101 resultados para Sólido

em Universidade Federal do Rio Grande do Norte(UFRN)


Relevância:

20.00% 20.00%

Publicador:

Resumo:

Given the environmental concern over global warming that occurs mainly by emission of CO2 from the combustion of petroleum, coal and natural gas research focused on alternative and clean energy generation has been intensified. Among these, the highlight the solid oxide fuel cell intermediate temperature (IT-SOFC). For application as electrolyte of the devices doped based CeO2 with rare earth ions (TR+ 3) have been quite promising because they have good ionic conductivity and operate at relatively low temperatures (500-800 ° C). In this work, studied the Ce1-xEuxO2-δ (x = 0,1, 0,2 and 0,3), solid solutions synthesized by the polymeric precursor method to be used as solid electrolyte. It was also studied the processing steps of these powders (milling, compaction and two step sintering) in order to obtain dense sintered pellets with reduced grain size and homogeneous microstructure. For this, the powders were characterized by thermal analysis, X-ray diffraction, particle size distribution and scanning electrons microscopy, since the sintered samples were characterized by dilatometry, scanning electrons microscopy, density and grain size measurements. By x-ray diffraction, it was verified the formation of the solid solution for all compositions. Crystallites in the nanometric scale were found for both sintering routes but the two step sintering presented significant reduction in the average grain size

Relevância:

20.00% 20.00%

Publicador:

Resumo:

The research and development of nanostructured materials have been growing significantly in the last years. These materials have properties that were significantly modified as compared to conventional materials due to the extremely small dimensions of the crystallites. The tantalum carbide (TaC) is an extremely hard material that has high hardness, high melting point, high chemical stability, good resistance to chemical attack and thermal shock and excellent resistance to oxidation and corrosion. The Compounds of Tantalum impregnated with copper also have excellent dielectric and magnetic properties. Therefore, this study aimed to obtain TaC and mixed tantalum oxide and nanostructured copper from the precursor of tris (oxalate) hydrate ammonium oxitantalato, through gas-solid reaction and solid-solid respectively at low temperature (1000 ° C) and short reaction time. The materials obtained were characterized by X-ray diffraction (XRD), Rietveld refinement, Scanning Electron Microscopy (SEM), Spectroscopy X-Ray Fluorescence (XRF), infrared spectroscopy (IR), thermogravimetric (TG), thermal analysis (DTA) and BET. Through the XRD analyses and the Reitiveld refinement of the TaC with S = 1.1584, we observed the formation of pure tantalum carbide and cubic structure with average crystallite size on the order of 12.5 nanometers. From the synthesis made of mixed oxide of tantalum and copper were formed two distinct phases: CuTa10O26 and Ta2O5, although the latter has been formed in lesser amounts

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Alternative and clean energy generation research has been intensified in last decades. Among the alternatives, fuel cells are one of the most important. There are different types of fuel cells, among which stands out intermediate temperature solid oxide fuel cell (IT-SOFC) matter of the present work. For application as cathode on this type of devices, the ceramic Ba0.5Sr0.5C0.8Fe0.2O3-δ doped with rare earth ions (Nd, Sm) have been quite promising because they show good ionic conductivity and operate at relatively low temperatures (500 - 800°C). In this work, Ba0.5Sr0.5Co0.8Fe0.2O3-δ, (BaSr)0.5Sm0.5Co0.8Fe0.2O3-δ and (BaSr)0.5Nd0.5C0.8Fe0.2O3-δ were obtained by modified Pechini method, making use of gelatin as polymerizing agent. The powders were characterized by X-Ray Diffraction (XRD), Temperature Programmed Reduction (TPR) and Scanning Electron Microscopy (SEM). The perovskite phase was observed in all X-ray patterns for the materials Ba0.5Sr0.5C0.8Fe0.2O3-δ doped with rare earth ions (Nd, Sm). The SEM images showed that the materials have a characteristics porous, with very uniform pore distribution, which are favorable for application as cathodes. Subsequently, screen-printed assymmetrical cells were studied by impedance spectroscopy, to assess the kinetics of the cathode for the reduction reaction of oxygen. The best resistance to the specific area was found for the cathode BSSCF sintered at 1050 °C for 4 hours with around 0.15 Ω.cm2 at 750 °C as well as cathodes BSNCF and BSCF obtained resistances specific area of 0.2 and 0.73 Ω.cm2, respectively, for the same conditions. The polarization curves showed similar behavior to the best cathodes BSSCF and BSNCF, such combination of properties indicates that the film potentially depict good performance as IT-SOFC cathodes

