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Embedding Eggshell as Flux in Porcelain Clay Products to Reduce Firing

Temperature via Extrusion Process

Article  in  Middle East Journal of Scientific Research · January 2016

DOI: 10.5829/idosi.mejsr.2016.24.05.23462

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Middle-East Journal of Scientific Research 24 (5): 1616-1621, 2016
ISSN 1990-9233
© IDOSI Publications, 2016
DOI: 10.5829/idosi.mejsr.2016.24.05.23462

Embedding Eggshell as Flux in Porcelain Clay Products

to Reduce Firing Temperature via Extrusion Process
1
Nuchnapa Tangboriboon, 1Suchanthip Pornsimma and 2Anuvat Sirivat

1
The Materials Engineering Department, Faculty of Engineering,
Kasetsart University, Bangkok 10900, Thailand
2
The Petroleum and Petrochemical College,
Chulalongkorn University, Bangkok, 10330, Thailand

Abstract: The porcelain clay products were prepared by extrusion. Eggshells embedded into porcelain clay
products can reduce the firing temperature and firing time due to anorthite or calcium feldspar or calcium
aluminum silicate (CaAl2Si2O8) phase formation. The main composition of eggshells is 96.23%wt calcium
carbonate (CaCO3) and 3.27%wt other oxide compounds [1]. The calcium carbonate can transform to calcium
oxide (CaO) and react to alumina and silica in porcelain clay to form anorthite phase formation acted as a flux
to decrease the firing temperature from 1250°C to 800°C. In addition, eggshell acted as a filler to reinforce and
increase mechanical-thermal properties of the porcelain clay products. The porcelain clay products added
8%V/V eggshells can be fired at low temperature 800°C for 2 hrs., to get good physical, mechanical and thermal
properties. The true density, volume shrinkage, water absorption, modulus of elasticity, compressive strength
and thermal expansion coefficient of porcelain clay products added 8%V/V eggshells and fired at 800°C for 2
hrs., are 2.4186±0.0920 g/cm3, 28.7863±1.9300%, 17.8603±4.6500%, 522.95 MPa, 61.16 MPa and 2.2149x10 6 (°C) 1,
respectively, consistent with the theoretical values. The compressive strength and water absorption of standard
clay products are more than 7.0 MPa and less than 25%wt. Furthermore, X-ray diffraction (XRD), UTM and
dilatometer, are used to investigate phase composition and phase transformation, mechanical and thermal
properties of porcelain clay products reported here.

Key words: Eggshell Extrusion Flux Anorthite Porcelain clay

INTRODUCTION applications: dielectrics, dental and bone implantation,

gypsum, catalysts and also fillers used for in a variety
Eggs have been used as foods, drugs, cosmetics and industries such as rubber, ink, foodstuff, cosmetic,
foodstuffs. Unfortunately, eggshells are an egg product pharmaceutical and fertilization.
industry residue that contributes toward environmental The basic knowledge in this research is calcium
pollution as it favors microbial actions. The by-product carbonate (CaCO3) from eggshells can react to alumina
eggshell represents approximately 11% of the total weight (Al 2O3) and silica (SiO2) from porcelain clay and then
about 60 g of egg [1-2]. Eggshell is one kind of sources of transform to calcium feldspar or anorthite (CaAl 2Si 2O8)
calcium carbonate (CaCO3) known as calcite which is the functioned as a flux in order to reduce the firing
more stable polymorph at room temperature. An eggshell temperature of porcelain products. Feldspars are an
is a rich source of mineral salts, mainly calcium carbonate inorganic substance of the tectosilicates mineral
(96.23%), calcium phosphate (1%), magnesium carbonate group (SiO4- and AlO4- tetrahedral form) framework [3-8].
(1%) and organic substances (1.67%) [2]. However, an The interstitial site of their structures are filled with
important composition of eggshell is the calcium univalent or divalent cations such as Na +, K+, Ca2+, Ba2+,
carbonate, which can be used in various material NH4+ etc. Almost feldspars can be classified as mixtures of

Corresponding Author: Nuchnapa Tangboriboon, Kasetsart University, Materials Engineering Department,

Faculty of engineering, 50 Phaholyothin rd., 10900, Bangkok, Thailand.
Tel: +662-797-0999, Fax: +662-9551811.
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a ternary system: orthoclase (KAlSi 3O8), albite catalyst industries as it possesses good physical
(NaAlSi3O8) and anorthite (CaAl2Si2O8) as shown in properties such as low thermal expansion coefficient, high
scheme I. Anorthite is the calcium end member of thermal shock resistance, high hardness and low dielectric
plagioclase feldspar. Plagioclase is an abundant mineral in constant [6-9]. The chemical formula of pure anorthite is
the Earth’s crust which is an important component in CaAl2Si2O8 with a melting point of 1553°C [6-9] consistent
various industries such as electronics, automotive, with the ternary phase diagram of CaO-SiO2-Al2O3 as
construction, insulation, dental and biomedical and shown in scheme II.

