Applied Clay Science 27 (2004) 151 157 www.elsevier.

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Gas release during clay firing and evolution of ceramic properties

R. Toledo, D.R. dos Santos, R.T. Faria Jr., J.G. Carrio , L.T. Auler, H. Vargas*
Laborato rio de Cie ncias F sicas, Universidade Estadual do Norte Fluminense, 28013-600, Campos dos Goytacazes, RJ, Brazil Received 18 February 2003; received in revised form 14 January 2004; accepted 24 May 2004 Available online 13 August 2004

Abstract Gas release, crystalline structure and ceramic properties were analysed during firing of clay raw materials and extruded bricks. Carbon monoxide, carbon dioxide, nitrogen oxides, and methane emissions were measured during the firing cycle. Ammonia and sulphur dioxide were not observed within the detection limits. The evolution of crystalline phases, open porosity, volumetric shrinkage, rupture tension and apparent density were correlated to the amount of gases produced at different temperatures, ranging from 300 to 1200 8C. These results can be applied for optimising the production process. D 2004 Elsevier B.V. All rights reserved.
Keywords: Traditional ceramics; Firing; X-ray diffraction; Porosity; Gas emission

1. Introduction Industrial or manufacturing processes that use clay raw material have been implemented for a long time. Nevertheless, research work continues to a better understanding of the processes involved and tailoring the desired properties of the final product. In addition, society presently draws increasing attention to the environment, requiring the adjustment of industrial activities according to laws and norms that rule the sector. Clay deposit areas have a high economic potential, and soil mineralogical composition, plasticity and porosity are fundamental properties for industrial applications. The resulting ceramic products

* Corresponding author. Fax: +55 22 2726 1532. E-mail address: vargas@uenf.br (H. Vargas). 0169-1317/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.clay.2004.06.001

present a network of capillary pores that vary according to the firing cycle. In the last few years, porous ceramics have received increasing attention for their successful applications as bio-ceramics, catalyst supports, hot gas filters, sensors or membrane reactors. Important ceramic properties such as hardness, water absorption, gas permeability, shrinkage, density as well as the vitrification temperature range are intrinsically correlated to the porous system (Rice and Dekker, 1998). Clay firing generates gaseous compounds that are released into the atmosphere. The volatiles commonly evolved are water vapour H2O, oxygen O2, carbon monoxide CO, carbon dioxide CO2, sulphur dioxide SO2, ammonia NH3, and in some cases chlorine and fluorine compounds, which are environmentally unsafe emissions and cause serious deterioration of furnace linings (Morgan, 1993). Therefore, the iden-

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tification of soil components that release gases, such as organic matter, clay minerals, carbonates, sulphides and sulphates, as well as the determination of the amount of released gases is essential for an evaluation of the environmental impact of this industrial activity. The composition of clay raw materials is important for controlling the production process, since the constituents determine the firing characteristics and properties of the end-product, such as degree of vitrification, porosity and crack development, bloating and black coring. X-ray diffraction and thermal analysis have been used for studying the composition of clay raw materials and for technological control of ceramic firing processes. Thermal analysis has also shown that the amount of gases released from these key phases is strongly correlated to the material porosity (Delbrouck et al., 1993; Morgan, 1993; Parsons et al., 1997; Rice and Dekker, 1998). In this work, results are presented on the thermal, mechanical and structural properties of clay deposits localized in northern Rio de Janeiro state in Brazil, where this kind of soil is abundant and exploited for production of ceramics, mainly bricks and roof tiles. The relationship between open porosity, apparent density, shrinkage, rupture tension and the evolved gases as a function of the firing temperature is examined. In addition, X-ray diffraction analysis is used to determine the amorphous/crystalline phase transitions that occur during firing. This work is part of a larger project aiming at a complete characterization of regional clays (Alexandre et al., 1999; Manha es et al., 2002), in order to enhance the quality of final products, to optimise the production processes and to evaluate the environmental impact of this extraction activity.

