Materials Science and Engineering A 419 (2006) 306309

Effect of marble and granite sludge in clay materials

W. Acchar a, , F.A. Vieira b , D. Hotza c
Department of Physics, Federal University of Rio Grande do Norte (UFRN), 59072-970 Natal-RN, Brazil b Post-Graduation Program in Materials Engineering, UFRN, Natal-RN, Brazil c Department of Chemical Engineering (EQA), Federal University of Santa Catarina, 88040-900 Florian opolis-SC, Brazil Received 14 July 2005; received in revised form 30 November 2005; accepted 2 January 2006
a

Abstract The use of industrial waste materials as additives in the manufacture of ceramic products has been attracting a growing interest from researchers in recent years and is becoming common practice. This work describes the changes in the behavior of the clay material used in a red-clay industry due to additions of a granite and marble sludge, produced in an ornamental stone processing industry in Rio Grande do Norte-Brazil. Mixtures of clay and waste material (1050 wt.%) were uniaxially pressed and sintered at temperatures ranging from 950 to 1150 C. Results from chemical and mineralogical analysis (XRD and XRF), thermal analysis (DTA, TG and dilatometry), apparent density, water absorption and exural strength, show that the granite and marble sludge can be added to the clay material with no detrimental effect on the properties of the sintered red-clay products. The reject acts as a ux agent, reducing the sintering temperature of the clay material. 2006 Elsevier B.V. All rights reserved.
Keywords: Industrial waste; Red-clay ceramics; Recycling; Marble; Granite

1. Introduction Nowadays industrial activities are responsible for the generation of large amounts of solid wastes (e.g. paper and textile industries, petroleum renery, urban waste, ashes, Al-rich sludge, etc.) [16]. Industries have been looking for technological alternative in order to optimize their process, producing less waste material. The ceramic industry, especially the sector devoted to the fabrication of building products is very capable of incorporing and reusing different types of industrial waste materials [712]. The most used raw materials in the traditional ceramic industries can be basically divided into three categories: plastic components (clays), uxing components (feldspar) and inert components (quartz and sand). Clay materials used in the red ceramic industry show an extensive range of compositions, what permit the incorporation of a variety of industrial waste materials. Some wastes are very analogous in composition to the raw materials used actually and often contain materials that can also be helpful in the fabrication of ceramic products. Intense industrial activity related to ornamental stones, especially granite is maintained in

Rio Grande do Norte-Brazil. The large amount of marble and granite rejects produced during the industrial process are becoming a serious problem for industrial and environmentalists. The rejected mud produced during the cutting process is discarded into rivers and lagoons, without any treatment, causing a serious ambiental problem. Marble and granite are formed predominantly by calcite (CaCO3 ), feldspar and quartz. Recent studies demonstrated the possibility of incorporating granite reject into clay-based ceramic products [1318]. The results have shown that this type of reject has a good potential to be used as a sintering additive of the ceramic material. The objective of this work is to study the possibility to incorporate marble and granite reject in clay products, without to degrade their properties. 2. Experimental procedure A typical clay material used in the red ceramic industry and a marble and granite reject, collected directly from the ornamental stone cutting industry, were selected and characterized. The characterization included chemical composition (X-ray uorescence, EDX-700, Shimadzu), mineralogical composition (X-ray diffraction, XRD-6000, Shimadzu), and thermal behavior (differential thermal analysis (DTA-50, Shimadzu), thermogravi-

Corresponding author. Tel.: +55 84 32010655; fax: +55 84 32153791. E-mail address: acchar@dfte.ufrn.br (W. Acchar).

