Materials Science and Engineering A 373 (2004) 115121

Incorporation of granite waste in red ceramics

C.M.F. Vieira , T.M. Soares, R. Snchez, S.N. Monteiro
Advanced Materials Laboratory-LAMAV, State University of the North Fluminense-UENF, Av. Alberto Lamego, 2000, Campos dos Goytacazes, RJ 28015-620, Brazil Received 22 September 2003; received in revised form 23 December 2003

Abstract This work has as its objective to evaluate the effect of granite powder waste incorporation in a red ceramic body. The granite waste came from an industry of stone sawing operations located in the municipal area of Santo Ant nio de Pdua, State of Rio de Janeiro, Brazil. Initially o the granite sawing waste was characterized in terms of chemical composition, particles size distribution and X-ray diffraction. After that, clay mixtures with 0, 10, 20, 30 and 40 wt.% of granite waste were prepared. Red ceramic specimens were fabricated by extrusion and then red in an industrial furnace at 970 C. The specimens were also tested to determine the water absorption, linear shrinkage and three points bending exural strength. Microstructural evaluation was carried out by scanning electron microscopy, X-ray diffraction and mercury porosimetry. The results indicate that granite waste presents favorable characteristics for addition into red ceramics due to facilities on the drying stages and decrease in porosity. 2004 Elsevier B.V. All rights reserved.
Keywords: Clay; Incorporation; Red ceramics; Granite; Waste

1. Introduction The industrial sector of red ceramics in Brazil is very signicant with more than 10,000 plants that are responsible for 600,000 direct jobs [1]. The abundance of clays and relatively simple processing techniques favor the production of red ceramics in practically all regions in the country. The municipal area of Campos dos Goytacazes, Campos for short, located in the north region of the State of Rio de Janeiro, has a great production (135 106 pieces per month) of red ceramics. Most of this production corresponds to wall bricks followed by a comparatively small percentage of pressed roong tiles. The ceramic bodies in Campos are usually composed by a blend of kaolinitic plastic clays. Sometimes sand is used to improve the workability and facilitate the drying stage. The kaolinitic predominance in the clay ceramic bodies and the presence of gibbsite are responsible for a refractory ring behavior [2,3]. As a consequence, some products such as roong tiles and extruded tiles do not reach the level of porosity compatible with the water absorption required by the Brazilian standards.
Corresponding author. Tel.: +55-22-27261533; fax: +55-22-27261533. E-mail address: vieira@uenf.br (C.M.F. Vieira). 0921-5093/$ see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2003.12.038

One technological alternative to reduce the refractoriness and the porosity is to increase the ux content in the bodies. Fluxes are raw materials with a high amount of alkaline oxides, mainly K2 O and Na2 O, which, in reaction with silica and alumina, promote liquid phase formation that facilitates the densication. The liquid phase surrounds the solid particles and by surface tension enables the particles approach, closing the porosity [46]. The powder waste from sawing operation of ornamental rocks, such as granite, is a potential raw material that could serve as a ux source. Its relatively low or practically no cost can be an economic advantage to the red ceramic sector. Granite is considered a ux material due to its large amount of alkaline oxides. These oxides derive from feldspars and micaceous minerals that are common constituents of granitic rocks. Previous works have utilized granite [7,8] and granite waste from sawing operations [9,10] in the production of ceramic products. The major observations were that granite waste shows physical and mineralogical characteristics similar to the raw materials used in the body composition and that the technological properties of some mixture full the required properties. The incorporation of granite waste in a conventional porcelain stoneware body improved the

