BOLSOC.ESP.CERAM.VIDR.

30 (1991) I, 5-9

Preparation of a ceramic floor tile body containing pure bentonite

as strengthening agent
T. MANFREDINI, G. C. PELLACANI, P. POZZI
Dipartimento di Chimica, Universit di Modena, Via Campi 183, 41100 Modena, Italy

G. MARZOLA, C. PASQUALI
FLOOR GRES Ceramiche S.p.A., Via Canaletto 24, 41042 Fiorano Modenese, Modena, Italy

ABSTRACT.Preparation of a ceramic floor tile body

containing pure bentonite as strengthening agent.
This paper demonstrates that the use of a low amount
(2 wt%) of alkali activated bentonite as strengthening
agent of low plastic ceramic body is greatly recommended since it appreciably reduces ruptures of unfred
ceramic tiles in their dry state during handling and
transporting, and enables the pre-firing steps of a ceramic
factory to be rationalised and productivity to be increased. Semi-industrial tests demonstrate that the addition
of 1-4 wt% of natural or alkali activated bentonites, containing a high smectite content (> 90 wt%), in a ceramic
body notably improves the mechanical strength and
favours greiflcation, while not affecting the other important bulk physico-chemical properties. Industrial tests
demonstrate that an amount of about 2 wt% of activated
bentonite is sufficient to fully substitute in a body the 7.5
wt% of bentonitic clay previously used, further improving mechanical, rheological and sintering properties.
KEY WORDS: ceramic floor tiles, ceramic bodies, unfred bodies, bentonites, strengthening agent.

RESUMEN.Preparacin de una pasta para pavimentos cermicos conteniendo bentonita pura como agente de reforzamiento.
Este artculo demuestra la conveniencia del uso de una
baja cantidad (2% peso) de bentonita activada alcalina
como agente de reforzamiento de pastas cermicas de baja
plasticidad, puesto que reduce apreciablemente las roturas de los pavimentos en crudo, en seco, durante su manipulacin y transporte y permite que las etapas de precocido se racionalicen aumentndose la produccin.
Ensayos a escala piloto han demostrado que la adicin
del 1 al 4% peso de bentonitas naturales o activadas con
lcalis, conteniendo una elevada proporcin de esmectitas (>90% peso) en una pasta cermica mejora notablemente la resistencia mecnica y favorece la gresificacin
sin afectar a otras importantes propiedades fisicoqumicas. Ensayos en la industria han demostrado que una cantidad de cerca del 2% en peso de bentonita activada es
suficiente para sustituir completamente en una pasta el
7,5% peso de arcilla bentontica previamente usada, mejorando las propiedades mecnicas, reolgicas y de sinterizacin.
PALABRAS CLAVE: pavimentos cermicos, pastas cermicas, bentonitas, agente de reforzamiento.

1.

INTRODUCTION

The problem of reinforcement of the mechanical strength

of green tiles, in order to avoid faults or breaking during
pre-firing steps, has hitherto concerned all the manufacturing of single fired ceramic tiles, as a result of the introduction of high-speed firing roller kilns. This has been generally obtained by tailored addition to the bodies, containing
a great amount of filler minerals, of various types of organic or inorganic binders, that lubricate the non-plastic particles during pressing and introduce cohesive forces between
particles, even though this may lead to new types of defect (1).
Among inorganic compounds the addition of large amounts
of bentonitic clays (4-7.4 wt%) has been demonstrated to
favour the increase of the modulus of rupture of the green
ceramic tiles (2,3), but at the same time it modifies the bulk
physico-chemical properties of the original bodies, in particular strongly deteriorating the rheological behaviour of the
concentrated slips (3). On the contrary, the same mechaniRecibido el 10-10-90 y aceptado el 22-2-90.
ENERO-FEBRERO, 1991

cal strength benefits can be obtained with the addition to the

bodies of treated bentonites, with high smectite content, in
such small amounts (1.5-2.5%) as to leave the rheological
behavior of the slips unaffected (3).
In order to complete our previous study, in this paper we
investigate the effects of the addition of treated bentonites
with high smectite content (>90 wt%) on the thermal and
mechanical properties of a ceramic body commonly used to
produce white floor gres tiles in the Sassuolo factories. The
results of this study have enabled design of a ceramic floor
tile body for fast single firing.
2.
2.1.

