Applied Clay Science 69 (2012) 5057

Contents lists available at SciVerse ScienceDirect

Applied Clay Science

journal homepage: www.elsevier.com/locate/clay

Combining mineral and clay-based wastes to produce porcelain-like ceramics: An

exploratory study
J.A. Junkes a, P.B. Prates a, D. Hotza a, A.M. Segades b,
a
b

Departments of Mechanical and Chemical Engineering (EMC/EQA), Federal University of Santa Catarina (UFSC), 88040-900 Florianpolis-SC, Brazil
Department of Ceramics and Glass Engineering (CICECO), University of Aveiro, 3810-193 Aveiro, Portugal

a r t i c l e

i n f o

Article history:
Received 6 May 2011
Received in revised form 17 May 2012
Accepted 13 August 2012
Available online 17 October 2012
Keywords:
Ceramics
Mineral waste recycling
Phase diagrams
Clay
Gneiss
Varvite

a b s t r a c t
The present work was aimed at producing waste-only ceramics with higher added value, while nding a viable
end-use, other than landlling, for wastes from extraction and beneciation of mineral resources. Based on their
uxing character and plasticity, four non-hazardous industrial wastes were selected and characterized: one clay
mining tail, the sludge from potable water treatment and two sludges from gneiss and varvite cutting processes.
Using the phase diagram of the SiO2Al2O3K2O system, four mixtures located within the wastes-dened polygon were formulated, uniaxially pressed and red for 40 min at 9001150 C. The results obtained for the properties of red samples show that water absorption values below 10% (ceramic tiles) and 3% (porcelain tiles) were
reached upon ring at 1100 and 1150 C, respectively, without ring warpage. Density values were also within
the usual range but exural strength, although adequate for common application, is lower than usual (at least
3 MPa). In terms of industrial production, although process adjustments are still required (green processing,
ring cycle) the obtained results demonstrate that porcelain-like ceramic tiles can be manufactured using only
the selected wastes as raw materials, suggesting that, for the composition range investigated, ring temperatures
should be ~1100 C and a fast-ring type processing might be feasible.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Ceramic processes have long been regarded as ideal to accomplish
inertization of potentially hazardous wastes (Bingham and Hand, 2006)
and, given the composition similarities between some wastes and
natural raw materials used in ceramics manufacture, this has led to the
general acceptance of ceramic industry, particularly the sector dealing
with construction materials, as a potentially high consumer of wastes
from other industrial sources (Acchar et al., 2006; Acchar et al., 2009;
Correia et al., 2009; Dondi et al., 1997; Menezes et al., 2009; Segades,
2006; Vieira and Monteiro, 2009). Some wastes often also contain materials that are benecial for the ceramics manufacture processes (Acchar
et al., 2005; Carty and Senapati, 1998; Lee et al., 2007; Leite et al.,
2009; Rawlings et al., 2006; Segades et al., 2005) and, therefore, promoting industrial wastes to alternative ceramic raw materials is both
technically and economically attractive.
In recent decades human kind has become growingly concerned
with the environment's degradation and wastes disposal, in particular. Industrialization brought about intensive extraction and beneciation of natural resources, which are examples of activities that can
cause landscape and ecosystems destruction and, if not controlled,
ecological unbalances with unpredictable consequences, but also a new
major concern about secondary pollution induced by end-products
Corresponding author. Tel.: +351 234 370 236; fax: +351 234 370 204.
E-mail address: segadaes@ua.pt (A.M. Segades).
0169-1317/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.clay.2012.08.009

resulting from primary waste treatment, such as wastewater treatment

sludges (Huang et al., 2001; Oliveira et al., 2007; Qi et al., 2010) and municipal solid waste incineration (MSWI) ashes (Gins et al., 2009;
Monteiro et al., 2008). Nowadays, industries of all kinds have optimized
their processes in order to reduce the amount of wastes they produce
and the corresponding negative environmental impact but are also
looking for alternative, less expensive raw materials.
Replacing natural raw materials by wastes can congure an opportunity to ameliorate today's waste management difculties. The valorization of industrial wastes and their up-grading to alternative raw
materials can present several advantages when compared with the
use of primary natural resources, namely reduction in the extraction
volume of natural raw materials (resource preservation), lower energy
consumption during subsequent processing (reduced costs), and lower
pollutant emission levels (improvement of population health and safety). Even if the waste incorporation is done in small amounts, high
production rates will translate into signicant consumption of waste
materials. Moreover, for the industry willing to use them, waste materials might constitute a cheap renewable raw material source (Dondi
et al., 1997; Lee et al., 2007; Rawlings et al., 2006; Segades, 2006;
Vieira and Monteiro, 2009).
From this perspective, recycling and nding reuse alternatives for
industrial wastes gain added relevance, and a number of potential applications have been proposed, namely in the production of clay-based
bricks (Acchar et al., 2006; Huang et al., 2001; Oliveira et al., 2007; Qi
et al., 2010), porcelainized tiles (Correia et al., 2009; Menezes et al.,

