Construction and Building

Construction and Building Materials 22 (2008) 781787

MATERIALS
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Characteristics of clays and properties of building ceramics in the state of Rio de Janeiro, Brazil
nchez, S.N. Monteiro C.M.F. Vieira *, R. Sa
State University of the North Fluminense Darcy Ribeiro UENF, Advanced Materials Laboratory LAMAV, Av. Alberto Lamego 2000, 28013-602 Campos dos Goytacazes, RJ, Brazil Received 30 November 2005; received in revised form 4 December 2006; accepted 29 January 2007 Available online 21 March 2007

Abstract The general characteristics and technological properties of four types of clays obtained from the same location at the north of the State of Rio de Janeiro, Brazil, have been investigated. These clays are intended for applications in ceramics such as bricks and roong tiles. Clays were rst analyzed by X-ray diraction, chemical composition particle size distribution, thermal analysis and plasticity. Extruded samples were red at temperatures varying from 850 to 1100 C to determine the linear shrinkage, water absorption and exural rupture strength. The results showed that three of the studied clays have adequate characteristics for brick fabrication. However, for two of these adequate clays it is necessary to add convenient materials to enhance the workability. The high porosity developed after ring impairs the use of these clays for roong tiles. This is a consequence of the kaolinitic nature of the clays as well as their elevated loss on ignition. 2007 Elsevier Ltd. All rights reserved.
Keywords: Clays; Characterization; Ceramics; Properties

1. Introduction Worldwide, clays are the main raw materials exploited in the fabrication of diversied ceramic products for building construction. Due to inherently complex physical, chemical and mineralogical characteristics, clays usually have unique properties related to their own natural diagenesis [14]. Normally, for economic reasons, the buildingrelated ceramic industry has to use clays from nearby deposits. As a consequence, the characterization and quality control of each clay is important for the technical performance of local products [5,6]. Moreover, a specic deposit may have distinct layers associated with dierent clays. This gives a regional industry the opportunity to mix dierent clays in order to adjust the properties of both the unred ceramic body and corresponding nal product.

Corresponding author. Tel./fax: +55 22 27261533. E-mail address: vieira@uenf.br (C.M.F. Vieira).

Brazil is one of the worlds largest producers and consumers of clayey ceramic. The northern region of the State of the Rio de Janeiro, southeast of Brazil, has an area of around 1000 square kilometers with abundance in alluvial clays formed by quaternary sediments carried by the Para ba River [7]. Today, this has motivated the development of a ceramic sector for bricks and roong tiles that comprises more than 100 small and medium size industries with a total production estimated at more than 100 million pieces/month. The regional industries rely on a large number of natural deposits from which to extract the clays. For the vast majority of existing deposits, only empirical knowledge is used to process the clay, which frequently result in products below specications. Since the microstructure and properties of any ceramic depends on the characteristics of the raw materials and processing parameters [8], to assure the quality of ceramic products, a complete characterization of the precursor clays as a function of the ring temperature is needed. The objective of the present work was to characterize the