of 1002010 mm. The bricks were dried in air at room temperature during one week and then at 110 8C for 24 h. Bricks were subsequently slowly heated in a furnace to a maximum temperature T f =300 8C, and kept at this temperature for 3 h. The same procedure was used for producing samples at maximum temperatures T f =400, 500 and 600 8C. The slow heating rate of 2 8C/min from room temperature to 600 8C is necessary in order to avoid cracks due to the aYh quartz phase transition at 575 8C. Other bricks were slowly heated to 600 8C, afterwards the temperature was increased to the maximum temperature T F and kept at this temperature for 3 h. This procedure was used for producing samples at maximum temperatures T f =700, 800, 850, 900, 950, 1000, 1050, 1100 and 1200 8C. The samples were finally cooled at a constant rate of 1.5 8C/min. The crystalline evolution of the different samples was analysed using X-ray diffraction, and the mechanical properties were determined as described further. In addition, dried (green) samples were submitted to heat treatment in a furnace specially designed for gas detection. 2.2. X-ray diffraction measurements X-ray powder diffraction data were measured at room temperature in Bragg-Brentano geometry, using CuKa radiation at a conventional diffractometer (Seifert URD65, Germany) operated at 40 kV/35 mA. The CuKh radiation was eliminated using a graphite diffracted beam monochromator. All the XRD data were collected under the same experimental conditions, in the angular range 38V2h V758 with step 0.038 and counting time 3 s (Moore and Reynolds, 1997). 2.3. Ceramic properties Volumetric shrinkage was determined using the relation (V 110VT F)/(V 110), where V 110 is the brick volume after drying at 110 8C and VT F is the brick volume after firing at a temperature T F. Open porosity was measured by water absorption. The brick was immersed in boiling water during 2 h, and cooled in the water during 24 h. In this condition the sample is water saturated, and its mass is called m i (still immersed in water) and m h (immediately after removed from the water). The values of m i and m h were measured using a hydrostatic scale, and the open porosity was calculated using the relation (m hm T F)/(m hm i), where m T F is the mass of the dry sample after firing at a temperature T F. The apparent (or skeletal) density was calculated from the ratio (m T F)/(V T F). The brick resistance under tension was determined using a device where the sample rests on two cylindrical supports while a progressive force F is applied perpendicular to its

2. Experimental part 2.1. Sample preparation Samples were taken from a quaternary sedimentary basin localized in northern Rio de Janeiro state, Brazil, where large clay deposits are quarried as raw material for red bricks and tiles. The samples were dried, ground and passed through a sieve with nominal aperture of 840 Am (mesh 20). The resulting homogeneous powder was very representative of the natural soil, which presents a high quantity (about 95 wt.%) of particles finer than 50 Am. This powder was mixed with water and extruded as bricks with average dimensions

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upper surface. The rupture tension was calculated using the relation P=(3FL )/(2de 2) where L , is the distance between the supports, d is the width and e the thickness of the brick. 2.4. Gas detection The gas analyser system (URAS14, from Hartmann and Braun) consists of a cell divided into two compartments: the measuring cell, through which the sampled gas flows, and the reference cell, filled with pure nitrogen. The infrared light emitted from a hot filament is modulated by a mechanical chopper and divided by a beam splitter. Each beam simultaneously goes through the measuring and reference cell. The analyser detector consists of two sealed chambers separated by a diaphragm capacitor. Both chambers are filled with pure gas of the chemical species under study. The light beams emerged from the sample and reference cells independently reach the two detector chambers, causing a differential pressure that is proportional to the light absorption of the sample. The pressure difference is converted by the diaphragm capacitor into an electrical signal. A detailed description of the URAS system has been reported by Harren and Reuss (1997). In our experimental set-up the concentrations of CO, CO2, SO2, NH3, NO, N2O, and CH4 were simultaneously analysed for a gas flow of 300ml/min using several analysing cells connected in series. Before each sample analysis the cells were calibrated using pure standard nitrogen. The heating temperature varied between room temperature and 1100 8C. The heating rate was always 4 8C/min. The gas released by the sample was directly collected from the furnace using a suction pump and an appropriate plastic bag. Gas samples were collected 20 min after the maximum temperature (respectively 300, 400, 500, 600, 700, 800, 850, 900, 950, 1000, 1050 and 11008C) was reached. The volatiles concentration emitted by the furnace was also measured and subtracted from the samples data. Due to the variable nature of clay raw materials, three runs were carried out for each sample. Since the results were reproducible, an average of the three sets was used. Samples were heated in powdered and extruded forms weighting in both cases 50 mg.

was performed for the natural powdered soil using the Rietveld refinement method (Fossum, 1999; Wilson, 1999) as already reported by Manha es et al. (2002). The Rietveld analysis was performed considering the angular range 108V2h V708, thus not taking into account the illite phase due to its peak shape. Kaolinite is the main crystalline phase with 86% mass fraction, followed by quartz (5%), anatase (5%) and gibbsite (4%). Iron oxides such as hematite, magnetite and illmenite were not detected. The diffractograms of the samples treated up to 400 8C show a similar mineral composition with kaolinite as the major phase (Fig. 1a). It was observed that between 400 and 500 8C the kaolinite dehydroxylation occurs, with the transformation to a non-crystalline phase, metakaolin: Al2Si2O5(OH)4YAl2Si2O7+2H2O. The other crystalline phases (illite and quartz) remain unchanged up to 900 8C. For this temperature range no more organic material is present in the amorphous component. This result is in agreement with the emissions of CO and CO2 observed at temperatures lower than 700 8C. Treatments at 1100 8C or higher cause new structural changes, with the formation of mullite, crystoballite and hematite phases (Fig. 1b). 3.2. Evolved gas analysis of powder samples As shown in the gas evolution profiles (Fig. 2), small quantities of CH4, NO and N2O gas and large quantities of CO and CO2 gas were observed. The major gas quantity is released at temperatures lower than 800 8C. The samples did not produce SO2 within our detection limits (1 ppm). The volumetric concentration of CO2 reached a maximum of 8600 ppm at 400 8C, mainly due to the combustion of organic material, decreasing to 600 ppm at 700 8C. Carbon dioxide is one of the most frequently occurring decomposition products in heatingfiring processes. Its large evolution peak is due to organic matter oxidation, while CO is due to an incomplete oxidation of organic matter, according to the reaction 2COYC+CO2. The interaction of carbon compounds with water vapour during combustion of organic matter results in less amounts of CO and more CO2, according to the following reactions: CO+H2OYCO2+H2 and C+2H2OYCO2+2H2. There is also a small concen-

