Papers by Author: Fernando A. Costa Oliveira

Abstract: The present paper focus on preliminary work carried out at INETI concerning the use of microwave radiation applied to sintering of both ceramic and metal powders. Due to the characteristics of materials-radiation interaction, microwaves can become an interesting power source in powder technology and other processing routes, since it is possible to lower the sintering temperature and shorten the sintering cycles, leading to time and energy savings. Alumina, hydroxyapatite, titanium and stainless steel powder compacts were sintered in a modified commercial oven of 2.45GHz and 1000W nominal power. Microwave susceptors were used to enable temperature rise during the initial stage of the sintering cycles. Results on densification and microstructural evaluation of microwave sintered samples are reported and compared to conventionally sintered ones, when available. For similar porosity levels upon sintering, microwave radiation generally reduces sintering times from several hours to minutes. The results obtained so far are quite encouraging since in the case of alumina and stainless steel compacts, a decrease of about 200°C in the sintering temperature was achieved. It was also found that the green density plays a key role in the densification of both metallic and ceramic powders.

Abstract: The use of ultra-bright, highly directional, high and variable energy associated to synchrotron radiation beams at SPring-8 when compared with conventional X-Ray diffraction analysis applied to slate powders heat treated at temperatures in the range of 600°C up to 1000°C is reported. Fe K-edge XAFS measurements of the products formed upon heating slate showed that in the temperature range 600-800°C, conversion of FeO present in the as-received slate powder into a mixed -Fe2O3/-Fe2O3 has occurred providing useful information on the short-range order atomic structure of the slate. Above 800°C, mainly -Fe2O3 was identified to be present in the slate. The change of the Fe valences within the slate network is most likely responsible for the detected colour change with the increasing temperature.

Abstract: Reticulated cordierite foams produced by a direct foaming method were successfully washcoated with platinum-based zeolite catalysts. For comparison purposes, commercial cordierite monoliths were also washcoated. The effect of the structural properties on the fluid dynamics and catalytic behaviour for the toluene combustion were evaluated. Foam supports revealed highest performances, in terms of conversion into CO2, when compared to conventional honeycomb monoliths. The experimental results suggest that the catalytic behaviour is critically dependent on the fluid dynamics provided by structural characteristics of the supports, such as porosity, density and size of pores. The randomness and tortuosity of foams enhance reactant mixing, as it was evidenced by the higher axial and radial dispersions of the gas flow across the foam structure. This leads to better mass and heat transfers in the reaction system, thus improving the catalytic behaviour.

Abstract: Synthesis of single-phase tungsten sub-carbide W2C was attempted by heating pellets made out of a source of carbon (graphite-G) and W powders with G/W atom ratio between 0.35 and 0.50 to two target temperatures, namely 1600°C and 1900°C in an argon atmosphere using a solar furnace at PROMES-CNRS in Odeillo (France). The results showed that synthesis of single-phase W2C phase was difficult at either target temperature yielding the W2C co-existed with free metallic W. It was noted that the thin top surface layer of the solar-synthesised tungsten carbide pellets heated to 1900°C was distinguishable from the rest of the bulk specimen showing localised growth of nano-meter scale WC whiskers over W2C grains. Detailed XRD (X-ray diffraction) results on the effect of both G/W ratio and temperature on W2C lattice parameters are discussed.

Abstract: The reactors used for Selective Catalytic Reduction (SCR) of NOx require low pressure drop structured catalyst packing. Structured packings, such as ceramic foams, are gaining increasing interest for application in low pressure drop reactors, membrane reactors and catalytic distillation units. In this work, cobalt ion exchanged mordenite (Co-HMOR)-coated cordierite-based foams produced by the replication method were evaluated for catalytic reduction of NOx with methane. The addition of 0.3 wt.% Pd to 2 wt.% Co-HMOR leads to a material that can convert 50 % NOx to N2 at 450 °C in a reaction mixture containing 2000 ppm CH4, 1000 ppm NOx, 5 % O2 and balance helium, at GHSV=17000 h-1. Although in an early stage of development, an efficient coating procedure was explored and different ways of exchange of Co and Pd cations into mordenite (Si/Al=10) were studied. Additions of 2 wt.% fumed silica enhanced adhesion of the zeolite onto the ceramic foam. Pd-exchanged Co-HMOR showed to be very sensitive to steam. A 50 % decrease in NOx conversion to N2 was observed after Pd/Co-HMOR samples were exposed at 450 °C to a reaction mixture containing 2 vol% H2O. Although further research is needed to ascertain the mechanism of this deactivation behaviour, agglomeration of Pd forming PdO particles is envisaged.

