Ceramics International 43 (2017) 4674–4679

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Ceramics International
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Synthesis and characterization of calcium silicate insulating material using MARK

avian eggshell waste
⁎
F.H.G. Leitea, T.F. Almeidaa, R.T. Faria Jr, b, J.N.F. Holandaa,
a
Laboratory of Advanced Materials/GMCer, State University of Northern Fluminense, Campos dos Goytacazes, RJ 28013-602, Brazil
b
Laboratory of Physical Sciences, State University of Northern Fluminense, Campos dos Goytacazes, RJ 28013-602, Brazil

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

Keywords: This work focuses on the synthesis of calcium silicate insulating material via solid state reaction using avian
A. Solid state reaction eggshell waste as alternative calcium source. The calcium silicate formulations were mixed in a molar ratio
B. Porosity SiO2:CaO (1:1) and fired at 1100 °C for 24 h. The calcium silicate formulations were characterized by XRD, TG-
D. Silicate DTA, dilatometry, SEM/EDS, and thermophysical properties (thermal diffusivity, heat capacity per unit volume,
E. Thermal applications
and thermal conductivity). The synthesized calcium silicate materials are composed mainly of wollastonite with
minor amounts of larnite and rankinite. It was found that a processing of the avian eggshell waste (raw eggshell
waste and calcined eggshell waste) had an influence on the thermophysical properties. Calcium silicate pieces
were prepared by uniaxial pressing at 82 MPa, curing, and then testing to determine their use as thermal
insulating material. The microstructure was evaluated by SEM. The results showed that both raw and calcined
avian eggshell wastes could be used as an alternative calcium source in the calcium silicate formulation. It was
found that the calcium silicate pieces reached low thermal conductivity values (0.252–0.293 W/mK). Thus, the
developed calcium silicate materials using avian eggshell waste act as a good thermal insulation ceramic
material.

1. Introduction includes applications such as calcium phosphate-based bioceramics

Every year the food processing industry produces vast amounts of
avian eggshell waste worldwide [1]. The avian eggshell waste contains a
protein-rich membrane that favors the microbiological activity. If
disposed in the environment, it attracts rats and vermin that cause
serious pollution and public health problems. For this reason, the final
disposal of avian eggshell waste is very limited worldwide, and is a
serious matter in the food processing plants [2]. At present, most of
this solid waste material is mainly disposed of in landfill sites without
any treatment in many countries, causing financial costs and environ-
mental impacts. In addition, the landfill sites of urban solid wastes
usually refuse to accept avian eggshell waste because of the protein-rich
membrane. Furthermore, the fills are quickly reaching full capacity.
The avian eggshell waste contains approximately 94 wt% of calcium
carbonate in form of calcite (CaCO3), 1 wt% of calcium phosphate, 1 wt
% of magnesium carbonate, and 4 wt% of organic matter [1,3,4]. This
indicates that the avian eggshell waste due its chemical composition
and availability has a high intrinsic economical value when used as
alternative calcium source in ceramic formulations. The reuse of avian
eggshell waste in the manufacture of value-added ceramic products
[1,5–8], adsorbent material for removal of ionic pollutants [9], cheap
solid catalyst for biodiesel production [10], and soil-cement bricks
[11].
The SiO2-CaO system is one of the most studied for production of
calcium silicates, especially wollastonite (CaSiO3) [12] used for pro-
duction of thermal insulator ceramic material. The calcium silicates are
usually produced via solid state reaction at high temperature.
Traditionally, the calcium silicate formulations contain essentially
non-renewable raw materials as calcium source such as hydrated lime,
quick lime, limestone, and calcium sulphate [12,13]. Recently, indus-
trial wastes such as marble, mussel shells, portlandite-rich waste, and
calcium chloride waste have been also used to produce calcium silicates
as alternative calcium source [14,15]. However, to our best knowledge,
there is no report in the literature about calcium silicate insulating
material prepared using avian eggshell waste.
The aim of this work is to investigate the possibility of reuse of
avian eggshell waste as an alternative calcium source, a renewable raw
material, into calcium silicate formulation for use as thermal insulation
ceramic material. Emphasis is given to the formulation characteristics,
their effects on the thermophysical properties of the synthesized

