Applied Clay Science 54 (2011) 4752

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Applied Clay Science

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Research paper

Inuence of aging on the technological properties of clays in the ceramic industry

Roberta Gaidzinski a,, Jamil Duailibi Fh. b, Lus Marcelo Tavares a
a
b

Department of Metallurgical and Materials Engineering. COPPE, Universidade Federal do Rio de Janeiro - UFRJ. Cx. Postal 68505, CEP 21941-900, Rio de Janeiro, RJ, Brazil
Diviso de Processamento e Caracterizao de Materiais, Instituto Nacional de Tecnologia (INT), Av. Venezuela 82. CEP 20081-312, Rio de Janeiro, RJ, Brazil

a r t i c l e

i n f o

Article history:
Received 22 October 2010
Received in revised form 11 July 2011
Accepted 17 July 2011
Available online 25 August 2011
Keywords:
Clays
Aging

a b s t r a c t
The use of stockpiling systems in the ceramic industry provides signicant improvements in the properties of
clays when compared to the use of freshly mined material. Clays are stored for some time before entering the
production plant. This work reports the inuence of aging on the technological properties of clays. The
moisture content showed the greatest inuence to the exposure. The improvement of such technological
properties also depended on the initial properties of the clays. Finally, the results suggested that aging would
be benecial during certain periods of the year.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Storing freshly mined clays in stockpiles and subjecting them to
the action of environmental elements during a reasonable period of
time before entering the production process is a practice often used by
the ceramic industry to improve the technological properties of the
clays. Aging improves the rheological behavior of the clays, in
particular the plasticity, and improves the workability of the clay
during ceramic processing, such as drawing and pressing (Abajo,
2000; Bender, 1989). Building stockpiles with clays, prior to their use,
also improves the homogeneity of the material (Bender, 1989; Lorenz,
1996), a practice that reduces the variability of the properties of the
ceramic products.
Unfortunately, the mechanisms of aging of the clays are not yet
thoroughly understood. Some researchers attributed the effect to
chemical factors, such as changes of the electric charge of the clay and
the oxidation of the organic matter (Abajo, 2000). On the other hand,
a number of studies explained the effect of aging as being primarily
the result of the action of biological factors. Organic acids, mainly
citric, gluconic and oxalic acids released during the bacterial growth
through oxidation of inorganic sulfur or nitrogen compounds are
capable of solubilizing Fe + 3 and Al + 3 ions from the clay mineral
structures (Abajo, 2000; Baranov et al., 1985; Groudeva and Groudev,
1995; Vaiberg et al., 1980; Velde, 1995). These affect the layer charge,
the specic surface area, as well as the pH of the dispersions, which
could contribute to increased plasticity (Abajo, 2000). Moreover,
some microorganisms are responsible for the secretion of polysaccharides, which can bridge the clay mineral particles, increase the
Corresponding author at: Centro Universitrio Estadual da Zona Oeste (UEZO) Av.
Manuel Caldeira de Alvarenga, 1203 - Campo Grande, Rio de Janeiro, Brazil. Tel.: + 55
21 23336934.
E-mail address: rgaidzinski@ig.com.br (R. Gaidzinski).
0169-1317/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2011.07.011

plasticity and reduce the shrinkage during drying (Abajo, 2000). Other
authors (Gaidzinski et al., 2009), however, demonstrated that the
indigenous microorganisms did not contribute to the improvement of
the clay properties during aging.
Besides these chemical and biological mechanisms, physical
mechanisms are cited as also being responsible for the improvement
of the technological properties of clays during aging (Abajo, 2000;
Lorenz, 1996). During this process, water molecules placed in
metastable positions evaporate, whereas water molecules of the air
become xed in more stable positions. The relocation of water
molecules to occupy positions of greater stability apparently occurs
more slowly at low moisture contents. However, at higher moisture
levels, it occurs more effectively and quickly. The increased moisture
content could also result in a better dispersion of the particles within
the stockpile (Abajo, 2000; Lorenz, 1996).
An appropriate understanding of the mechanisms during aging of
clays may allow a more efcient application of this important stage in
industrial ceramic processing. In addition, the understanding of the
relation between the climatic conditions to which clays are exposed
and the benet brought by aging will allow its more rational and
effective use in different geographical regions.
2. Materials and methods
2.1. Clay samples
Samples of two clays from Itaboras deposit (Rio de Janeiro State)
called as red and green, and a clay sample from Santa Gertrudes
deposit (So Paulo State), both from Brazil, were collected for the
study. The choice of these raw materials was made on the basis of
their different chemical and mineralogical compositions.
After being extracted from their deposits, the samples were
properly stored in sealed plastic bags. In the laboratory, the samples

