Applied Clay Science 46 (2009) 404408

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / c l a y

The use of sewage sludge and marble residues in the manufacture of ceramic
tile bodies
M.A. Montero a, M.M. Jordn a,, M.S. Hernndez-Crespo b, T. Sanfeliu c
a
b
c

Department of Agrochemistry and Environment, University Miguel Hernndez, Elche. Avda. de la Universidad s/n. 03202 Elche (Alicante), Spain
Group of Glassy and Ceramic Materials, Instituto Eduardo Torroja de Ciencias de la Construccin, CSIC. C/ Serrano Galvache 4. 28033 Madrid, Spain
Unit of Applied Mineralogy, Department of Agrarian Sciences and Environment, Jaume I University, Campus de Riu Sec s/n. 12080 Castellon, Spain

a r t i c l e

i n f o

Article history:
Received 1 June 2009
Received in revised form 13 October 2009
Accepted 14 October 2009
Available online 28 October 2009
Keywords:
Sewage sludge
Marble residue
Ceramic clays
Ceramic tiles
Recycling

a b s t r a c t
The substitution of clayey raw materials for other wastes, in this case urban sewage sludge and marble
sludge, in the production of traditional ceramics could be cost effective from the utilisation and recycling of
these wastes as a secondary raw material. At the same time, it can be helpful in tempering the environmental
problems associated with such wastes. This research shows the results of the addition of marble sludge and
urban sewage sludge in different proportions to clay in a ceramic body. The most suitable products were
selected regarding the mineralogical composition of the resulting ceramic material and its technological
behaviour. To evaluate the ceramic properties of the obtained material, several processing and product
properties (linear contraction, water absorption, bending strength) were determined. With regard to the
technological properties of the nal ceramic bodies, there does not seem to be any clear relation between the
linear contraction values and the content of residue. However, the increase in water absorption along with
the increase in the residue content is evident. The addition of residue decreased the bending strength. The
selection of the adequate content of sludge to be added to the ceramic body will be controlled by the usual
standards applied to construction materials.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Due to determinant environmental factors, water treatment and
purication processes have been generalised worldwide, especially
in countries with increasing scarcity of water resources. There are several water purication processes, and waste denominated as sewage
sludge is generated in every case and treatment type. If integral
treatment of all the sewage generated were developed in Spain, a
country of 42 million inhabitants, total production of about 3 million
tons of sludge per year would be reached. After composting, and
estimating that between 60% and 70% of the sludge is apt for agricultural
uses, about 500,000 tons of agriculturally-suitable composted sludge
would be reached per year. At the present time the disposal of these
wastes takes place in three ways, such as land or sea dumping, recycling
or utilisation with agricultural purposes, and nally incineration.
Therefore, it is necessary to investigate new applications for these
waste types. Sewage sludge is usually a heterogeneous solid material
whose composition is quite variable depending not only on the origin of
the efuent to be treated, but also on the technology used during its
treatment. These processes will determine the different quantities of the

Corresponding author. Tel.: +34 966658416; fax: +34 966658532.

E-mail address: manuel.jordan@umh.es (M.M. Jordn).
0169-1317/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2009.10.013

inorganic sludge compounds (Sommers, 1997), and thus the extent to

which these compounds are associated to the organic sludge fraction
(Dondi et al., 1997). The efuent origin will determine the presence of
toxic elements and agents. Sludge from large urban areas with
substantial industrial inuences usually shows higher concentrations
of metals typical in factories, such as Cr and Ni. The treatment the
sewage receives during the purifying process may increase the presence
of certain compounds in it, especially ferric or aluminium salts added in
order to favour occulation processes.
On the other hand, about 70% of the processing waste in the
Spanish natural stone industry is disposed of locally. Marble dusts are
usually dumped into riverbeds and this poses a major environmental
concern. In dry seasons, the marble powder/dust is suspended in the
air, transported by wind and can be deposited on vegetation and
crops, signicantly affecting the environment and local ecosystems.
The marble dust deposited in riverbeds and around the production
facilities reduces topsoil porosity and its permeability, resulting in
water logging. What's more, ne particles result in poor soil fertility
due to alkalinity increases (Montero et al., 2009).
Recently, residues have been constructively applied to resources in
recycling research, and related achievements are seen in engineering
applications, and different authors have investigated the incorporation
of different types of residues in the manufacture of traditional ceramic
materials (Dondi et al., 1997, 2002). However, very little research has