⁎
Corresponding author.
E-mail address: holanda@uenf.br (J.N.F. Holanda).

http://dx.doi.org/10.1016/j.ceramint.2016.12.146
Received 19 July 2016; Received in revised form 24 November 2016; Accepted 31 December 2016
Available online 02 January 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
F.H.G. Leite et al.
calcium silicate material, and also to the technological properties of the
calcium silicate pieces.
2. Experimental Procedure
Chamotte and avian eggshell waste were used as raw materials. The
raw eggshell waste sample was collected from a food processing plant
located in south-eastern Brazil (Campos dos Goytacazes-RJ). The
chamotte sample was collected from a local clay brick plant. In order
to prepare the mixtures of powders, both samples were dried at 110 °C
and then dry-ground using a laboratory mill to obtain a particle size <
150 mesh ( < 106 µm ASTM). In addition, part of the raw eggshell
waste powder produced was calcined at 1000 °C for 3 h, resulting in a
calcium oxide-rich material. This material is referred hereafter as
calcined eggshell waste.
Mineralogical analysis of the raw materials was performed by X-ray
diffraction (XRD 7000, Shimadzu), using Cu-Kα radiation at a scanning
speed of 1.5° (2θ)/min. The crystalline phases were identified from
peak positions and intensities using reference data from the ICDD-
JCPDS cards. The chemical composition was determined by using an
energy-dispersive X-ray spectrometer (EDX 700, Shimadzu). The loss
on ignition was determined by calculating the wt% differences between
dry sample at 110 °C and calcined sample at 1000 °C for 1 h.
Two calcium silicate formulations were prepared using raw eggshell
waste and calcined eggshell waste as a source of calcium oxide (CaO),
and chamotte as a source of silica (SiO2). Each formulation is labeled as
follow: MR contains raw eggshell waste and MCE contains calcined
eggshell waste. Both formulations were mixed and homogenized by
using a laboratory mixer for 2 h in a molar ratio of SiO2:CaO (1:1).
Then, the formulations were sintered in air at 1100 °C for 24 h in a
laboratory electrical kiln. The heating rate was 20 °C/min and soak
time was 24 h [14].
TG-DTA of the studied formulations were carried out with a
Netzsch Instrument STA 409E on the powder samples, under air
atmosphere from room temperature up to 1100 °C at a heating rate of
10 °C/min. Dilatometric analysis of the formulations was done with a
Netzsch DIL 402 C dilatometer on unfired test samples within the
25−1100 °C temperature range at a heating rate of 10 °C/min under air
atmosphere. The crystalline phases of the synthesized calcium silicate
material were identified by X-ray diffraction. The morphology of the
synthesized powder particles was studied by SEM/EDS (SEM SSX-550,
Shimadzu). The real density was determined by picnometry.
For the thermophysical properties measurements of the synthesized
calcium silicate material, samples in form of disk (10 mm diameter and
350 µm thick) with a smooth and flat surface were prepared by uniaxial
pressing at 82 MPa for 10 min. Each disk sample weighed about 75 mg.
Thermal diffusivity (α) measurements at room temperature of the
calcium silicate material were performed via the open photoacoustic
cell (OPC) technique [16,17]. Each disk sample was mounted on a
commercial electret microphone. It was then applied a light beam from
a He-Ne laser that was modulated with a mechanical chopper, before it
reached the sample surface. The sample is placed on the top of the
microphone gap in a sealed way. So a gas volume is formed, giving rise
to the PA chamber. When the sample is heated by the modulated light,
a higher temperature layer in the sample-chamber interface is pro-
duced. This causes a temperature gradient inside the chamber, gen-
erating acoustic waves, which is directly responsible for the electrical
signal (PA signal) with the help of a resistor connected to the electret
layer. The PA signal is sent to a lock-in amplifier used to register both
photoacoustic amplitude and phase signal as a function of the
modulation frequency with the aid of a specific software program.
Then, the values of thermal diffusivity were determined by using the
thermal diffusivity model to an optically opaque and thermally thick