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clays found in a micro-regional deposit located at the Fazenda Santa Helena (Saint-Hellen Farm) in the municipal area of Campos dos Goytacazes, northern Rio de Janeiro State. This is an important deposit comprising layers of four dierent clays locally named as: amarela (yellow), cinza (grey), preta (black) and tabatinga (and indian name for clay). These clays will be referred to, respectively, as Y, G, B and T. 2. Materials and methods The four types of clays, Y, G, B and T, used for the fabrication of bricks and roong tiles were extracted directly from the Saint-Hellen farm deposit. The clays were quarted to provide statistically valid samples. Initially, the samples were dried at 110 C and desegregated through a 20 mesh (840 lm) sieve. Powder samples were characterized by Xray diraction (XRD), chemical analysis, particle size distribution, dierential thermal analysis (DTA), thermogravimetric analysis (TGA), and plasticity measurement. Technological properties were evaluated for both, simply dried and red specimens. In simply dried specimens, the bulk density and the drying linear shrinkage (DLS) were determined. Water absorption and exural strength, were obtained in red specimens. Post-ring linear shrinkage (FLS) was also determined. The XRD was carried out in a Seifert, model URD 65 diractometer operating with Cu-Ka radiation for a 2h varying from 5 to 40. The chemical composition was determined by X-ray uorescence spectroscopy in a Philips PW 2400 equipment. The particle size distribution was determined by both, sieving and sedimentation methods, following the appropriate norm [9]. The DTA/TGA of the bodies was simultaneously conducted in a TA model SDT 2960 equipment, operating in static air and at a heating rate of 10 C/min. The plasticity was obtained through the determination of the Atterberg limits. These are the plasticity limit (PL), and plasticity index (PI), according to the norms [10,11]. Unred rectangular (100 25 10 mm) specimens, in lots of 10 for each clay, were molded using an extrusion apparatus. These specimen bodies were dried at room temperature for 72 h and then at 110 C for 24 h in a stove. The ring stage was carried out in the temperature range from 850 to 1100 C, at intervals of 50 C. The heating rate of the electric mue furnace used for ring was 3 C/min with 1 h soaking at the maximum temperature. Cooling occurred by natural convection inside the furnace after it was turned o. The technological properties were evaluated, as followed, using all specimen bodies and, for each type of clay, calculating the mean value and standard deviation. The dry bulk density was measured dividing the mass by the external volume for each specimen. The water absorption was determined according to standard procedure [12]. Both, DLS and FLS were obtained by the relative variation in length of the samples using a Mitutoyo calliper (precision of 0.01 mm). The exural rupture

strength was obtained using a three points bending test in an Instron 5582 universal testing machine, according to standard procedure [13]. 3. Results and discussion Fig. 1 presents the XRD pattern of the four types of clays investigated. It should be noted that all clays have their major peaks associated with kaolinite (K). This is in agreement with most clays found in the northern Rio de Janeiro [14]. In addition, all clays exhibit minor contributions of quartz (Q) and gibbsite (Gi). The Y and T clays, in particular, display diraction peaks corresponding to goethite (Go), lepidocrocite (L) and muscovite mica (M). Pyrite (P) was only detected in the T clay. The presence of pyrite (FeS2) is undesirable due to the formation of SO2 or SO3 during the ring stage [15]. The relatively high intensity of the quartz peaks in the Y clay, Fig. 1a, indicates a signicant presence of free silica. This can be conrmed by the greater SiO2/Al2O3 ratio and smaller loss on ignition (LoI) for the Y clay in Table 1. Table 1 shows the chemical composition of the clays, where it can be observed that all clays present SiO2 and Al2O3 as the most predominant oxides. These oxides are mainly associated with the kaolinite structure [1]. A minor part is due to the presence of muscovite mica. The SiO2 content is also associated with quartz particles and the Al2O3 is associated with gibbsite. The relatively low SiO2/ Al2O3 ratio of all clays is an indication of expressive amount of kaolinite, which represents 46.5 wt.% of SiO2 and 39.5 wt.% of Al2O3. The participation of kaolinite is more signicant in clays G and B. Iron oxide, Fe2O3, is the main colorant in the clays, being responsible for the reddish color after ring [15]. According to Table 1, clays Y, G and T have a comparatively high amount of Fe2O3. Clay B presents the lower amount of Fe2O3, which confers, to this type of clay, a lighter color after ring. This is an important technological aspect that renders possible the use of clay B in the fabrication of products with a cream tonality, especially for use in roong tiles and rustic oor tiles. Another important aspect with respect to the chemical composition of the clays is the low amount of K2O that is considered the main ux agent of clayey materials [15,16]. Again, this can be associated with the kaolinitic predominance of the clays. The value of LoI is related to the dehydroxylation of the clay minerals, organic matter oxidation, decomposition of carbonates, suldes, hydroxides, etc. [12]. The weight loss of the investigated clays will be discussed in details with the presentation of the DTA/TGA curves. Fig. 2 presents an extrusion prognostic using the plasticity of the mixtures [17]. The plasticity limit, PL, corresponds to the amount of water necessary for the clay to reach a plastic consistency, which makes it possible for it to be formed by extrusion. The plasticity index, PI, is associated with the range between plastic and sludge consistency. For practical purposes, the plasticity index must be above 10% [15]. Clays that present values of PI lower than

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24,9

783

Q K Q K

12,35

clay Y
Intensity (a.u.)

clay G

Intensity (a.u.)

