wall tiles
wall tiles
wall tiles
Ceramics International
journal homepage: www.elsevier.com/locate/ceramint
A R T I C LE I N FO A B S T R A C T
Keywords: This work focuses on the reuse of grits waste, from cellulose industry, as a raw material to replace traditional
A. Firing carbonate material in ceramic wall tiles. Wall tile formulations bearing up to 15 wt% of the grits waste were
B. Porosity prepared for replacement of calcareous. The tile manufacturing route consisted of dry powder granulation,
E. Structural applications uniaxial pressing, and firing at temperatures ranging from 1100 °C to 1180 °C by using a fast-firing cycle. The
Grits waste
wall tile specimens were tested to determine their physical and mechanical properties (linear shrinkage, water
absorption, apparent porosity, apparent density, breaking strength, and flexural strength). The firing behavior,
phase transformations, and microstructure were evaluated by dilatometry, XRD, and SEM. The results showed
that the fired wall tile specimens are composed of anorthite and quartz, as major mineral phases, and mullite as a
minor phase. It was found that the grits waste had a positive influence on the properties and microstructure of
the wall tile specimens. The results also revealed that the grits waste from cellulose industry could be used as a
total replacement of traditional calcareous material in wall tile formulations.
⁎
Corresponding author.
E-mail address: holanda@uenf.br (J.N.F. Holanda).
https://doi.org/10.1016/j.ceramint.2018.07.203
Received 12 May 2018; Received in revised form 5 July 2018; Accepted 23 July 2018
0272-8842/ © 2018 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Please cite this article as: Siqueira, F.B., Ceramics International (2018), https://doi.org/10.1016/j.ceramint.2018.07.203
F.B. Siqueira, J.N.F. Holanda Ceramics International xxx (xxxx) xxx–xxx
Table 1 Table 3
The proportions of the blends for the wall tile formulations (wt%). Crystalline phases identified in the raw materials.
Formulation Kaolin Quartz Calcareous Grits waste Raw materials Crystalline phases
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Fig. 1. X-ray diffraction patterns of the green wall tile formulations: a) MF0;
and b) MF15. 1 - kaolinite; 2 - quartz; 3 - mica; 4 - calcite; 5 - dolomite; 6 -
pirssonite; and 7 - portlandite.
Fig. 3. X-ray diffraction of the wall tile formulations fired at different tem-
peratures: a) MF0; and b) MF15. 1 - anorthite; 2 – gehlenite; 3 - mullite; 4 –
quartz; and 5 - diopside.
Table 4
Physical parameters of the wall tile formulations.
Formulation ρ (g/cm3) Rs (%) LL (%) PL (%) PI (%) HR
Fig. 4. Wall tile formulations plotted in the ternary phase diagram of CaO-
MF0 2.51 2 39.1 21.3 17.8 1.20 Al2O3-SiO2 system.
MF5 2.51 1 37.6 20.1 17.5 1.25
MF10 2.52 3 37.5 20.2 17.3 1.27
MF15 2.52 2 37.0 19.8 17.2 1.29 the Atterberg method (IP = UPL – LPL, in which the UPL is the upper
plastic limit and LPL is the lower plastic limit.). There is no significant
difference in the plastic index (IP = 17.2–17.8%) of the wall tile
powders. In addition, a good interaction between the primary particles powders. These values of plasticity are adequate for ceramic tile pro-
that enhances the physical and chemical reactions during the fast-firing duction. The rheological behavior of the granulated tile powders was
cycle should be expected. The plastic index (IP) was determined using evaluated in terms of Hausner ratio [17–19]. As observed in Table 4,
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Table 5
Technical properties of the wall tile specimens in the dried state at 110 °C.
Properties Formulation
Fig. 6. SEM micrographs of wall tile specimens fired at 1140 °C: a) MF0; b) MF5; c) MF10; and d) MF15.
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Fig. 7. Physical properties of the fired wall tile specimens: a) linear shrinkage; b) apparent density; c) water absorption; and d) apparent porosity.