EXPERIMENTAL PROCEDURE
Raw materials and sample preparations

The white spray-dried body (hereafter indicated as body

or base body) with a typical composition used in the factories of Sassuolo (Italy) was obtained by mixing 35% illitic
and kaolinitic clays and 65% of non-plastic raw materials
(feldspar and quartz).

T. MANFREDINI, G. C. PELLACANI, P. POZZI, G. MARZOLA, C. PASQUALI

The examined bentonites were a natural Na/Ca bentonite

(Bl) and the same bentonite, purified and alkali-activated with
Na2C03 (B2). Their analyses are reported in Table I. As
previously reported (3) the natural bentonite (Bl) presents
a smectite content of about 90%, the treated bentonite (B2)
of about 95%.
The bentonites were added to the body in amounts of 1,
2, 3 and 4 wt%. Higher percentages were not considered
since at these levels they can be considered true body components, which strongly modify the bulk physico-chemical
properties of the ceramic body.

of 10C/min from 25C to 1,200C. Modulus of rupture

of green and fired tiles were determined using a Gabbrielli
apparatus. Linear shrinkages and water absorptions in the
900-1,200C temperature range of the bodies were determined with the procedure indicated in refs. (4) and (5) on
specimens 4 0 x 4 0 x 5 mm, obtained in a small pilot press.

3.

RESULT AND DISCUSSION

3.1.
TABLE I

3.1.1.

CHEMICAL ANALYSIS OF THE DRIED BENTONITES

Bentonite
SO2
AI2O3
TO2
FesOg

MgO
CaO
K2O
Na20

Ignition loss

Green tiles

Bl

B2

60.2
21.4
0.3
3.3
4.5
1.5
0.1
1.1
7.5

59.4
21.0
0.3
3.1
4.5
1.4
0.1
2.8
7.5

The mechanical and thermal measurements were performed on semi-industrial samples prepared as follows: 8 kg
of aqueous slips (body+bentonite+deflocculant (about 0.3
wt% of tripolyphosphate sodium salt or 1:1 mixture of tripolyphosphate and metasilicate) + industrial water) (70 wt%
of solid content) were ground for 8 hours in a bal mill (15
1). The slips wereftiUydried at 115 C and the powders further dry-ground and humidified up to 5.2-6 wt% of water
in order to fully reproduce the characteristics of the powders obtained from the industrial spray-drying process. The
powders were pressed with a hydraulic press (250-270
kg/cm2) ijjto 213x213x8 mm tiles. On these dried green
tiles the modulus of rupture and the dilatometric and thermal (water absorption and linear shrinkage) measurements
were performed.
Industrial tests were measured on powders pressed at 300
kg/cm2 jj^to 337x337x8 mm tiles and on these tiles fired
in a high-speed roller kiln with thermal cycle of 45 minutes.

MECHANICAL STRENGTH

As shown in Table II the modulus of rupture of green tiles sharply increases on increasing the amount of bentonite,
significantly larger for B2 than Bl, in agreement with the
smaller particle size dimensions and higher smectite content
of B2, which enables an otimum lubricating effect to be exerted on the non-plastic particles (feldspar and quartz). It is
known that the strengthening effect of bentonites on green
tiles of low plastic bodies is afforded by the electrostatic attractive forces among bentonite colloidal particles (3).
It is work remarking that the addition of only a mere 2
wt% of activated bentonite to the low plastic base body enables an increase of the modulus of rupture of the green ceramic tiles greater than 100% as compared to that of unfired
tiles from base body.
3.1.2.

THERMAL RESULTS

The differential thermal (DTA) and thermogravimetric

(TGA) analyses of the low plastic base body are shown in
Figure 1. The weight loss at about 500-600C may be due

0
""^Nfc^

0
LU
X

" ^
\
C/)

(/>
0

- 2.