M.A. Montero et al. / Applied Clay Science 46 (2009) 404408

been focused on ways to improve the properties of clay tiles. It is well

known that the mechanical properties of ceramics are an important
parameter for dening their uses and applications (Zweben, 1991). It is
also obvious that the raw materials in ceramics manufacturing have an
important inuence on the ceramic properties.
Following this trajectory, a study with residues of a different
nature is being carried out in order to improve different behaviour
and defects in traditional ceramic products like bricks and roong
tiles. From the economic and environmental point of view, the use of
such residues could suppose additional advantages as they are converted from residues into secondary raw materials.
This paper reports the rst results when partially substituting
ceramic pastes of a clay type rich in silica with residues. The ceramic
pieces were moulded by pressing and the mineralogical characterisation was carried out after ring.
During the ring process of ceramic pastes a series of reactions and
transformations take place in the clay minerals and accompanying
minerals like quartz, feldspar, calcite, dolomite and hematite, which
will be decisive in establishing the nal properties of the ceramic
products (Jordan et al., 1999). There is a substantial amount of literature on the disappearance and the neomineralisation of clay
bodies by ring. Gonzlez-Garca et al. (1990) studied the formation
of gehlenite and anorthite in calcareous clays which were originally
composed of illite, kaolinite, quartz and calcite. Jordan et al. (1999)
studied Cretaceous clays from Castellon and their behaviour when
heat treated by fast ring. Jordan et al. (2006) discusses the behaviour
of two calcareous clays from the areas around Agost (Alicante) and La
Rioja (Spain) mixed with different quantities of sewage sludge.
The aim of this work is to study the effects on the technological
properties of a ceramic material when clay is substituted for urban
sewage sludge and marble residue in different proportions.
2. Materials and methods
2.1. Characterisation of raw materials
A standard ceramic clay and three sewage sludge samples (A, B and C)
2
coming from three different sewage plants were selected. Soluble SO
4

and Cl (expressed in ppm) were analysed by gravimetry and titration,

respectively. The total organic matter was determined by calcination at
500 C while the loss of mass was determined by calcination to 1000 C.
The CaCO3 content was determined by calcimetry. The content of heavy
metals and trace elements were analysed by X-ray uorescence in all the
samples. The mineralogical analysis of the clay samples was carried out by
XRD on oriented aggregates (normal, heated to 550 C during 2h and
treated with ethylene glycol) using a Siemens D-500 with BraggBretano
geometry.
A representative sample of a residue rich in calcium carbonate
(sludge) was selected from different marble plants of the natural
stone industry of Alicante province (Spain).
Chemical characterisation of the residue employed was done by X-ray
uorescence (XRF) with a PW2400 X-ray spectrometer with rhodium
target X-ray tube, controlled by SuperQ/Quantitative version 1.1 software.
2.2. Design of the green body
Some experimental tests were carried out with the ceramic clay,
sewage sludge B and the marble residue. Such tests consisted of the
preparation of mixtures with the following sludge contents: 0 (control),
1, 2, 3, 4, 5 and 10 (mass. %) and 0 (control), 15, 20, 25, 30 and 35% of
marble residue, respectively.
The test bodies were pressed with a laboratory Mignon-S Nanetti
uniaxial press, at 40 MPa, and shaped on discs of 20 mm diameter,
5 mm thick and approximate weights of 3.5 g. The usual industry
sector ring cycles were designed (0500 C: 2 h; 500650 C: 2 h;
650Tmax: 2 h; Tmax: 4 h), and maximum temperatures (Tmax) of