(2 + n) → 2CaO.Al2O3. SiO2 + nCaO.SiO2). Then, anorthite is quickly metakaolinite, resulting in shrinkage. Between ~ 700 °C and 850 °C, a
formed due to the reaction between gehlenite and silica and alumina new expansion has been identified in the dilatometric curves. It cor-
phases from the metakaolinite breakdown (2CaO.Al2O3. SiO2 + 3SiO2 responds to the carbonate decomposition to form mainly CaO and CO2
+ Al2O3 → 2(CaO.Al2O3.2SiO2)). However, the proportion of the an- degassing. Then, a new reaction between amorphous metakaolinite
orthite phase in the grits waste bearing wall tile formulations tends to (Al2O3.2SiO2) and calcium oxide (CaO) quickly occurred. This reaction
be increased due to the higher amount of calcite in the used grits waste. resulted in the formation of anorthite as shown in Fig. 3. Such reaction
In fact, the grits waste is mostly composed of calcite (92 wt%) followed also tends to inhibit the formation of liquid phase during the firing
by pirssonite (7 wt%) and portlandite (1 wt%) [25]. process. Above 850 °C, a new shrinkage mainly caused by solid state
The mineral phases formed during the fast-firing process of ceramic sintering mechanisms can be observed. Finally, on firing, the wall tile
wall tile formulations could be predicted by the ternary phase diagram formulations presented low shrinkage (~ 1.95–2.10%). However, the
SiO2-Al2O3-CaO [24]. The studied wall tile formulations, when plotted MF0 formulation (free-waste formulation) had higher firing shrinkage.
in this phase diagram (Fig. 4), are all delimited to the anorthite area on SEM micrographs of fracture surfaces of wall tiles fired at 1140 °C
the triangle of compatibility anorthite-quartz-mullite. This means that were compared to each other in Fig. 6(a)–(d). They show the typical
the grits waste could totally replace traditional calcareous raw material sequence of densification behavior of wall tiles, with an increased grits
in ceramic wall tile formulations. waste amount. As can be observed from the SEM micrograph of the MF0
The sintering behavior of the wall tile formulations is presented in formulation (free-waste formulation) in Fig. 6(a), a large amount of
Fig. 5. It can be seen that only slight differences in the sintering be- open pores of different sizes was developed. Such open pore network
havior of the wall tile formulations occurred. The sintering behavior that appears to form communication channels results primarily from
could be described as follows. All curves exhibited a small shrinkage the decomposition of calcite particles and the release of CO2. This
from the room temperature up to 170 °C. This event is mainly related to porous microstructure is typical of ceramic wall tile materials. As in-
the release of free moisture of the clay minerals particles. However, in dicated by the XRD analysis (Fig. 3), it consists essentially of anorthite
grits waste bearing wall tile formulations the dehydration of pirssonite phase with quartz and mullite in minor amounts. MF5 formulation
also occurred. Between ~ 170 °C and 575 °C, a small expansion (Fig. 6(b)) had a porous microstructure very similar to that of waste-
(< 0.5%) has been identified in the dilatometric curves. It was caused free wall tile specimens. However, the microstructures of MF10 and
by the thermal expansion of solid particles of the green wall tile for- MF15 formulations differ from that of the reference specimens, as
mulations. In addition, at ~ 573 °C, allotropic transformation of α-β shown in Fig. 6(c) and (d). A denser fractured surface can be seen. This
quartz happened. This transformation is accompanied by the volu- effect suggests the formation of liquid phase during the fast-firing cycle.
metric expansion of quartz particles. Between ~ 575 °C and 700 °C, all In fact, the pirssonite decomposition in the grits waste with con-
curves showed an inflexion event with strong slope. This effect is comitant melting of sodium carbonate (NaCO3) contributes to closing
mainly linked to the dehydroxylation of the kaolinite (removal of the pores in the fired wall tile structure. This indicates that additions of
OH- groups of the crystal lattice) that transforms to amorphous high concentrations of grits waste into wall tile body cause changes in
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F.B. Siqueira, J.N.F. Holanda Ceramics International xxx (xxxx) xxx–xxx
ceramic wall tile materials. It can be seen in Fig. 7(a) that the wall tile
specimens presented firing shrinkage values between 0.99% and 1.45%.
This means that all wall tile specimens produced had good dimensional
control, independently of the added grits waste amount. Also note that
the linear shrinkage presented only slight variations within a wide
firing temperature range. This is very important because possible
thermal gradients within the fast-firing roller kiln do not cause di-
mensional instability of fired wall tiles. In addition, the linear shrinkage
of the wall tile pieces was positively influenced by the grits waste ad-
dition. The effect of the grits waste was to decrease the linear shrinkage,
as shown in Fig. 7(a). This behavior may be attributed to higher loss on
ignition of the grits waste (Table 2). Therefore, it appears that the re-
placement of calcareous for grits waste is suitable for a better dimen-
sional stability of the fired wall tile specimens.