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R. Gaidzinski et al. / Applied Clay Science 54 (2011) 4752

were air-dried, crushed by using a laboratory smooth double roll

crusher, blended and quartered by building a longitudinal pile, aiming
to guarantee the samples to be as representative as possible of the
original material collected. Representative samples of about 10 kg
were prepared from each clay.
2.2. Aging
The 10-kg samples were placed in 20-liter uncovered plastic
containers and subjected to aging outdoors and indoors. For outdoor
aging, the samples were placed in the yard behind the laboratory,
located in the city of Rio de Janeiro (Brazil), thus exposing them to
environmental action, including rainfall and sun. For indoor aging, the
samples were stored without sunlight or rain, therefore to more
limited temperature and moisture changes. An additional sample was
used for the characterization of the unaged clays.
Samples were aged six months, with sample collection in month
and bi-month periods. The testing procedure consisted of measuring
the enzymatic activity. This is an important property to assess the
microbiological activity in the material (Gaidzinski et al., 2009). For
those tests, small amounts of the clays were taken with a sterile
spatula, from different depths, within the container. The samples were
divided by coning and quartering.
2.3. Initial characterization of the unaged samples
The chemical composition of the raw materials was determined by
X-ray uorescence spectrometry. Loss on ignition and moisture
content were determined by gravimetric methods. The plasticity of
the clays was determined according to Associao Brasileira de
Normas Tcnicas (1984a,b) by calculating the Atterberg indices:
plasticity limit (LP), liquid limit (LL) and plasticity index (PI).
Particle size analyses were conducted initially by wet sieving down
to the 63 m sieve; subsequently, by gravity sedimentation in an
Andreasen pipette.
Mineralogical analyzes were conducted only for the b2 m
fraction. The identication of the clay minerals present was carried
out with the aid of X-ray diffraction patterns (original, heated and
reacted with ethylene glycol) (Jackson, 2005), whereas the estimation
of the proportion of illite in each clay was conducted by measuring the
K2O content by X-ray uorescence spectrometry (Santos, 1998). The
b2 m fraction was obtained by letting the clay suspensions dispersed
using an ammonium hydroxide (NH4OH) solution settle in a beaker
for 24 hours. The supernatant was then carefully siphoned with the
aid of a pipette, dried at 100 C in an oven, and then, deagglomerated.
2.4. Analyzes after aging
Chemical characterization consisted of the measurement of pH of
the aqueous dispersion (Thomas, 1996), redox potential by using
potentiometric methods (Patrick et al., 1996) and measurement of the
amount of organic matter by the Walkley and Black method (Paula
and Duarte, 1997). Cation exchange capacity was determined by
methylene blue adsorption (American Standard for Testing Materials,
1999).
Biological characterization was conducted by measuring the
enzymatic activity (Adam and Duncan, 2001). Eight replicates of
each sample were prepared, as well as a reference. Statistical analyzes
consisted of Q tests at 90% condence (Ohlweiler, 1984).
For the technological tests, the samples were rst screened by
using the 590 m sieve and granulated by wetting the samples with
water, until a moisture content of 6.5% (dry basis) was reached. If the
moisture content of the sample after aging was N6.5%, the sample was
dried in air for a maximum of four days, with the moisture content
controlled daily. The samples were then maintained in sealed plastic
bags for 24 hours to ensure uniform distribution of the moisture. Test