3. Results and discussions 3.1. X-ray diffraction Fig. 1 shows the XRD patterns as a function of the firing temperature T F. A quantitative phase analysis

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Fig. 1. X-ray diffraction patterns for bricks fired at different temperatures T F. The XRD intensities are vertically displaced for better visualisation, where m is mullite, h is hematite, c is cristobalite, q is quartz, i is illite, and k is kaolinite.

tration of CH4 at 300 8C as a result of organic matter on the surface of the powder grains. Besides carbonate gases, small fractions of N2O were observed between 300 and 500 8C, and NO between 300 and 600 8C. These nitrogen compounds are not frequently detected in clay material analysis. The maximum quantity of N2O was observed at 300 8C, while for NO a small peak of 4 ppm was observed at 400 8C. 3.3. Evolved gas analysis of extruded samples Conditions in a powder heated in an oxidizing environment are not analogous to those within an

extruded piece, where clay particles are tightly packed and a pore system is present. Even if firing takes place in an oxidizing environment, access of oxygen will be restricted and volatiles may be kept within the pore system, allowing chemical reactions with the solid phase. In order to investigate gases released under conditions that simulate normal firing practices, thermal analysis was carried out on extruded pieces. The results are presented in Fig. 3. Organic matter combustion, as represented by the CO2 evolution profile, occurred at an approximately constant rate as from 300 to 500 8C, then decreased continuously to 600 ppm at 700 8C, and reached zero at 1100 8C. As in the case of powder samples, a small

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TWA values (threshold limit valuetime weighted average), and the typical concentrations in the surrounding air (Lide, 1993). TLVTWA is an airborne concentration under which it is believed that nearly all workers may be repeatedly exposed day after day without adverse health effect. The quantity tabulated is the time weighted average for a normal 8h workday and 40-h workweek. Remark that N2O, CO2, and, mainly, CO emissions are quite above the allowed values. 3.4. Ceramic properties In order to complete the characterisation, the physical properties of the bricks as a function of the firing temperature were finally taken into account. Evolution of the apparent density, open porosity, rupture tension, and volumetric shrinkage is presented in Fig. 5. Between 300 and 700 8C, small variations of these physical properties were observed, which are associ-

Fig. 2. Gas evolution profiles for powder samples.

concentration of CH4 was detected at 300 8C due to the removal of organic matter from the brick surface (open pores). It is worth to note that a small quantity of N2O was detected as from 300 up to 800 8C, while NO was not observed during the complete cycle. This behaviour is different compared to the observed concentrations for powder samples, where N2O was produced in higher quantities and at lower temperatures. This result indicates that the open powder system enhances the interaction with external oxygen, while within the solid sample the gas is trapped by the pore system and is released at higher temperatures. The same situation was observed for CO2 and CO since the gases of the powdered material were also released in higher concentration than for the solid pieces (Fig. 4). In bricks, the gas is released as the pore system varies, which occurs during the expulsion of adsorbed water (about 175 8C), dehydroxylation (from about 400 to 700 8C) and quartz expansion (at 575 8C) resulting in a closure of cracks. Table 1 compares the maximum concentration of gases released during the clay firing, the TLV

Fig. 3. Gas evolution profiles for extruded samples.

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Fig. 4. Comparison between powder and brick emissions of CO and CO2 gases.

