A dimensionless study of the evaporation and drying stages in spray pyrolysis

An original dimensionless study of the pure evaporation and precipitation stages of a spray pyrolysis process has been performed. An estimation of the evaporation time is proposed and the influence of the main processing parameters has been investigated. For operating conditions corresponding to industrial requirements, the main limiting step of the evaporation stage is thermal transfer from the column walls to the gas, not mass or thermal transfer at the droplet surface. Therefore, gas and liquid temperatures remain equal and constitutive equations can be greatly simplified. Moreover, in these conditions, neither solute concentration nor temperature gradients exist inside micronic droplets. Some data from the literature have been modelled and show the large range of validity of the equations and explanations proposed. Finally, with the assumptions made here, the dimensionless study of the precipitation stage shows that the presence of a crust can increase the drying time four-fold. However, a filled particle can still be formed

Experimental study on fluidization of micronic powders

The fluidization behavior of yttrium oxide (Y2O3) powders of high density and micronic diameter belonging to the group C of Geldart’s classification has been investigated. Large interparticle forces lead to bed cracking, slugging and channelling, and cause the powder not to fluidize consistently. Different fluidization technologies have been tested, such as mechanical agitated fluidization, vibrated fluidization and addition of easyto-fluidize large particles to fine particles. The quality of fluidization has been studied through pressure drop diagrams for decreasing gas velocities and for various fixed bed heights to column diameter ratios. In the case of stirred fluidization, several stirrer geometries have been tested (helix, turbine, etc.). However, the fluidization has not been satisfactory. By adding larger particles to fine powders, convenient fluidization conditions have been obtained. An inertia effect proportional to the initial bed weight seems to contribute to fluidization. Some evaluation of interparticle forces governing the tested mixture of fine/large particles has been performed by studying the influence of mass percentage of fine particles on the Hausner ratio and the angle of repose. Fluidization under vibration allows to partly overcome the adhesion forces between powders. The fluidization behavior has been improved for the highest vibration strengths

Multifluid eulerian modelling of a silicon fluidized bed chemical vapor deposition process : analysis of various kinetic models

Using the multifluid Eulerian code MFIX, the silicon Fluidized Bed Chemical Vapor Deposition process from silane (SiH4) has been modelled under transient conditions. In order to constitute an experimental database, a preliminary experimental study has been performed using a bed of Geldart’s group B particles. After a detailed analysis and comparison of the kinetic models available in the literature, four of them have been implemented in the MFIX code and two hydrodynamic models have been tested. 3-D simulations have shown that a strong interaction exists between the bed hydrodynamics, heat and reactive mass transfers and that Si deposition from silane mainly occurs in the dense zones of the bed whereas the unsaturated species silylene (SiH2) forms in bubbles and slugs and leads to Si deposition mainly at their periphery; its contribution to deposition can be locally as high as that of SiH4. The average contribution of SiH2 to deposition increases with the inlet concentration of silane and can reach 30%. The kinetic models derived from the law of Furusawa et al. and from the data compiled by Buss et al. and the hydrodynamic model based on the true granular energy equation and the Princeton solid phase stress model have revealed to be the most appropriate ones for the conditions tested

High temperature annealing of micrometric Zn2SiO4:Mn phosphor powders in fluidized bed

Micrometric Zn1.8Mn0.2SiO4 phosphor powders prepared by spray pyrolysis have been annealed between 900 and 1200°C under ambient air atmosphere to exalt their luminescence properties. Two original gas-solid fluidization processes have been tested in order to limit sintering phenomena, and the post-treated products have been compared with those annealed using a conventional process in crucible. The crystallinity, the size distribution, the outer morphology and the luminescence properties of powders before and after treatment have been analysed. Massive sintering phenomena occur in crucible from 1000°C, whereas the original granulometry and spherical morphology are preserved till 1100°C in fluidized bed. The luminescence efficiencies are comparable for the three processes and maximal after annealing at 1200°C. It has been established that residual ZnO and manganese ions at oxidation state higher than 2, still present after treatment at 1100°C, are detrimental to good luminescence efficiency. Both disappear from samples post-treated at 1200°C

Hydrodynamic study of fine metallic powders in an original spouted bed contactor in view of chemical vapor deposition treatments

An original gas–solid contactor was developed so as to treat by chemical vapor deposition, fine (mean diameter 23 μm) and dense (bulk density 7700 kg/m3) NiCoCrAlYTa powders with large size distribution. In order to avoid the presence of a distributor in the reactive zone, a spouted bed configuration was selected, consisting in a glass cylindrical column associated through a 60° cone to an inlet tube, connected at its bottom to a grid so as to support the powders at rest. A hydrodynamic study was conducted at ambient temperature and pressure, combining pressure drop measurements and visual observations as a function of gas velocity and of the ratio H/D of the height of the bed at rest over the bed diameter. Using conventional alumina particles belonging to Geldart's group B, it was shown that this equipment is able to ensure conventional spouted bed behavior, especially for H/D ratio equal to 1. From numerous experiments conducted with the fine metallic powders of interest, it was shown that (i) conventional pressure drop curves for spouted beds are obtained for H/D ratios between 1 and 1.8, (ii) due to the large grain size distribution of particles, minimum spouted bed velocities occur in a range rather than at precise values. Visual observations reveal the presence of the spout and fountain at the minimum spouted bed velocity and for H/D equal to 1

Modelling of an industrial moving belt chemical vapour deposition reactor forming SiO2 films