J.A. Junkes et al. / Applied Clay Science 69 (2012) 5057

2009; Segades et al., 2005), mortars and concrete (Gins et al., 2009;
Raupp-Pereira et al., 2007), ceramic pigments (Leite et al., 2009), and
glass-ceramics (Mello-Castanho et al., 2011; Monteiro et al., 2008), to
name a few. The waste materials involved range from ore tailings and
ornamental stone cuttings to potable and residual water treatment
sludges, metal anodizing and other surface treatment sludges, MSWI
and thermal power plant ashes, and also include agro-industrial and forestry wastes. As a consequence, recycling has become common practice,
particularly in those countries where raw materials are strategic and
waste disposal is both strict and costly. But also in traditionally more
permissive countries the ecological awareness has been awakened and
stricter laws for environmental control and licensing of waste generation
by industrial activities are being implemented.
With ceramics manufacture in mind, the present work was aimed not
only at nding a viable end use, other than landlling, for abundant
non-hazardous mineral and clay-based wastes, but also, and most importantly, at meeting the challenge of producing waste-only ceramics
with higher added value.
Thus, wastes were selected based on location and availability, in order
to minimize transportation costs, and in the roles raw materials must
play in ceramics manufacture (i.e. plastics, inerts and uxes). To ensure
the necessary plasticity, the sludge from the purication/clarication of
potable water and one clay mining tail, regarded also as waste, were
selected (plastic components); between the two, there should be enough
sand to full the need for inert components; to guarantee low temperature ring (uxing components), two sludges from industrial stone
cutting processes (gneiss and varvite) were selected. Although such
waste materials have already been object of some investigation as
individual additives in ceramic formulations, to the best of our knowledge
there is no published work dedicated to their combined use as ceramic
raw materials.
Potable water preparation processes for human consumption generates high volume of a waste sludge that consists basically of clay minerals, calcium hydroxide, aluminium sulphate, calcite and sand, with a
moisture level generally above 80 wt.%. Several published studies evaluated the effects of its addition to ceramic mixtures and found that,
although the nal mechanical properties were changed, in general the
product remained within the set limits for building construction applications (Huang et al., 2001; Oliveira et al., 2007; Qi et al., 2010; RauppPereira et al., 2007; Teixeira et al., 2006).
Similarly, surface layers of clay deposits that are usually abandoned
and discarded as waste due to the reddish coloration they impart to
red ceramic tiles, were shown to be adequate in the production of
good quality building products (Menezes et al., 2009; Modesto et al.,
2003).
Gneisses are metamorphic rocks, which can develop from a wide
variety of igneous and sedimentary materials. Generally, gneisses
show a coarse granular texture in alternating dark and light bands
of minerals. Varvite is a special kind of layered sedimentary rock
whose formation was controlled by the yearly succession of seasonal
deposits. Works reported in the literature (Cunha, 2007; Moreira et
al., 2008) showed that, upon ring at the adequate temperature,
ceramic building materials containing comparatively high contents
of gneiss or varvite wastes could be produced with suitable properties
(linear shrinkage, water absorption and mechanical strength).
Based on the promising results of those studies on the individual
wastes, the present work explores the possibility of combining them
in such a way that novel ceramic products can be obtained, seeking a
waste-only porcelain-like formulation and simultaneously one way to
reduce both the manufacturing costs and the negative environmental
impact caused by industrial activity.
2. Experimental
The sludge from potable water preparation processes (PWS) was provided by potable water treatment plant in Blumenau (SAMAE, producing

51

an average of 2400 l per month of a slurry containing ~63 wt.% water).