Gi C Q L GoGi M M L M M K
K

Gi 20 K Q
26,65

38,45 35 18,3 Gi 10,15 16,75 18,8 26,15 23,4

K
K

Q Q K

K K Q

K QK

36,95

10

15

20

25 2

30

35

40

10

15

20

25 2

30

35

40

K
19,85

26,6

clay B
Q Q
38,4 34,9 18,25

clay T
Intensity (a.u.)
Gi K Q

Gi K

Intensity (a.u.)

K
K K

M Gi L Go M K P P M
K P

K
Q

Gi
11,1 14,8 10 14,3 19,05 16,7 23,2 25,95

K 39,15
Q 36,9 QK

10

15

20

25 2

30

35

40

10

15

20

25 2

30

35

40

Fig. 1. X-ray diraction patterns of the clays. K = kaolinite; Gi = gibbsite; Go = goethite; L = lepidocrocite; M = muscovite mica; P = pyrite; and Q = quartz.

10% are not appropriate for building-related ceramic production due to the risk of problems during the extrusion process. These problems are related to a possible variation in the amount of extrusion water, causing inappropriate dimensional characteristics and even cracks in the green pieces. Fig. 2 reveals that the simple clay is located outside both the acceptable and optimum extrusion regions. The result in Fig. 2 reveals that none of the investigated clays are located inside the optimal extrusion region. Clays Y and B are located inside the region still considered acceptable. On the other hand, clays G and T are inappropriate for extrusion due to their high plasticity parameters. Fig. 3 presents the particle size distribution of the clays. Within each graph the corresponding clay, silt and sand fractions are indicated according to the International Society of Soil Science [1]. The clay fraction is associated with very ne clay minerals that are the main responsible for the plasticity of clayey materials. According to Fig. 3, clay
Table 1 Chemical composition of the clays (wt.%) Clays Determination SiO2 Y G B T 43.86 43.64 44.81 38.13 Al2O3 27.52 33.76 33.97 26.81 Fe2O3 12.82 5.36 3.93 6.70 TiO2 1.23 1.36 1.30 1.01

Fig. 2. Extrusion prognostic through the Atterberg limits [17].

G displays the highest amount of clay fraction, 68 wt.%. This is the reason for its elevated plasticity as already presented in Fig. 2. By contrast, clay T presents the lowest

K2O 1.50 1.20 1.09 0.80

Na2O

CaO 0.19 0.16

MgO 0.89 0.79

LoI 11.57 13.75 14.74 26.56

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100 Cumulative mass percent finer

100 Cumulative mass percent finer 90 80

clay Y
22.4 silt 37.6 sand

clay G

90 80 70 60 50 40 30 20 1 10 100 1000

40 70 clay
60 50 40 30 20 1

68 clay

25.3 silt

6.7 sand

10

100

1000

Particle size (m)

Particle size (m)

100 Cumulative mass percent finer 90 80 70 60 50

Cumulative mass percent finer

clay B

100 90 80

clay T
32 31.4 silt 36.6 sand

70 clay 60 50 40 30 20 1

59

40 clay 30 20 1

29.3 silt

11.7 sand

10

100

1000

10

100

1000

Particle size (m)

Particle size (m)

Fig. 3. Particle size distribution of the clays.

Fig. 4. ATD/TG/DTG curves of the clays.