sample [18]. For this case of 350 µm thick calcium silicate samples, the
amplitude of the PA signal decreases exponentially with the modulation
frequency, whose cut-off frequency is within the 0.77–1.13 Hz range.
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Ceramics International 43 (2017) 4674–4679
Heat capacity per unit volume (ρcp) measurements were carried out
using the photothermal technique of temperature increase caused by
continuous illumination of the sample by a He-Ne laser in vacuum
[17]. The thermal conductivity (ks) of the samples is obtained as follow:
Ks = αρc p (1)
Calcium silicate pieces of 25 mm in diameter and 10 mm in height
were prepared by uniaxial pressing at 82 MPa. The resulting pieces
were cured by immersing them in water at room temperature (5 min
per day for 7 days), and then dried at 110 °C for 48 h [14].
The cured calcium silicate pieces were characterized in terms of
water absorption, apparent density, water suction, and tensile strength.
The water absorption and apparent density of the samples were
determined according to the ASTM C373 standard. The water suction
was determined according to the UNE 67031 standard. The tensile
strength of the calcium silicate pieces obtained by the diametral
compressive method was determined by using an universal testing
machine (model 5582, Instron) at a loading rate of 0.5 mm/min. The
cured microstructure of the samples was observed by scanning electron
microscopy (SSX 550 model, Shimadzu), with accelerating voltage at
15 kV. Electrical charging was avoided by a platinum coating on the
specimens.
3. Results and discussion
The XRD patterns of the raw materials are shown in Fig. 1. The
main crystalline phases identified in the chamotte sample (Fig. 1a)
were quartz (SiO2) and minor amounts of illite ((K,H3O)
Al2Si3AlO10(OH)2), and hematite (Fe2O3). Note that a small amor-
phous band between 2θ=10° and 30° can be observed. This is due to
the presence of amorphous metakaolinite. In fact, the chamotte sample
used in this work is originated of fired clay bricks produced with red
clays rich in kaolinite [19]. The raw eggshell waste (Fig. 1b) is
composed essentially of calcite (CaCO3). However, the calcined eggshell
waste (Fig. 1c) was composed essentially of portlandite (Ca(OH)2).
Presumably, the portlandite comes from the moistening of CaO from
the calcite decomposition product [20].
The results of chemical composition and loss on ignition of the raw
materials are presented in Table 1. The chamotte sample is composed
predominantly of SiO2 (46.52 wt%), but also considerable amounts of
Al2O3 (36.37 wt%) and Fe2O3 (9.09 wt%) were present. The low loss on
ignition (1.20 wt%) may be attributed to the removal of free moisture
on the chamotte particles. As expected, the raw and calcined eggshell
waste samples are composed essentially of calcium oxide (CaO). The
high loss on ignition (45.60 wt%) of the raw eggshell waste was due to
the calcite decomposition and combustion of organic matter. However,
the loss on ignition of the calcined eggshell waste (8.91 wt%) is mainly
attributed to the dehydration of portlandite.
XRD patterns of the calcium silicate materials synthesized at
1100 °C are shown in Fig. 2. The results indicated that the studied
formulations underwent a series of phase transformations during
synthesis. For both formulations the main crystalline phases found
were wollastonite (CaSiO3), larnite (Ca2SiO4), and rankinite
(Ca3Si2O7), with predominance of wollastonite. Small amounts of
Ferrobustanite ((Ca,Fe,Mn)3SiO9), gehlenite (Ca2Al2SiO7), and an-
orthite (CaAl2Si2O8) were also identified. Such phases are related to
the use of chamotte as a silica source, which contains impurities as
aluminum oxide (Al2O3) and iron oxide (Fe2O3). Both formulations
also presented an amorphous hump between 2θ=15° and 40°, which is
more pronounced in the calcined eggshell waste containing formula-
tion. The results of XRD also showed that small differences in the
diffraction peak intensities occurred. It can be concluded, therefore,
that the mineral nature of the calcium sources (CaCO3-rich raw
eggshell waste and CaO-rich calcined eggshell waste) used has influ-
enced the course of the solid state reaction during the synthesis step at
F.H.G. Leite et al. Ceramics International 43 (2017) 4674–4679