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Fuel cells are electrochemical devices that convert chemical energy in electrical energy by a reaction directly. The solid oxide fuel cell (SOFC) works in temperature between 900ºC up to 1000ºC, Nowadays the most material for ceramic electrolytes is yttria stabilized zirconium. However, the high operation temperature can produce problems as instability and incompatibility of materials, thermal degradation and high cost of the surround materials. These problems can be reduced with the development of intermediate temperature solid oxide fuel cell (IT-SOFC) that works at temperature range of 600ºC to 800ºC. Ceria doped gadolinium is one of the most promising materials for electrolytes IT-SOFC due high ionic conductivity and good compatibility with electrodes. The inhibition of grain growth has been investigated during the sintering to improve properties of electrolytes. Two-step sintering (TSS) is an interesting technical to inhibit this grain growth and consist at submit the sample at two stages of temperature. The first one stage aims to achieve the critical density in the initiating the sintering process, then the sample is submitted at the second stage where the temperature sufficient to continue the sintering without accelerate grain growth until to reach total densification. The goal of this work is to produce electrolytes of ceria doped gadolinium by two-step sintering. In this context were produced samples from micrometric and nanometric powders by two routes of two-step sintering. The samples were obtained with elevate relative density, higher than 90% using low energy that some works at the same area. The average grain size are at the range 0,37 μm up to 0,51 μm. The overall ionic conductivity is 1,8x10-2 S.cm and the activation energy is 0,76 eV. Results shown that is possible to obtain ceria-doped gadolinium samples by two-step sintering technique using modified routes with characteristics and properties necessary to apply as electrolytes of solid oxide fuel cell

Relevância:

20.00% 20.00%

Publicador:

Resumo:

The refractory metal carbides have proven important in the development of engineering materials due to their properties such as high hardness, high melting point, high thermal conductivity and high chemical stability. The niobium carbide presents these characteristics. The compounds of niobium impregnated with copper also have excellent dielectric and magnetic properties, and furthermore, the Cu doping increases the catalytic activity in the oxidation processes of hydrogen. This study aimed to the synthesis of nanostructured materials CuNbC and niobium and copper oxide from precursor tris(oxalate) oxiniobate ammonium hydrate through gas-solid and solid-solid reaction, respectively. Both reactions were carried out at low temperature (1000°C) and short reaction time (2 hours). The niobium carbide was produced with 5 % and 11% of copper, and the niobium oxide with 5% of copper. The materials were characterized by X-Ray Diffraction (XRD), Rietveld refinement, Scanning Electron Microscopy (SEM), X-Ray Fluorescence Spectroscopy (XRF), infrared spectroscopy (IR), thermogravimetric (TG) and differential thermal analysis (DTA , BET and particle size Laser. From the XRD analysis and Rietveld refinement of CuNbC with S = 1.23, we observed the formation of niobium carbide and metallic copper with cubic structure. For the synthesis of mixed oxide made of niobium and copper, the formation of two distinct phases was observed: CuNb2O6 and Nb2O5, although the latter was present in small amounts

Relevância:

20.00% 20.00%

Publicador:

Resumo:

