Minerals Engineering 19 (2006) 525527 This article is also available online at: www.elsevier.

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Technical note

Study of pore size distribution of slate ceramic pieces produced by slip casting of waste powders
A.A.P. Mansur, A.E.C. Peres *, L. Palhares, H.S. Mansur
Department of Metallurgical and Materials Engineering, Federal University of Minas Gerais, Rua Esprito Santo, 35/206, 30160-030 Belo Horizonte/MG, Brazil Received 18 July 2005; accepted 3 October 2005 Available online 15 November 2005

Abstract One crucial problem in quarries associated with mining dimension stones is the generation of enormous amounts of waste, which strongly impacts on the environment. Slate mining and processing generate large amounts of ne powder during extraction, cutting and polishing procedures. In the present work, suspensions were produced by mixing slate powder with dierent solid fractions in water, and then casting into plaster moulds (slip casting process). The green samples (as cast) were characterised according to density and pore size distribution by mercury porosity and X-ray diraction techniques. Ceramic pieces from slate powder, produced through slip casting were red at 1000 C/4 h. The results show that slate powder waste has a potential use in the manufacturing of ceramic pieces by the slip casting process. 2005 Elsevier Ltd. All rights reserved.
Keywords: Waste processing; Environmental; Mineral processing

1. Introduction Brazil is very important in relation to the dimension stones industry. Slate quarrying generates a higher amount of waste compared to the mining of other minerals, being estimated as 80 wt.% of total production, with 25% as slurry (Mansur and Mansur, 2004). In order to minimise clay extraction, alternative ways of using waste materials have been attempted, including their incorporation in clay-based ceramic products (Moreira et al., 2003). In the present work, the objective was to evaluate the pore size distribution of ceramic pieces manufactured with slate powder wastes by the slip casting process. Several characterisation tests were conducted before and after ring in order to investigate pore structure changes during thermal treatment and morphology modications.

2. Experimental Slate powder samples were supplied by a mining plant located in Pompeu, Minas Gerais, Brazil. Chemical analysis was performed by aqueous titration using waste powder as the sample. Mineralogical analysis was carried out by X-ray diraction (XRD, PHILIPSPW/1710, CuKa = 1.5418 A, JCPDS database). Scanning Electron Microscopy (SEM, model: JEOL-JSM/5410) coupled to EDX microprobe (NORAN, USA) in order to evaluate morphological aspects of the slate samples (Au-coated). Ceramic pieces were manufactured by the slip casting process. Aqueous suspensions of slate powder were prepared with dierent solid fraction (wt%: 48%; 68%; 73%; 78%) and dispersant concentration (0.5%; 1.0%; 1.5; 2.0%; 2.5%). Poly(ammonium acrylate) was used as dispersant and poly(vinyl alcohol) (PVA, Brazil) was used as binder (2.0% v/v). After casting, the pieces were dried at room temperature for 24 h followed by oven heating at 100 C/24 h. Green samples were then transferred to a furnace and the temperature raised from 100 C to 1000 C (rate = 10 C/min).

Corresponding author. Tel./fax: +55 31 3238 1717. E-mail address: aecperes@demet.ufmg.br (A.E.C. Peres).

0892-6875/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.mineng.2005.10.001

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Mineralogical analyses of red samples were performed by XRD. Porosity and pore size distribution for green samples and for samples after thermal treatment were determined by mercury porosimetry (MICROMERITICS, Autopore-III). Prior to porosity tests, the slate samples were oven-dried at 105 C/24 h, the samples then being placed in a vacuum chamber for 5 min for outgassing (0.050 mm/Hg). 3. Results and discussion 3.1. Microstructural characterisation of slate powder A typical SEM photomicrograph of slate powder particles is shown in Fig. 1a. The presence of particles with

irregular size, shape and lamellar structure associated with cleavage (arrow, Fig. 1a) can be seen. The chemical analysis (equivalent oxide content) has indicated the presence of major components such as silica, alumina and iron oxide (wt%: 63.8% 1.4; 16.5% 0.5; 7.5% 0.5, respectively). Other minor constituents were also detected (Na2O = 1.3%; K2O = 1.6%; MgO = 2.8%; CaO = 1.7%; TiO2 = 0.9%). Mineralogical composition obtained by XRD (Fig. 1b) has revealed the presence of albite, chlinoclore, calcite, hematite, muscovite and quartz as major crystalline phases, similar to those usually reported in the literature (Moore and Reynolds, 1997). The high amount of quartz in the slate sample would be important in producing low shrinkage during the ring process. Calcite is expected to act as a

Fig. 1. (a) SEM photomicrograph (2000) of slate powder, with lamellar phase (arrow); (b) X-ray diraction pattern of slate powder sample (Aalbite, Cchlinoclore, Cacalcite, Hhematite, Mmuscovite, Qquartz); SEM photomicrographs of slate ceramics with solid fraction = 73% and dispersant = 2% after ring at (c) 500 C; (d) 1100 C.