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C.M.F. Vieira et al. / Materials Science and Engineering A 373 (2004) 115121 Table 1 Elaborated mixtures Mixtures Raw materials (wt.%) Clay B0G B10G B20G B30G B40G 100 90 80 70 60 Granite waste 0 10 20 30 40

sintering process and reduced the water absorption [9]. However, results obtained by incorporating granite waste from sawing operations into red ceramic bodies for bricks [10], indicated a reduction in mechanical strength and increase in water absorption. In the municipal area of Santo Ant nio de Pdua, located o at 150 km from Campos, there exists an intense industrial activity related to the extraction and dressing of ornamental stones. A production of 700,000 t per month of granite waste from sawing operations is estimated to occur in that area. This waste could then be economically used as an addition to the ceramic bodies in Campos with the advantage of improving their technological properties. In the present paper the effect of granite waste on red ceramic bodies was investigated to nd out the optimum incorporation. An attempt was made to give an explanation for the technological results obtained in terms of ux action on the decreasing of porosity.

2. Experimental procedure The raw materials used in this investigation were collected from local industries: a typical clay from Campos and granite waste from Santo Ant nio de Pdua. These raw materio als were dried at 110 C, manually crushed and then sieved to 20 mesh (0.840 mm) before representative samples were separated by quartering. Afterwards, they were submitted to the following characterization techniques: X-ray diffraction (XRD), chemical composition and particle-size distribution. The XRD of 0.5 g of randomly oriented powder was carried out in a Sheifert model URD 65, diffractometer, equipped with a graphite monochromator, operating with Cu K radiation for a 2 range from 5 to 40 . The chemical composition was carried out by uorescence spectrometry (Philips, PW 2400) on 7.8 g of pressed powder pellets. The loss on ignition (LoI) was obtained by determining the weight difference between samples calcinated at 1000 C and dried at 110 C. The particle-size distribution of the raw materials was obtained by wet sieving using 20, 40, 60, 100 and 200 mesh, and by sedimentation method according to the Brazilian standard [11]. This sedimentation method is accomplished by dispersing 70 g of the material in 125 ml of water with addition of 5.7 g of sodium hexametaphosphate and 1.0 g of sodium carbonate. The solution is agitated during 15 min in a mixer and set into test tubes. The equivalent spherical diameter of the material is then calculated using Stokes law. The plasticity of the bodies was determined by the Atterberg method; only plastic limit (PL) and plastic index (PI) are reported. Clay body mixtures with addition of 0, 10, 20, 30 and 40 wt.% of granite waste were homogenized in a dry mixer. The elaborated compositions are shown in Table 1. In this table, B corresponds to clay ceramic body while G stands for granite waste. Moisture was then added, according to the plastic limit of the ceramic bodies, until the proper con-

sistence to form extruded specimens with 2.5 cm 1.5 cm in cross-section was attained. The extrusion operation was performed without vacuum and the specimens were cut with 10 cm in length. All specimens were dried at room temperature for 48 h and then at 110 C in a laboratory oven until constant weight was achieved. The ring of the specimens was performed at 970 C in a Hoffmann type industrial furnace with 6 h soaked at the maximum temperature. Five specimens for each composition were then tested to obtain the ring technological properties related to the bulk density, linear shrinkage, water absorption and three points exural rupture strength. The bulk density was measured dividing the dry mass by the external volume. The water absorption was determined according to standard procedure [12]. The linear shrinkage was obtained by the length of the samples before and after the ring stage using a paquimeter Mitutoyo (precision of 0.01 mm). The exural rupture strength was determined in an Instron 5582 Universal Testing Machine, according to standard procedure [13]. The microstructure of the fracture surface of selected red samples was studied by scanning electron microscopy, SEM, using a Zeiss model DSM 962 equipment. The pore-size distribution between 0.00648 to 8.8884 m was obtained by mercury intrusion porosimetry, using a contact angle of 140 , in an Autoscan 33 Quantachrome Porosimeter. Major crystalline phases were determined by XRD in sectioned pieces, collected from the center of red specimens, according to the previously described parameters employed for the unred materials.