The thermoelectric energy conversion can be performed directly on generators without moving parts, using the principle of SEEBECK effect, obtained in junctions of drivers' thermocouples and most recently in semiconductor junctions type p-n which have increased efficiency of conversion. When termogenerators are exposed to the temperature difference (thermal gradient) eletromotriz a force is generated inducing the appearance of an electric current in the circuit. Thus, it is possible to convert the heat of combustion of a gas through a burner in power, being a thermoelectric generator. The development of infrared burners, using porous ceramic plate, is possible to improve the efficiency of heating, and reduce harmful emissions such as CO, CO2, NOx, etc.. In recent years the meliorate of thermoelectric modules semiconductor (TEG's) has stimulated the development of devices generating and recovery of thermal irreversibility of thermal machines and processes, improving energy efficiency and exergy these systems, especially processes that enable the cogeneration of energy. This work is based on the construction and evaluation of a prototype in a pilot scale, for energy generation to specific applications. The unit uses a fuel gas (LPG) as a primary energy source. The prototype consists of a porous plate burner infrared, an adapter to the module generator, a set of semiconductor modules purchased from Hi-Z Inc. and a heat exchanger to be used as cold source. The prototype was mounted on a test bench, using a system of acquisition of temperature, a system of application of load and instrumentation to assess its functioning and performance. The prototype had an efficiency of chemical conversion of 0.31% for electrical and heat recovery for cogeneration of about 33.2%, resulting in an overall efficiency of 33.51%. The efficiency of energy exergy next shows that the use of primary energy to useful fuel was satisfactory, although the proposed mechanism has also has a low performance due to underuse of the area heated by the small number of modules, as well as a thermal gradient below the ideal informed by the manufacturer, and other factors. The test methodology adopted proved to be suitable for evaluating the prototype

Relevância:

20.00% 20.00%

Publicador:

Resumo:

This thesis aimed to assess the increase in solubility of simvastatin (SINV) with solid dispersions using techniques such as kneading (MA), co-solvent evaporation (ES), melting carrier (FC) and spray dryer (SD). Soluplus (SOL), PEG 6000 (PEG), PVP K-30 (PVP) e sodium lauryl sulphate (LSS) were used as carriers. The solid dispersions containing PEG [PEG-2(SD)], Soluplus [SOL-2(MA)] and sodium lauryl sulphate [LSS-2(ES)] were presented with a greater increase in solubility (5.02, 5.60 and 5.43 times respectively); analyses by ANOVA between the three groups did not present significant difference (p<0.05). In the phase solubility study, the calculation of the Gibbs free energy (ΔG) revealed that the spontaneity of solubilisation of SINV occurred in the order SOL>PEG >PVP 75%>LSS, always 80%. The phase diagrams of PEG and LSS presented solubilization stoichiometry of type 1:1 (type AL). The diagrams with PVP and SOL tend to 1:2 stoichiometry (type AL + AP). The stability coefficients (Ks) of the phase diagrams revealed that the most stable reactions occurred with LSS and PVP. The solid dispersions were characterized by Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), particle size distribution (PSD), near-infrared spectroscopy imaging (NIR-CI) and X-ray diffraction of the powder using the Topas software (PDRX-TOPAS). The solid dispersion PEG-2(SD) presented the greatest homogeneity and the lowest degree of crystallinity (18.2%). The accelerated stability study revealed that the solid dispersions are less stable than SINV, with PEG-2(SD) being the least stable, confirmed by FTIR and DSC. The analyses by PDRX-TOPAS revealed the amorphous character of the dispersions and the mechanism of increasing solubility

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Solid substrate cultivation (SSC) has become an efficient alternative towards rational use of agro industrial wastes and production of value-added products, mainly in developing countries. This work presents the production and functional application results of phenolic extracts obtained by solid substrate cultivation of pineapple (Ananas comosus L.) and guava (Psidium guajava L.) residues associated to soy flour and bioprocessed by Rhizopus oligosporus fungus. Two experimental groups were tested: (1) 9g of fruit residue and 1g of soy flour (A9 or G9); (2) 5g of fruit residue and 5g of soy flour (A5 or G5). After SSC, 100ml of distilled water was added to each Erlenmeyer flask containing 10g of bioprocessed material in order to obtain the phenolic extracts. Samples were taken every two days for total phenolic concentration (TPC) and antioxidant capacity evaluation by DPPH test during 12-day cultivation. The 2-day and 10-d ay extracts were selected and concentrated by ebullition until 1/10 of original volume was reached. After that, both non-concentrated and concentrated extracts were evaluated for their antimicrobial activity against Staphylococcus aureus and Salmonella enterica and a-amylase inhibitory capacity. It was observed an inverse relationship between total phenolic concentration (TPC) and antioxidant capacity during the cultivation. Besides that, the concentrated pineapple samples after two days were able to inhibit both pathogens tested, especially S. aureus. Guava concentrated extracts after 2 days showed expressive inhibition against S. enterica, but negative results against S. aureus growth. When it comes to a-amylase inhibition, A9 extracts after 2 days, both concentrated or not, completely inhibited enzyme activity. Similar behavior was observed for G9 samples, but only for concentrated samples. It was shown that concentration by ebullition positively affected the enzymatic inhibition of G9 and A9 samples, but on the other side, decreased antiamylase activity of A5 and G5 samples

