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Effect of Marble and Granite Sludge in Clay

Materials
Article in Materials Science and Engineering A March 2006
Impact Factor: 2.57 DOI: 10.1016/j.msea.2006.01.021

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Universidade Federal do Rio Grande do Norte

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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
a

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

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 flexural 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 flux 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 refinery, 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), fluxing 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

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

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 fluorescence, EDX-700, Shimadzu), mineralogical composition (X-ray
diffraction, XRD-6000, Shimadzu), and thermal behavior (differential thermal analysis (DTA-50, Shimadzu), thermogravi-

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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 five 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 specified by the European standard EN 99. The crystalline phases
of the raw materials and the sintered samples were identified 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 significant 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 fluxing 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 identified 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 shrink-

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 confirming 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 significantly at 1100 and 1150 C.
This behavior is related to the lower viscosity of the liquid
phase and the consequently improvement on the densification
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 flexural 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.

Table 1
Chemical composition of the raw materials, as determined by XRF

Clay
Reject

Al2 O3

SiO2

Fe2 O3

CaO

Na2 O

K2 O

MgO

TiO2

P2 O 5

MnO

LoI

27.02
13.65

40.61
37.86

12.07
3.56

1.42
19.92

0.80
3.58

4.40
4.32

2.88
3.49

1.41
0.61

0.17
0.27

0.18
0.07

8.48
12.37

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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 figure, the incorporation of reject (no
plasticity material) reduces slightly the flexural 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 flexural strength, that can be attributed to an
improvement of the densification process. The strength, water

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

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

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309

References

Fig. 7. Variation of the flexural 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.

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