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Physicochemical Determination of Calcium Carbonate (CaCO3) from Chicken

Eggshell

Article  in  Key Engineering Materials · April 2020

DOI: 10.4028/www.scientific.net/KEM.840.478

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Key Engineering Materials Submitted: 2019-03-28
ISSN: 1662-9795, Vol. 840, pp 478-483 Revised: 2019-07-03
© 2020 Trans Tech Publications Ltd, Switzerland Accepted: 2019-11-11
Online: 2020-04-24

Physicochemical Determination of Calcium Carbonate (CaCO3) from

Chicken Eggshell
Poppy Puspitasari1,a*, Dwi Mardi Utomo1,b, Herin Fikri Naufal Zhorifah2,c,
Avita Ayu Permanasari1,d and Rara Warih Gayatri3,e
1
Mechanical Engineering Department, Engineering Faculty, Universitas Negeri Malang, Semarang
Street No. 5 Malang, East Java, Indonesia
2
Magister Program in Mechanical Engineering Department, Engineering Faculty, Universitas
Negeri Malang, Semarang Street No. 5 Malang, East Java, Indonesia
3
Health and Science Department, Health and Sport Faculty, Universitas Negeri Malang, Semarang
Street No. 5 Malang, East Java, Indonesia
a
[email protected], [email protected], [email protected], [email protected],
e
[email protected]

Keywords: Physicochemical, calcium carbonate, eggshell

Abstract. To overcome the increased processing of eggshell waste in East Java, Indonesia, the
important solution is to synthesize chicken eggshells into calcium carbonate. The process of
synthesizing eggshells into calcium carbonate is carried out by a mechanochemical process using a
ball milling machine for 10 h and the sintering time for 120 min at a temperature of 900, 1000, 1100,
and 1200 °C. The results of the eggshell synthesis were characterized using X-ray Diffraction, SEM,
Raman spectroscopy and FTIR. Those characterizations aimed to obtain the result of phase
identification, morphology, physicochemical, and functional group of calcium carbonate. From the
phase identification, calcium carbonate obtained from eggshell sintered 1000 °C shows the single-
phase triangular structure with agglomeration and spherical morphology. The physicochemical results
show that phonon interaction of calcium carbonate obtained from eggshell sintered at 1200 °C has
the highest intensity at Raman shift 1083 cm‒1 which indicates the C‒O symmetric stretching band.
The functional group of calcium carbonate shows from FTIR results at 3642, 2987, 2508 cm‒1 for O‒
H bond, and 1790, 1507 cm‒1 for C‒H bond, and 874, 712 cm‒1 for calcite bonds respectively.

Introduction
Recently, the needs of calcium carbonate (CaCO3) is increasing due to the high demand of the usage
for biomaterial development such as hydroxyapatite for dental and bone tissue application. Synthesis
of calcium carbonate was obtained from various method and source to become hydroxyapatite [1-4].
In Indonesia, the consumption of eggs is continuing to increase and increasing eggshell waste. In
fact, eggshell waste is generated not only from households and food industries but also
hatcheries [5]. Eggshells are often regarded only as waste by many, and thus only a few make use of
them. Eggshells are resources that can be converted into useful materials; they can be used as an organic
fertilizer that is essential for the growth of chili plants and turned into artwork like painted eggshells
[5]. If not managed properly, eggshells will become a medium for microbial growth and cause
environmental pollution [6]. One alternative to deal with the problem of eggshell waste is to transform
eggshells into calcium compound and hydroxyapatite—a well-known material for a bone graft
substitute [5]. This affects the physicochemical properties that need to be studied using the results of
the characterization of Raman spectroscopy [7].
Infrared spectroscopy characterization method is widely used to analysis the functional group of
biomaterial calcium carbonate and it is help the researcher to reveal the composition of molecular group
of the sample [8]. The spectrum of calcium carbonate use infrared spectroscopy reveal at
560-3650 cm‒1 [9].