bodies measuring 11.4 2.5 1.0 cm were then formed by uniaxial

pressing at 30 MPa.
After drying at 110 C, the apparent density and exural strength
of the test bodies were measured. The samples were sintered in air at
1050 C, with a heating/cooling ramp of 10 C/min, maintaining them
at the set temperature for 1 h. The following parameters were then
measured: apparent density, linear retraction, exural strength
(American Standard for Testing Materials, 1988b), water absorption
(American Standard for Testing Materials, 1988a) and loss on ignition.
3. Results and discussion
3.1. Characterization of samples prior to aging
Itabora clays present low silica (SiO2) and high alumina (Al2O3)
content, whereas the opposite occurs for Santa Gertrudes clay
(Table 1). The contents of alkaline oxides (Na2O and K2O) are high
for Santa Gertrudes and low for the Itabora clays. The contents of
earth-alkali oxides (CaO and MgO) in the Santa Gertrudes clay were
high, which may indicate the presence of carbonates (Monteiro and
Vieira, 2004).
The qualitative mineralogical characterization of b2 m fraction
indicated the presence of illite and kaolinite in the red Itabora clay,
kaolinite, illite and smectite in green Itabora clay and kaolinite, illite
and interstratied smectite-vermiculite in the Santa Gertrudes clay.
Semi-quantitative mineralogical analysis (Santos, 1998) of this size
fraction resulted in estimates of 9% illite content in the red Itabora
clay, 24% in the green Itabora clay and 47% in the Santa Gertrudes
clay.
Size analyzes results shown in Table 2 demonstrated the presence
of large amounts of material contained in the clay sizes (b2 m) for
Itabora clays, with a comparatively lower content for Santa Gertrudes
clay. According to the Atterberg plasticity index for extruded products
(Marsigli and Dondi, 1997), red Itabora clay showed optimal
plasticity (1525%), green Itabora clay was highly plastic (2535%),
whereas Santa Gertrudes clay showed low plasticity (1015%)
(Table 2). The low plasticity of Santa Gertrudes clay is consistent
with its comparatively lower amount of b2 m particles, predominantly represented by clay minerals.
Table 3 reports the results of chemical and biological characterization of the unaged Itabora and Santa Gertrudes clays. Itabora
green clay had a comparatively higher initial moisture content. Santa
Gertrudes clay was mildly alkaline, whereas the Itabora clays were
acidic due to the lower contents of alkali and earth-alkali ions (Ca + 2,
Mg + 2, Na + and K +), as well as to the presence of organic matter
(Thomas, 1996). The redox potentials (Eh), within the interval of
100 to +100 mV, characterize the samples as reducing clays. The
lower absolute value for the Santa Gertrudes clay signaled the
predominance of metabolism of strictly anaerobic microorganisms.
The redox potential for the Itabora clays is typical of metabolism of
strictly aerobic microorganisms (Patrick et al., 1996). Furthermore,
the Itabora green clay had a higher cation exchange capacity due to
the presence of smectite.
3.2. Properties of the aged clays
3.2.1. Indoors aging
The Itabora red clay revealed, after six months of aging, a loss of
moisture and organic matter of about 74% and 41% (Table 3). Cation
exchange capacity was reduced after the 4th month of exposure.
However, the other chemical and biological properties of the clays did
not show statistically signicant changes during the whole time of
indoors exposure.
The moisture content of Itabora green clay did not change during
the whole time of exposure. With the sole exception of the organic
matter, which decreased by about 12%, no signicant changes were

R. Gaidzinski et al. / Applied Clay Science 54 (2011) 4752

49

Table 1
Chemical composition of the clays (mass %).
Clay sample

Al2O3

SiO2

TiO2

Fe2O3

CaO

Na2O

MgO

K2O

P2O5

Mn2O3

*LOI

Itabora red
Itabora green
Santa Gertrudes

31.58
25.46
15.05

42.47
47.87
69.62

1.49
1.11
0.70

9.35
7.62
5.28

0.06
0.81

0.06
0.13
1.98

0.25
1.25
2.55

0.71
1.92
3.78

0.07
0.08
0.19

0.04
0.04

14.04
14.46
8.20

*Loss on ignition.