"-^1 \/V"

LU

' \

Chemical analyses of the raw materials and of the prepared mixtures were performed with a Philips PU 9000 Atomic Absorption Instrument. X-ray powder spectra on orientated samples were recorded with a Philips PW 1050 diffractometer, using a Ni filtered Cu-Ka radiation (X= 1.5418 )
in the 26 angle range from 4 to 40. Differential thermal
analyses were carried out with a Netzsch Sta 409 thermobalance on about 50 mg of finely powdered clay samples heated at 10C/min from 25C to 1,250C in a Pt crucible, using
fired kaolin as reference. Dilatometric measurements were
performed with a Netzsch dilatometer on samples of
40 X 8 X 8 mm obtained from dried green tiles at heating rate

LU

ce
LU
Li.
LL

-J

2.2. Measurements and apparatus

^,^^

UJ

0
LU

){

ce

V
!J

5 -4_

ce
LU

Q.

UJ

-6.

400

800

1200

TEMFERATURE ("C)
Fig. \. TG (

) and DTA (

} curves of hase body.

BOL.SOC.ESP.CERAM.VIDR. VOL. 30 - NUM. 1

T. MANFREDINI, G. C. PELLACANI, P. POZZI, G. MARZOLA, C. PASQUALI

to dehydroxylation of the clay minerals, whereas at higher

temperatures some endothermic transformations affect firing
reactions.
The thermal behavior of dehumidified bentonites are discussed in ref. (3). Although they present some relevant and
interesting characteristics, due to the loss of uncoordinated
water molecules and structural hydroxyl groups and to firing phenomena (6, 7), when present in 0-4 wt% amounts
in the body they do not significantly affect its thermal trend
in the 20-l,200C temperature range.
3.1.3.

DILATOMETRIC ANALYSES

In Table II the linear thermal expansion coefficients of the

bodies with 0-4 wt% amount of natural and treated bentonites are reported in the temperatures below 800C. The presence of bentonites (Bl and B2) up to 4 wt% does not affect
the dilatometric behaviour of the low-plastic base body in
the 20-800C temperature range, agreeing with DTA and
DTG results.

800

900

1000

1100

1200

TEMPERATURE (C)
Fig. 2.Dilatometric behaviour of green tiles with 0 {
-), 2 (-- -) and
4 ^_._._._j ^t% of natural bentonite (Bl).

TABLE II

MODULUS OF RUPTURE (AV. OF 5 MEASUREMENTS)

(N/mm2) AND DILATOMETRIC RESULTS [a ' 10^ CC'^)]
OF THE UNFIRED TILES IN PRESENCE
OF BENTONITE (wt%)
Bentonite

2.66
2.99

2.90
3.28

MODULUS OF RUPTURE
1.27
1.27

Bl
B2

1.94
2.24

2.24
2.69

DILATOMETRIC RESULTS
Bl (25-400C)
B2 (25-400C)

9.90
9.90

9.37
9.56

9.36
9.84

Bl (25-800C)
B2 (25-800C)

12.50
12.50

12.30
12.10

12.20
12.30

9.46
9.65

12.30
12.20

800

900

1000

1100

1200

TEMPERATURE CQ
At higher temperatures (850-1,200 C) relevant shrinkages are observed (Figure 2 and Figure 3). In fact the dilatometric behavior of base body shows a slight contraction due
to a first sinterization step in the 850-1,000C temperature
range, followed by a more marked shrinkage in the
1,000-1,200 C temperature range for the firing reactions
which form a glassy that enhances the bulk densification.
After 1,200C pyroplastic deformation occurs.
In the same temperature range, the presence in the body
of increasing amounts of bentonites enhances the linear shrinkage of the samples, in agreement with their alkaline and
alkaline-earth cation content, which favours the melting and
thermal reactivity of the samples. Furthermore, the very fine particle size dimensions (high specific surface area) of
the bentonites strongly favours the vitrification of the samples (8). This can be also supported by the fact that the acvated bentonite (B2), with higher alkali ion content, has more
pronounced shrinkage effects on the samples than does Bl.
ENERO-FEBRERO, 1991

Fig. 3.Dilatometric behaviour of green tiles which 0 (

), 2 (
4 (
) wt% of activated bentonite (B2).

) and

3.2. Fired tiles

3.2.1.