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 Key Engineering Materials Vol. 840 479

Experimental Section
The synthesis was performed to obtain single-phase CaCO3/CaO particles by putting the flakes of
eggshell in a ball milling machine. 300 g of eggshells mixed with 30 mL acetone and 5 zirconia ball
inserted in the machine. Acetone used as a dispersed phase in calcium carbonate and have quick dry
as soon as the solid-state process ended. The as-prepared calcium carbonate from the eggshell powder
was milled in wet conditions in a planetary ball-mill machine (QM-3SP2) for 10 h at 570 rpm inside
4 zirconia container. Next, the as-synthesized samples were taken out and dried in an oven at 110 °C
for 1 h which resulted in a dry eggshells powder. The dried eggshell powder was crushed for 1 h. The
crushing procedure was done to eliminate the agglomeration of the eggshell powder. After the drying
process, the eggshell powder was sintered in an air furnace at 900, 1000, 1100, 1200 °C for
60 minutes.
The crystalline phase of the eggshell powder before and after heat treatment was analyzed using
X-ray diffraction with Cu Kα radiation (XRD; Xpert Pro, PANalytical). The phase identification was
obtained by comparing the experimental diffractograms with the standards card from Joint
Committee on Powder Diffraction Standards (JCPDS). The phonon interaction analyzed using
Raman spectroscopy (Horiba Jobin Yvon HR800) and the IR band using FTIR (Shimadzu IR Prestige
21).

Results and Discussion

Table 1 shows that the eggshell nanopowder after being synthesized with variations in sintering
temperature had a bigger crystal size than that of the raw eggshell nanopowder (59.58 nm). As shown
in Table 1, the size of the raw eggshell powder was smaller than that of eggshell powder synthesized
with sintering for 120 min and at 900, 1000, 1100, and 1200 °C.
Fig. 1 shows the development of eggshell nanopowder during the ball milling process. The
intensity is a peak that indicates the purity level of calcium carbonate from eggshell powder.
Fig. 1 shows that the change or shift from the peak of eggshell nanopowder is obvious. The peak that
underwent such a shift is peak [104] and [221]. Peak [104] is like the fingerprint of calcite, while
[221] indicates the aragonite [10]. Calcium carbonate has several peaks from the standard card,
indexed at [110], [104], and [221]. Shifting and peak intensity containing one of the above peaks of
eggshell nanopowder indicate that the purity level of eggshell nanopowder is increasing. The
synthesis at the sintering temperatures of 900, 1000, 1100, and 1200 °C can remove organic
compounds and convert calcium carbonate into calcium oxide.
Fig. 1 shows the XRD patterns of the eggshell samples milled for 10 h and synthesized with
variations in sintering temperature (900, 1000, 1100, and 1200 °C) for 2 h. Heat treatment temperature
plays an important role in the formation of calcium carbonate. The formation of single-phase calcium
carbonate began at 900 ℃. According to the XRD pattern, more calcium carbonate particles were
formed at higher heating temperatures. Also, it suggests that the product formed at 1200 °C was more
complete, hence the pure form of calcium carbonate. Among the four sintering temperatures, the
temperature of 1000 °C generated the most favorable eggshell nanopowder with the crystalline
intensity of 701.69 counts, the crystal size of 85.22 nm, and the FWHM of 1.718 rad. In fact, the
result of sintering at 1000 °C for 2 h had the highest purity level and crystallinity degree.
Table 1. Phase identification of calcium carbonate from chicken eggshell
X-Ray Diffraction
Sample Intensity Crystallite size
FWHM (rad) d-spacing (Å)
(counts) (nm)
Eggshell Raw 1606.40 2.406 3.035 59.58
Eggshell 900 °C 785.81 2.406 3.037 59.58
Eggshell 1000 °C 701.69 1.718 2.404 85.22
Eggshell 1100 °C 1025.46 1.718 3.039 83.47
Eggshell 1200 °C 607.14 2.062 2.406 70.99
480 Symposium of Materials Science and Chemistry II