Table 2
Physical properties of the clays.
Clay

Coarse sand
(20.2 mm)

Fine sand
(0.20.05 mm)

Silt
(0.050.002 mm)

Clay
(b 0.002 mm)

Plasticity (%)
LP

LL

PI

Itabora red
Itabora green
Santa Gertrudes

3.6
8.0
30.6

3.2
4.6
21.8

35.2
21.4
25.6

58.0
66.0
22.0

27.39
36.24
22.30

49.80
69.00
34.20

22.5
32.8
11.9

LP: plastic limit, LL: liquid limit, PI: plasticity index.

observed during aging. Nevertheless, the exural strength, prior to

sintering, was increased by 31% after aging (Table 4).
Samples of Santa Gertrudes clay showed a limited increase of the
moisture content during aging. After the 4th month of exposure, the
cation exchange capacity and exural strength of both sintered and
non-sintered samples were signicantly reduced (Tables 3 and 4). A
loss of organic matter of about 58% was also observed (Table 3).
3.2.2. Outdoors aging
The Itabora clays samples revealed a similar response to outdoors
aging. During the rst four months of exposure, the moisture content
and the exural strength, prior to sintering, increased signicantly,
but chemical and biological property changes were not observed. In
the last two months of exposure, however, moisture content,
enzymatic activity (aerobiosis) and exural strength, prior to
sintering, were considerably reduced (Tables 5 and 6). For the
Itabora red clay, a reduction of the cation exchange capacity was also
observed during this period. The reduction in organic matter during
the entire exposure period was of 45% and 29% for the Itabora red and
green clays (Table 5).
In the case of the Santa Gertrudes clay, the moisture content was
reduced during the rst four months of aging. During this period, the
cation exchange capacity decreased, the enzymatic activity (aerobiosis and anaerobiosis) increased and the strength, prior to sintering,
decreased. In the last two months of exposure, the moisture content
decreased. Unlike in the case of the Itabora clays, this reduction was

not accompanied by changes in the other properties. A 58% loss of

organic matter during the entire exposure period was also observed
(Table 5).
3.3. Response to aging
A statistical analysis of the exural strength data of the nonsintered samples and the moisture content was carried out by using a
two-factor variance analysis (ANOVA) (Hogg and Ledolter, 1987),
considering the effects of aging time and type of exposure (Table 7).
The analysis demonstrated that the different clays did not respond the
same way to aging. Time and type of exposure (indoors, outdoors)
inuences on the moisture content were highly signicant. The same
was found for the exural strength of the unsintered Itabora red and
Santa Gertrudes samples, whereas statistically signicant effects of
exposure time and type were not found for the Itabora green sample.
It is important to emphasize that the measurement of the technological properties that include the green body strength of all bodies was
conducted with the initial moisture content of 6.5% (dry basis), as
described above.
The more signicant variations of several properties of the clays
were observed for outdoors aging. In some cases, direct and inverse
correlations were identied among some properties, with the rainfall
and the average temperature during exposure (Table 8).
In general, as observed for the Itabora clays, the signicant
increase of the moisture content was followed by an increase of the

Table 3
Chemical and biological characterization of the clays after aging indoors.
Sample

Aging time
(months)

Moisture
(%)

Itabora red

0
1
2
4
6
0
2
4
6
0
1
2
4
6

15.43 (0.30)
6.97 (0.00)
5.25 (0.15)
4.24 (0.30)
4.01 (0.04)
7.12 (0.03)
8.12 (0.13)
7.95 (0.30)
7.15 (0.12)
3.70 (0.05)
3.97 (0.00)
4.40 (0.01)
4.16 (0.08)
4.11 (0.06)

Itabora green

Santa Gertrudes

E.A (ng/min.g)

Aerobiosis

Anaerobiosis

30.4
53.7
20.2
42.0
13.1
74.4
34.3
12.7
10.7
37.8
47.3
40.0
26.4
17.1

21.5 (0.01)
n
n
0.0 (0.00)
0.2 (0.00)
3.0 (0.00)
0.5 (0.00)
0.9 (0.00)
0.6 (0.00)
0.4 (0.02)
1.5 (0.00)
0.4 (0.00)
0.4 (0.00)
0.8 (0.00)

(0.01)
(0.01)
(0.00)
(0.01)
(0.03)
(0.02)
(0.01)
(0.01)
(0.01)
(0.00)
(0.01)
(0.00)
(0.01)
(0.00)

b
Eh
(mV)

pH

c
O.M.
(g/kg)

d
CEC
(meq/100 g)