The residual clay was supplied by Eliane (Cocal do Sul, circa 3000 tons
accumulated residual clay). The two sludges from industrial stone cutting
processes (gneiss and varvite) were supplied by Pedras Morro Grande
(Araquari, which generates an average of 700 m3 of damp waste per
month) and Ramos Universo (Trombudo Central, which generates an
average of 250 m3 of damp waste per month), respectively. All raw materials sources are located in Santa Catarina State, Brazil.
The as-received waste materials were dried at 60 C until constant
weight, disaggregated in a ball mill for 20 min and sieved through 48
mesh (300 m). From each of these, homogeneous batches of ~5 kg
were collected and used throughout the work. These powders were
characterized in terms of chemical composition (Xray uorescence,
XRF), mineralogical composition (Xray diffraction, XRD), thermal
behavior up to 1000 C and particle size distribution (PSD).
In the XRF characterization, the fused bead method was used: a representative sample of the material was mixed with lithium tetraborate
and lithium nitrate and heated in a platinum crucible at 1000 C until
complete melting. The resulting homogeneous glass was then cast
into a 40 mm diameter disc and analyzed in a Phillips PW 24000 spectrometer at 3 kW and Rh anode.
The XRD characterization identies the crystalline phases present
in the material: powder samples were lightly compacted onto a glass
slide and analyzed in a Phillips Xpert diffractometer using the Cu K
radiation ( = 1.5418 ) and a Ni lter at 40 kV and 30 mA, with a
scanning speed of 6 2 min 1 between 4 and 80 2. Crystalline
phases were identied against the JCPDS-ICDD diffraction les.
Simultaneous thermogravimetric and differential thermal analysis (TG/DTA) enable the identication of thermal events, like phase
transformations, and the associated mass loss, by comparison with
those of a standard sample (alumina powder): analysis were carried
out in air on powder samples up to 1000 C, using a Netzsch STA 409
and 10 C min 1 heating rate, alumina crucibles and Pt-Pt10Rh
thermocouples.
For the PSD, deagglomerated aqueous suspensions (10 wt.% solids)
were prepared and the particle sizes (0.04500 m) were determined
by laser diffraction using a Cilas 1064 L equipment.
Based on the wastes chemical composition and the SiO2Al2O3K2O
phase diagram (Levin et al., 1974), four ceramic formulations were chosen, as discussed in Section 3 below. After homogenization, the chosen
formulations were humidied (7 wt.% water) and uniaxially pressed at
50 MPa into 25 mm diameter cylindrical pellets and 60 mm x 20 mm
rectangular tiles.
The use of different waste proportions results in variable compaction
responses, hence diverse levels of initial green body porosities. The use of
relatively high compaction pressure was aimed at mitigating those differences, thus producing comparable green body porosity, so that its effect on the nal properties of sintered bodies could be neglected.
Based on thermal analysis results and the indications of the SiO2
Al2O3K2O phase diagram, the formulations were red for 40 min at temperatures between 900 and 1150 C, with a heating rate of 5 C min1.
Sintered cylindrical pellets were used to determine water absorption, open porosity and apparent density by Archimedes' water displacement method (from the relationships between dry, water
immersed and watersoaked weights of each sample). Geometric
density was calculated from the pellets weight and dimensions and
bulk density was calculated from the values of open porosity and
water absorption. Density of ground powder was determined by
Helium pycnometry (Multipycnometer, Quantachrome).
Sintered rectangular tiles were characterized by XRD, as well as
linear shrinkage, relative to the unred original length, and threepoint bending exural strength (modulus of rupture), using a universal testing machine Emic DL 2000 with a constant crosshead speed of
0.5 mm.min 1.
Every result reported is the average of measurements carried out on
ve test pieces.

52

J.A. Junkes et al. / Applied Clay Science 69 (2012) 5057

Table 1
Chemical composition (wt.%) of dried raw materials, as determined by XRF.

Table 2
Particle size distribution of dried raw materials, as obtained by laser diffraction.

Oxides

Clay

PWS

Gneiss

Varvite

SiO2
Al2O3
Na2O
K2O
CaO
MgO
Fe2O3
MnO
TiO2
P2O5
Loss on ignition

63.01
19.55
0.05
2.83
0.04
0.77
6.51
0.02
0.91
0.07
6.30

53.30
22.10
0.24
2.11
0.12
1.20
7.02
0.09
0.83
0.24
12.76

59.22
16.75
4.48
4.31
5.98
1.63
4.56
0.14
0.43
0.75
1.74

74.32
8.79
3.12
1.48
2.68
1.74
2.43
0.16
0.51
0.18
4.59

3. Results and discussion

The chemical compositions of the dried waste materials obtained
by Xray uorescence are gathered in Table 1. It can be observed
that varvite presents the highest SiO2 content (74.32 wt.%) whereas
the highest Al2O3 contents can be found in PWS (due to the addition
of aluminium sulphate, used for agglomeration of solid particles on
the settling tanks) and clay (22.10 and 19.55 wt.%, respectively). On
the other hand, the highest alkaline contents (Na2O and K2O) are
found in gneiss (uxing effect), while PWS and clay show high levels
of iron oxide, 7.02 and 6.51 wt.%, respectively (coloration effect).
The silica/alumina weight ratios in clay and PWS are higher than
the theoretical value for kaolinite (46.5% silica to 39.5% alumina),
which is an indication of the presence of quartz in both materials.