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Pectinolytic enzymes, or simply pectinases, are complex enzymes that degrade pectic polymers. They have many uses, such as fruit juice extraction and purification, textile fiber treatment and vegetal oil extraction. The aim of this work was to study the kinetics of pectinases production by solid-state fermentation, using dry cashew apple residue as substrate and the microorganism Aspergillus niger CCT 0916. The influence of the initial medium moisture and medium supplementation with a source of nitrogen and phosphorus was evaluated using the factorial experimental planning and response surface methodology. Ammonia sulphate and potassium phosphate were used as nitrogen and phosphorus source, respectively. The variables time of contact (T) and ratio volume solvent/fermented medium (RZ), in systems with and without agitation, were evaluated in order to study the best extraction condition of the produced enzyme. Washed and unwashed cashew apple residues were tested as the growth medium. The unwashed residue was obtained by drying the residue after the extraction of the juice, while the washed residue was obtained by water washing 5 times using the proportion of 1 kg pulp/2 liters of water. Samples were taken every 12 hours for moisture content, pH, protein, reducing sugars, polygalacturonase activity (PG) and viscosity reduction. The physical-chemical composition of the residues had different sugar and pectin levels. For the unwashed residue, the peak activity was reached with 40% of initial moisture content, 1% of nitrogen supplementation without phosphorus addition after 30 hours of process. These conditions led to 16 U/g of PG activity and 82% of viscosity reduction. The calculated models reached similar values to the experimental ones in the same process conditions: 15.55 U/g of PG and 79.57% of viscosity eduction. Similarly, the greatest enzyme production for washed residue was reached with 40% initial moisture content, 1% nitrogen supplementation without phosphorus addition after 22 hours of cultivation. In this condition it was obtained polygalacturonase activity of 9.84 U/g and viscosity reduction of 81.36%. These values are close to experimental values that were of 10.1 U/g and 81%, respectively. The conditions that led to the best PG activity results was the agitated one and the best extraction condition was obtained with 100 minutes of solvent/medium contact and RZ of 5 (mL/g)

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Ameloblastoma and adenomatoid odontogenic tumor are odontogenic tumors arising from the odontogenic epithelium with distinct clinical behavior. In attempt to comprehend the interaction between the odontogenic tumor cells and the extracellular matrix, the present work evaluated and compared the immunohistochemical expression of the matrix metalloproteinases-1 (MMP-1), -2 (MMP-2) and -9 (MMP-9) in 20 cases of ameloblastoma and 10 adenomatoid odontogenic tumor. MMP-1 exhibited exuberant expression in the parenchyma and in the stroma of both studied tumors, while the MMP-2 showed varied expression with about of 80% and 60% of the neoplastic cells exhibiting positivity in the ameloblastoma and adenomatoid odontogenic tumor, respectively. With relation to the MMP-2 expression by the mesenchymal cells, it was observed that 65% of the ameloblastoma and 80% of the adenomatoid odontogenic tumor were positive. The immunoreactivity of MMP-9 was detected in all studied cases, although its expression had occurred predominantely in less than 50% of the parenchyma cells of the ameloblastoma, while in about of 60% of the adenomatoid odontogenic tumor more than 50% of cells were positive. The mesenchymal cells were positive to MMP-9 in 65% of the ameloblastoma and in 80% of the adenomatoid odontogenic tumor, respectively. Statistically significant difference was observed to the MMP-1 expression with relation to MMP-2 and MMP-9 in the ameloblastoma (p < 0.001). It was not possible to perform statistical analysis to the cases of adenomatoid odontogenic tumor, however there was a tendency toward a differential expression of the MMP-1 with relation to other studied MMPs. These results suggest that MMP-1, - 2 and -9 are implicated in the growth and progression of both tumors analyzed as well as the more pronounced participation of the stroma in the ameloblastoma could together to be related to the higher clinical aggressiveness