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neomineralisation agent, after its decomposition to CaO by reacting with quartz and other minerals, producing calcium-silicates phases. In addition, XRD results indicated a considerable amount of uxing agents (Na2O + K2O + Fe2O3 = 10.4%) in the crystalline form of feldspar, hematite and muscovite. As a consequence, a eutectic temperature ranging from 985 C to 900 C would be expected. Therefore, the possibility of forming liquid during the sintering process in the ceramic production is an important property of the slate powder as a potential substitute for clays. 3.2. Characterisation of slate samples after ring XRD results on slate samples after ring have revealed the presence of albite, gehlenite, muscovite, mullite, quartz and spinel phases. Albite was also observed in the raw material. The formation of gehlenite was expected, due to the presence of calcite as raw material. Gehlenite is formed when a calcium oxide nucleus reacts with the Si and Al from the decomposed clay (Jordan et al., 2001). The remaining mica peak detected was probably due to the residual muscovite akes. It is believed that neomineralisation of mullite was caused by high concentrations of quartz and alumina. Based on XRD results on slate and red ceramic pieces, it was possible to identify several important changes during ring that may have contributed to creation of porosity. Evaporation of free water, both physically and chemically adsorbed (250 C and 320 C, respectively), dehydroxylation of clays with elimination of structural water (muscovite and chlinoclore, 570580 C) and calcite decomposition with CO2 release (800950 C) are events which increase porosity (Mansur and Souza, 2004). Another important aspect is related to the gaseous products resulting from burnout of polymers used as dispersant and binders. Poly(vinyl alcohol) initially loses its hydroxyl side groups (150250 C), with the elimination of water vapour, followed by the degradation of the hydrocarbon chain at temperatures from 150 C to 500 C, causing volume expansion (Reed, 1988). SEM micrographs of slate samples red at temperatures of 500 C and 1100 C are shown in Fig. 1c and d, respectively. At higher temperature (Fig. 1d), the occurrence of sintering with the presence of a liquid phase, reduction of grain boundaries and remaining porosity are all clearly seen. Mercury porosimetry intrusion curves of slate samples as cast indicated that the higher solid content (48%, 63% and 73%) the lower was the porosity, while keeping the concentration of dispersant and binder constant. It is

believed that this is due to the smaller amount of water eliminated during the casting and drying processes. The pore distribution curve for the slate sample (as cast) was multi-modal, varying in the range of macroporous (length > 0.05 lm) and mesoporous (0.05 lm < length < 0.002 lm), with average pore size of l = 0.30 lm. After sintering, porosity was reduced but the pore size remained mostly in the macroporous range, with a higher average size (0.70 lm). The eect of PVA as dispersant on ceramic pore distribution was investigated and the results have indicated that the average pore size was reduced by increasing the concentration of dispersant from 0.5% to 1.5%. It is believed that the dispersant acted as a deocculant agent, improving the packing density of slate particles in green samples. For this reason, ceramic pieces were produced with low porosity after sintering with high dispersant concentration. 4. Conclusions The slip casting process using slate powder wastes produced green ceramic pieces with high porosity. After ring, the novel slate based ceramics had lower porosity with higher average pore size, a consequence of the sintering densication process. It was also observed that the porosity of slate ceramics can be optimised by an adequate choice of solid fraction and dispersant content. Acknowledgement Gratitude is expressed to CNPq/FAPEMIG/CAPES for supporting this work. References
Jordan, M.F., Sanfeliu, T., Fuente, C. de la, 2001. Firing transformations of tertiary clays used in the manufacturing of ceramic tile bodies. Appl. Clay Sci. 20, 8795. Mansur, H.S., Souza, L.P., 2004. Production and characterization of ceramic pieces obtained by slip casting using slate powder wastes. J. Mater. Process. Technol. 145, 1420. Mansur, A.A.P., Mansur, H.S., 2004. Characterization and production of novel ceramic roof tiles obtained using slate powder waste. In: Pecchio, M. et al. (Ed.), Applied MineralogyDevelopments in Science and Technology, ICAM, Sao Paulo, pp. 10131016. Moore, M.M., Reynolds, R.C., 1997. X-ray Diraction and the Identication and Analysis of Clay Minerals, second ed. Oxford University Press, Oxford. Moreira, J.M.S., Freire, M.N., Holanda, J.N.F., 2003. Utilizacao de resduo de serragem de granito proveniente do estado do Esprito Santo em ceramica vermelha. Ceramica 49 (312), 262267. Reed, J.S., 1988. Introduction to the Principles of Ceramic Processing, second ed. John Wiley & Sons Inc., New York.