Wastes

Clay
PWS
Gneiss
Varvite

Particle size range (m)

10% under

50% under

90% under

100% under

0.86
0.87
1.37
1.04

5.30
4.37
13.37
7.87

21.03
17.67
42.10
21.53

45.00
36.00
71.00
36.00

Fig. 1 shows the Xray diffractograms of the as received (dried)

wastes and after ring at 1100 and 1150 C. The Xray diffractograms
of clay (Fig. 1a) and PWS (Fig. 1b), just like their chemical compositions, are very similar given that major contaminants of river water
are organic matter and clay. Both wastes diffraction patterns showed
peaks of quartz (SiO2), muscovite (KAl2(Si3Al)O10(OH,F)2) and kaolinite (Al4(SiO10)(OH)8) and, after ring at 1100 and 1150 C, peaks
of quartz, mullite (Al6Si3O13, the end-product of the thermal transformation of aluminosilicates) and hematite (Fe2O3). The aluminium
oxide produced in the decomposition of sulphates present in PWS can
be observed after ring at 1100 C. The remainder constituents contribute to liquid phase formation below 1100 C and stay in the glassy
phase upon cooling. The Xray diffractograms of gneiss (Fig. 1c) showed
the expected presence of quartz and sodium and potassium feldspars
(albite (NaAlSi3O8) and microcline (KAlSi3O8), respectively). Iron oxides usually occur in deposits of metamorphic rocks such as gneiss,
and hematite and magnetite (Fe3O4) were also detected. As expected,
crystalline phases do not change signicantly upon ring at these

Fig. 1. Xray diffractograms of the wastes, as received and after ring at 1100 and 1150 C.

J.A. Junkes et al. / Applied Clay Science 69 (2012) 5057

53

Table 3
Proportions (wt.%) of dried raw materials in formulations F1 to F4.

Fig. 2. Thermodifferential and thermogravimetric analysis curves (DTA and TG) of the
individual wastes.

comparatively low temperatures. The Xray diffractogram of varvite

(Fig. 1d) showed peaks of quartz and albite, as well as clinochlore
(magnesium chlorite, (Mg,Fe)5Al(Si3Al)O10(OH)8) and traces of dolomite

Formulations

Clay

PWS

Gneiss

Varvite

F1
F2
F3
F4

40
20
20
30

10
65
10
20

45
10
5
10

5
5
65
40

(CaMg(CO3)2). Upon ring at 1100 C, both dolomite and clinochlore dissociate and forsterite (magnesium silicate, Mg2SiO4) is formed. These results were conrmed by thermal analysis (TG/DTA), as discussed below,
and show that the use of these wastes as alternative ceramic raw materials should not arouse new concerns about environmental issues related
with CO2 emissions.
The particle size distribution of each raw material is presented in
Table 2. It can be noticed that in all cases particle sizes are below
71 m. In terms of average particle size (d50), the wastes with ner
particles are PWS and clay. These results raise good perspectives
toward adequate plasticity in future processing operations.
The thermal behavior of individual wastes was studied by DTA/TG
and the corresponding curves are shown in Fig. 2. The DTA curve of
PWS shows an endothermic event near 120 C (water release) and
a broad exothermic event between 240 and 500 C (organic matter
burn out). Another endothermic peak can be seen at 580 C, attributable to the dehydroxylation of kaolinite, followed by an exothermic
peak near 620 C, due to sulphates decomposition. All events are
accompanied by mass losses, whose observed total was less than
20% (TG curve), which is in reasonable agreement with the XRF
results.
A similar series of events can be observed in the DTA curve for
the clay, namely, water release near 120 C, organic matter burn out
between 230 and 530 C and dehydroxylation of kaolinite at 580 C.
Again, these events are accompanied by mass losses that total 11%

Fig. 3. Up-dated version of Kingery's (1976) leucitesilicamullite diagram, showing typical commercial porcelain composition ranges and the location of the compositions of the
wastes and the four formulations investigated in this work, F1 to F4.

54

J.A. Junkes et al. / Applied Clay Science 69 (2012) 5057

Fig. 4. Effect of ring temperature on water absorption.