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Biodiesel production has increased over the last decade because of the benefits associated with this fuel, including renewability, domestic feedstock, lower toxicity, and biodegradability. From 2008, the use of beef tallow as a feedstock for biodiesel production in Brazil has increased in significance, representing the second largest source of biodiesel, after soybeans. However, the performance of biodiesel in cold weather conditions is worse than diesel because of deposition of insoluble at low temperatures, accelerating the plugging of fuel filters and injectors of the vehicle engine. Studies have been conducted on beef tallow biodiesel, mostly related to the properties of thermal and oxidative stability. However, few studies have described the nature of the precipitate formed and its influence on product quality. Research suggests that the cause of deposition is related to the nature of saturated esters and monoacylglycerols as inducing agents. This study monitored the levels of mono-, diand triacylglycerols, the oxidation stability and the cold filter plugging point (CFPP) in beef tallow biodiesel samples from two commercial producers in Brazil for a period of twelve months. Filtered precipitates were analyzed by comparative techniques of GCFID, HPLC-UV/VIS, HPLC-MS-IT-TOF and TG to verify the nature, using monopalmitin and monostearin as reference standards. The formation of precipitate reduced the levels of monoacylglycerols in the beef tallow biodiesel. GC-FID and LCMS- IT-TOF results confirmed the nature of the deposit as saturated monoacylglycerols, predominantly monostearin and monopalmitin as the second major component. Moreover the TG analysis of the residue indicated similar thermal decomposition of the reference standards. The precipitate did not affect the oxidation stability of beef tallow biodiesel and the CFPP characteristic of blends up B60. However, the presence of iron reduced significantly the oxidation stability of biodiesel

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Biodiesel production has increased over the last decade because of the benefits associated with this fuel, including renewability, domestic feedstock, lower toxicity, and biodegradability. From 2008, the use of beef tallow as a feedstock for biodiesel production in Brazil has increased in significance, representing the second largest source of biodiesel, after soybeans. However, the performance of biodiesel in cold weather conditions is worse than diesel because of deposition of insoluble at low temperatures, accelerating the plugging of fuel filters and injectors of the vehicle engine. Studies have been conducted on beef tallow biodiesel, mostly related to the properties of thermal and oxidative stability. However, few studies have described the nature of the precipitate formed and its influence on product quality. Research suggests that the cause of deposition is related to the nature of saturated esters and monoacylglycerols as inducing agents. This study monitored the levels of mono-, diand triacylglycerols, the oxidation stability and the cold filter plugging point (CFPP) in beef tallow biodiesel samples from two commercial producers in Brazil for a period of twelve months. Filtered precipitates were analyzed by comparative techniques of GCFID, HPLC-UV/VIS, HPLC-MS-IT-TOF and TG to verify the nature, using monopalmitin and monostearin as reference standards. The formation of precipitate reduced the levels of monoacylglycerols in the beef tallow biodiesel. GC-FID and LCMS- IT-TOF results confirmed the nature of the deposit as saturated monoacylglycerols, predominantly monostearin and monopalmitin as the second major component. Moreover the TG analysis of the residue indicated similar thermal decomposition of the reference standards. The precipitate did not affect the oxidation stability of beef tallow biodiesel and the CFPP characteristic of blends up B60. However, the presence of iron reduced significantly the oxidation stability of biodiesel

