 83-173 K, and the resulting density of the hydrate crystal at 273 K was estimated to be . These results are essential for applying natural gas hydrates as an alternative natural fuel resources.     

Kinetics and equilibrium of dissolved oxygen adsorption on activated carbon

The macroscopic adsorption behavior of dissolved oxygen on a coconut shell-derived granular activated carbon has been studied in batch mode at 301 and 313 K for initial dissolved oxygen concentrations of 10-30 mg/l and oxygen/carbon ratios of 2-180 mg/g. BET (Brunauer, Emmett, and Teller) surface area, micropore volume, and pore size distribution were determined from N₂ isotherm data for fresh and used samples of carbon. The surface groups were characterized using Boehm titrations, potentiometric titrations, and FTIR study. The material is characterized by its high specific surface area , microporocity (micropore volume ), its basic character ( total basic groups) and its high iron content (15,480 ppm Fe). BET n-layer isotherm describes adsorption equilibrium suggesting cooperative adsorption and important adsorbate-adsorbate interactions. Kinetic data suggest a process dependent on surface coverage. At low coverage a Fickian, intraparticle diffusion rate model assuming a local equilibrium isotherm (oxygen dissociation reaction) adequately describes the process. The calculated diffusion coefficients (D) vary between and for initial oxygen concentration of 10 and 20 mg/l, respectively. Sensitivity analysis shows that the oxygen dissociation equilibrium constant determines the equilibrium concentration, whereas the diffusion coefficient controls the kinetic rate of the adsorption process having no effect at the final equilibrium concentration. A combined kinetic mass transfer model with concentration-dependent diffusion (parabolic form) has been developed and successfully applied on the dissolved oxygen adsorption system at high surface coverage. For equilibrium uptake of the estimated mean mass transfer coefficient and adsorption rate constant are and , respectively.     

Laser desorption-ionization time of flight mass spectrometry of various carbon materials

The possibilities of commercially available MALDI-TOF mass spectrometric instrumentation equipped with 337 nm nitrogen laser in carbon materials analysis have been examined. Laser desorption-ionization of synthetic diamond, graphite, glassy carbon, carbon nano-tubes, and diamond-like thin layer results in the formation of two positively charged ( and odd-numbered 44-346) and one negatively charged carbon cluster set (). Fullerene C₆₀ was analyzed for comparison. From the clusters mass spectra, several similarities, concerning “magic number” ions with high signal intensities, can be observed. It is concluded that differing carbon materials are subjected by UV-laser pulses to similar physico-chemical changes. Heavy carbon clusters of low stability and characteristic loss of neutral C₃ particle in case of the smaller clusters during post-source decay (PSD) implies that the species observed do not possess stable fullerene structure, which might have been expected for C_n species with n ? 20.     

A comparative study of PtCo, PtCr, and PtCoCr catalysts for oxygen electro-reduction reaction

A comparative study of carbon supported Pt₃₀Co₇₀, Pt₃₀Cr₇₀, and Pt₃₀Co₃₀Cr₄₀ catalysts for oxygen electro-reduction reaction (ORR) activity was performed. In alloy catalysts synthesized via NaBH₄ reduction, more than a 3-fold improvement was observed in ORR specific activity compared with that of Pt/C catalyst, while mass activities did not show significant improvement. After annealing at 900 °C under reducing conditions, the ORR specific activities of the alloy catalysts increased to give a relative ORR catalytic activity ordering of PtCo/C-900 (2800 μA ) > PtCoCr/C-900 (1770 μA ) > PtCr/C-900 (871 μA ) > Pt/C-900 (393 μA ) > Pt/C (334 μA ). On the other hand, the ORR mass activity followed an order of PtCr/C-900 (140 mA ) > PtCoCr/C-900 (111 mA ) > PtCo/C-900 (84.1 mA ). Cyclic voltammetry results suggest that incorporation of Cr resulted in a large electrochemically active surface area producing higher mass activity in the PtCr/C-900 catalyst although it showed the lowest specific activity among the alloy catalysts. The intermediate EAS and ORR activity values of the PtCoCr/C-900 catalyst suggest that the characteristics of the PtCo/C-900 (low mass and high specific activities) and PtCr/C-900 (high mass and low specific activities) are combined by alloying of Pt with both Co and Cr.     