(TG curve), in reasonable agreement with the XRF results. Near the
end of the test, at 984 C, the curve suggests the onset of an exothermic peak with no associated mass loss. This would likely be the spinel
formation preceding mullite.
As for the rock wastes, two endothermic events accompanied by
mass loss can be observed in the DTA of gneiss, namely, water release
near 100 C and carbonate decomposition at 808 C. The exothermic
peak near 500 C suggests the burn out of residual organic matter.
The total mass loss recorded approaches 3% (TG curve). The DTA curve
of varvite also shows a shallow water release peak near 60 C and

the peaks corresponding to the two-step decomposition of clinochlore

(endothermic release of constitutional water near 580 C from the
interlayer octahedral sheets and near 850 C from the 2:1 layers), immediately followed by an exothermal event at 870 C attributable to the
recrystallization into spinel, forsterite and enstatite (Villieras et al.,
1994). The total mass loss recorded in the TG curve was 5.8%.
Based on the characterization studies carried out with the individual waste materials, it is envisioned that it might indeed be possible to produce typical ceramic products from their mixtures. The
phase equilibrium diagram of the Al2O3SiO2K2O system is the
best approach to select adequate compositions for the ceramic products, as it describes the effect of K2O (uxing oxide) on the Al2O3SiO2
phase equilibrium (Carty and Senapati, 1998; Kingery, 1976; Levin et
al., 1974; Segades, 2006). The uxing effect of Na2O, also present in
the raw materials, is rather similar to that of K2O, their corresponding
phase diagrams with alumina and silica being morphologically identical. As for the alkaline earth oxides (CaO+ MgO), their content is only
signicant in gneiss and varvite, but they will promote the uxing effect
of the alkali oxides. Therefore, the global uxing effect is best
discussed in terms of the Al2O3SiO2K2O phase diagram, using the
joint (CaO + MgO + K2O + Na2O) content as equivalent K2O content. Within that diagram, the sub-system leucitesilicamullite is
particularly relevant.
Fig. 3 is an up-dated version of Kingery's (1976) leucitesilicamullite
diagram and shows that typical commercial porcelain compositions lie in
the primary phase eld of mullite and in the feldsparsilicamullite
compatibility triangle, within which rst melting occurs at 985 C. Fig. 3
also shows the location of the wastes, plotted on the basis of their X-ray

Fig. 5. Effect of ring temperature on samples density: (a) pycnometric powder density, (b) apparent density, (c) bulk density, and (d) geometric density.

J.A. Junkes et al. / Applied Clay Science 69 (2012) 5057

Fig. 6. Comparison of red tiles of formulations F1 to F4 (broken halves produced in

exural strength tests).

uorescence analysis and the reasoning above (i.e. in terms of their silica,
alumina and equivalent K2O contents), and their relation to the composition ranges of the various typical porcelains.
It can be seen from Fig. 3 that it is possible to combine the four waste
materials to produce such compositions, even if the rock wastes lie just
outside the compatibility triangle. Clearly, the rock wastes will act as
uxes whereas PWS and clay must full the role of plastic components.
There are two possible rst melting tie-triangles, between the rst liquid
formed at 985 C and two solid phases, namely mullite+silica or
mullite+feldspar, and it was decided to explore formulations in both.
Also, given that today's industrial practice favours fast ring schedules,
it was decided to investigate formulations lying closer to the invariant
point (higher amount of rst liquid and lower complete melting
temperature).
Based on this reasoning, four formulations F1 to F4, also plotted in
Fig. 3, were selected, combining the four waste materials, i.e. within
the polygon dened by them. F1 lies roughly half way between gneiss
and clay, in the liquid+ mullite+ feldspar tie-triangle, and is expected
to form ~50% liquid at rst melting (calculated using the lever rule
and the tie-triangle) and reach complete melting near 1450 C. The
other three formulations lie in the liquid+mullite+silica tie-triangle.
F2 was chosen as to lie near the vitreous tile composition range and
used as basis to study the effect of varvite content; thus, F3 and F4,
with higher varvite contents, are roughly aligned between F2 and
varvite, with complete melting expected near 1350 and 1500 C,
respectively, and increasing amounts of rst liquid (~65% for F2, ~80%
for F4 and ~90% for F3). In the real multicomponent system, melting
will start at an even lower temperature but fast heating rates and short
ring times will add to the difculty that liquid will experience in
dissolving the crystalline phases present in the raw materials, hence,
approaching equilibrium. From the chosen locations of F1 to F4 marked
in Fig. 3, the lever rule can be used to calculate the amounts of the four
raw materials needed to reach each of the desired formulation. Table 3
shows the actual proportions of as received (dried) wastes used to
prepare formulations F1 to F4.
Pellets of the formulations were then prepared and red at 900,
950, 1000, 1050, 1100 and 1150 C, and characterized in terms of
geometric, bulk and apparent (Archimedes) densities and water
absorption. Powders obtained from ground pellets were used to
determine the solid's density by pycnometry.
Fig. 4 shows the effect of ring temperature on water absorption,
which shows the expected trend (effect of liquid phase formation
and development) and is similar for all formulations: water absorption