C.M.F. Vieira et al. / Construction and Building Materials 22 (2008) 781787 Table 2 Dierential thermoanalysis data for the ceramic bodies Clays Peak temperature (C) (I) Y G B T 54.0 65.7 (II) 100.3 (III) 275.5 263.3 272.3 268.0 (IV) 352.8 (V) 499.3 493.3 491.4 488.6 (VI) 574.1 (VII) 960.0 975.2 970.3 Y G B T Table 3 Pre-ring parameters of the clays Clay Parameters Extrusion water (%) 27.5 40.0 34.4 38.2 Dry bulk density (g/ cm3) 1.62 1.53 1.55 1.46

785

Drying linear shrinkage (%) 2.6 5.3 3.6 5.5

amount of clay minerals, 32 wt.%. Since clay T is the second most plastic in terms of its plasticity limit, one may conclude that its silt fraction also helps the development of plasticity. Clays Y and T present relatively high amounts of sand fraction, 37.6 and 36.6 wt.%, respectively, which are associated with particles with an equivalent spherical diameter above 20 lm. Fig. 4 shows the DTA/TGA/DTG curves for each clay, while Table 2 lists the data corresponding to DTA peaks temperatures. The rst endothermic peak (I) in clays B and T, and the second (II), in clay T, are characteristics of a loss of hygroscopic water. The third endothermic peak (III), from 263.6 C (G) to 275.5 C (Y) can be related to Al and Fe hydroxides decomposition such as gibbsite, lepidocrocite and goethite. The presence of both aluminum and iron hydroxides is undesirable since they demand an additional energy input for decomposition. Moreover, the formation of the corresponding oxides, Al2O3 and Fe2O3, increases the refractoriness of the ceramic bodies as well as their loss on ignition. The weight losses associated with these hydroxides are 1.9%, 2.0%, 2.3% and 4.3% for clays Y, G, B and T, respectively. After these endothermic peaks, an exothermic peak (IV) is observed for clay T. This peak is associated with organic matter decomposition. Pyrite oxidation also involves an exothermic transformation in the temperature range 350500 C [15,18]. However, this transformation is partially hidden by the kaolinite dehydroxylation. This reaction corresponds to the fourth endothermic peak (V), from 488.6 C (T) to 499.3 C (Y). The comparatively larger weight loss, 15.9%, of clay B and 10.9% of clay G is an indication that these clays have a composition richer in kaolinite. The last endothermic peak, associated with the allotropic transformation of quartz (VI), was only detected for clay Y. This result is in accordance with the particle size distribution, Fig. 3, indicating that clay Y has the largest amount of quartz. Clay T is the only one to present weight loss associated with temperature peaks above 500 C. At 615.3 C the weight loss of 3.8% is probably related to the dehydroxylation of constitution water of micaceous mineral. The last weight loss was detected at 746.2 C, which may be associated to the elimination of hydroxyl groups of esmectite clay minerals, which are not detected by XRD. Finally, the exothermic peak (VII) from 960 C (Y) to 975 C (G) is characteristic of metakaolinite dissociation [19]. As a complementary remark regarding the thermal analysis, it should be mentioned that the common characteristics for all clays are the presence of two ranges of

endothermic peaks, which are related to the decomposition of Al and Fe hydroxides and the dehydroxylation of the kaolinite. Table 3 presents the parameters associated with the forming and drying stages for the investigated clays. In this Table one should observed that the least plastic clay, Y, which need less extrusion water, presents the highest degree of compactness, given by its bulk density, and the lowest drying linear shrinkage. By contrast, the most plastic clays, G and T, present the highest amount of extrusion water, lowest dry bulk density and greatest drying linear shrinkage. The shrinkage of the clays during the drying stage can be related to both, the degree of compactness and the amount of extrusion water. Excessive shrinkage may cause dimensional problems in the pieces and the appearance of cracks. For these reasons, clays G and T need the addition of non-plastic materials to adjust their plasticity. Figs. 5 and 6 present, respectively, the graphs corresponding to the gresication diagram and exural rupture strength of the clays as a function the ring temperature. These results indicate that all clays present only moderate changes in the red properties from 850 to 1000 C. However, above 1050 C signicant changes can be observed such as an increase in the linear shrinkage and the exural rupture strength together with a decrease in the water absorption. This high temperature behaviour is associated with the sintering mechanism, essentially of viscous-ow type, that promotes the densication of the samples, reducing the porosity [8]. In Fig. 5 one should notice that clay T presents the greatest water absorption and linear shrinkage of the investigated clays at all temperatures. This behaviour is associated with its low dry bulk density and high weight loss during the ring stage. In general, all clays show a signicant decrease in water absorption above 1000 C due to more eective sintering mechanisms, as discussed previously. The exural strength in Fig. 6 is a property which is strongly dependent on the porosity and microstructural defects of the specimen. Within the standard deviation, one may conclude that practically no change occurred up to 1050 C. At 1100 C, however, there is a noticeable tendency of increasing strength for the average values. As previously mentioned, these results can be explained by the kaolinitic predominance of the clays due to their refractory behaviour from 850 to 1050 C, which is associated with poor sintering consolidation by both, solid state and viscous-ow mechanisms. Above 1050 C, the viscous-ow

