UCTEA Chamber of Metallurgical & Materials Engineers
Usage of Boron Wastes in the Commerically Produced and
Used ZrCMS System Opaque Frit Composition
Proceedings Book
Fatma Aksu¹, Ayşe Tunalı¹, Neslihan Tamsu Selli¹,
Buğra Çiçek², Emre Talşık¹
¹Eczacıbaşı Building Product Co., ²Yıldız Technical University Türkiye
Abstract
Over the past two decades there was growing interest in
the development of frits that are able to crystallise on
firing because of the need for improvement in the
mechanical and chemical properties of glazed tiles. The
ZrO2-CaO-MgO-SiO2 (ZrCMS) glass-ceramic system is
one of these and exhibits high resistance to abrasion and
surface scratches. In this present study, boron wastes of Eti
Mine Boron Company, which appear at huge amounts
during processess, were characterized and added into the
commerically produced and used ZrCMS system opaque
frit composition. New compositions were applied on tile
bodies, and then fast fired under industrial working
conditions. Newly-produced glazes were characterized in
terms of optical, mineralogical and microstructural
properties.
1. Introduction
Boron is a metalloid chemical element with symbol B and
atomic number is 5. It is not found naturally on Earth. It
takes part more than in 230 mineral in nature [1]. The 90
% of the boron minerals used in industry worldwide are
sodium and calcium borates, as borax, kernite, colemanite
and ulexite. There are more than 300 end uses linked with
borates (glass, agriculture, ceramics, cleaning products
(detergents, soaps, bleaches), metallurgy, corrosion
inhibitors, flame retardation, wood preservation, adhesives
and abrasives) [2].
The world’s largest boron reserves are located in Turkey,
U.S.A and Russia. Turkey is the luckiest country
possessing 72.1 % of total world boron reservations [1].
Boron is mined Bigadiç, Emet, KÕrka and BandÕrma region
of Turkey by Eti Mine Boron Company. The most
important boron minerals in Turkey are colemanite, ulexite
and tincal. These boron minerals are concentrated to
increasing the grade of B2O3 and wastes are discharged
during the concentrated processes [2]. A problem is the
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large quantity of boron wastes which are generated and
have to be disposed. The increasing costs of some
traditional raw materials for ceramics industry are leading
to a necessity for the use of complementary alternatives.
The aim of the present study is to utilize Eti Mine
BandÕrma Boron Company colemanite wastes in a
commerically produced ZrCMS glass-ceramic system
opaque frit composition instead of boric acid. New
compositions were applied on wall tile bodies, then fast
fired under industrial working conditions. Finally, newlyproduced glazes were characterized.
2. Experimental Procedure
Colemanite wastes (A5 and A6) were suplied by Eti Mine
BandÕrma Boron Company. The wastes of chemical
compositions were presented Table 1.
Table 1. Chemical compositions of the colemanite wastes
(in wt. %)
18 th International Metallurgy & Materials Congress
Oxides
A5
A6
B2O3
29,52
31,12
Na2O
0,91
0,82
MgO
0,82
0,60
Al2O3
0,11
0,63
SiO2
0,39
1,28
P2O5
0,01
0,01
SO3
0,56
0,77
K2O
0,04
CaO
52,75
33,42
Fe2O3
0,14
0,14
Cr2O3
0,04
SnO2
0,34
*L.I.
14,80
30,80
Total
100,00
100,00
*L.I.: Losses on ignition.
Bildiriler Kitabı
TMMOB Metalurji ve Malzeme Mühendisleri Odası
The mat opaque frit, which has been produced by
EczacÕbaúÕ Building Product Co., is accepted as a reference
(MOF1). MOF1 frit, which is huge amounts produced, is
used in glazes and engobes recipes. New recipes were
prepared with colemanite wastes to utilizing colemanite
wastes in MOF1 frit recipes. The frit that was formed with
A5 was coded MOF1-A5 and the frit that was formed with
A6 was coded MOF1-A6.
Table 2. Compositional details of studied frits (in moles)
COMPONENT
Content
Oxides
ratio
B2O3
MOF1
MOF1A5
MOF1A6
1,17
1,3
1,32
35,50
35,75
35,4
6,60
6,55
6,64
R2O
(Na2O, K2O)
RO
(CaO, MgO, ZnO)
R2O3
(B2O3, Al2O3, Fe2O3)
RO2
(SiO2, ZrO2)
TOTAL
SiO2/Al2O3
MgO/CaO
Total B2O3
56,73
56,4
56,7
100
45,587
0,910
0,146
100
44,725
0,901
0,143
100
42,987
0,905
0,145
*B2O3 (BW)
0
0,143
0,145
colouring and roughness parameteres of the glazes were
determined using a Konica Minolta Multi Gloss 268 Plus
model gloss meter, a X-rite model colorimeter and a
Ceramic Instruments KR 100 model profilometer.