Fig. 5. Evolution of the ceramic properties as a function of the firing temperature T F.

ated with the loss of adsorbed structural water, organic matter combustion and kaolinite dehydroxylation. In this temperature range, the brick samples maintain a certain stability of their ceramic properties. Between 700 and 1000 8C, the apparent porosity diminishes slowly, while the apparent density, shrinkage and rupture tension increase. Above 1000 8C, the open porosity (as well as the water absorption) abruptly
Table 1 Maximum concentration of released gases from bricks and powder samples, maximum values allowed by the TLVTWA and typical concentrations in the surrounding air Gas CO2 CO CH4 NO N2O Powder (ppm) 8600 1100 2.3 4 8 Brick (ppm) 6500 800 9 6 TLVTWA (ppm) 5000 25 25 2 Surrounding air (ppm) 345 0.1 1.7 0.1 0.0002

The TLVTWA data are given in parts per million (ppm) by volume in air at 25 8C and 1 atm.

decreases from 39.4 to 2.6 vol.%, while the apparent density increases from 1.61 to 2.31 g/cm3 (Fig. 5a). This densification is accompanied by a strong shrinkage, from 15.0 to 41.9 vol.% and a rupture tension enhancement from 9.15 to 28.24 MPa (Fig. 5b). XRD results showed that these variations are associated to a recrystallisation in the samples, with the formation of mullite, crystoballite and hematite. This behaviour suggests that a sintering process occurred, leading to the improvement of the ceramic properties. As can be seen, there is good agreement between thermal, microstructural and rheological results. The organic matter oxidation, with the formation of carbon and nitrogen compounds are active in the range between 200 and 800 8C, where small variations of physical properties, such as density, porosity, shrinkage and strength were observed. CH4 only reacts at the lowest temperature, when combustion of the organic matter on the external brick surface occurs. The differences observed in the CO and CO2 evolution are in fact correlated with the porosity system

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variations, which occur in the same temperature range (Figs. 4 and 5a). The clay mineral dehydroxylation takes place above 400 8C, simultaneously with the transformation of kaolinite as major phase to a less crystalline metakaolin phase.

Acknowledgments The authors acknowledge financial support from CNPq and FAPERJ, the governmental Brazilian agencies for the scientific and technological development. References
Alexandre, J., Saboya, F., Marques, B.C., Ribeiro, M.L.P., Salles, C., daSilva, M.G., Sthel, M.S., Auler, L.T., Vargas, H., 1999. Photoacoustic thermal characterization of kaolinite clays. Analyst 124, 1209 1214. Delbrouck, O., Janssen, J., Ottenburgs, R., Van Oyen, P., Viaene, W., 1993. Evolution of porosity in extruded stoneware as a function of firing temperature. Appl. Clay Sci. 8, 187 192. Fossum, J.O., 1999. Physical phenomena in clays. Physica, A 270, 270 277. Harren, F., Reuss, J., 1997. Spectroscopy. Encycl. Appl. Phys. 19, 413 414. Lide, D.R., 1993. Handbook of Chemistry and Physics. (74th ed.) CRC Press, Boca Raton, FL. Manha es, R.S.T., Auler, L.T., Sthel, M.S., Alexandre, J., Massunaga, M.S.O., Carrio , J.G., dos Santos, D.R., da Silva, E.C., Garcia-Quiroz, A., Vargas, H., 2002. Soil characterisation using X-rays diffraction, photoacoustic spectroscopy, and electron paramagnetic resonance. Appl. Clay Sci. 21, 303 311. Moore, D.M., Reynolds Jr., D.C., 1997. X-ray Diffraction and the Identification and Analysis of Clay Minerals, (2nd ed.) Oxford Univ. Press, New York, pp. 378 379. Morgan, D.J., 1993. Thermal analysisincluding evolved gas analysisof clay raw materials. Appl. Clay Sci. 8, 81 89. Parsons, A.J., Inglethorpe, S.D.J., Morgan, D.J., Durham, A.C., 1997. Evolved gas analysis (EGA) of brick clays. J. Therm. Anal. 48, 49 62. Rice, R.W., Dekker, M., 1998. Porosity of Ceramics. Elsevier, New York. Wilson, M.J., 1999. The origin and formation of clay minerals in soils: past, present and future perspectives. Clay Miner. 34, 7 25.

4. Conclusions Evolved gas analysis is a powerful tool for examining clay raw materials for ceramics as it provides chemical information that can readily be utilized. In the case of powder clays, for example, this technique provides information on the nature and quantity of gases released during heating and helps to identify those components responsible for individual thermal reactions such as dehydroxylation and oxidation. Gases emissions during the firing process of powder and brick ceramics were analysed. Except for NO, the concentration peaks are higher than the values depicted at the TLVTWA table. A straight correlation among the emitted gases concentration and the microstructural and rheological ceramic properties, as a function of the firing temperature, was observed. The results presented in this work are part of a larger project that comprises the optimisation of procedures adopted for the production of bricks and roof tiles, as well as the analysis of the mineralogical composition of the raw material and its relation to the optical and thermal properties of the extruded pieces. Concentration profiles of gases emitted by the combustion fuels commonly utilized by the ceramic linings in the firing industrial processes, such as BPF oil and wood, were also analysed but will be reported in a subsequent paper.