405

975, 1000, 1025 and 1050 C were reached. The mineralogical analysis
of the red test bodies was carried out by XRD using the usual
conditions and techniques.
2.3. Determination of linear contraction and water absorption capacity
The linear contraction was calculated in both dried (DLC) and
heated (HLC) samples. The linear contraction was determined following the conventional techniques.
The water absorption capacity (%) was determined in ceramic tile
bodies following ISO-10545-3.
2.4. Bending strength
With the aim of determining the extent that the residue introduction
in the ceramic paste affects the mechanical properties of the product, the
bending strength of both the dried and heated samples was carried out
using INSTRON 1011 equipment with the 3-point loading method
(Montero et al., 2009).
Before carrying out the test the load speed was xed at 0.02 mm/s for
dried bodies and 0.05 mm/s for heated ceramic samples. The test was
performed on ten specimens of each sample following the Montero et al.
(2009) methodology.
3. Results and discussion
3.1. Characterisation of the employed clays and residues
Table 1 shows the chemical composition of the clays. The application of sludge would slightly increase the contents of chlorides and
sulphates in the paste (Table 1). However, due to the low amount of
added sludge, the content of total soluble salts in the new raw material
(clay + residue) will be similar to at currently applied in local ceramic
industries.
The clays used contained kaolinite, illite, chlorite, illite/smectite and
chlorite/smectite, quartz and small quantities of feldspars (plagioclase
and orthoclase), hematite, calcite, dolomite and gypsum (in traces). The
analysis of the glycolated samples detected the presence of interstratied minerals (I/S and C/S) as well as montmorillonite (Table 2).
Tables 3 and 4 show the chemical composition and the heavy metal
content of the sewage sludge. All of these metals, cadmium, chrome,
copper, mercury, nickel, lead and zinc appear in Spanish regulations, and
their concentration in the sludge is the factor determining their possible
agricultural use. Cadmium and mercury were not detectable in either
the sludge or the ceramic clays. Chromium appeared in sludge A in a
concentration similar to the one appearing in the ceramic clays, while in

Table 1
Chemical analysis of ceramic standard clay.
Parameter

Units

Ceramic clay

O.M. 500 C
Deads (1000 C)
CaCO3
2
SO
(solubles)
4
Cl (solubles)
SiO2
Al2O3
Fe2O3
CaO
MgO
Na2O
K2O
TiO2
MnO
P2O5
Total SO3

%
%
%
ppm
ppm
%
%
%
%
%
%
%
%
%
%
%

1.96
12.23
21.00
4358
212.85
52.69
17.85
7.15
11.29
4.24
0.394
4.23
0.868
0.0502
0.195
0.570

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M.A. Montero et al. / Applied Clay Science 46 (2009) 404408

3.2. Characterisation of the red test bodies

Table 2
Mineralogical composition (%) of the clay.
Raw material

Clay fraction

Phy

Cc

Do

Hm

I/S

C/S

35

45

10

45

25

10

15

Legend: Q: quartz; F: feldspars; Phy: clay minerals; Cc: calcite; Do: dolomite; hem: Hematites;
I: illite; K: kaolinite; C: chlorite; I/S: illite/smectite; C/S: chlorite/smectite; x: <5%.

Table 3
Chemical analysis of sludge (W.W.T.P.: Waste Water Treatment Plant).
Parameter

Units

W.W.T.P-A

W.W.T.P-B

W.W.T.P-C

O.M. 500 C
Deads .(1000 C)
CaCO3
2
SO
(solubles)
4
Cl (solubles)
SiO2
Al2O3
Fe2O3
CaO
MgO
Na2O
K2O
TiO2
MnO
P2O5
Total SO3
Total

%
%
%
ppm
ppm
%
%
%
%
%
%
%
%
%
%
%
%

58.13
65.98
7.86
8048.82
849.10
9.53
5.37
16.70
26.24
2.55
1.23
1.65
0.883

28.36
4.95
97.46

54.13
64.64
20.25
657.18
2664.43
12.15
6.19
15.24
32.18
1.66
0.584
0.997
1.15

13.39
13.34
96.88

56.20
66.12
16.52
672.24
1786.23
17.09
8.80
4.26
42.46
1.73
0.349
1.46
1.25
0.0260
17.39
3.31
98.13

Table 4
Heavy metals content in sludge from waste water treatment plants A, B and C (mass %
oxide).
Heavy metals

W.W.T.P.-A

W.W.T.P.-B

W.W.T.P.-C

V2O5
Cr2O3
Co3O4
NiO
CuO
ZnO

0.0087
0.0195
0.0138
0.0050
0.068
0.311

0.0176
0.0309
0.0114
0.0221
0.269
0.438

0.0241
0.0397
<d.l.
0.0141
0.167
0.338

<d.l.: less than the detection limit.

sludge B and C its concentration is slightly higher. In the case of the

wastes, sludge A presents low Cu contents, which increases in the case of
sludge B and even more in C. Nickel appeared in low concentrations in
sludge A, and increases in sludge B and C. Sludge A and C showed lower
Pb contents than sludge B. Therefore, the use of the sludge for
manufacturing traditional ceramics would be more convenient than
for agricultural applications.
The marble sludge (Table 5) was very rich in calcium carbonate
(98.7%). The dry marble residue presented a very ne particle size
distribution (Montero et al., 2009).