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42 39 Water absorption-WA (%) 36 33 30 27 24 21 18 15 12 850

C.M.F. Vieira et al. / Construction and Building Materials 22 (2008) 781787

8

42 39 Water absorption-AA (%) 36 33 30 27 24 21 18 15 12 850 900 950 1000 o Temperature ( C) 1050 1100

clay Y
WA FLS Linear shrinkage-FLS (%)
6

clay G
WA FLS Linear shrinkage-FLS (%) 6

900

950

1000
o

1050

1100

Temperature ( C)
42 39 Water absorption-WA (%) 36 33 30 27 24 21 18 15 12 850 900 950 1000
o

42 Water absoorption-WA (%) 39 36 33 30 27 24 21 18 15 12 850 900 950 1000

o

clay B
WA FLS Linear shrinkage-FLS (%)
6

clay T
Linear shrinkage-FLS (%)
6

WA FLS

1050

1100

1050

1100

Temperature ( C)

Temperature ( C)

Fig. 5. Gresication diagram of the clays.

type of sintering, known as vitrication, causes a reduction in porosity. As a consequence, the clays should experience an increase in mechanical strength.
26 24 22 20 18 16 14 12 10 8 6 4 2 850 900

Finally, it is worth mentioning that according to the Brazilian norm [20], all clays from Saint-Hellen Farm present satisfactory characteristics and properties for brick pro26 24 22 20 18 16 14 12 10 8 6 4 2 850 900

Flexural rupture strength (MPa)

Flexural rupture strength (MPa)

clay Y

clay G

950 1000 1050 o Temperature ( C)

1100

950 1000 1050 o Temperature ( C)

1100

26 24 22 20 18 16 14 12 10 8 6 4 2 850 900

Flexural rupture strength (MPa)

Flexural rupture stregth (MPa)

clay B

26 24 22 20 18 16 14 12 10 8 6 4 2 850 900

clay T

950

1000
o

1050

1100

950

1000
o

1050

1100

Temperature ( C)

Temperature ( C)

Fig. 6. Flexural rupture strength of the clays as a function the ring temperature.

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duction. The only exception being clay T below 1100 C. By contrast, due to their relatively high porosity and consequently high water absorption, none of the clays attend the norm [21] for roong tiles red below 1100 C. Reduction in porosity could be attained by the addition of ux material. 4. Conclusion The characteristics of four types of clays from the same deposit in Campos dos Goytacazes, State of Rio de Janeiro, Brazil, and the eect of the ring temperature on their properties led to the following conclusions:  All clays present kaolinitic predominance, with quartz and gibbsite as common accessory minerals. Clays Y and T also present iron hydroxides and muscovite mica. Clay T is the only one that has pyrite.  Due to the relatively high amount of Al2O3 and low amount of uxes, all clays have a refractory ring behaviour, which results in small variations in the properties at low temperatures.  Clays G and T have an extrusion behavior that is not acceptable for clayey body processing and, therefore, would require addition of non-plastic material to improve their workability.  Clays Y, G and B present characteristics and ring behaviour satisfactory for brick production. Clay T is inappropriate for building-related ceramic fabrication, mainly due to the presence of pyrite and organic matter.  None of the clays attends the water absorption requirement for roong tiles below 1100 C. This can be solved by ux addition.

Acknowledgements The support provided by the Brazilian Agencies: FAPERJ, CNPq and FENORTE/TECNORTE is gratefully acknowledged. References
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