55

depends on the open porosity and decreases when the ring temperature increases, particularly for ring temperatures above 1050 C.
Given that all four formulations lie in the same compatibility triangle
(same initial melting temperature), the densication effect due to the
presence of the liquid phase should become apparent in all at the
same temperature. Because liquid phase has to dissolve particles during
densication, coarser particles can result in a delay of this effect. Fig. 4
shows that water absorption (i.e. open porosity) starts to decrease in
all formulations near 1050 C, except for F2. Formulation F2 shows a
slightly better densication behavior, from ~950 C upwards (i.e. near
the actual initial melting temperature shown in the phase diagram
reproduced in Fig. 3), which can be attributed to easier reactions
among the ner particles of the original minerals present in the clay
and PWS (major components in F2). Upon ring at 1100 C, water
absorption reaches the required level for ceramic tiles (b10%) and at
1150 C is below 3%, which is the requirement for porcelain tiles. These
results suggest that industrial ring temperatures should at least be
1100 C, but can be lower for formulations such as F2.
Fig. 5 shows the effect of ring temperature on samples density.
Again, the effect is similar for all formulations. Pycnometric powder
density (Fig. 5-a) tends to decrease when the ring temperature increases, in response to the progressive formation of a silica-rich liquid
phase (glass, with 2.2 g cm3) that tends to dissolve the higher
density original quartz grains (= 2.65 g cm3). However, the increasing viscosity of that silica-rich liquid phase might result in increased difculty in pore lling and close pores will tend to be left behind. The fact
that apparent density values of red pieces (Fig. 5-b) tend to be lower
than the corresponding powder density values suggests the presence of
some closed porosity. Above 1100 C, the departure between the two increases, suggesting an increase in closed porosity likely due to over ring
(bloating due to the expansion of gas entrapped inside closed pores).

Fig. 7. Effect of ring temperature on tile properties: (a) linear shrinkage, and (b) exural
strength.

56

J.A. Junkes et al. / Applied Clay Science 69 (2012) 5057

Fig. 8. X-ray diffractograms of formulations F1 to F4 after ring at 1100 and 1150 C.

Calculated bulk density and measured geometric density also closely

follow each other, which suggests that distortion due to ring (warpage)
is not signicant, and both increase with increasing ring temperature.
Despite the contradicting trend observed between water absorption
(Fig. 4) and apparent density (Fig. 5-b), particularly above 1100 C, the
results in Fig. 5-c and d are an obvious sign of the dominant effect of
the liquid phase present during ring at higher temperatures, leading
to decreasing open porosity, even if accompanied by increasing closed
porosity. These results support the over ring hypothesis previously
commented upon. The nal density values reached (between 2.03 and
2.61 g cm3 for 1100 and 1150 C, respectively) are within the usual
range for ceramic tiles.
Based on the above results, 1100 and 1150 C were selected as
ring temperatures and new test pieces (rectangular tiles) were prepared for a more detailed characterization. Fig. 6 illustrates the aspect
of the corresponding sintered test pieces (broken halves produced in
the exural strength tests). The presence of iron oxides is obvious in
all formulations, whose color varies from light to dark reddish
brown and darkens as the ring temperature increases. Also, bloating
is rather obvious in F1 after ring at 1150 C (F1 is the only mixture
lying in the liquid + mullite + feldspar tie-triangle). The earlier densication (early shrinkage) of F2 can also be observed, whereas F3 and
F4 only show signicant shrinkage after ring above 1100 C.
These observations can be conrmed by the linear shrinkage and
the three-point bending exural strength results of red formulations, shown in Fig. 7. Both properties are related with the presence
of a liquid phase (glass, after cooling from sintering temperature),
whose amount increases with the ring temperature, reducing open
porosity. Thus, both properties always show higher values for the samples sintered at 1150 C. The easier approach to equilibrium commented