Fig. 1. X-ray diffraction patterns of the raw materials: a) chamote; b) raw eggshell waste; and c) calcined eggshell waste.

Table 1 1100 °C.

Chemical compositions of the raw materials (wt%). The real density of the calcium silicate materials were determined
to be 2.89 g/cm3 (MR formulation) and 2.87 g/cm3 (MCE formula-
Compounds Raw eggshell waste Calcined eggshell waste Chamotte
tion). These values reflect their mineralogy composed mainly of
CaO 52.51 90.61 0.64 wollastonite (Fig. 2). In addition, these values are in accordance with
SiO2 – – 46.52 the true density of pure wollastonite (2.91 g/cm3) [21]. Relative density
Al2O3 – – 36.37 of the disk samples were determined according to the standard
Fe2O3 – – 9.09
K2O 0.80 – 2.40
equation (relative density = bulk density/real density), resulting in
MnO – – 0.11 high densification (94.46–95.12%).
SrO 0.10 0.08 0.01 Fig. 3 shows the SEM images of the synthesized calcium silicate
SO3 0.99 0.42 1.97 powders. There was little difference in the morphology of the calcium
LoIa 45.60 8.91 1.20
silicate powder particles synthesized by using different eggshell wastes.
a
LoI – loss on ignition.
Both powders are composed mainly of irregular-shaped particles with
particle size range < 10 µm. The stacking together of the calcium

Fig. 2. X-ray diffraction patterns of the synthesized calcium silicate materials: a) MR formulation; and b) MCE formulation.

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Fig. 3. Morphology of the calcium silicate powder: a) MR formulation; and b) MCE formulation.

Fig. 4. EDS line spectrum of the calcium silicate material: a) MR formulation; and b) MCE formulation.

silicate particles to form agglomerates can be observed. This is due to
the synthesis step at high temperature. Note also that the powder
obtained with the raw eggshell waste (MR formulation) displays a
rougher texture due to decomposition of calcite. The EDS line
spectrums of the synthesized powders are shown in Fig. 4, where Si,
Ca, O, Al, and Fe were detected. These results are in agreement with the
chemical composition (Table 1) and X-ray diffraction data (Fig. 2).
The TG-DTA curves for the calcium silicate formulations in a molar
ratio of SiO2:CaO (1:1) are shown in Fig. 5. In the DTA curve of the raw
eggshell waste containing formulation (Fig. 5a) a small endothermic
event at ~150 °C due to the evaporation of physical water may be
observed. An exothermic event at ~525.5 °C due to the burning of
organic matter was observed. The endothermic event related to the
allotropic inversion of α-β quartz should have probably overlapped. It
was found a new endothermic event at 815.7 °C related to the calcite
decomposition present in the raw eggshell waste sample. It can be
observed a small exothermic event without mass loss around 930 °C.
This event is due to the formation of calcium silicate phases as
indicated by XRD (Fig. 2). It is possible also to observe in the TG
curve an intense process of mass transfer in the raw eggshell waste
containing formulation. A total mass loss of about 20.25% was
observed. In the DTA curve of the calcined eggshell waste containing
formulation (Fig. 5b) the following thermal events were identified:
three endothermic events in sequence as temperature rises related to
the release of physical water around 150 °C, dehydration of portlandite
at 466.7 °C, and residual calcite decomposition around 750 °C. An
exothermic event without mass loss at 868.6 °C corresponds to the
formation of calcium silicate phases. The total mass loss of the calcined
eggshell waste containing formulation was about 6.24%.
The thermal expansion-shrinkage and shrinkage rate curves of the
studied calcium silicate formulations are presented in Fig. 6. As it can
be observed, the dilatometric curves presented small but important
differences between them. Both formulations showed a small inflexion
around 564.6 °C (MR formulation) and 566.2 °C (MCE formulation)
related mainly to the allotropic inversion of α-β quartz. An expansion
between ~500 °C and 800 °C due to the calcite decomposition may be

Fig. 5. TG-DTA curves of the calcium silicate formulations: a) MR formulation; and b) MCE formulation.