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Sulfur compounds emissions have been, on the late years, subject to more severe environmental laws due to its impact on the environment (causing the acid rain phenomena) and on human health. It has also been object of much attention from the refiners worldwide due to its relationship with equipment’s life, which is decreased by corrosion, and also with products’ quality, as the later may have its color, smell and stability altered by the presence of such compounds. Sulfur removal can be carried out by hydrotreating (HDT) which is a catalytic process. Catalysts for HDS are traditionally based on Co(Ni)-Mo(W)/Al2O3. However, in face of the increased contaminants’ content on crude oil, and stricter legislation on emissions, the development of new, more active and efficient catalysts is pressing. Carbides of refractory material have been identified as potential materials for this use. The addition of a second metal to carbides may enhance catalytic activities by increasing the density of active sites. In the present thesis Mo2C with Co addition was produced in a fixed bed reactor via gas-solid reaction of CH4 (5%) and H2(95%) with a precursor made of a mix of ammonium heptamolybdate [(NH4)6[Mo7O24].4H2O] and cobalt nitrate[Co(NO3)2.6H2O] at stoichiometric amounts. Precursors’ where analyzed by XRF, XRD, SEM and TG/DTA. Carboreduction reactions were carried out at 700 and 750°C with two cobalt compositions (2,5 and 5%). Reaction’s products were characterized by XRF, XRD, SEM, TOC, BET and laser granulometry. It was possible to obtain Mo2C with 2,5 and 5% cobalt addition as a single phase at 750°C with nanoscale crystallite sizes. At 700°C, however, both MoO2 and Mo2C phases were found by XRD. No Co containing phases were found by XRD. XRF, however, confirmed the intended Co content added. SEM images confirmed XRD data. The increase on Co content promoted a more severe agglomeration of the produced powder. The same effect was noted when the reaction temperature was increased. The powder synthesized at 750°C with 2,5% Co addition TOC analysis indicated the complete conversion from oxide material to carbide, with a 8,9% free carbon production. The powder produced at this temperature with 5% Co addition was only partially converted (86%)

Relevância:

20.00% 20.00%

Publicador:

Resumo:

The PSFC (Pr0.5Sr0.5Fe1-xCuxO3-δ) is a new mixed oxide perovskite and has been studied and evaluated the cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs), mainly due to its good compatibility with the electrolyte (CGO) and its high ionic conductivity and electronic in intermediate temperature. In this work, PSFC powders with two different compositions (Pr0,5Sr0,5Fe0,8Cu0,2O3- PSFC5582 and Pr0,5Sr0,5Fe0,6Cu0,4O3-PSFC5564) were synthesized by the citrate method using a new route. The powders obtained were characterized by thermal analysis (Differential Scanning Calorimetry and Thermogravimetry), and the material calcined at 800, 900 and 1000 °C for 5h were analyzed by X-ray diffractometry (XRD), with the Rietveld refinement of the diffraction data and dilatometry. PSFC5582 composite films were obtained by screen printing of powder calcined at 1000 °C. The films were deposited on substrate ceria doped with gadolinia (CGO) and then sintered at 1050 °C for 2h. The electrochemical performance of the electrodes was evaluated by impedance spectroscopy and the interface electrode/electrolyte was observed by scanning electron microscopy (SEM). The specific resistance area (ASR) was 0.44 Ω.cm² at 800 °C, slightly lower than those reported in the literature for cathodes containing cobalt. The thermal expansion coefficients of both the PSFC compositions were obtained and varied between 13 and 15 x 10-6 °C-1 , in a temperature range of 200 to 650 °C, demonstrating the good thermal compatibility of cathodes with Ce0,9Gd0,1O1,95 electrolytes (CET = 12 x 10-6 °C).

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Given the environmental concern over global warming that occurs mainly by emission of CO2 from the combustion of petroleum, coal and natural gas research focused on alternative and clean energy generation has been intensified. Among these, the highlight the solid oxide fuel cell intermediate temperature (IT-SOFC). For application as electrolyte of the devices doped based CeO2 with rare earth ions (TR+ 3) have been quite promising because they have good ionic conductivity and operate at relatively low temperatures (500-800 ° C). In this work, studied the Ce1-xEuxO2-δ (x = 0,1, 0,2 and 0,3), solid solutions synthesized by the polymeric precursor method to be used as solid electrolyte. It was also studied the processing steps of these powders (milling, compaction and two step sintering) in order to obtain dense sintered pellets with reduced grain size and homogeneous microstructure. For this, the powders were characterized by thermal analysis, X-ray diffraction, particle size distribution and scanning electrons microscopy, since the sintered samples were characterized by dilatometry, scanning electrons microscopy, density and grain size measurements. By x-ray diffraction, it was verified the formation of the solid solution for all compositions. Crystallites in the nanometric scale were found for both sintering routes but the two step sintering presented significant reduction in the average grain size