Scheme I: Three types of feldspar [6].

Scheme II: Ternary phase diagram of CaO-SiO2-Al2O3[5].

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 Middle-East J. Sci. Res., 24 (5): 1616-1621, 2016

The objective of this study is to prepare porcelain and then added 10-15%wt water as shown in Table 1.
clay products via extrusion process added eggshell The eggshells acted as a disperse phase or filler to
powder acted as a calcium source to react with increase thermal, mechanical and physical properties.
aluminosilicate in porcelain clay. It can form anorthite or Then put the clay mixture into the hopper of extruder and
calcium feldspar to reduce the firing temperature and extruded pass through the mold in the cylindrical-tube
increase mechanical, thermal and physical properties. shape. After that, let it dry in the oven at 110°C for 24 hrs.
Furthermore, the physical properties (true density, bulk The dried porcelain products before firing called green
density and the percentage of water absorption), porcelain samples and characterized the physical
mechanical properties (compressive strength, properties such as bulk density and volume shrinkage.
compressive Young’s modulus) and thermal properties After that, the green porcelain samples were fired at
(thermal expansion coefficient) of porcelain clay products 600°, 700° and 800°C for 2 hrs., at each firing temperature.
also reported here. The fired porcelain clay products are characterized the
physical, mechanical and thermal properties.
Experimental
Raw Materials and Methods: Porcelain Clay was Table 1: Formula of porcelain samples preparation
purchased from Compound Clay Co., Ltd. Thailand. The Porcelain Water Eggshell % V/V of
Samples Clay (g) (g) powder (g) eggshell powder
chemical compositions composed of 63.40%wt SiO2,
Formula 1 1700 225 0 0
22.30%wt Al2O3, 0.95%wt Fe2O3, 0.22%wt MgO, 0.24%wt
Formula 2 1700 225 46 2
CaO, 0.76%wt Na2O, 3.52%wt K 2O and 0.20%wt TiO2. The Formula 3 1700 225 115 5
ignition loss and viscosity of porcelain clay are 8.41% and Formula 4 1700 225 184 8
2.0-4.0 poise, respectively.
Eggshells were collected from a local cafeteria. Raw RESULTS AND DISCUSSIONS
hen eggshells were washed with tap water until the egg
white was completely removed and dried in the air at room
Physical Properties and Characteristics of Raw
temperature. The raw hen eggshells were broken into
Materials and Porcelain Clay Products: The chemical
small pieces, crushed by a porcelain mortar and pestle and
compositions of porcelain clay and eggshell powder are
ground by a high speed mill with a porcelain ball mill for
shown in Table 2. The main composition of porcelain clay
80 minutes into a fine powder and kept in desiccators at a
is 63.40%wt SiO2, 22.30%wt Al2O3, 3.52%wt K2O and
room temperature.
10.78%wt other oxide compounds. While the main
composition of eggshell powder is 96.23%wt CaCO3,
Instruments: X-ray diffraction (XRD) was taken and
1.12%wt MgO and 2.65%wt other oxide compounds.
analyzed using a Bruker AXS analyzer (D8 Discover)
The bulk density values of green porcelain added 0,
with VANTEC-1 Detector. Samples were analyzed by
2, 5 and 8%V/V eggshells are 1.8308±0.1100,
using a double-crystal wide-angle goniometry. Scans were
measured from 5°-80° 2 at a scan speed of 5° 2 /min 1.8371±0.1070, 1.8734±0.1540 and 1.8916±0.1450 g/cm3,
in 0.05° or 0.03° 2 increments using CuKá radiation respectively. The true density, volume shrinkage and
( = 0.15406 nm). Peak positions were consistent with water absorption of porcelain clay products fired at 600°,
those of the International Center for Diffraction Data 700° and 800°C for 2 hrs., were measured as data tabulated
Standard (JCPDS) patterns to identify crystalline phases. in Table 3. The true density values of porcelain products
Muffle furnace (Nebertherm with thermocouple type after firing have trend to increase when the amount of
K, NiCr-Ni) was used to fire the porcelain clay products at eggshells adding and firing temperature increase from
600°, 700° and 800°C for 2 hrs., with a heating rate of 600°C to 800°C. While the water absorption of porcelain
5°C/min. products after firing decreases when the amount of
Extruder or Filter Press was used to prepare the eggshells adding and the firing temperature increases
porcelain clay products supplied by Petkasem Ceramic from 600°C to 800°C consistent with the trend of
Machine Co., Ltd., Thailand. Filter press composed of anorthite-based ceramic fabrication reported by Cheng et
motor 2Hp, 380 volts with vacuum pump. al. [8]. The percentage of volume shrinkage of porcelain
products after firing has trend to increase when the
Preparation of Porcelain Clay Products by Extrusion: amount of eggshells and firing temperature increase. It
Porcelain clay products prepared by mixing and kneading means the obtained porcelain products are densification
porcelain clay added 0, 2, 5 and 8%V/V eggshell powder at low temperature less than the theoretical firing