0921-5093/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2006.01.021

W. Acchar et al. / Materials Science and Engineering A 419 (2006) 306309

307

metric analysis (TGA-51, Shimadzu) and dilatometry (TMA-50, Shimadzu)). Mixtures containing 10, 20, 30, 40 and 50 wt.% reject were homogenized for 4 h in a planetary ball mill and uniaxially pressed into bars (50 mm 4 mm 4 mm) under a load of 30 MPa. Subsequently, the compacted samples were sintered at temperatures between 950 and 1150 C for 1 h, with a heating rate of 10 C/min. The mechanical strength of the sintered specimens (average of ve bodies for each value) was measured with a universal testing machine (Shimadzu AG-25TA) in three-point bending testes at a constant cross-head speed of 0.5 mm/min. Water absorption and the apparent density values was calculated by using the Archimedes water displacement method, as specied by the European standard EN 99. The crystalline phases of the raw materials and the sintered samples were identied by X-ray diffraction. 3. Results and discussion Table 1 gives the chemical compositions of the raw material used in this work. The clay material presents a typical composition and are constituted mainly by silica and alumina and minor contents of Mg, Ti, Ca, Na and K oxides. The signicant amount of iron oxide (12.07 wt.%) is responsible for a darker coloring of the sintered samples. The loss on ignition (8.48%) is within usual range for red-clay material and is associated with volatile components and organic matter. The marble and granite reject is formed basically by SiO2 , Al2 O3 and CaO, with small amounts of MgO, Fe2 O3 , K2 O and Na2 O. The loss on ignition (LoI) is higher as the clay material and results from the decomposition of carbonates (calcite and dolomite). The high alkaline earth oxide content (particularly CaO and K2 O), present in the reject material will act as a uxing agent during the sintering process. Fig. 1 shows the X-ray diffraction patterns of the clay and the reject material. It can be noted that the clay material is constituted by quartz and kaolinite and minor amounts of muscovite, rutile and ilite. The reject contains quartz, biotite, dolomite, albite, anorthite, calcite and ortoclase. The crystalline phases identied are in agreement with the results observed by XRF (Table 1). Fig. 2 shows the thermal behavior of the marble and granite reject. The material presents a small weight loss from 40 to 700 C, associated with the adsorbed water and volatile materials, followed by a weight loss of approximately 11% that can be attributed to the carbonates decomposition (CaCO3 = CaO + CO2 ) (Fig. 2a). The DTA curve (Fig. 2b) shows two endothermic peaks at 40.70 and 736.46 C, that are associated with the weight loss presented in Fig. 2a. Fig. 2b shows also an exothermic peak at 1112 C, that can be attributed to the formation of mullite (3Al2 O3 2SiO2 ). Fig. 3 shows the dilatometric behavior of the raw materials used in this work. The clay shows a typical clay material behavior characterized by expansion up to 900 C, followed by shrinkTable 1 Chemical composition of the raw materials, as determined by XRF Al2 O3 Clay Reject 27.02 13.65 SiO2 40.61 37.86 Fe2 O3 12.07 3.56 CaO 1.42 19.92 Na2 O 0.80 3.58 K2 O 4.40 4.32 MgO 2.88 3.49 TiO2 1.41 0.61 P2 O 5 0.17 0.27 MnO 0.18 0.07 LoI 8.48 12.37

Fig. 1. X-ray diffraction pattern of: (a) clay and (b) reject material.

age. The reject present a expressive shrinkage at 800 C, that is characteristic of the formation of a liquid phase, followed by a strong expansion, that can be attributed to the formation of a new crystalline phase among calcium oxide and alumino-silicates (e.g. anorthite-CaOAl2 O3 2SiO2 ). Similar behavior was also reported in the literature for clay materials with high calcium oxide content [19]. Fig. 4 shows the X-ray diffraction pattern obtained for clay + 30 wt.% reject sintered at 1050 C. The material shows the presence of quartz, hematite and also the presence of anorthite, thus conrming the expansion behavior observed in Fig. 3. Figs. 5 and 6 present the changes in water absorption and apparent density of sintered specimens as a function of the sintering temperatures and reject content, respectively. The water absorption values decreases signicantly at 1100 and 1150 C. This behavior is related to the lower viscosity of the liquid phase and the consequently improvement on the densication process produced at these temperatures. The temperature effect on the apparent density is similar to that observed for the water absorption. The best apparent density values were obtained for T > 1050 C. Fig. 7 shows the variation in the exural strength as a result of the reject addition and sintering temperature. Flexural strength values are increased by higher temperatures. The strength of pure clay was not showed in Fig. 7, for comparison purposes, because this clay material cannot be sintered alone.

308

W. Acchar et al. / Materials Science and Engineering A 419 (2006) 306309

Fig. 4. X-ray diffraction pattern of clay + 30 wt.% reject, sintered at 1050 C.