125.1
129.9
160.2
112.1
111.5
98.9
96.2
113.8
101.8
43.2
85.0
58.7
93.1
72.3

4.7
4.7
4.7
4.8
4.6
4.8
4.6
4.8
5.0
7.8
8.3
7.8
9.1
8.3

2.2
1.7
1.6
1.3
1.3
1.7
1.7
1.5
1.5
1.9
1.9
1.9
1.0
0.8

6.3
8.7
8.5
8.2
3.0
9.0
8.7
8.2
7.7
5.5
5.2
5.2
3.2
3.3

Enzymatic activity, bOxidation and reduction potential, cOrganic matter, dCation exchange capacity. Standard deviation in parentheses. n: no data measured.

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R. Gaidzinski et al. / Applied Clay Science 54 (2011) 4752

Table 4
Technological properties of the clays after aging indoors.
Non-sintered
Aging time
(months)

Density
(g/cm3)

Flexural strength
(MPa)

Itabora red

0
1
2
4
6
0
2
4
6
0
1
2
4
6

1.96
1.97
1.95
1.92
1.90
2.19
2.16
2.18
2.17
2.07
2.04
2.10
2.15
2.03

2.06
2.36
2.07
2.04
1.77
2.24
2.94
2.46
2.33
3.00
3.53
3.00
2.26
2.16

14.78 (0.06)
14.52 (0.07)
14.60 (0.06)
14.73 (0.20)
14.38 (0.04)
14.73 (0.06)
14.91 (0.08)
14.76 (0.09)
16.28 (0.81)
8.76 (0.33)
8.96 (0.04)
9.25 (0.07)
8.72 (1.65)
7.14 (0.04)

Itabora green

Santa
Gertrudes

Sintered

Sample

(0.03)
(0.04)
(0.04)
(0.03)
(0.03)
(0.07)
(0.04)
(0.03)
(0.03)
(0.05)
(0.04)
(0.04)
(0.05)
(0.02)

(0.25)
(0.24)
(0.19)
(0.23)
(0.30)
(0.51)
(0.33)
(0.42)
(0.69)
(0.51)
(0.12)
(0.13)
(0.14)
(0.23)

LOI

(%)

Density
(g/cm3)

Flexural strength
(MPa)

Water absorption
(%)

Linear retraction
(%)

1.87
1.97
1.92
1.89
1.84
2.21
2.10
2.15
2.21
2.33
2.30
2.39
2.40
2.38

5.19 (0.59)
6.70 (0.91)
5.24 (0.67)
5.12 (0.47)
4.45 (0.16)
6.52 (1.50)
7.52 (0.79)
7.95 (0.93)
7.74 (0.14)
28.03 (1.98)
31.39 (1.28)
29.15 (2.54)
27.16 (1.20)
26.77 (4.64)

17.72 (0.42)
16.95 (0.28)
17.26 (0.65)
17.32 (0.13)
19.79 (0.32)
9.93 (0.10)
9.74 (0.08)
9.57 (0.09)
9.69 (0.00)
0.35 (0.04)
0.33 (0.11)
0.45 (0.07)
1.27 (0.04)
2.22 (0.09)

3.91 (0.09)
4.36 (0.36)
4.32 (0.43)
3.75 (0.08)
3.78 (0.03)
5.42 (0.10)
4.62 (0.55)
4.72 (0.07)
5.37 (0.39)
6.75 (0.07)
6.95 (0.11)
6.96 (0.15)
6.73 (0.68)
6.57 (0.20)

(0.07)
(0.06)
(0.05)
(0.03)
(0.04)
(0.06)
(0.07)
(0.03)
(0.02)
(0.03)
(0.05)
(0.05)
(0.11)
(0.02)

Loss on ignition. Standard deviation in parentheses.