In order to improve the efficiency of an industrial atmospheric pressure chemical vapour deposition (APCVD) moving belt reactor depositing silicon dioxide SiO2 films from tetraethoxysilane Si(OC2H5)4 (TEOS) andozone O3, a 2D simulation model based on the computational fluid dynamics (CFD) software ESTET has been developed. On the basis of the global chemical scheme of Zhou et al. [1997. Fifth International Conference on Advanced Thermal Processing of Semiconductors, RTP’97, New Orleans, LA, USA, pp. 257–268], a new kinetic model has been developed to conveniently represent our own set of experimental data. In particular, a chemical limitation for TEOS has been introduced, conferring increased chemical validity to the model. Simulations have shown that for the nominal conditions, TEOS conversion into SiO2 layers was too low andthat an increase in ozone concentration or in the nitrogen flow rates through the injector did not offer any advantage. Conversely, a decrease in the curtain nitrogen flow rate or an increase in that of the shieldcan enhance the process productivity and TEOS conversion

Chemical Vapor Deposition of silicon nanodots on TiO2 submicronic powders in vibrated fluidized bed

Silicon nanodots have been deposited on TiO2 submicronic powders in a vibrated Fluidized Bed Chemical Vapor Deposition (FBCVD) reactor from silane SiH4. Deposition conditions involving very low deposition rates have been studied. After treatment, powders are under the form of micronic agglomerates. In the operating range tested, this agglomerates formation mainly depends on the fluidization conditions and not on the CVD parameters. The best results have been obtained for anatase TiO2 powders for which the conditions of fluidization have been the most optimized. For these anatase powders, agglomerates are porous. SEM and TEM imaging prove that silicon nanodots (8-10 nm in size) have been deposited on the surface of particles and that this deposition is uniform on the whole powders and conformal around each grain, even if not fully continuous. Raman spectroscopy shows that the TiO2 powders have been partially reduced into TiO2-x during deposition. The TiO2 stoichiometry can be recovered by annealing under air, and IR spectroscopy indicates that the deposited silicon nanodots have been at least partly oxidized into SiO2 after this annealing

Y2O3:Eu micronic particles synthesised by spray pyrolysis: Global modelling and optimisation of the evaporation stage

There are a number of some major advantages to be gained in processing micronic europium-doped yttrium oxide Y2O3 particles for phosphor applications using spray pyrolysis. In order to maximise production rates, it is tempting to use relatively dense sprays, but then coalescence occurs increasing final particle diameters, which must be prevented. Moreover, the influence of the operating conditions on the process behaviour is poorly understood. A complete one-dimensional model of the evaporation stage of micronic water/Y(NO3)3 droplets considering only the evaporation process and then both evaporation and gravity-induced coalescence phenomena has been established. Calculations of pure evaporation have shown that the amounts of evaporated water and droplet compositions depend only on the local temperature and not on the thermal history of the spray. Coupled calculations have shown that, in comparison with evaporation, coalescence plays a minor role on droplet diameter, but non-negligible as the increase of the final mean droplet diameter due to coalescence reaches up to 10% at low flow rates in the operating conditions tested. Injecting a preheated air flow directly into the nebuliser is a promising method to minimise coalescence effects: optimal operating conditions for which coalescence is completely insignificant were obtained by simulation

Crystallization of microscopic Y2O3 powders by different techniques of fluidization at high temperature

Ahigh temperature fluidized bed reactor (HTFBR)working at 900 to 1200 ◦Chas been developed to crystallize microscopic yttria (Y2O3) powders synthesized by spray pyrolysis. Such crystallization is classically performed in crucible or in moving belt furnaces. In order to demonstrate the advantages of the fluidized bed process over the conventional static mode treatments, a comparative study of the main characteristics of particles after heat treatment in a crucible and in the HTFBR has been performed. The high interparticle forces existing in such Geldart group C powders made it necessary to activate their fluidization. Following previous results, two activated fluidization processes were studied: addition of coarse powders to fine particles and vibrated fluidization. The hydrodynamic behavior of these fluidized beds was analyzed through pressure drop measurements. Convenient fluidization conditions were obtained for the two activated fluidization processes, leading to isothermal beds. The size distribution, the crystallinity and the outer morphology of particles before and after thermal treatments were analyzed and compared for the three processes tested. Some pre-sintering phenomena occurred at 1200 ◦C, which were clearly more intense in crucible than in activated fluidization. The crystallinity of the samples treated was equivalent for the three methods of thermal treatment. The interest of fluidization processes to post-treat microscopic particles is thus fully demonstrated

Principles and applications of CVD powder technology

Chemical vapor deposition (CVD) is an important technique for surface modification of powders through either grafting or deposition of films and coatings. The efficiency of this complex process primarily depends on appropriate contact between the reactive gas phase and the solid particles to be treated. Based on this requirement, the first part of this review focuses on the ways to ensure such contact and particularly on the formation of fluidized beds. Combination of constraints due to both fluidization and chemical vapor deposition leads to the definition of different types of reactors as an alternative to classical fluidized beds, such as spouted beds, circulating beds operating in turbulent and fast-transport regimes or vibro-fluidized beds. They operate under thermal but also plasma activation of the reactive gas and their design mainly depends on the type of powders to be treated. Modeling of both reactors and operating conditions is a valuable tool for understanding and optimizing these complex processes and materials. In the second part of the review, the state of the art on materials produced by fluidized bed chemical vapor deposition is presented. Beyond pioneering applications in the nuclear power industry, application domains, such as heterogeneous catalysis, microelectronics, photovoltaics and protection against wear, oxidation and heat are potentially concerned by processes involving chemical vapor deposition on powders. Moreover, simple and reduced cost FBCVD processes where the material to coat is immersed in the FB, allow the production of coatings for metals with different wear, oxidation and corrosion resistance. Finally, large-scale production of advanced nanomaterials is a promising area for the future extension and development of this technique