SINTERING DIAGRAMS

The considerations above reported, based on the thermal

and thermomechanical measurements, were fully confirmed
by firing trials (tests). Figures 4 and 5 report the changes
of the linear shrinkage as a function of the firing temperature for the green tiles added with different amounts of natural and treated bentonites. In particular, for all the samples
the sinterization phenomena are observed to start at about

Preparation of a ceramic floor tile body containing pure bentonite as strengthening agent

900-1,000C with an increase in Unear shrinkage and a consequent decrease in open porosity.
Increasing amounts of bentonites in the body, which leave the water absorption unaffected, slightly increase the linear shrinkage of tiles during firing, since, by providing more
areas of contact between the particles (8), as suggested above, they favour the vitrification processes. All samples present a maximum linear shrinkage value at about 1,1801,200C. This value is strictly dependent on the bentonite
content, varying from 5.40% for the base body to 6.50%
for samples containing 4% of untreated bentonite (Bl) or
to 7.00% for samples containing 4% of treated bentonite
(B2). In further agreement with the above reported results,
the samples containing activated bentonite (B2) present higher maximum shrinkage values than those containing the natural bentonite (Bl), in accordance with a stronger flux effect of B2, which promotes earlier liquid formation and hence
vitrification.
Furthermore, it is important to note that the presence of
pure bentonites, having a strong flux action, in a non-plastic
base body significantly reduces the optimum greification range and therefore amounts higher than 4/5 % can produce undesirable effects.

900

1000

1100

1200

TEMPERATURE (C)
Fig. 4.Linear shrinkage (%) against firing temperature {C) for green
tiles with 0 (O), 2 {) and 4 (Dj wt% of natural bentonite (Bl).

4. INDUSTMAL TESTS
On the basis of the above results obtained on a laboratory
scale and of economic considerations, the addition of about
2 wt% of treated bentonite to low plastic base bodies seems
to be the most appropriate from the industrial point of view.
For these reasons, at the floor gres factory of Sassuolo (Italy)
we performed some tests in order to verify the industrial compatibility of the base body, added with 2 wt% of activated
bentonite (B2), and to compare the results with those obtained with the same base body added with 7.5% of a natural
bentonitic clay, containing about 40 wt% of smectitic minerals, hitherto used for floor tile production.
In Table III the modulus of rupture, water absorption and
linear shrinkage of green floor tiles obtained from body containing 7.5 wt% of bentonitic clay or 2 wt% of treated bentonite are compared. The most striking result is a strengthening action of 2 wt% of activated bentonite 30% greater than

TABLE III

COMPARISON BETWEEN THE MODULUS OF RUPTURE

(N/mm2) WATER ABSORPTION (%) AND LINEAR
SHRINKAGE (%) OF INDUSTRIALLY PREPARED
TILES FROM BODY CONTAINING 7.5 wt%
OF BENTONITIC CLAY (A) AND 2 wt%
OF TREATED BENTONITE (B2) (B)^^)
Modulus of
Rupture*

900

1000

1100

1200

TEMPERATURE (C)
Fig. 5.Linear shrinkage (%) against firing temperature CQ for green
tiles with 0 (O), 2 () and 4 (Oj wt% of activated bentonite (B2).

PRESS 1
PRESS 2

Water
Absorption**

Shrinkage**

1.35
1.33

1.72
1.70

3.0
2.9

3.0
2.7

6.9
6.9

6.8
6.7

^^^ The measurements were performed on unfired (*) and fired

(**) tiles and the values average the results performed on nine
samples (three dies for each press).
BOL.SOC.ESP.CERAM.VIDR. VOL. 30 - NUM. 1

T. MANFREDINI, G. C. PELLACANI, P. POZZI, G. MARZOLA, C. PASQUALI

that of 7.5 wt% of natural bentonitic clay. The values of the

modulus of rupture of about 1.71 N/rtim^ in the industrial
tests as against about 2.69 N/mm^ obtained in the laboratory tests depend on the different technological sample preparation. On fired tiles no relevant changes in modulus of
rupture (about 48.5-49.5 N/mm^) are observed among base body or in presence of 2 wt.% of treated bentonite or 7.5
wt% of natural bentonitic clay.

sintering processes and (c) they do not cause the defects

(black core, reduction of oxides, which alters color, etc.)
characteristic of the organic strengthening agents.
The lesser amount of activated bentonites necessary to enhance mechanical strength of green ceramic tiles from low
plastic bodies and their clearness make them inorganic additives rather than true components of the body, and therefore they do not appreciably affect the bulk physicochemical properties of the bodies. At the same time, their chemical
composition promotes the sinterization processes.

