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Ceramics International xxx (xxxx) xxx–xxx

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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


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-

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

Corresponding author.
E-mail address: (M.D. Tier).
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),
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
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
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
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.

F.Z. Sobrosa et al. Ceramics International xxx (xxxx) xxx–xxx

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)

Kaolin clay 0.46

KC/1 3 8
KC/2 4 9
KC/3 4 7
Kaolin clay 0.47
with 5%
KS5/1 3 7
KS5/2 4 12
KS5/3 4 6
Kaolin clay 0.47
with 10%
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

F.Z. Sobrosa et al. Ceramics International xxx (xxxx) xxx–xxx

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
Similar behaviour was observed in the compressive strength test, as
Fig. 7. Typical cracking cases and rupture in the investigated samples. shown in Fig. 6.
The average compressive strength ranged from 116.93 MPa for the
allow this phase transformation. reference ceramic (KC) to 140.06 MPa for the 20% RHS ceramic
The presence of mullite occurs is due to the reaction between (KS20) – an increase of 19.77%. With the 10% RHS replacement, the
alumina and silica present in the mixture, which reached stoichiometry increase was 10.50%.
in this crystalline phase and corresponds to 3Al2O3·2SiO2. The higher tensile strength in bending and the higher compressive
Furthermore, cristobalite emerged due to free silica crystallization, strength observed for samples KS 10 and KS 20 may be associated with
which increased its peak as the clay replacement for RHS concentration the reduction of apparent porosity.
increased (Sadik [26]). Table 4 shows the results of thermal shock resistance tests carried
RHS did not react with other chemical elements to form mullite out on three samples for each concentration.
because mullite peaks remained unchanged with substitution of clay From the thermal shock test, it was observed that the 20% RHS
for RHS. ceramic broke sooner because the cycle interval between the sample's
first crack and rupture was shorter.
3.2. Density and porosity Fig. 7 shows ruptures in the investigated material. KC, KS5 and
KS10 ceramics showed higher crack propagation.
According to Fig. 4, RHS concentration increased and there was a According to Sabree et al. [27], the development of cracks can be
decrease in apparent porosity. related to the presence of microstructural defects that increase the
Because silica's specific mass (2.03 g/cm3) is lower than the specific appearance of internal stresses. In this case, these defects may be
mass of refractory clay (2.73 g/cm3), it would be expected that an related to the porosity in these samples, as shown in Fig. 4. Porosity for
increase in RHS concentration would result in a decrease in the sample KS20 was approximately 0.37%, lower than the other samples,
material's density. However, it is observed in Fig. 4 that the density and therefore crack propagation was also lower.
obtained with 20% silica substitution was almost the same as that For fracture formation in these ceramics, crack propagation pro-

Fig. 8. Fracture forms from the thermal shock test: (a) KC; (B) KS5; (C) KS10; (D) KS20.

F.Z. Sobrosa et al. Ceramics International xxx (xxxx) xxx–xxx

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