Ceramics International xxx (xxxx) xxx–xxx

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Development of refractory ceramics from residual silica derived from rice

husk ash
⁎
F.Z. Sobrosa, N.P. Stochero, E. Marangon, M.D. Tier
Universidade Federal do Pampa, Unipampa, PPEng, Campus Alegrete, RS, Brazil

A R T I C L E I N F O A BS T RAC T

Keywords: Rice husk has been used as a thermal energy source for electricity generation, resulting in the formation of silica
Refractory ceramic from rice husk as a by-product. This research aims to develop refractory ceramic materials by replacing kaolin
Kaolin clay clay with rice husk silica at 5%, 10% and 20% volume percentages. The samples were investigated in terms of
Silica from rice husk their density, apparent porosity, tensile strength in three-point bending test, compressive strength, thermal
Sustainable development
shock and mineralogical composition. The use of 20% silica resulted in an increase in the formation of
Renewable energy sources
cristobalite, higher packing of granular mixtures, and consequently, an improvement in the tensile strength and
compression strength of the samples. However, the material that was most successful in increasing the
mechanical strength without decreasing the thermal shock strength was the sample processed with 10% clay
replacement by silica from rice husk.

1. Introduction by decreasing chloride penetration, decreasing permeability and in-

Rice is considered one of the most important staples and is
consumed by almost half the world's population (Bhullar [1],
Manishanka [2]). According to Seck et al. [3], it will be necessary to
increase rice production between 8 and 10 million tons per year over
the next decade to meet growing global demand.
Rice husk (RH) is released during rice processing; due to its high
caloric value (16,720 kJ/kg) RH has great potential as a thermal energy
source (Della [4]).
Rice husk burning generates new waste, namely rice husk ash
(RHA), which according to Kishore et al. [5] corresponds to 20% of
husk volume. Folleto et al. [6] and Kumar et al. [7] reported that ash
contains high silica content ( > 92%), making it a residue with high
economic potential. This material has great applicability in industries
including electronics, construction, chemicals and ceramics, among
others.
Several studies report the advantages of rice husk silica (RHS)
addition to concrete matrices, including inhibition of the alkali-
aggregate reaction due to the reduction of concrete permeability and
decreased porosity of the matrix. These decreases lead to an increase in
the concrete's compressive strength, as well as reduced carbon dioxide
emissions to the atmosphere by the cement industries (Chatveera [8],
Raman [9], Chopra [10]).
Saraswathy and Song [11] reported that 25% RHS mass incorpora-
tion into concrete results in better control of reinforcement corrosion
creasing resistance. Kishore et al. [5] reported that cement replacement
by 10% RHS resulted in improvement in workability and mechanical
resistance of the samples.
Different studies have shown the efficiency in using RHS as silica
precursor, especially to produce ceramic materials. Prasad et al. [12]
investigated the effect of quartz replacement in whiteware ceramic and
found that RHS resulted in a reduction of maturation temperature and
an increase in strength. Andreola et al. [13] evaluated the use of RHS to
the synthesis of ceramics pigments. They found more stable pigments
and higher intensity for red color when compared to pigments from
pure quartz, while Andreola et al. [14] reported that glass-ceramics
produced with RHS present bending strength values and higher Mohs
hardness when compared to commercial glass-ceramics.
Della et al. [15] reports that the high melting point of silica,
combined with its wide availability and low cost, has some of the
greatest potential for RHS in manufacturing of refractory ceramics for
use in the steel industry. This research aims to diversify the use of
residual silica from rice husk, since its application in concrete and
plaster is already a reality. The prepared material demonstrates
improved mechanical properties and reduced production costs. It is
thus intended to improve the mechanical and thermal properties of
refractory ceramic materials and to add value to residual silica by
burning rice husks.

⁎
Corresponding author.
E-mail address: marcotier@unipampa.edu.br (M.D. Tier).

http://dx.doi.org/10.1016/j.ceramint.2017.02.147
Received 19 September 2016; Received in revised form 22 February 2017; Accepted 27 February 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Sobrosa, F.Z., Ceramics International (2017), http://dx.doi.org/10.1016/j.ceramint.2017.02.147
F.Z. Sobrosa et al. Ceramics International xxx (xxxx) xxx–xxx