Figure 1. Phase identification of calcium carbonate from chicken eggshell at various sintering
temperatures
The reaction of the sintering process of calcium oxide derived from calcium carbonate:
CaCO3(s) → CaO(s) + CO2(g) (1)
Eq. 1 shows the sintering process at 900, 1000, 1100, and 1200 °C for converting CaCO3 into CaO
and CO2. After the sintering process, the specimen was slowly furnace-cooled to room temperature.
Calcium precursor of Ca(OH)2 can be obtained by reacting calcium oxide and water. Also, calcium
oxide can be produced by utilizing eggshell waste that has been sintered at various sintering
temperatures.
As shown in Fig. 2, the non-uniformity of the grain size and shape on the surface indicates that
agglomeration occurred and was big in size after undergoing synthesis with sintering temperatures of
900, 1000, 1100, and 1200 °C for 120 min. This occurred due to the sintering temperature, the
sintering time, the uneven crushing, and the duration of the crushing process. It could also be affected
by the magnification used to observe the morphology of calcium carbonate from eggshell powder.
The average particle size derived from Scherer equation [11-13] in XRD results found to be 71.2 nm.
As the sintering temperature increased, the agglomeration particle was less agglomerated but the
shape was the irregular round shape and the particle size tended to be larger.
Fig. 3 shows the parts of atomic vibration, namely vibration mode 1 (v1) for symmetric
C‒O stretching mode, v3 for asymmetric C‒O stretching mode, and v4 as doubly degenerated in-plane
OCO deformation bending mode. Those are the active vibrations for calcium carbonate polymorphs
[14]. The two regions for phase identification of calcite are the special range of 760-680 cm‒1. The
Raman bands at 700-750 cm‒1 indicated the aragonite, calcite, and vaterite respectively [15]. The
main band of calcium carbonates at 1085 cm‒1 indicates the symmetric stretching of C‒O [16],
whereas this research shows at 1083 cm‒1.
The spectrum formed from the results of milling eggshells on Fig. 4 shows the O‒H stretching
vibration region at 3642 cm‒1 which shows a relationship with the bond at 1790 cm‒1 and
1504 cm‒1 of CaO occurring on the surface. The calcite phase appears dominant above the
800 cm‒1 region which is 874 cm‒1, 2508 cm‒1, and 2987 cm‒1. The peak of the carbonate group is
seen at 712 cm‒1. These peaks were also similar to the previous research of quantitative result of FTIR
on calcium carbonate which appeared at 875-630 cm‒1 [17, 18].
 Key Engineering Materials Vol. 840 481

a b

c d

Figure 2. Morphology of eggshell nanopowder, (a) raw material, (b) as-prepared sample sintered at
900 °C, (c) 1000 °C, (d) 1100 °C, and (e) 1200 °C

Figure 3. Raman spectra of eggshell 900 °C, Figure 4. FTIR spectra for eggshell 900 °C,
eggshell 1000 °C, eggshell 1100 °C, and eggshell 1000 °C, eggshell 1100 °C, and
eggshell 1200 °C eggshell 1200 °C

Summary
The phase identification shows the single-phase calcium carbonate found at eggshell sintered at
above 900 °C with triangular structure. Morphology of calcium carbonate shows agglomeration with
482 Symposium of Materials Science and Chemistry II

irregular round shape and increasing with the increase sintering temperature. The average particle
size is ranging from 59-83 nm. The highest Raman intensity found at calcium carbonate from eggshell
sintered at 1200 °C. The peak of Raman shift at 708 cm‒1 is the mode for the vibration of calcium
carbonate whereas 276 cm‒1 and 353 cm‒1 are the modes for vibrations at calcite bonding. The bond
of O‒H stretching vibration region at 3642 cm‒1 shows the bond of CaO at 1790 cm‒1 and
1504 cm‒1. Therefore, heat treatment temperature plays a vital role in the formation of calcium
carbonate among the four sintering temperatures, the temperature of 1000 °C generated the most
favorable eggshell nanopowder.

Acknowledgement
The authors thank to Ministry of Research, Technology, and Higher Education for Hibah
Penelitian Dasar Unggulan Perguruan Tinggi 2020 with SP DIPA 2020.

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