Abstract: The structure and morphological aspects of highly porous (higher than 90%) cordierite (Mg2Al4Si5O18) foams, prepared by a direct foaming method, have been evaluated by Scanning Electron Microscopy analysis. The resulting ceramic foams consisted of a three-dimensional array of struts forming a well-defined open-cell structure. This type of structure seems very attractive for catalyst support purposes. Attempts have been made in order to control the pore structure since it directly affects the physical properties, namely the mechanical strength. In this respect, the use of a dip coating method to improve the strength of the resulting foams was found to be effective in reducing defects (e.g. pores, flaws) in the struts. Based on image analysis, estimated mean cell sizes were about 550 µm whereas strut thicknesses varied in the range of 60-70 µm. The compressive strength of the developed foams increased by one order of magnitude (0.1 to 1 MPa) by increasing the relative density from 0.06 to 0.18.

Abstract: The damage imposed on open-cell mullite ceramic foams was evaluated in pre-mixed radiant gas burners. After exposure to the prevailing combustion environment, foams suffered moderate strength degradation as a result of thermal stresses being imposed on the material during service. There was evidence of chemical attack during combustion although thermal shock measurements suggest that damage sustained by the foams results mainly from thermal shock rather than chemical degradation. Indeed, samples from burners subjected to ageing tests did not show additional damage compared to those subjected to short ageing tests indicating that most of damage occurred during start-up. For comparison purposes, a set of ceramic foam samples were subjected to a water quench test so that the extent to which the foams were damage by exposure to the combustion environment, under well controlled conditions, could be established. The strength retained after thermal shock by open-cell mullite foams decreased gradually with increasing quench temperatures. This suggests a cumulative damage mechanism reflecting an increase in damage throughout the material rather than sudden failure owing to propagation of pre-existing cracks along a plane. Damage in mullite foams was mainly localised at the top layer of the burners where higher temperatures and steeper thermal gradients were imposed on the material. Surprisingly, needle-like mullite crystals with a large aspect ratio were also found to have grown at the surface of the burners via a vapour feed gas-liquid catalyst-solid needle-like growth (VLS) mechanism.

Abstract: This study focus on the synthesis of Ca-deficient apatites (CDA) by using the wet chemical precipitation method in demineralised water solutions at pH=7 and synthesis temperature of 90 °C. Upon calcination at 1000°C, the resulting HAP powders decomposed leading to the formation of small amounts of β-TCP. Surprisingly, under some conditions, minor amounts of α- TCP were also formed at 1000°C together with β-TCP. The appearance of α-TCP is favoured by the absence of mineral ions in the precipitation medium, which in turn depends on the purity of the water used. Factors affecting the formation of both β-TCP and α-TCP are discussed.

Abstract: When preparing β-tricalcium phosphate (β-TCP), it is difficult to industrialise traditional methods because of the problem of particle aggregation. In this paper, β-TCP was prepared by calcining calcium-deficient hydroxyapatite (CDHA) powders obtained by the wet precipitation method at pH=6 and 40 °C, together with additions of poly (ethylene glycol) (PEG), in order to prevent powder agglomeration. The effect of the Ca/PEG mass ratio on the particle size distribution and the morphology of the resulting powders was evaluated. For comparison purposes, one powder without PEG addition was also synthesized. All synthesized powders were characterized by means of X-ray diffraction analysis, particle size analysis and scanning electron microscopy prior and after calcination in static air at 1000 °C for 15 h. Single-phase β-TCP powders have been obtained by calcining CDHA powders in the temperature range of 850°C-1150°C. It was also found that increasing the PEG content in solution decreased the particle size distribution of the agglomerated particles and the β→α-TCP transition temperature. A plausible explanation consistent with these experimental findings is proposed.

Abstract: Hydroxyapatite (HA) is widely used as a bone repair material. The use of microwave radiation as energy source for powders densification opens new opportunities for sintering HA at lower temperatures than by conventional sintering (electric furnace). The aim of this work was to compare the densification behaviour of a commercial hydroxyapatite powder under microwave and conventional heating conditions through evaluation of the elastic properties of the resulting sintered materials. The effect of green density, sintering temperature and dwell time on the Young’s modulus E (measured by the impulse excitation of vibration method) of microwave sintered HA was evaluated by using the Taguchi method. Under the set of controlled parameters investigated, green density was the most significant factor affecting E. It was verified that the highest E values obtained with each sintering process are similar (104 and 105 GPa for microwave and conventional sintering, respectively). These values were obtained at 1250°C for 2 h in conventional sintering and at 1200°C for 10 min with microwave sintering. This illustrates the advantage of microwave processing on energy and time savings over conventional sintering.