3. Results and discussion 3.1. Characteristics of the raw materials Figs. 1 and 2 show the XRD patterns of the raw materials. These diffractograms indicate that the clay is predominantly kaolinitic with the presence of quartz, a micaceous mineral, gibbsite and goethite. In the granite waste the presence of a micaceous mineral, amphibole, quartz, plagioclase (calciumsodium feldspar) and potash feldspar can be observed. Both the micaceous mineral and feldspar are the sources of K2 O and Na2 O, which act as uxes to improve the sintering process.

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600 500
K

117

100

Cumulative mass percent finer

80

Intensity (counts)

400
K

Q Q

60 Granite waste Clay

300
M K

40

200
Gi MK M Go

K K

100 0 10 20 30

20

0
40

10

100

1000

2
Fig. 1. X-ray pattern of the clay. Gi: gibbsite; Go: goethite; K: kaolinite; M: micaceous mineral; Q: quartz.

Equivalent spherical diameter (m)

Fig. 3. Particle-size distribution of the raw materials.

3000 2500

2000 1500 1000

Q

M Fk Pl

M M Pl Fk Fk

500
Am Pl Fk M Pl

Pl M Fk

M Q Fk Q

0 10 20 30 40

2
Fig. 2. X-ray pattern of the granite waste. Am: amphibole; Fk: potash feldspar; M: micaceous mineral; Pl: plagioclase; Q: quartz.

Table 2 shows the chemical composition and the LoI of the raw materials. The chemical composition of the clay is typical of a kaolinite-based material with low amounts of alkaline oxides and relatively high amount of Al2 O3 . The high percentage of LoI indicates an elevated fraction of clay minerals. The chemical composition of the granite waste, in addition to SiO2 and Al2 O3 , shows a relatively large amount of alkaline and alkaline earth oxides. This conrms the ux potential of the granite. The signicant amount of Fe2 O3 in both raw materials is responsible for the reddish color of the specimen after ring.

Fig. 3 shows the particle-size distribution of the raw materials. One may notice that the clay has a regular distribution with average particle size of 6.8 m. The percentage of clay minerals, i.e., that with particle size below 2 m, is 34.6%. The coarser fraction of the clay, i.e., that with particle size above 20 m, is 38%. Conversely, the granite waste has a coarser particle size when compared to that of the clay. As a non-plastic material, however, the granite waste has a relatively ne particle size with 14% of the particles retained in 325 mesh (44 m). Its average particle size is 10 m. This characteristic of the granite waste is of great importance for the red ceramic process. In Campos, the ceramic plants use a pan mill with 0.81.2 mm of light between rolls. This equipment is not adequate to mill hard materials such as granite. In this case, the ceramic process would be more expensive, since it would be necessary to invest in special milling equipment such as a hammer mill. Table 3 presents the calculated chemical composition of the investigated mixtures. One should notice that with increasing granite waste addition there occurs an increase in the percentage of alkaline uxes as well as a decrease in the LoI and alumina content as compared to the simple clay ceramic body, B0G. 3.2. Technological properties Fig. 4 presents an extrusion prognostic using the plasticity of the mixtures [14]. This prognostic is related mainly to the workability and productivity of the green pieces. It can be observed that the simple clay is located outside both,

Table 2 Chemical analysis of the raw materials (wt.%) Raw materials Oxide compositions SiO2 Clay Granite waste 48.84 67.14 Al2 O3 25.94 14.92 Fe2 O3 9.14 4.40 TiO2 1.30 0.73 K2 O 1.91 5.18 Na2 O 0.46 2.93 CaO 0.30 1.91 MgO 0.83 0.73 LoI 10.90 0.50

Intensity (counts)

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Table 3 Chemical analysis of the mixtures (wt.%) Raw materials Oxide compositions SiO2 B0G B10G B20G B30G B40G 48.84 50.67 52.50 54.33 56.16 Al2 O3 25.94 24.84 23.74 22.64 21.54 Fe2 O3 9.14 8.67 8.19 7.72 7.24 TiO2 1.30 1.24 1.19 1.13 1.07 K2 O 1.91 2.24 2.56 2.89 3.22 Na2 O 0.46 0.67 0.87 1.08 1.29 CaO 0.30 0.46 0.62 0.78 0.94 MgO 0.83 0.82 0.81 0.80 0.79 LoI 10.90 9.86 8.82 7.78 6.74