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 Middle-East J. Sci. Res., 24 (5): 1616-1621, 2016

temperature (1300-1400°C) in the CaO-SiO2-Al2O3 ternary (29.466°, 39.489°, 36.039°), respectively. The XRD peak
phase diagram [10-12] as shown in scheme II. Especially patterns of green porcelain products added 2, 5 and
porcelain sample added 8%V/V eggshells and fired at 8%V/V eggshells before firing show crystalline phase at
800°C show the best condition having true density, the same peak position of porcelain clay and calcium
volume shrinkage and water absorption equal to carbonate consistent with the JCPDS file nos. 00-003-0418
2.4186±0.0920 g/cm3, 28.7863±1.9300% and and 01-085-1108 as well.
17.8603±4.6500%, respectively. The XRD peak patterns of porcelain products added
0, 2, 5 and 8%V/V eggshells and fired at 600°, 700° and
Table 2: Chemical composition of raw materials by XRF 800°C for 2 hrs., at each firing temperature are shown in
As received dried Eggshell Figure 2. All XRD peak patterns of porcelain products
Composition porcelain clay (%wt) powder (%wt) after firing show crystalline phase consistent with the
SiO2 63.40 0.04 JCPDS file no. 01-086-1629 (26.686°, 20.904° and 50.227°)
Al2O3 22.30 - in terms of silicon oxide or quartz belonging to hexagonal
Fe2O3 0.95 - phase formation and JCPDS file no. 01-087-1616 (23.399°,
MgO 0.22 1.12 31.520° and 35.056°) of calcium aluminum silicate
CaO 0.24 - (CaAl2Si2O8) or calcium feldspar in hexagonal phase
Na2O 0.76 0.23
formation consistent with the XRD patterns of anorthite
K2O 3.52 0.11
phase formation reported by Ke et al. [13]. After firing
TiO2 0.20 -
porcelain clay products shows calcium feldspar or calcium
CaCO3 - 96.23
aluminum silicate or anorthite (CaAl2Si2O8) acted as a flux
P 2O5 - 1.19
of porcelain products consistent with the intersection
SO3 - 0.98
point in the ternary phase diagram of 64.40%wt SiO2-
Cl - 0.06
SrO - 0.04
13.3%wt CaO-22.30%wt Al2O3 as shown in scheme II. The
Loss of ignition 8.41 -
obtained calcium feldspar (CaAl2Si2O8) can be fired
“-” means not measured.
completely at low temperature 800°C for 2 hrs.

Table 3: Physical properties of porcelain samples added 0, 2, 5 and 8%V/V

after firing at 600°, 700° and 800°C for 2 hrs
True density Volume Water
Samplesa (g/cm3) shrinkage (%) absorption (%)
600-0 1.9984±0.0460 14.6350±0.9200 21.0475±1.0100
700-0 2.0570±0.0600 18.4405±2.4400 20.7036±2.2100
800-0 2.0865±0.0200 22.3882±2.7600 20.3880±1.1000
600-2 1.9604±0.0600 17.2317±2.2400 21.1209±1.7000
700-2 2.0257±0.0700 18.2502±4.0300 20.6712±2.8600
800-2 2.0872±0.0650 18.3985±2.9500 20.1411±0.9900
600-5 2.1571±0.0470 16.9964±1.0800 19.4028±3.5900
700-5 2.1645±0.1000 21.4814±4.2500 18.4336±0.8400
800-5 2.1698±0.0830 26.7148±1.5900 18.4294±1.0900
600-8 2.3128±0.0120 27.1477±1.2700 18.6408±0.7600
700-8 2.3669±0.0480 28.7518±1.3200 18.6917±4.2100
800-8 2.4186±0.0920 28.7863±1.9300 17.8603±4.6500
mean encoded samples: firing temperature-%V/V eggshell adding
a

The XRD peak patterns of porcelain clay, eggshells

and green porcelain products added 2, 5 and 8%V/V
eggshells are shown in Figure 1. Porcelain clay and
eggshells show crystalline phase consistent with the Fig. 1: XRD peak patterns of raw materials and porcelain
JCPDS files nos. 00-003-0418 (26.587°, 20.835° and 29.455°) clay added 2, 5 and 8%V/V eggshell powder
and 01-085-1108 in terms of rhombohedral phase formation before firing.