The apparent density of the fired wall tile specimens was in the
range of 1.89 – 1.94 g/cm3, as shown in Fig. 7(b). For all wall tile
formulations, the apparent density was essentially unaltered with the
increasing firing temperature. This finding is mainly associated with the
following main effects: i) mass loss due to the decomposition of calcite
with concomitant formation of open porosity; ii) sintering dominated
by the growth of particle-to-particle necks via solid state sintering
mechanisms; and iii) anorthite phase formed practically without liquid
present. On the other hand, the effect of the grits waste was to decrease
the apparent density. This finding is important because the ceramic
wall tile material is characterized by low weight per square meter. The
decrease of apparent density is mainly related to the presence of higher
amount of calcite in the grits waste, which causes increased mass loss
and formation of higher amount of anorthite phase. The formation of
anorthite is also accompanied with an expansion in the fired tile volume
[27].
Fig. 7(c) shows the water absorption of the fired wall tile specimens.
This physical property is the main standard requirement of ceramic tile
materials. It is related to the open porosity level of ceramic tile mate-
rials that reflects their fired microstructure and degree of densification.
Fig. 8. Mechanical strength of the fired wall tile specimens: a) flexural strength; The ISO 13006 standard [28] prescribes a value of water absorption
and b) breaking strength. (open porosity) for ceramic wall tile materials above > 10% (class
BIII). However, ceramic wall tiles of high technical quality have water
the texture and porosity of the fired specimens. absorption between 13% and 18%. Water absorption values between
The drying process of ceramic tile materials consists of the water 15.82% and 17.61% were found for the wall tile specimens prepared in
removal of pressed green tiles via superficial evaporation. The control this study, indicating their conformity to ISO 13006 standard. The high
of the drying process is of high importance in the ceramic tile proces- values of water absorption can be mainly attributed to the carbonate
sing and in the final product quality. In this work, the drying process decomposition, which generates open pores in the fired microstructure,
was monitored through technological properties in the dried state at as shown in Fig. 6. It may also be seen that the water absorption of the
110 °C such as linear shrinkage, bulk density, and green strength wall tile specimens containing grits waste was lower than that of the
(Table 5). The grits waste addition had a very insignificant effect on the waste-free specimens (MF0 formulation). This trend can be explained
drying shrinkage. All green wall tile specimens presented low drying by the incorporation of pirssonite particles of the grits waste, which
shrinkage. This is very important in order to avoid cracks, fissures, and influence the densification behavior of the wall tile specimens. In fact,
warpage in the specimens. The drying density of the tile specimens, as as shown in Fig. 6, the wall tile specimens incorporated with higher
shown in Table 5, presented small variations with the added grits waste grits waste amount revealed a denser microstructure. This is in agree-
amount. In addition, the values of drying bulk density obtained ment with apparent porosity, as shown in Fig. 7(d).
(1.90–1.93 g/cm3) are within the dry green density feature for wall tile The mechanical properties of the fired wall tile specimens are shown
materials [26]. The dried tile specimens exhibited flexural strength in Fig. 8(a)-(b). The correlation between flexural strength (Fig. 8a) and
values in the range of 2.74–3.52 MPa, which is in agreement with the breaking strength (Fig. 8b) of the fired wall tiles is well established. As
safe limits for production of wall tile materials (> 2.50 MPa). This is can be seen, both mechanical properties increased with the rise in the
very important because the dry green strength influences the amount of grits waste amount and firing temperature. Such increase is essentially
rejected dry wall tile materials due to losses on handling. associated with two main factors: i) anorthite phase formed of higher
The final quality of ceramic wall tile specimens after fast-firing cycle mechanical strength [29]; and ii) lower water absorption of the wall tile
was determined on the basis of physical properties (linear shrinkage, specimens, as shown in Fig. 7(c). According to the ISO 13006 standard
apparent density, water absorption, and apparent porosity) and me- [28], the fired wall tiles of thickness < 7.5 mm and water absorp-
chanical properties (breaking strength and flexural strength). tion > 10% should have values of flexural strength > 15 MPa and
Fig. 7 shows the physical properties of the fired wall tile specimens. breaking strength > 200 N. As shown in Fig. 8, wall tiles bearing grits
The linear shrinkage is an important physical property of ceramic tile waste could be produced with the MF5 formulation fired between
materials. It affects the dimensional stability during fast-firing cycle. 1120 °C and 1180 °C and MF10 and MF15 formulations fired between
Although it is not a standardized requirement in technical standards, 1100 °C and 1180 °C. This result suggests that the grits waste is parti-
values of linear shrinkage < 1.5% are recommended for production of cularly well suitable for ceramic single fast-firing wall tile production
(group BIII – ISO 13006 standard) of high quality, including total
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