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Fig. 6. Dilatometric curves of the calcium silicate formulations: a) MR formulation; and b) MCE formulation.
observed. It is more significant in the raw eggshell waste containing
formulation (Fig. 6a). After about 800 °C, both formulations have
shrank. The calcined eggshell waste containing formulation (Fig. 6b)
shrank more. Note that the MR formulation shrinks about 1.3%, while
the MCE formulation shrinks about 3.2%. The delay in the shrinkage
observed for the raw eggshell waste containing formulation is due to
the decomposition of high amount of calcite. Finally, the maximum
shrinkage rates (dL/dt) at 896.5 °C (MR formulation) and 886.1 °C
(MCE formulation) were observed.
The thermophysical properties of the synthesized calcium silicate
material are given in Table 2. As can be observed, the distinct calcium
sources (raw and calcined eggshell wastes) used in the studied
formulations had an influence on the thermophysical properties. The
thermal diffusivity is an important thermophysical property that
measures the rate of heat diffusion in the sample. At room temperature,
the phonons (lattice vibrations) are primarily responsible for the heat
flow in ceramic materials [22]. The calcium silicate materials presented
low thermal diffusivity values within the 0.00294–0.00435 cm2/s
range. These values are relatively well in accordance with values
reported for wollastonite coating (0.00270–0.00310 cm2/s) [23] and
xonotlite-type calcium silicate insulator material (0.00354 cm2/s) [24].
The results also showed that the use of calcined eggshell waste reduces
the thermal diffusivity of the synthesized calcium silicate material.
Presumably, this behavior can be related to the thermal diffusivity of
the different phases (crystalline and amorphous phases) in the
synthesized materials. Thus, the decrease of thermal diffusivity ob-
served in the MCE formulation is mainly associated to its higher
amount of amorphous phase (Fig. 2). In fact, according with literature
[22,25] an amorphous phase has a lower thermal diffusivity than a
crystalline phase. It was also found that the calcium silicate materials
presented low thermal conductivity values (0.456–0.527 W/mK). A
small increase of thermal conductivity of the calcined eggshell waste
containing formulation was observed. This could be due to differences
observed in the XRD patterns (Fig. 2) and the rough texture (Fig. 3) of
the synthesized calcium silicate materials. The results also showed that
the heat capacity per unit volume behaved in a similar way to the
thermal conductivity.
SEM micrographs of the fractured surfaces of the cured calcium
silicate pieces are shown in Fig. 7. Apparently, the microstructures had
no large difference among them. Both specimens are characterized by a
rough texture and highly interconnected porous structure. A very large
Table 2
Thermophysical properties of the calcium silicate materials synthesized at 1100 °C.
Property Formulation
MR Formulation MCE Formulation
−3
α, 10 cm /s2
4.35 ± 0.04 2.94 ± 0.04
ρCp, J/cm3K 1.05 ± 0.01 1.79 ± 0.16
ks, W/mK 0.456 ± 0.01 0.527 ± 0.01
α – Thermal diffusivity; ρCp – Heat capacity per unit volume; ks – Thermal conductivity.
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number of open pores of different sizes could be observed. This porous
microstructure tends to favour good thermal insulation properties of
the calcium silicate pieces.
The calcium silicate pieces produced by pressing and curing were
tested to assess their application as thermal insulation ceramic
material. The results of the technical properties are summarized in
Table 3. It was found that the processing of the eggshell waste have no
significant effect on the apparent density of the cured calcium silicate
pieces (1.87–1.88 g/cm3). The water absorption is related to the
amount of open pores, that is, the pores that are connected with the
cured specimen's surface. The water absorption was in the range of
14.38–17.30%. Note that the calcium silicate pieces produced with
calcined eggshell waste exhibited a slight increase in water absorption.
However, all the calcium silicate pieces met values of water absorption
for application as thermal insulator ceramic material, independently of
the type of used eggshell waste. The calcium silicate pieces had very low
water suction value (0.014–0.047 kg/m2min). This result is very
important because high values of water suction should be avoided. It
can also be seen that the calcined eggshell waste containing pieces
(MCE formulation) presented higher water suction. This result is in
agreement with the higher water absorption value (open porosity)
obtained for this formulation. Despite this, all calcium silicate pieces
presented water suction values lower than the reference value of
4.500 kg/m2min established by the UNE-67031 standard [26]. The
mechanical strength of the cured calcium silicate pieces was deter-
mined in terms of diametral tensile strength. It can be seen that the
tensile strength of the MCE formulation is the lowest. Such behavior is
mainly related to the higher open porosity that tends to induce flaws in
the cured porous ceramic structure.
The thermal conductivity is the thermophysical property that
measures the efficiency of the ceramic material in the conduction of
heat. For this reason, it is the primary thermophysical property for
selection of thermal insulation construction material. The calcium
silicate pieces produced are composed of a dense solid skeleton
(synthesized calcium silicate material) and a porous network. Thus,
the thermal conductivity (kT) of the two-phase system can be deter-
mined by using the equation suggested by Kingery et al. [22] given by
kT = ks[(1–fp)/(1 + fp/2)] (2)
in which ks corresponds to the thermal conductivity of the calcium
silicate material synthesized at 1100 °C and fp is the porosity of the
cured bulk pieces.
The thermal conductivity of the cured calcium silicate pieces are
presented in Table 3. As can be observed, only a small difference in the
thermal conductivity values occurred. This difference also was reflected
in the results of thermal conductivity of the calcium silicate material
determined via OPC technique, technical properties, and cured micro-
structure. The thermal conductivity of the calcium silicate pieces was in
the range of 0.252–0.293 W/mK, which is within the range required by
UNE-EN 1745 standard ( < 0.430 W/mK) [27] for manufacture of
thermal insulation ceramic material. Thus, the reuse of raw and
calcined eggshell wastes as alternative calcium sources could result in
F.H.G. Leite et al. Ceramics International 43 (2017) 4674–4679