exural strength of the unsintered samples, which was directly

related to the plasticity. In analogy, the large reduction of the moisture
content within a certain period of outdoors aging corresponded to the
reduction of the exural strength, prior to sintering (Table 6). The
literature suggests that factors such as mineralogical composition, size
distribution, clay mineral fraction, lamellar habit of the clay minerals,
layer charge, the presence of organic matter, the cation exchange
capacity (but also the nature of the exchangeable cations) have great
inuence on the plasticity of the samples (Dondi et al., 2008;
Fernandes et al., 1998; Hajjaji et al., 2010; Modesto and Bernardin,
2008). However, our results showed that the increase of the exural
strength of non-sintered samples was neither correlated to an
increase of the cation exchange capacity nor to the amounts of
organic substances. These results can indicate that increased plasticity
may not be directly associated to chemical parameters such as organic
matter and cation exchange capacity.
The enzymatic activity during the exposure period, both indoors
and outdoors, oscillated (Tables 3 and 5). More signicant differences
were observed only for the outdoors samples, when enzymatic
activity was considerably reduced during periods of low rainfall
succeeding the rainiest periods. This may point to a reduction of the
bacterial population during this period. According to the literature,
swelling and contracting of the particles due to moisture changes
could be harmful to the survival of the microbial populations. This
enzymatic activity reduction could be related to the difculty

microorganisms have to cope with such drastic climatic changes

(Kostopoulou and Zotos, 2005; Van Gestel et al., 1993). Moreover, the
increase in moisture content and the exural strength of unsintered
clay products were not accompanied by an enzymatic activity
increase. This fact could suggest that the microbiological action is
not directly related to the aging process, as observed before
(Gaidzinski et al., 2009).
The results also demonstrated that chemical parameters such as
pH and redox potential (Eh) as well as the size distribution of the clay
particles did not signicantly change during the period of the
experiment.
Consumption of some organic matter by microorganisms during
the entire exposure period was observed for all clays, both indoors
and outdoors, although the reduction was minor during the indoors
aging of the Itabora green clay. According to the literature, raw
materials with large amounts of ne particles, as for the green clay,
can hinder the mineralization of the organic substance. This can
possibly occur due to the physical connement of microorganisms in
small pores, which makes them less active (Baldock and Skjemstad,
2000; Wang et al., 2003). The type of organic matter in the clays could
also inuence these results. The ease with which the organic
substance is decomposed by microorganisms depends on the type
of organic components. For instance, organic components that contain
large quantities of aromatic substances are more difcult to
decompose (Egli et al., 2006).

Table 5
Chemical and biological characterization of the clays samples exposed to aging outdoors.
Sample

Itabora red

Itabora green

Santa Gertrudes

Aging
time
(months)

Moisture
(%)

0
1
2
4
6
0
2
4
6
0
1
2
4
6

15.43 (0.30)
38.42 (0.50)
44.19 (0.22)
38.39 (0.65)
13.70 (0.07)
7.12 (0.03)
29.64 (0.29)
28.65 (0.31)
12.44 (0.25)
3.70 (0.05)
27.37 (0.06)
27.46 (0.93)
26.26 (0.70)
9.47 (0.15)

E.A (ng/min.g)

Aerobiose

Anaerobiosis

30.4 (0.01)
39.9 (0.02)
21.2 (0.00)
26.6 (0.00)
8.9 (0.04)
74.4 (0.02)
11.2 (0.01)
21.3 (0.01)
9.7 (0.00)
37.8 (0.00)
36.8 (0.00)
102.3 (0.01)
83.6 (0.01)
36.2 (0.01)

21.5 (0.01)
0.4 (0.00)
n
0.9 (0.00)
1.5 (0.00)
3.0 (0.00)
3.8 (0.00)
4.4 (0.00)
2.5 (0.00)
0.4 (0.02)
4.4 (0.00)
12.2 (0.00)
4.9 (0.00)
7.4 (0.00)

b
Eh
(mV)

pH

c
O.M.
(g/kg)

d
CEC
(meq/100 g)

125.1
130.5
125.5
101.5
134.4
98.9
91.4
90.2
96.6
43.2
51.1
57.6
57.5
107.7

4.7
4.7
4.7
4.7
4.7
4.8
5.0
4.8
5.1
7.8
7.7
7.9
7.7
8.9

2.2
1.6
1.6
1.2
1.2
1.7
1.7
1.2
1.2
1.9
1.9
1.7
1.2
0.8

6.3
7.5
6.7
6.7
2.5
9.0
6.7
6.7
7.5
5.5
4.0
3.7
3.5
3.5

Enzymatic activity, bOxidation and reduction potential, cOrganic matter, dCation exchange capacity. Standard deviation in parentheses. n: no data measured.