Fig. 4. Extrusion prognostic through Atterberg limits [14]. ( ) Locations of the compositions.

the acceptable and optimum extrusion regions. The result in Fig. 4 reveals that the progressive incorporation of granite waste has a very signicant effect on the extrusion behavior. Mixtures with 30 and 40 wt.% of granite waste are located in the region of optimum extrusion conditions. The apparently unsuitable behavior of clay sample B0G has, however, some practical advantages as an industrial body. The red ceramic industries in Campos prefer to use excessively plastic ceramic bodies due to processing advantages, such as less wear of the equipment, and also by the fact that it can increase both, production and the mechanical strength of the pieces. Fig. 5 plots the variation of the extrusion water versus the granite waste content. The extrusion water is the water con36

tent required for a body to achieve suitable consistence for processing [15]. A linear behavior with a good correlation coefcient can be observed. The decreasing of the extrusion water with increasing granite waste content has signicant consequences, as it fosters the drying by reducing the total time to accomplish this stage and also by decreasing energy costs. As shown in Fig. 6, the increase in granite waste decreases the drying shrinkage. Less drying shrinkage is a factor that may contribute to reduce the risk of appearance of cracks and dimensional defects in ceramic pieces. On the other hand, an excessive amount of granite waste or other non-plastic material can promote cracks due to low particles bonding and, consequently, reduce the mechanical strength. Fig. 7 shows the graphs corresponding to the results of the technological properties after ring. These results indicate that the granite waste addition increases the linear shrinkage, Fig. 7(a), and the bulk density, Fig. 7(b), while the water absorption, Fig. 7(c) is decreased. Within the error, the exural strength, Fig. 7(d) remains constant with granite waste addition. The increase in linear shrinkage and bulk density as well as the decrease in water absorption with granite waste addition are consequences of the higher uxes content, Table 2, as compared to that of the clay. At higher temperatures the uxes cause an increase in the liquid phase promoting densication. Here it is relevant to mention that the dry bulk densities of the mixtures before ring had practically the same value of 1.70 0.02 g/cm3 . This indicates that the observed differences on the technological properties
6 Drying linear shrinkage (%) 5 4 3 2 1 0 0 10 20 30 40
Y = 4.892 -0.088*X R = -0.9999

34

Y = 33.882 -0.283*X R = -0.9947

Extrusion water (%)

32 30 28 26 24 22 0 10 20 30 40

Granite waste (%)

Granite waste (%)

Fig. 5. Variation of the extrusion water with granite waste concentration.

Fig. 6. Variation of the drying linear shrinkage with granite waste concentration.

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3.6 3.6
1.82 1.80 1.78
Bulk density (g/cm )
3

119
1.82

(a)
3.4 3.4 3.2 3.0 2.8 2.6 2.4 2.2

(b)
1.80 1.78 1.76 1.74 1.72 1.70 1.68 1.66
0 10 20 30 40

Linear Shrinkage (%)

3.2 3.0 2.8 2.6 2.4 2.2 2.0 0 10 20 30 40

1.76 1.74 1.72 1.70 1.68 1.66

2.0

Granite Waste (%)

Granite waste (%)

25 24

25

12

12

(c)

24

(d)
11
11 10 9 8 7 6

Water absorption (%)

Flexural strength(MPa)

23 22 21 20 19 18 0 10 20 30 40

23 22 21 20 19 18

10 9 8 7 6 0 10 20 30 40

Granite Waste (%)

Granite waste (%)

Fig. 7. Technological properties of the mixtures after ring: (a) linear shrinkage; (b) bulk density; (c) water absorption; (d) exural strength.