Solid circulation rate in a circulating fluidized bed in the presence of fine powders

Fine powders (Geldart's group C) are added to a circulating fluidized bed (CFB) of coarse particles (Geldart's group A) and the solid circulation rate (SCR) is investigated with addition of fine powders of different sizes and different fractions (different hold-ups) to the bed. Experiments were carried out in a CFB of 2 m in height and 0.052 m in diameter, using FCC catalyst particles of as the coarse particles and cohesive aluminum hydroxide powders of 0.5- as the fine powders. The effects of hold-up of fine powders in the bed, fine powders size, and superficial gas velocity on the SCR were investigated.The SCR strongly depended on the hold-up of fine powders of 0.5- in size and noticeably decreased with increasing the hold-up of fine powders under constant gas velocity. This dependency disappeared when the size of fine powders was larger than . Thus, depending on the size of fine powders added to the CFB, two distinct regions for the changes of SCR could be clearly identified.     

Hydrodynamic similarity in circulating fluidized bed risers

Hydrodynamic similarity in the fully developed zone of co-current upward gas-solid two-phase flow systems under different operating conditions was investigated by measuring the axial profiles of pressure gradient, radial profiles of solid concentration and particle velocity in two circulating fluidized bed (CFB) risers of 15.1 and 10.5 m high, with FCC and sand particles, respectively. The experimental data obtained from this work and in the literature show that when the scaling parameter, G_s/(ρ_pU_g), is modified as , a detailed hydrodynamic similitude of the gas-solid flow in the fully developed zone of the risers under different operating conditions can be achieved. Furthermore, the experimental results from different gas-solid flow systems also show that as long as remains constant, there is the same solid concentration in the fully developed zone of different CFB risers with different particles. With the same , the local solid concentrations, the descending particle velocities, the cluster frequencies and the solid concentrations inside clusters in the fully developed zone of the risers all display the same axial and radial distribution, respectively. In other words, the empirical similarity parameter, , appears to have incorporated the effects of operating parameters (G_s and U_g), so that, the gas-solid flow in the fully developed zone of CFB risers under those different operating conditions but having the same shows similar micro- and macro-hydrodynamic characteristics. The study shows that the empirical similarity parameter, , is also independent of the upward gas-solid flow systems.     

Quantifying desorption and rearrangement rates of carbon monoxide on a PEM fuel cell electrode

A simple procedure to quantify the rates of carbon monoxide (CO) desorption from, and simultaneous rearrangement on, supported platinum fuel cell electrode (Pt on Vulcan XC-72R) is reported. The surface coverage of CO on Pt electrode in equilibrium with bulk CO was measured from the anodic peaks in the CO stripping voltammogram. The decline in these surface coverages due to desorption and rearrangement, once CO was replaced by N₂ in the gas phase was recorded and used in conjunction with a kinetic model to quantify the respective rates. Two distinct CO oxidation peaks observed in the voltammogram due to the oxidation of two distinct ad-species, namely weakly and strongly adsorbed CO ( and ), were baseline corrected and deconvoluted using a bimodal Gaussian distribution. Saturation surface coverage of decreased with increasing temperature, while the opposite was true for . Rearrangement from to was faster than the desorption rate of either CO species. The desorption rate of was at least an order of magnitude lower than that of molecules at all temperatures studied. The activation energies for desorption of and were estimated to be 24.08 and 27.99 kJ/mol, respectively. The activation energy for rearrangement from to was 35.23 kJ/mol and that from to was 27.55 kJ/mol.