R. Gaidzinski et al. / Applied Clay Science 54 (2011) 4752

51

Table 6
Technological properties of clays after aging outdoors.
Non-sintered
Aging time
(months)

Density
(g/cm3)

Flexural strength
(MPa)

Itabora red

0
1
2
4
6
0
2
4
6
0
1
2
4
6

1.96
2.01
2.07
1.94
1.95
2.19
2.25
2.25
2.05
2.07
2.25
2.25
2.05
2.19

2.06
2.67
3.30
2.27
1.75
2.24
2.63
2.85
1.86
3.00
2.63
2.85
1.86
2.72

14.78 (0.06)
15.19 (0.08)
15.42 (0.17)
14.81 (0.15)
14.54 (0.16)
14.73 (0.06)
15.09 (0.09)
14.93 (0.08)
16.36 (0.42)
8.76 (0.33)
7.60 (0.05)
7.03 (0.08)
7.83 (0.46)
7.02 (0.31)

Itabora green

Santa
Gertrudes

Sintered

Sample

(0.03)
(0.03)
(0.04)
(0.03)
(0.02)
(0.07)
(0.04)
(0.05)
(0.03)
(0.05)
(0.04)
(0.02)
(0.05)
(0.05)

(0.25)
(0.32)
(0.44)
(0.33)
(0.28)
(0.51)
(0.14)
(0.50)
(0.18)
(0.51)
(0.95)
(0.31)
(0.02)
(0.28)

LOI

(%)

Density
(g/cm3)

Flexural strength
(MPa)

Water absorption
(%)

Linear retraction
(%)

1.87
1.98
2.02
1.88
1.90
2.21
2.20
2.23
2.08
2.33
2.20
2.23
2.08
2.24

5.19 (0.59)
7.15 (1.20)
7.42 (1.20)
5.51 (0.70)
5.93 (0.70)
6.52 (1.50)
6.81 (0.50)
7.26 (1.68)
4.85 (0.68)
28.03 (1.98)
30.56 (1.90)
27.60 (1.80)
27.19 (2.40)
23.32 (2.50)

17.72 (0.42)
16.96 (0.62)
16.75 (0.21)
17.20 (0.01)
17.62 (0.51)
9.93 (0.10)
9.69 (0.00)
9.72 (0.04)
10.50 (0.40)
0.35 (0.04)
0.24 (0.02)
0.95 (0.15)
1.08 (0.00)
1.27 (0.18)

3.91 (0.09)
4.03 (0.40)
4.17 (0.22)
3.70 (0.02)
3.75 (0.06)
5.42 (0,10)
5.08 (0.65)
4.66 (0.60)
5.26 (0.18)
6.75 (0.07)
6.79 (0.15)
6.46 (0.06)
6.23 (0.13)
6.29 (0.09)

(0.07)
(0.04)
(0.03)
(0.03)
(0.03)
(0.06)
(0.02)
(0.05)
(0.04)
(0.03)
(0.03)
(0.02)
(0.06)
(0.05)

Loss on ignition. Standard deviation in parentheses.

3.4. Aging process and initial properties of clays

The response of the clays may also be associated to the initial
properties of the clays such as plasticity, particle size distribution and
moisture content.
For the Itabora red clay, aging outdoors appeared to be more
favorable, leading to a statistically signicant increase of the exural
strength of the non-sintered samples (Table 7). This improvement of
the technological properties seems to be related mainly to the
increase in the moisture content of the samples. On the other hand,
exposure indoors was not favorable due to the loss of moisture of the
samples over time, resulting in the reduction of the exural strength
of the non-sintered material. Therefore, in the case of aging of this clay
indoors, it would be advisable to use canvases for covering the
stockpile to prevent moisture loss over time. Indeed, this is a
procedure often used in the ceramic industry (Fugmann, 1989).
In the case of the green Itabora clay with greater moisture
retention capacity, higher initial plasticity and ner particles, the
exposure of samples to aging seems more favorable when carried out
indoors, since the samples did not lose signicant amounts of
moisture over time. That increases the plasticity and exural strength
of the non-sintered samples during the period of exposure.
In the case of the Santa Gertrudes clay, the signicant increase of the
moisture content during outdoors aging did not increase the exural
strength of the non-sintered samples. In the case of exposure indoors,
when the moisture content was maintained relatively constant, the
exural strength of the non-sintered samples did not increase. This
demonstrates that not all clays will benet from aging. Thus, clays with
low proportions of clay minerals, low plasticity and very low moisture