Fig. 2. Thermal analysis of the reject material: (a) TGA and (b) DTA.

This material is used industrially with another clay material to form a mixture with ideal plasticity to be extruded. As can be also noticed from this gure, the incorporation of reject (no plasticity material) reduces slightly the exural strength of the sintered bodies at temperatures lower as 1050 C. At higher temperatures (T > 1050 C), the increase of the reject has caused an improvement of the exural strength, that can be attributed to an improvement of the densication process. The strength, water

Fig. 5. Changes in water absorption as a function of the reject content and the sintering temperature.

absorption and density values obtained in this work for clay with marble and granite reject are much better, for all sintering temperatures investigated in this work that the clay products of the ceramic industry produced at the same conditions. The results described above shows that the clay + reject material satisfy the class II-b of ISO 13006 standards, making the granite and marble reject a potential raw material to be used in the traditional red ceramic industry.

Fig. 3. Dilatometric behavior of the clay and the reject material.

Fig. 6. Changes in apparent density as a function of the reject content and the sintering temperature.

W. Acchar et al. / Materials Science and Engineering A 419 (2006) 306309

309

References
[1] J.M.F. Ferreira, P.J. Guedes, P. Torres, R.S. Manjate, H.R. Fernandes, in: Pecchio, et al. (Eds.), Recycling of Industrial Wastes-na Overview about Successful Case Studies, Applied Mineralogy, ICAM-BR, S ao Paulo, 2004, p. 33. [2] A. Gorokhovsky, V. Gorokhovsky, D. Mescheryakov, Glass Sci. Technol. 73 (2000) 374. [3] M. Dondi, M. Marsigli, B. Fabbri, Tile Brick Int. 13 (1997) 302. [4] M. Dondi, M. Marsigli, B. Fabbri, Tile Brick Int. 13 (1997) 218. [5] N.I.W. Silva, O. Zwonok, F. Chies, Tile Brick Int. 14 (1998) 247. [6] R. Caligares, N. Quaranta, M. Caligares, E. Benavidez, Bol. Soc. Esp. Ceram. Vidrio 39 (2000) 623. [7] H.A. Oliveira, E.C. Rabelo, J.C. Bressiani, Tile Brick 17 (2001) 29. [8] J.C. Knight, Br. Ceram. Trans. 98 (1999) 24. [9] M. Knirsch, A. Penschke, S. Krebs, W. Russ, H. Mortel, W. Mayer, Tile Brick Int. 14 (1998) 93. [10] J.M. Ferreira, H.M. Alves, A.M. Mendonc a, Bulletin de la Sociedad Espanola de Cer amica y Vidro 38 (1999) 127. [11] A.R. Boccaccini, J. Schwohl, H. Kern, B. Schunk, J.M. Rincon, M. Romero, Glass Technol. 41 (2000) 99. [12] J.M. Ferreira, S.M. Olhero, J. Eur. Ceram. Soc. 22 (2002) 2243. [13] P. Torres, H.R. Femandes, S. Agathopoulos, D.U. Tulyaganov, J.M. Ferreira, J. Eur. Ceram. Soc. 24 (2004) 3177. [14] S.N. Monteiro, L.A. Pec anha, C.M.F. Vieira, J. Eur. Ceram. Soc. 24 (2004) 2349. [15] M.S. Hernadez-Crespo, J.M. Rinc on, Ceramurgia 34 (2001) 111. [16] G.A. Neves, PhD Thesis, Campina Grande-Brazil, 2002. [17] A.G. Verduch, J. Requena, 238 (1995) 697. [18] J.J. Rinc on, M. Romero, Geogaceta 20 (1996) 1552. [19] T. Hatzl, P. Gehiken, ZI 12 (2001) 20.

Fig. 7. Variation of the exural strength values as a function of the reject content and the sintering temperature.

4. Conclusions The results obtained in this work show that reject content up to 50 wt.% can be incorporated into clay materials, without degrading their mechanical properties. The presence of the marble and granite reject allow to obtain a clay material with better properties as the conventional clay material at lower temperatures as the normally used for clay products in the ceramic industry, resulting in energy saving and waste reduction. The possibility to use the marble and granite reject as an alternative raw material in the production of clay products will also induce a relief on waste disposal concerns.