Table 1 Table 3
Chemical composition of KC and RHS. Nomenclature used for mixes.
Source: Helager Industria e Comércio Ltda/Sílica Verde do Arroz Ltda
Mixes Abbreviation
Element KC RHS
KC KC
Percentage (%) Percentage (%) KC with 5% of RHS KS5
KC with 10% of RHS KS10
SiO2 57.83 91.48 KC with 20% of RHS KS20
CaO 0.13 0.36
MgO 0.36 0.32
Fe2O3 2.25 0.05 initial drying, the CPs were placed in a kiln at a temperature of 105 ±
Al2O3 27.52 ND
Na2O < 0.001 0.04
10 °C for 24 h.
K2O 1.87 1.40 Subsequently, all samples were sintered at 1300 °C in a muffle-type
TiO2 0.38 0.003 furnace. Cooling was performed naturally in the oven after shutdown.
MnO < 0.01 0.32
SO3 – 0.15
P2O5 – 0.45 2.3. Testing and analysis
Loss to fire 8.63 3.50
To evaluate the physical properties of the samples, porosity and
apparent mass density tests were performed by employing a water bath
2. Materials and methods
with a digital thermostat and a hydrostatic balance, in accordance with
the ISO 5017:2015 standard (NBR [20]).
2.1. Raw materials
The mechanical properties were investigated through tensile
strength using three-point bending and compressive strength testing.
The raw materials used for manufacturing the refractory ceramics
The thermomechanical properties were evaluated by thermal shock
were kaolin clay (KC) and rice husk silica (RHS). KC was chosen due to
testing.
low availability of iron oxide, which favours refractivity.
Flexural strength was assessed using three-point bending tests in a
RHS was produced using a rice husk combustion process in a
Shimadzu universal testing machine with a 5-kN load capacity,
fluidized bed with controlled temperature (below 650 °C), resulting in
following the ISO 5014: 2012 standard guidelines (NBR [21]).
silica extraction with an amorphous structure (Yalçin [16]; Pandolfelli
The compressive strength test was performed according to ISO
[17]; Nair [18]). Table 1 shows the chemical composition of KC and
standards 201410059-2:2014 (NBR [22]) in an EMIC brand universal
RHS.
testing machine with a 200-KN load capacity. The samples were
previously capped with Sikadur 32 epoxy glue on both sides to level
2.2. Test parts manufacturing the surface. This prevents sample rupture through shearing caused by
eventual irregularities on the surface.
Initially, the effects of RHS on the plasticity limit and the liquidity The thermal shock resistance test was performed following [23]
limit of ceramic mass were evaluated by testing in accordance with ISO specifications. For each cycle, samples remained at 1200 °C for 10 min
17892-12: 2004 [19]. Table 2 shows the plasticity index values, and were immediately removed and added into a tank of water, where
indicating that replacement of silica led to a decrease in clay plasticity. they remained for 5 min. The samples were removed from the tank and
The calculated kaolin clay plasticity index indicated a plasticity after 5 min at room temperature were placed back in the furnace for a
suitable for shaping until the 20% threshold of KC substitution by RHS. new cycle. This procedure was performed until the CPs ruptured.
Four formulations were used to manufacture the test parts (CPs) RHS mineralogical analysis by XRD were performed using an R θ2θ
with up to 20% clay replacement with silica. The first composition Ultima IV diffractometer with Bragg Brentano geometry.
consisted of 100% kaolin clay, and the second, third and fourth
formulations were carried out with replacements of 5%, 10% and 3. Results
20% of KC with RHS. Table 3 presents the nomenclature used to
identify CPs. 3.1. X-ray diffraction
The refractory ceramics were processed by extrusion under 28 kg/
cm³ operating pressure; 35% moisture content was defined by pre- According to Fig. 1, RHS is predominantly amorphous since it
testing aimed towards adequate plasticity. Below this value, it was presents a wide and diffuse peak between 20° and 30° as reported by
difficult to shape parts. During extrusion, the material was subjected to
manual cutting. The dimensions of the test parts were
10 cm×3.13 cm×2.14 cm.
After the cutting procedure, the CPs were wrapped in damp cloths
and covered to prevent accelerated moisture loss, which could cause
defects and imperfections such as curling of the parts. This natural
drying was performed at room temperature for 20 days. After this

Table 2
Plasticity index.

Mixes PL LL PI Variation PI %

KC 19.07 38.55 19.49 –

KC with 5% of RHS 19.87 38.37 18.50 −5.07
KC with 10% of RHS 22.26 37.41 15.15 −22.26
KC with 15% of RHS 26.22 37.35 11.13 −4289
KC with 20% of RHS 26.93 37.19 10.26 −47.35
Fig. 1. XRD of rice husk silica.

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Fig. 5. Tensile strength in bending at three points.

Fig. 2. XRD before burning: KC, KS5, KS10 and KS20.

Fig. 6. Compressive strength.

Table 4
Fig. 3. XRD after burning: KC, KS5, KS10 and KS20. Results of resistance to thermal shock.

Mixes Average resistance to Number of first Number of total

thermal shock (r.t. crack cycle (A) break cycles (B)
s=A/B)