on earlier, is clearly visible for F2, for which ring at 1100 C produces
results that the other formulations only reach after ring at 1150 C.
All samples sintered at 1150 C presented exural strengths above
3 MPa, adequate for common application, and the low standard deviation value conrms a good repeatability of the data. When compared
to commercial oor tiles, with mechanical strength above 18 MPa, the
lower values now obtained for all formulations might be explained by
the presence of signicant closed porosity at this ring temperature.
The X-ray diffractograms of red formulations F1 to F4 are shown in
Fig. 8 and all show strong quartz peaks whose intensity decreases at the
higher ring temperature. Although silica is a compatible phase after
rst melting in all but F1 formulation, original quartz particles are
slow to dissolve in the liquid formed during ring and residual quartz
tends to remain in the composition. Mullite is obviously a product of
the reactions that occur during ring and mullite peaks can also be identied in all formulations, stronger after sintering at 1150 C. Despite the
coloration, F3 has the lowest iron oxide content (3.8 wt.%) and its XRD
does not show hematite peaks, present in all others. Other crystalline
phases identied in each formulation depend on the minerals originally
present and the approximation to equilibrium.
Thus, F1, composed predominantly of gneiss (45%) and clay (40%),
with high Na2O and CaO contents (2.2 and 2.9 wt.%, respectively),
seems to be near equilibrium, presenting the phases expected to coexist
with liquid, namely, mullite and feldspars (albite and anorthite, CaAl2Si2O8), and residual quartz.
The diffractograms of F2, constituted primarily by PWS (65%) and
clay (20%), show mullite, feldspar (anorthite) and quartz peaks, as
expected from equilibrium, and residual hematite.
F3, containing mostly varvite (65%) and clay (20%), has the highest
MgO content (1.5 wt.%). In the diffractograms, enstatite, Mg2(Si2O6),

J.A. Junkes et al. / Applied Clay Science 69 (2012) 5057

produced from the decomposition of the original clinochlore, and feldspars (albite and anorthite) can still be detected after ring at 1100 C.
However, at 1150 C, only peaks of quartz, mullite and albite are
observed.
F4, whose major constituents are varvite (40%) and clay (30%), shows
peaks of quartz, mullite and anorthite at 1100 C, and of quartz, mullite
and albite at 1150 C. Small peaks of mayenite (calcium aluminate,
Ca12Al14O33) were also observed at this higher sintering temperature.
4. Conclusions
This exploratory study suggests that the manufacture of ceramic
tiles using only wastes is possible and porcelain-like ceramics can
be produced.
The phase diagram was successfully used to guide mixture formulation and to help choosing the process parameters. In all cases, it provided a basis for making predictions of material behavior under several
conditions of service or processing. Technical characteristics such as
the relatively homogeneous particle size distribution of the wastes promote suitable packing and densication of the various materials.
In terms of ceramics manufacture, the obtained results suggest that
ring temperatures for formulations within the composition range investigated should be near 1100 C, at which temperature water absorption reaches the required level for ceramic tiles (b10%). Below 1100 C,
only formulations such as F2, containing ner particles, will mature adequately. Above 1100 C, on the other hand, an increase in closed porosity is observed due to over ring, which hinders exural strength even if
water absorption is further reduced to values below 3%, which is the
requirement for porcelain tiles. The bloating effect of a viscous silicarich liquid phase might be ameliorated by longer rings at lower temperatures. Bulk density and geometric density increase for higher ring
temperatures, a sign of decreasing open porosity, as suggested by the
trend observed in water absorption, and closely follow each other,
suggesting that distortion due to ring (warpage) is not signicant.
The nal density values reached (between 2.03 and 2.61 g cm3 for
1100 and 1150 C, respectively) are within the usual range for ceramic
tiles.
Further work is being carried out in order to observe changes that
might be introduced by modied green processing.
Acknowledgments
The authors acknowledge the nancial support from the Brazilian
funding agencies CAPES and CNPq.
References
Acchar, W., Ramalho, E.G., Fonseca, Y.A., Hotza, D., Segades, A.M., 2005. Using granite
rejects to aid densication and improve mechanical properties of alumina bodies.
Journal of Materials Science 40, 39053909.
Acchar, W., Vieira, F.A., Segades, A.M., 2006. Using ornamental stone cutting rejects
as raw materials for red clay ceramic products: properties and microstructure
development. Materials Science and Engineering A 435436, 606610.