Fig. 7. SEM micrographs of cured specimens: a) MR formulation; and b) MCE formulation.

Table 3 EDX, Am. Microsc. Anal. 53 (2002) 23–24.

[5] E.R. Munoz, R. Curiel, R. Rodríguez, Selectivity in the hydroxyapatite synthesis
Technical properties of the cured calcium silicate pieces.
from eggshell using different thermal treatment, Mater. Res. Innov. 7 (2003)
85–90.
Property Formulation
[6] C. Balázsi, F. Wéber, Z. Kövér, E. Horváth, C. Németh, Preparation of calcium-
MR Formulation MCE Formulation phosphate bioceramics from natural resources, J. Eur. Ceram. Soc. 27 (2007)
1601–1606.
Real density, g/cm3 2.89 ± 0.01 2.87 ± 0.01 [7] G.S. Kumar, A. Thamizhavel, E.K. Giriza, Microwave conversion of eggshell into
Apparent density, g/cm3 1.88 ± 0.01 1.87 ± 0.01 flower-like hydroxyapatite manufacture for biomedical applications, Mater. Lett. 76
Water absorption, % 14.38 ± 0.27 17.30 ± 0.17 (2012) 198–200.
Water suction, kg/m2.min 0.014 ± 0.002 0.047 ± 0.001 [8] W.F. Ho, H.C. Hsu, S.K. Hsu, C.W. Hung, S.C. Wu, Calcium phosphate bioceramics
Tensile strength, MPa 0.45 ± 0.01 0.35 ± 0.03 synthesized from eggshell powders through a solid state reaction, Ceram. Int. 39
Thermal conductivity, W/m. K 0.252 ± 0.01 0.293 ± 0.01 (2013) 6467–6473.
[9] W.T. Tsai, K.J. Hsien, H.C. Hsu, C.M. Lin, K.Y. Lin, C.H. Chiu, Utilization of ground
eggshell waste as an adsorbent for the removal of dyes from aqueous solution,
Bioresour. Technol. 99 (2008) 1623–1629.
calcium silicate materials with excellent technical properties for use as [10] Z. Wei, C. Xu, B. Li, Application of waste eggshell as low-cost solid catalyst for
thermal insulator ceramic material. biodiesel production, Bioresour. Technol. 100 (2009) 2883–2885.
[11] M.C. Amaral, A.Z. destefani, F.B. Siqueira, J.N.F. Holanda, Soil-cement bricks
incorporated with eggshell waste, Waste Resour. Manag. 106 (2013) 137–141.
4. Conclusions [12] I. Kotsi, A. Bologh, Synthesis of wollastonite, Ceram. Int. 15 (1989) 79–85.
[13] T.R.Krowl, Calcium silicate insulating material containing blast furnace slag
The results of this study demonstrate that avian eggshell waste can cement, Patent US 6,869,475B1, 2005.
[14] M. Felipe-Sesé, D. Eliche-Quesada, F.A. Corpas-Iglesias, The use of solid residues
be easily employed for sustainable production of calcium silicate derived from different industrial activities to obtain calcium silicates for use as
materials suitable for thermal insulation construction material. The insulating construction materials, Ceram. Int. 37 (2011) 3019–3028.
tested formulations using raw and calcined eggshell wastes as alter- [15] V. Morales-Flórez, A. Santos, A. López, I. Morina, L. Esquivias, Calcium silicates
synthesised from industrial residues with the ability for CO2 sequestration, Waste
native calcium source in a molar ratio SiO2:CaO (1:1) presented small
Manag. Res. 32 (2014) 1178–1185.
but important changes on the phase composition, thermal behavior, [16] H. Vargas, L.C.M. Miranda, Photoacoustic and related photothermal techniques,