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 Middle-East J. Sci. Res., 24 (5): 1616-1621, 2016

strength of the porcelain products added 8%V/V

eggshells are 522.95 Mpa and 61.61 MPa, respectively,
consistent with the elastic modulus (E) results of fired
ceramic sample at 800°C reported by Serra et al. [12].

Table 4: Mechanical properties of porcelain samples added 0, 2, 5 and

8%V/V after firing at 800°C for 2 hrs.
Elastic Young Compressive
Samples a Modulus (E, MPa) strength (MPa)
800-0 105.48 11.31
800-2 328.80 24.91
800-5 452.76 59.91
800-8 522.95 61.16
a
means codes of samples composed of firing temperature and the percentage
of eggshells adding i.e. 800-0 means firing temperature at 800°C without
adding eggshells.
800-2 means firing temperature at 800°C added 2%V/V eggshells.
800-5 means firing temperature at 800°C added 5%V/V eggshells.
800-8 means firing temperature at 800°C added 8%V/V eggshells.

The data of porcelain clay products added 0 and

8%V/V eggshells after firing at 800°C for 2 hrs., are
measured the thermal expansion coefficient from
room temperature (25°C) to 900°C and reported in Table 5.
Fig. 2: XRD peak patterns of porcelain products added 0, The thermal expansion coefficient values of porcelain
2, 5, 8%V/V eggshells and firing at 600°, 700° and clay products added 0 and 8%V/V eggshells and fired at
800°C for 2 hrs. 800°C are 4.1098 x 10 6 and 2,2149x 10 6 (°C) ,1
respectively. The obtained thermal expansion
Mechanical and Thermal Properties of Porcelain coefficient values in this study are less than the thermal
Products: The porcelain products added 0, 2, 5 and expansion values reported by Ke et al. [12] (4.9-7.2 x10 6
8%V/V eggshell and fired at 800°C for 2 hrs., are tested the K 1). It means the lower thermal expansion coefficient, the
mechanical and thermal properties as data tabulated in better thermal shock resistance. The porcelain clay
Table 4. The porcelain products added 8%V/V products added 8%V/V eggshells and fired at 800°C for 2
eggshells and fired at 800°C for 2 hrs., are the best hrs., has low thermal expansion coefficient value.
condition. The modulus of elasticity and compressive Therefore, the obtained porcelain clay products are good
strength increase when the amount of eggshells adding thermal shock resistance suitable for thermal insulation
increases. The modulus of elasticity and compressive applications.

Table 5: Thermal expansion coefficient of porcelain samples added 0 and 8%V/V after firing 800°C for 2 hrs.
Samples a Temperature (°C) Thermal expansion coefficient (°C) 1

800-0 Porcelain products without eggshells adding 25°-900°C 4.1098 x 10 6

800-8 Porcelain products added 8%V/V eggshells 25°-900°C 2.2149 x 10 6

a
means codes of samples composed of firing temperature and the volume percentage of eggshells adding.
800-0 means firing temperature at 800°C no adding eggshells.
800-8 means firing temperature at 800°C added 8%V/V eggshells.

CONCLUSIONS advantages of adding eggshells into porcelain clay

products are to reduce energy consuming and investment
The obtained porcelain clay products added 8%V/V cost and to increase physical, mechanical and thermal
eggshells prepared by extrusion and fired at 800°C for 2 properties. Calcium carbonate contained in eggshells can
hrs., are good physical, mechanical and thermal properties react with alumina and silica or aluminosilicate in porcelain
suitable for insulation applications i.e. automotive clay to form calcium feldspar or anorthite acted as a flux to
assemblies, electronic devices, catalysts, household reduce the firing temperature and firing time of porcelain
applications and medical-dental applications. The clay products. Furthermore, Serra et al. reported calcium