Kaolin clay 0.46

KC/1 3 8
KC/2 4 9
KC/3 4 7
Kaolin clay 0.47
with 5%
RHS
KS5/1 3 7
KS5/2 4 12
KS5/3 4 6
Kaolin clay 0.47
with 10%
RHS
KS10/1 4 7
KS10/2 4 10
KS10/3 3 7
Kaolin clay 0.73
with 20%
Fig. 4. Apparent bulk density and porosity. RHS
KS20/1 3 3
Yalçin et al. [16] and Della et al. [4]. The presence of amorphous KS20/2 3 5
KS20/3 3 5
(reactive) or crystalline (almost inert) silica is directly linked to
temperature and the method of silica production (Pereira [24]).
When the RHS burning temperature is low or the exposure to high for quartz (SiO2), kaolinite and montmorillonite.
temperatures was short, the silica contained in the ash is predomi- After burning, the ceramic specimens showed changes in their
nantly amorphous (Benassi [25]). mineralogical phases. According to Fig. 3, replacing clay with RHS
X-ray diffractograms for refractory clay in before and after burning resulted in the appearance of a cristobalite peak.
mixtures are shown, respectively, in Figs. 2 and 3. The presence of quartz (SiO2) is likely because the burning
The spectrum for mixtures before burning essentially showed peaks temperature (1300 °C) and/or sintering time used are insufficient to

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F.Z. Sobrosa et al.
Fig. 7. Typical cracking cases and rupture in the investigated samples.
allow this phase transformation.
The presence of mullite occurs is due to the reaction between
alumina and silica present in the mixture, which reached stoichiometry
in this crystalline phase and corresponds to 3Al2O3·2SiO2.
Furthermore, cristobalite emerged due to free silica crystallization,
which increased its peak as the clay replacement for RHS concentration
increased (Sadik [26]).
RHS did not react with other chemical elements to form mullite
because mullite peaks remained unchanged with substitution of clay
for RHS.
3.2. Density and porosity
According to Fig. 4, RHS concentration increased and there was a
decrease in apparent porosity.
Because silica's specific mass (2.03 g/cm3) is lower than the specific
mass of refractory clay (2.73 g/cm3), it would be expected that an
increase in RHS concentration would result in a decrease in the
material's density. However, it is observed in Fig. 4 that the density
obtained with 20% silica substitution was almost the same as that
Fig. 8. Fracture forms from the thermal shock test: (a) KC; (B) KS5; (C) KS10; (D) KS20.
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obtained with refractory clay. Thus, it is believed that the use of silica
resulted in improved packing of mixture grains.
3.3. Mechanical and thermomechanical properties
Fig. 5 shows the results obtained for tensile strength in a three-
point bending test.
It was observed that the use of silica promoted an increase in the
mechanical strength of samples for replacement contents of 10% and
20%. The average flexural strength ranged from 19.26 MPa in KC
ceramic to 27.98 MPa in 20% RHS ceramic, an increase in flexural
strength of 45.27%. With 10% RHS replacement, this increase was
25.3%.
Similar behaviour was observed in the compressive strength test, as
shown in Fig. 6.
The average compressive strength ranged from 116.93 MPa for the
reference ceramic (KC) to 140.06 MPa for the 20% RHS ceramic
(KS20) – an increase of 19.77%. With the 10% RHS replacement, the
increase was 10.50%.
The higher tensile strength in bending and the higher compressive
strength observed for samples KS 10 and KS 20 may be associated with
the reduction of apparent porosity.
Table 4 shows the results of thermal shock resistance tests carried
out on three samples for each concentration.
From the thermal shock test, it was observed that the 20% RHS
ceramic broke sooner because the cycle interval between the sample's
first crack and rupture was shorter.
Fig. 7 shows ruptures in the investigated material. KC, KS5 and
KS10 ceramics showed higher crack propagation.
According to Sabree et al. [27], the development of cracks can be
related to the presence of microstructural defects that increase the
appearance of internal stresses. In this case, these defects may be
related to the porosity in these samples, as shown in Fig. 4. Porosity for
sample KS20 was approximately 0.37%, lower than the other samples,
and therefore crack propagation was also lower.
For fracture formation in these ceramics, crack propagation pro-
F.Z. Sobrosa et al.
ceeded in a zigzag form, as shown in Fig. 8. The materials containing
only kaolin clay and 5% and 10% RHS showed a more irregular fracture
surface and a longer path, suggesting higher fracture total energy and,
consequently, greater thermal shock resistance.
4. Conclusions
In this study the physical, mechanical and thermal proprieties of
refractory ceramic materials with and without KC by RHS replacement
were investigated. KC by RHS replacement was limited to 20%, due to
the loss of plasticity observed in the mixture and difficulties in shaping.
The following conclusions were obtained:
– Use of RHS in manufacturing refractory ceramics favoured the
appearance of cristobalite while maintaining unchanged mullite
peaks.
– Greater mechanical strength was found in refractory ceramics made
of 10% and 20% KC using RHS replacement.
– Thermal shock tests showed that the 20% RHS replacement material
broke after fewer cycles and smaller cycle intervals, indicating a
weaker ceramic.
– 5% and 10% RHS replacement materials did not show significant
variation in resistance to thermal shock compared to KC.
– 10% RHS replacement material was the one for which better
mechanical and thermomechanical properties were obtained, as it
showed a mechanical strength increase without decreasing resis-
tance to thermal shock.
Acknowledgments
The authors thank Sílica Verde do Arroz Ltda. from the Pilecco
Nobre Group and Helager Indústria e Comércio Ltda. for supplying raw
materials. The authors also thank CNPq for financial support, through
Project 482225/2011-4.
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