Table 7
Statistical analysis from two-factor analysis of variance (p values).
Measured property

Effect

Non-sintered exural Time of

strength
exposure
Place of
exposure
Interaction
Moisture content
Time of
exposure
Place of
exposure
Interaction

content may not benet from aging. This conclusion is consistent with
previous observations (Gaidzinski et al., 2005).
In short, samples of the three clays studied presented a similar
response to exposure outdoors during periods of low rainfall between
periods of heavy rainfall. The high loss of moisture in short periods
was harmful to the properties of the raw material, evidenced by the
loss of the mechanical properties. All these results reveal that
signicant climatic variations must be prevented. The time of the
year when the clay is exposed to aging is a very important factor for
the success of the operation. These observations were also veried by
previous studies (Gaidzinski, 2002; Gaidzinski et al., 2005).
4. Conclusions
Aging of clays generally improved some technological properties,
as shown by the increase in exural strength of the samples both
before and after sintering and the reduction of water absorption.
Distinct clays responded differently to aging. Aging place and time
signicantly inuenced the moisture content of the clays, but did not
show a signicant inuence on the exural strength of non-sintered
material in the case of the Itabora green clay with high initial plasticity
and high content of ne particles. For clays with low initial moisture,
clay mineral content and plasticity, aging did not result in a measurable
improvement of the properties of the clay for ceramic processing.
Within this context, one of the main results is that the effectiveness of
aging depends on the initial properties of the clays such as plasticity,
particle size distribution, moisture content, and composition.
Indoors and outdoors exposures led to signicantly different
changes in the clays. In the case of clays with limited moisture
retention, indoor aging was not favorable, so that aging should only be
performed if the stockpile is covered by canvases to limit moisture
loss. An alternative would be the use of water addition by dripping on
the top of the stockpiles. In the case of clays with high initial plasticity

Clay
Itabora
red

Itabora
green

Santa
Gertrudes

0.000004

0.024883

0.000012

0.000739

0.573811

0.000431

0.000711
0.326825
b0.000001 b0.000001

0.001039
b 0.000001

b0.000001 b0.000001

b 0.000001

b0.000001 b0.000001

b 0.000001

Table 8
Monthly precipitation and average temperature of the period of exposure of the clay
samples to aging.
Months

Aging time
(months)

Average temperature
(C)

Monthly precipitation
(mm)

March
April
May
June
July
August
September

0
1
2
3
4
5
6

24.7
24.4
22.4
21.2
19.8
21.9
20.9

112.8
116.6
51.8
30.0
67.6
5.4
49.6

52

R. Gaidzinski et al. / Applied Clay Science 54 (2011) 4752

and moisture retention, aging indoors might be more advisable. Aging

outdoors became unfavorable during drought periods after high
rainfall, reducing the technological properties that were achieved
during the initial period of exposure. In addition, the moisture content
of the material has to be reduced to achieve the required value for
pressing. The initial properties of the clays are essential in the
planning of the clays aging procedure, mainly the selection of the
appropriate place for aging, i.e., indoors or outdoors.
The moisture content was identied as one of the main factors
responsible for the increase of the exural strength of the non-sintered
samples during aging. In general, the increase in the moisture content
could be directly related to the increase of the exural strength of the
non-sintered clays, whereas changes of the chemical properties (cation
exchange capacity and organic matter content) were not observed.
Acknowledgments
The authors would like to thank the nancial support from the
Conselho Nacional de Desenvolvimento Cientco e Tecnolgico of
Brazil, CNPq. The authors also thank Dr. Patricia Osterreicher-Cunha for
her assistance in the analysis of the microbiological characterization
results.
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