At 975 C CaCO3 decomposed and CaO was formed inside the

material (Table 6). The illite transformed into spinel-type phases
(Gonzlez-Garca et al., 1990; Jordan et al., 1999). CaO reacted with
quartz and metastable wollastonite and gehlenite appeared (Jordan
et al., 1999). With increasing temperature, the gehlenite amount
decreased and augite is formed at 1025 C. The mineral transformations can be evaluated from the ternary equilibrium diagram CaO
Al2O3SiO2. In this diagram, the compatibility triangles (Fig. 1) are
SiO2CaO.SiO2CaO.Al2O3.2SiO2 (QuartzWollastoniteAnorthite)
for low contents of added residue. Nevertheless, the addition of a
high content of residue with an elevated CaO content moves the
nal composition of the body to the CaO.SiO2CaO.Al2O3.2SiO2
2CaO.Al2O3.SiO2 (WollastoniteAnortiteGehlenite) compatibility
triangle (Fig. 1). A part of CaO did not react because its quantity
was in excess of the free silica able to react with it (Jordan et al,
2001).
The new formulations subjected to commonly used ceramic
industry ring processes yielded mineralogical compositions similar
to those obtained with marls or carbonated clays.
Fig. 2 shows the results of linear contraction tests in both dried and
heated samples. There was no clear tendency, conrming that this
technological property was not related to the added amounts of
sludge. In contrast, water absorption (Fig. 3) increased with the
quantity of sludge in the body. This was expected since calcium
carbonate in the residue was transformed during the thermal process
and leads to an increased amount of the open pores of the ceramic
bodies (Weng et al., 2003; Jordan et al., 2006).
The bending strength (Table 7) decreased when the amount
of sludge was increased. Thus, the content of sludge to be added
to the body must be controlled to achieve the standards of specic
construction materials. The ceramic tile body bending strength
meets the required specication when 16% to 22% of the clay in the
ceramic tile bodies was substituted by the residue (Liew et al.,
2004).
4. Conclusions
Added residues (sewage sludge and marble sludge) have been
demonstrated to possess great reactivity and, therefore, reacts easily
with the clay minerals and quartz, providing better sintering of
original powders. The main advantages of these residues in the
manufacture of traditional ceramics include the recycling of wastes
whose production increases every day, immobilisation of heavy
metals, and a reduction in raw material costs. Using the residues in
the manufacture of bricks and roong tiles affects the nal properties
of these products. With regards to the technological properties of the
nal ceramic products manufactured, incorporation of the residues is
limited due to the increase of the water absorption and decrease of the

Table 6
Mineral phases present and formation of new mineral phases (in c.p.s.) according to the
ring temperature of the green body.
Table 5
Composition (mass % oxides) of the marble residue uses for the compositional design of
the body. LOI: Mass loss by ignition.
%

Marble

Marble

CaO
MgO
Al2O3
SiO2
Fe2O3
LOI

75.70
0.26
0.36
1.00

22.60

SrO
SO3
P2O5
TiO2
MnO

0.01
0.06
0.01

T (C)

Mineral phase (c.p.s.)

Q

CaO

975
1000
1025
1050
d ()

3500
1860
1710
1190
3.34

162
189
155
2.49

Plg
425
520
518
3.20

Au

758
861
2.98

Gh

Hm

875
635
329
2.85

301
180
132
100
2.69

Es

285

600

2.46

3.83

Cc

Or

294

254

9.98

3.03

414
432
379
409
3.24

Legend: Q = quartz; CaO = calcium oxide; Plg = plagioclase; Au = augite; Gh =

gehlenite; Hm = hematite; Es = spinel; W = wollastonite; I = illite; Cc = calcite; Or =
orthoclase.

M.A. Montero et al. / Applied Clay Science 46 (2009) 404408

407

Fig. 1. CaOAl2O3SiO2 system for the ve compositions.

Table 7
Bending strength of the original green body and the sintered ceramic after thermal
cycling.
Bending strength (MPa)

Fig. 2. Drying linear contraction (DLC) and heating linear contraction (HLC) expressed in %.

bending strength. The amount of added wastes must be controlled in

such a way that the product adequately meets the specic standards
required for construction materials.

Residue (%)

Green

Sintered

0
16
22
28
34
40

2.05
1.76
1.71
1.06
1.25
1.09

13.50
10.26
9.00
8.30
8.10
4.90

Acknowledgements
The authors would like to express their gratitude to the Generalitat
Valenciana (Project code: AE07/12) and Dr. Lagaly for the revision of
this manuscript.

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