TABLE IV

PHYSICO-CHEMICAL PROPERTIES OF SLIPS

OF BASE BODY (A) AND CONTAINING
BENTONITIC CLAY (7.5 wt%) (B) OR TREATED
BENTONITE (B2) (2 wt%) (C)

Density (gr/cm^)
Apparent viscosity (mPa s)
Solid content (wt%)
Residue (wt%) at 60 im
Residue (wt%) at 45 fim

1.68
120
70
3.9
9.5

1.68
205
70
4.4
9.8

1.69
140
70
3.8
9.4

ACKNOWLEDGEMENTS
The authors are grateful to C.N.R. for financial support,
to Ceramco S.r.l. of Sassuolo (Italy), who supplies us the
bentonites and to Floor Gres Ceramiche S.p.a. Sassuolo
(Italy) whose cooperation is greatly acknowledged.
6.

1. PiNCUS, A. and SHIPLEY, L . : The role of organic binders in ceramic processing, Cer. Ind., 92. (1969) (4),
106.
2.

Another very important advantage in substituting natural

bentonitic clay (7.5 wt%) with activated bentonite (2 wt%)
is the fact that the rheological behavior of the industrial slip
remains unmodified, as observed in Table IV which compares some significant physical properties of slips of base body,
base body added with 2 wt% of activated bentonite or with
7.50 wt% of bentonitic clay. The high amount of bentonitic
clay necessary to improve a low plastic body drastically increases the apparent viscosity of the slip, since it acts as a
true body component and not an additive.
5.

REFERENCES

EL-KHOLI, M . B., MOSTAFA, M . Z . , EL-DEFRAWY, S.

A. and ABDEL-FATTAH, W . I.: Strengthening of parian

porcelain casting bodies, Interceram, 37 (1988) (1),
21-24.
3.

MARZOLA, G . , PASQUALI, C , BOSCARDIN, L . , MAN-

FREDINI, T., PELLACANI, G. C. and Pozzi, P.: Bentonites as strengthening agents of low-plastic bodies for
the production of floor gres ceramic tiles. Mat. Eng.,
in press.
4.

AMORS ALBARO, J. L., BLASCO FUENTES, A., ENRIQUE NAVARRO, J. E . , ESCARDINO BENLLOCH, A. and
BELTRN PORGAR, V . : Variables en la compactacion de

soportes cermicos de pavimento y revestimiento. Tcnica Cermica, 105 (1982), 792-812.

CONCLUSIONS
5.

The addition of low amounts (1.5-2.5%) of pure bentonites with a high smectite content to low-plastic ceramic body
seems particularly indicated from an industrial point of view,
since it notably improves the mechanical strengti of the green
tiles, which permits handling and transporting of unfired ceramic tiles in their dry state with a noticeable reduction in
ruptures. This enables the pre-firing steps of a ceramic factory to be rationalised, and the productivity to be increased.
Other advantages which strongly recommend the use of
1.5-2.5 wt% treated bentonites in low plastic bodies are: pure
bentonites (a) do not significantly modify the rheological behavior of the slips nor the thermal behavior of the base body,
(b) they speed up the vitrification, favouring the firing and

ESCARDINO BENLLOCH, A., AMORS ALBARO, J. L .

and ENRIQUE NAVARRO, J. E . : Estudio de gres para pavimentos. Bol. Soc. Esp. Cerm. Vidr., 20 (1981) (1),
17-24.
6.

DEL PENNING, U . , MAZZEGA, E . , VALERI, S., ALIET-

Ti, A., BRIGATTI, M . F . and POPPI, L . : Interlayer water and swelling properties of monoionic montmorillonites. J. Coll. Int. Se, 84, 301 (1981).
7. ALIETTI, A . and PALUMBO, G . : Mineral with an intermediate behaviour ween saponite an corrensite. Miner.
Petrogr. Acta, XXX, 247 (1986-87).
8. GRIMM, R. E . and GUVEN, N . : Bentonites Geology,
Mineralogy, Properties and Uses. Elsevier Publ. Co.
Ed., 1978.

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