57

Acchar, W., Rulff, B.M., Segades, A.M., 2009. Effect of the incorporation of a spent catalyst
reject from the petroleum industry in clay products. Applied Clay Science 42,
657660.
Bingham, P.A., Hand, R.J., 2006. Vitrication of toxic wastes: a brief review. Advances in
Applied Ceramics 105, 2131.
Carty, W.M., Senapati, S., 1998. Porcelainraw materials, processing, phase evolution,
and mechanical behavior. Journal of the American Ceramic Society 81, 320.
Correia, S.L., Dienstmann, G., Folgueras, M.V., Segades, A.M., 2009. Effect of quartz
sand replacement by agate rejects in triaxial porcelain. Journal of Hazardous Materials 163, 315322.
Cunha, J.P., 2007. Desenvolvimento de um novo material a partir da composio dos
resduos da minerao de varvito e da produo de cal. MSc Thesis, Federal University of Paran, Brazil (in Portuguese).
Dondi, M., Marsigli, M., Fabbri, B., 1997. Recycling of industrial and urban wastes in
brick productiona review. Tile Brick International 13, 302308.
Gins, O., Chimenos, J.M., Vizcarro, A., Formosa, J., Rosell, J.R., 2009. Combined use of
MSWI bottom ash and y ash as aggregate in concrete formulation: environmental
and mechanical considerations. Journal of Hazardous Materials 169, 643650.
Huang, C., Pan, J.R., Sun, K.D., Liaw, C.T., 2001. Reuse of water treatment plant sludge
and dam sediment in brick-making. Water Science and Technology 44, 273277.
Kingery, W.D., 1976. Introduction to Ceramics. Wiley, New York.
Lee, W.E., Boccaccini, A.R., Labrincha, J.A., Leonelli, C., Drumond-III, C.H., Cheeseman,
C.R., 2007. Green engineering ceramic technology and sustainable development.
American Ceramic Society Bulletin 86, 1825.
Leite, A., Costa, G., Hajjaji, W., Ribeiro, M.J., Seabra, M.P., Labrincha, J.A., 2009. Blue cobalt
doped-hibonite pigments prepared from industrial sludges: formulation and characterization. Dyes and Pigments 81, 211217.
Levin, E.M., Robbins, C.R., McMurdie, H.F., 1974. Phase diagrams for ceramists. In:
Reser, M.K. (Ed.), American Ceramic Society, Columbus (Fig. 407).
Mello-Castanho, S.R.H., Ferreira, M.C., Acchar, W., Segades, A.M., 2011. Assessment of
reuse potential of high alumina industrial waste as devitrication aid in common
aluminalimesilica glasses. Advances in Applied Ceramics 110, 426432.
Menezes, R.R., Brasileiro, M.I., Gonalves, W.P., Santana, L.N.L., Neves, G.A., Ferreira,
H.S., Ferreira, H.C., 2009. Statistical design for recycling kaolin processing waste
in the manufacturing of mullite-based ceramics. Materials Research 12, 201209.
Modesto, C., Bristota, V., Menegalia, G., Brida, M., Mazzucco, M., Mazona, A., Borba, G.,
Virtuoso, J., Gastaldona, M., Oliveira, A.P.N., 2003. Obteno e caracterizao de
materiais cermicos a partir de resduos slidos industriais. Ceramic Industry 8,
1418 (in Portuguese).
Monteiro, R.C.C., Figueiredo, C.F., Alendouro, M.S., Ferro, M.C., Davim, E.J.R., Fernandes,
M.H.V., 2008. Characterization of MSWI bottom ashes towards utilization as glass
raw material. Waste Management 28, 11191125.
Moreira, J.M.S., Manhes, J.P.V.T., Holanda, J.N.F., 2008. Processing of red ceramic using
ornamental rock powder waste. Journal of Materials Processing Technology 196,
8893.
Oliveira, E.M.S., Sampaio, V.G., Holanda, J.N.F., 2007. Effect of waterworks waste addition
on densication and properties of clay ceramics. Industrial Ceramics 27, 191196.
Qi, Y., Yue, Q., Han, S., Yue, M., Gao, B., Yu, H., Shao, T., 2010. Preparation and mechanism
of ultra-lightweight ceramics produced from sewage sludge. Journal of Hazardous
Materials 176, 7684.
Raupp-Pereira, F., Silva, L., Segades, A.M., Paiva, H., Labrincha, J.A., 2007. Effects of
potable water ltration sludge on the rheological behaviour of one-coat plastering
mortars. Journal of Materials Processing Technology 190, 1217.
Rawlings, R.D., Wu, J.P., Boccaccini, A.R., 2006. Glassceramics: their production from
wastesa review. Journal of Materials Science 41, 733761.
Segades, A.M., 2006. Use of phase diagrams to guide ceramic production from wastes.
Advances in Applied Ceramics 105, 4654.
Segades, A.M., Carvalho, M.A., Acchar, W., 2005. Using marble and granite rejects to
enhance the processing of clay products. Applied Clay Science 30, 4252.
Teixeira, S.R., Souza, S.A., Souza, N.R., Alssio, P., Santos, G.T.A., 2006. Effect of the addition of sludge from water treatment plants on the properties of structural ceramic
material. Cermica 52, 215220 (in Portuguese).
Vieira, C.M.F., Monteiro, S.N., 2009. Incorporation of solid wastes in red ceramics: an
updated review. Matria (Rio de Janeiro) 14, 881905.
Villieras, F., Yvon, J., Cases, J.M., Donato, P., Lhote, F., Baeza, R., 1994. Development of
microporosity in clinochlore upon heating. Clays and Clay Minerals 42, 679688.