Cumulative intrusion volume x 103(cm3/g)

of the specimens are not inuenced by the dry bulk density or compactness of the ceramic. It is also important to mention the signicant reduction observed on the water absorption with granite waste addition. For example, the body with 40 wt.% of granite waste, B40G, shows water absorption approximately 20% lower than the simple clay body without granite waste B0G. This is an indication that the formation of a larger amount of liquid phase contributes to reduce porosity. The exural strength is a property strongly dependent on the porosity and microstructural defects of the specimen. In principle, due to the densication, one would expect an increase on the exural strength with the granite waste addition. However, by observing the standard deviation on the values of this property, Fig. 7(d), one can conclude that practically no change occurred. This result can be explained by the higher amount of quartz content, Table 3, introduced with the granite waste addition. The quartz can promote the appearance of micro-cracks due to their volumetric variation at 573 C. These micro-cracks are known to act as stress raisers, contributing to reduce the mechanical strength [16,17]. 3.3. Microstructure The pore-size distribution curves are plotted in Fig. 8, for the elaborated mixtures red at 970 C in industrial fur-

nace. These curves demonstrate that the granite waste incorporation played an important role both on the amount of porosity and the pore-size distribution. The volume of pores decreased with increasing granite waste while the pore-size distribution becomes gradually ner. This is due to the increase in the amount of uxes, K2 O+Na2 O, that results in a liquid phase sintering process (vitrication). The decreasing in weight loss with granite waste addition also contributes to the reduction of the open porosity. By contrast, The median
180 160 140 120 100 80 60 40 20 0 0.001 0.01 0.1 1 10
B0G B10G B20G B30G B40G

Pore diameter (m)

Fig. 8. Porosimetry curves of the compositions red at 970 C.

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Fig. 9. SEM photomicrographs of fractured region of the composition B0G. (a) 300; (b) 1000.

pore diameter of the different compositions were: 0.180, 0.294, 0.440, 0.588 and 0.799 m, respectively, for 0, 10, 20, 30 and 40 wt.% granite waste. Apparently, this increase in pore size in initial and intermediate sintering states, with increasing amount of ux from granite waste addition could be attributed to the removal of pores having a small diameter. This leads to differential shrinkage in microdomains of the ceramic piece with coarsening of the larger size pores [18]. Scanning electron micrographs of the fracture surface of bodies without addition, B0G, and with 40 wt.% of granite waste, B40G, are shown, respectively, in Figs. 9 and 10. It can be observed that both bodies present a rough fractured surface. The micrographs of B0G show a comparatively larger amount of defects such as cracks and voids. By contrast, B40G shows a better-sintered microstructure with

fewer defects and smoother areas as compared to B0G. This may be due to the ux action of the granite waste and the lesser LoI. According to what was already mentioned, the incorporation of granite waste promotes a increasing in the ux content, that makes possible a more efcient vitrication process. On the other hand, the higher LoI of body B0G contributes signicantly to increase the porosity, predominantly through the elimination of constitution water from the clay minerals. In principle one should wonder why the enhanced densication provided by the ux action of the granite waste does not translate into a better mechanical performance, Fig. 7(d). As mentioned above, even though the granite waste addition contributes to reduce the open porosity, the median pore diameter increases markedly. This, together with the higher amount of quartz, may introduce large

Fig. 10. SEM photomicrographs of fractured region of the composition B40G. (a) 300; (b) 1000.

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Q

121

Fk

B40G
M Fk Pl

Q M

Pl Fk Pl Fk Fk Pl Mu M M Q Q

B30G B20G B10G B0G

The SEM microstructural analysis showed that the composition with 40 wt.% of granite waste has a ner fracture surface with less defects as compared to the clay without granite waste incorporation. XRD analysis indicated that no signicant effect on the crystalline phases was observed with granite waste incorporation. The use of granite waste in red ceramic can be a technological solution to the problems caused by the indiscriminate disposal into the environment.

Intensity (a.u.)