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 Middle-East J. Sci. Res., 24 (5): 1616-1621, 2016

carbonate (CaCO3) can increase the sintering ability of 2. Nys, Y., J. Gautron, J.M. Garcia-Ruiz and
the materials [12]. Ke et al. reported anorthite-based M.T. Hincke, 2004. Avian eggshell mineralization:
porcelains can be prepared from three different sources biochemical and functional characterization of matrix
i.e. dolomite (CaCO3.MgCO3), wollastonite (CaO.SiO2 ) and proteins. Comptes Rendus Palevol., 3: 549-562.
calcite (CaCO3) [13]. Therefore, eggshell is a calcium oxide 3. Yoo, S., J.S. Hsieh, P. Zou and J. Kokoszka,
source useful for using as a flux to reduce the firing 2009. Utilization of calcium carbonate particles
temperature and firing time in the ceramic industries. from eggshell waste as coating pigments for
There are many advantages of using eggshell: to save ink-jet printing paper. Bioresource Technology,
energy, to reduce cost and to decrease eggshell waste in 100: 6416-6421.
daily. The true density, volume shrinkage, water 4. Tangboriboon, N., R. Kunanuraksapong and
absorption, modulus of elasticity, compressive strength A. Sirivat, 2012. Preparation and properties of calcium
and thermal expansion coefficient of porcelain products oxide from eggshells via calcinations. Materials
added 8%V/V eggshells and fired at 800°C for 2 hrs., are Science-Poland, 30/4: 313-322.
2.4186±0.0920 g/cm3, 28.7863±1.9300%, 17.8603±4.6500%, 5. Tangboriboon, N., R. Kunanuraksapong and
522.95 MPa, 61.16 MPa and 2.2149x10 6 (°C) 1, A. Sirivat, 2012. Meso-porosity and phase
respectively. The theoretical compressive strength, transformation of bird eggshells via pyrolysis.
hardness and water absorption values of fired ceramics Journal of Ceramic Processing Research,
according to the Thai Industrial Standard Institute 13/4: 413-419.
243/2530 and the ASTM C 373-72 should have the values 6. Rehren, T. and M. Yin, 2012. Melt formation in lime-
more than 7.0 MPa, 6.0 HV and less than 25%wt, rich proto-porcelain glazes, Journal of Archaeological
respectively. Therefore, the obtained porcelain clay Science, 39: 2969-2983.
products added 8%wt eggshell powder and fired at 800°C 7. Hecker, C., M. Van der Meijde and D.F. Van der Meer,
for 2 hrs., are potential to use as porcelain clay 2010. Thermal infrared spectroscopy on feldspars
applications i.e. construction and thermal insulation. ¯Successes, limitations and their implications for
remote sensing. Earth Science Reviews, 103: 60-70.
ACKNOWLEDGEMENTS 8. Cheng, X., S. Ke, Q.Wang, H. Wang, A. Shui and
P. Liu, 2012. Fabrication and characterization of
The authors would like to thank the following: anorthite-based Ceramic Using Mineral Raw
The Petroleum and Petrochemical College and the Materials. Ceramics International, 38: 3227-3235.
Scientific and Technological Research Equipment Centre, 9. Gdula, R.A., 1971. Anothite ceramic dielectrics,
at Chulalongkorn University, Thailand; the Department of American Ceramic Society Bulletin, 50: 555-557.
Materials Engineering, at Kasetsart University for the use 10. Boudchicha, M.R., S. Achour and A. Harabi, A., 2001.
of their analytical equipment. We have to thank the Crystallization and sintering of cordierite and
financial support from Agricultural Research Development anorthite based binary ceramics. Journal of Materials
Agency (Public Organization), ARDA fiscal year 2012- Science Letters, 20: 215-217.
2014. We also would like to acknowledge the financial 11. Kaneko, K., 1994. Determination of pore size and pore
support from Conductive and Electroactive Polymers size distribution 1, Adsorbents and catalysts. Journal
Research Unit of Chulalongkorn University, the Thailand of Membrance Science, 96: 59-89.
Research Fund (TRF-BRG) and the Royal Thai 12. Serra, M.F., M. Picicco, E. Moyas, G. Suárez,
Government. F.F. Aglietti and N.M. Rendtorff, 2012. Talc,
Spodumene and Calcium Carbonate Effect as
REFERENCES Secondary fluxes in Triaxial Ceramic Properties.
Proceeding of Materials Science, 1: 397-402.
1. Tsai, W.T., J.M. Yang, C.W. Lai, Y.H. Cheng, C.C. Lin 13. Ke, S., X. Cheng, Y. Wang, Q. Wang and H. Wang,
and C.W. Yeh, 2006. Characterization and adsorption 2013. Dolomite, wollastonite and calcite as different
properties of eggshells and eggshell membrane. CaO sources in anorthite-based porcelain. Ceramics
Bioresource Technology, 97: 488-493. International, 39: 4953-4960.

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