and thermophysical properties of the synthesized calcium silicate Phys. Rep. 161 (1988) 43–101.
materials. It was found that the calcium silicate materials synthesized [17] L. Mota, R. Toledo, F.A.L. Machado, J.N.F. Holanda, H. Vargas, R.T. Faria Jr,
Thermal characterization of red clay from the northern region of Rio de Janeiro
at 1100 °C are mainly composed of wollastonite, larnite, and rankinite, state, Brazil using an open photoacoustic cell in relation to structural changes on
with predominance of wollastonite. The results of thermal conductivity firing, Appl. Clay Sci. 42 (2008) 168–174.
showed that all cured calcium silicate pieces could be conveniently used [18] A. Rosencwaig, A. Gersho, Theory of the photoacoustic effect with solids, J. Appl.
Phys. 47 (1976) 64–69.
as thermal insulating material, with advantages including the use of [19] F.A.C. Milheiro, M.N. Freire, A.G.P. Silva, J.N.F. Holanda, Densification behavior
avian eggshell waste (raw eggshell waste or calcined eggshell waste) as of a red firing Brazilian kaolinitic clay, Ceram. Int. 31 (2005) 757–763.
added value raw material and environmental and economical benefits. [20] J.G. Pereira, F. Okumura, L.A. Ramos, E.T.G. Cavalheiro, Thermogravimetry: a new
approach for the classic determination of calcium in eggshell, Quím. Nova 32
(2009) 1661–1666.
Acknowledgements [21] H.P. Wong, S.Q. Xu, S.Q. Lu, S.L. Zhao, B.L. Wang, Dielectric properties and
microstructure of CaSiO3 ceramics with B2O3 addition, Ceram. Int. 35 (2009)
2715–2718.
The authors would like to thank CNPq (Process no.: 472608-2013- [22] W.D. Kingery, H.K. Bowen, D.R. Uhlmann, Introduction to ceramics, Second ed.,
4) for the financial support to this work. John Wiley & Sons, New York, 1976.
[23] X. Liu, C. Ding, Thermal properties and microstructure of a plasma sprayed
wollastonite coating, J. Therm. Spray. Technol. 11 (2002) 375–379.
References
[24] G. Wei, X. Zhang, F. Yu, K. Chen, Thermal diffusivity measurements on insulation
materials with the laser flash method, Int. J. Thermophys. 27 (2006) 235–243.
[1] S.M. Naga, H.H. El-Maghraby, M. Sabed, E.A. Saad, Highly porous scaffolds made [25] J.J. Alvarado-Gil, H. Vargas, F. Sánchez-Sinencio, J. González-Hernández,
of nanosized hydroxyapatite powder synthesized from eggshell, J. Ceram. Sci. L.C.M. Miranda, Effect of lime content on the processing conditions of cooked
Technol. 6 (2015) 237–244. maize tortillas: changes of thermal structural and rheological properties, Opt. Eng.
[2] M.J. Quina, M.A.R. Soares, A.A. Ribeiro, A.P. Marques, I.H. Costa, M.C. Magalhães, 36 (1997) 348–357.
Feasibility study on windrow co-composting to recycle industrial eggshell waste, [26] UNE-EN 67031: 1986, Burned Clay Bricks. Suction Test.
Waste Biomass-. Valor 5 (2014) 87–95. [27] UNE-EN 1745: 2013, Masonry and Masonry Products – Methods for Determining
[3] A.H. Parsons, Structure of the eggshell, Poult. Sci. 61 (1982) 2013–2021. Thermal Properties.
[4] A.C. Frasen, M. Cusak, Investigation of partridge eggshell cuticle using SEM and

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