Mu

10

15

20

25

30

35

40

2
Fig. 11. X-ray diffraction patterns of the mixtures red at 970 C. Fk: potash feldspar; M: micaceous mineral; Mu: mullite; Pl: plagioclase; Q: quartz.

Acknowledgements The support provided by the Brazilian Agencies: FAPERJ (process number E-26/151.544/2001), CNPq and FENORTE/TECNORTE is gratefully acknowledged.

enough pores and micro-cracks to compromise the mechanical strength.Fig. 11 shows the XRD patterns of the mixtures red at 970 C in an industrial furnace. One should notice that the granite waste incorporation did not change the major crystalline phases. The following phases were identied: a micaceous mineral, plagioclase, potash feldspar, quartz and mullite. Feldspars can form residual phases, especially after ring, in the case of the mixtures with high amount of granite waste. Quartz and the micaceous mineral are residual phases for both bodies. Mullite, an aluminum silicate phase formed from the metakaolinite decomposition at temperatures around 9501000 C [19], did not seem to be affected by the granite waste incorporation.

References
[1] J.F.M. Motta, A. Zanardo, M. Cabral Jr., Cer mica Industrial 6 a (2001) 28. [2] S.N. Monteiro, C.M.F. Vieira, Tile Brick Int. 18 (2002) 152. [3] C.M.F. Vieira, S.N. Monteiro, J. Duailibi Filho, Cer mica Industrial a 6 (2001) 43. [4] W.D. Kingery, H.K. Bowen, D.R. Uhlmann, Introduction to Ceramics, 2nd ed., Wiley, New York, 1975, p. 495. [5] G.P. Emiliani, F. Corbara, Tecnologa CermicaLa Lavorazione, Gruppo Editoriale Faenza Editrice, Faenza, 1999, p. 97. [6] Ch. Schmidt-Reinholz, H. Schmidt, Tile Brick Int. 11 (1995) 79. [7] A. Garca-Verduch, J. Requena, Tcnica Cer mica 237 (1995) 616. a [8] A. Garca-Verduch, J. Requena, Tcnica Cer mica 238 (1995) 697. a [9] M.S. Hernndez-Crespo, J.Ma. Rincn, Ceram. Int. 27 (2001) 713. [10] R.R. Menezes, H.S. Ferreira, G. de A. Neves, H.C. Ferreira, Cer mica a 48 (2002) 1. [11] ABNT (Associao Brasileira de Normas Tcnicas), Determinao da Anlise Granulomtrica dos solos, NBR 7181 (1984) 113. [12] ASTM (American Society for Testing and Materials), Water Absorption, Bulk Density, Apparent Porosity, and Apparent Specic Gravity of Fired Whiteware Products C373 (1972) 312313. [13] ASTM (American Society for Testing and Materials), Flexural Properties of Ceramic Whiteware Materials C674 (1977) 674677. [14] M. Marsigli, M. Dondi, LIndustria dei Laterizi 46 (1997) 214. [15] V. Beltrn, E. Ferrando, J. Garca, E. Snchez, Tile Brick Int. 11 (1995) 169. [16] M.F. Abajo, Manual Sobre Fabricacin de Baldosas Tejas y Ladrillos, Beralmar, S.A., Terrassa, 2000, p. 14. [17] V. Kilikoglou, G. Vekinis, Y. Maniatis, Acta Metall. Mater. 43 (1995) 2959. [18] M.J. Ortz, A. Escardino, J.L. Amors, F. Negre, Appl. Clay Sci. 8 (1993) 193. [19] W.M. Carty, U. Senapati, J. Am. Ceram. Soc. 81 (1998) 3.

4. Conclusions The incorporation of granite waste from sawing operation up to 40 wt.% in a clay body for red ceramic has led to the following conclusions: The granite waste can improve the extrusion process, optimizing the plasticity. The granite waste incorporation facilitates the drying stage through the decrease in the working water and the linear shrinkage. The granite waste incorporation decreases the open porosity of the red clay. Consequently, the water absorption decreased with the granite waste content. The exural strength practically did not change.