3. Results and Discussion
If the values of brightness and surface roughness of glazes
were presented in Table 3, it can be seen that MOF1-A5 is
more similar to the standard glaze. MOF1-A6 glaze is
brighter than the standard glaze and its surface roughness
is rather less. As far as brightness values are compared, the
comparison would be MOF1-A6 > MOF1-A5 > MOF1
and as far as surface roughness values are compared, it
would be MOF1-A5 > MOF1 > MOF1-A6. When the
whiteness are compared, it is seen that MOF1-A5 and
MOF1-A6 have close values to each other and little less
values than MOF1 glaze.
Table 3. Glossiness, colouring and roughness parameteres
of the glazes
*B2O3 (BW): B2O3 amount from wastes
COLOUR
Boric acid that is used in MOF1 recipe, was removed in
MOF1-A5 and MOF1-A6 frits recipes. Furthermore, the
amount of dolomite that used as source of CaO and MgO,
decreased in the new recipes. Thus, all amount of B2O3
and a far amount of CaO and MgO were provided from the
wastes.
The weighed and thoroughly mixed batches were melted in
alumina crucibles in a Protherm series laboratory type
electrically heated furnace at 1450°C for 1 h. The melt was
then quenched by pouring into cold water to obtain frits
under laboratory working conditions. In order to prepare
glazes suitable amounts of frit, kaolin, carboxyl methyl
cellulose (CMC), sodium tripolyphosphate (STPP) and
water were mixed in a Ceramic Instruments Rapid MillsModuler System SD series jet-mill containing alumina
balls for 14 minutes. The slurries were applied onto
industrial wall tile body without engobe. The glazed tiles
were dried in a Nüve FN 40 laboratory type furnace at 100
o
C for 2 h. After drying, glazed tiles were fired in a fast
firing furnace in Eczacibasi Building Product Co. at 1145
o
C for a total time of 36 minutes. The glaze that was
formed with MOF1-A5 frit was coded MOF1-A5 glaze
and the frit that was formed with MOF1-A6 was coded
MOF1-A6 glaze.
Microstructural changes and phase formations of the
glazes were inspected with a Rigaku Rint 2000 series
diffractometer (XRD) and a Zeiss Evo 50 EP series
scanning electron microscope (SEM/EDX). Glossiness,
BRIGHTNESS
ROUGHNESS
MOF1
MOF1-A5
MOF1-A6
L
92,47
90,94
90,45
a*
-0,1
0,22
0,32
b*
0,76
1,4
1,64
20 °
1,1
1,1
1,4
60 °
2,4
2,7
6,2
80 °
2,4
2,9
7,2
—m
18,72
19,35
10,13
According to the XRD results were presented in Figure 1,
diopside and zircon crystals in addition to a small amount
of amorphous phase were determined in all glazes. While
the wide elevation at 20-35o 2ࣝ, which belongs to
amorphous phase, do not be seen clearly MOF1 glaze, it is
rather clearer in the new glazes. In standard MOF1 glaze,
the peak intensities of diopside crystals are higher than the
ones in zircon crystals. In MOF1-A5 glaze, peak
intensities of zircon and diopside crystals have become
almost equal.
18. Uluslararası Metalurji ve Malzeme Kongresi
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IMMC 2016
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UCTEA Chamber of Metallurgical & Materials Engineers
Proceedings Book
(a)
Figure 1. X-ray diffraction paterns of the MOF1, MOF1A5 and MOF1-A6 glazes.
When investigated the microstructure of MOF1, MOF1A5, MOF1-A6 glazes, two different crystals can be seen
homogenously distributed light ones and dark ones. It is
also observed that the light crystals are a thin stick while
the dark ones are in a larger and dispersed way. As a result
of the EDX analysis made on the crystals marked as “Z” in
Figure 2,3 and 4, were detected peaks which belong to the
elements Zr and Si. As a result of the EDX analysis made
on the crystals marked as “D” in Figures 2, 3 and 4, were
detected peaks which belong to the elements Si, Mg, Ca
and Al. The EDX results agreed with the XRD data
confirming both zircon and diopside cyristallizations.
(b)
(d)
Figure 3. (a) SEM micrographs of the MOF1-A5, (b)
EDX analyses taken from “Z” (Zircon) cyrstal and (c)
EDX analyses taken from “D” (Diopside) cyrstal.
(a)
(a)
(b)
(b)
(c)
Figure 4. (a) SEM micrographs of the MOF1-A6, (b)
EDX analyses taken from “Z” (Zircon) cyrstal and (c)
EDX analyses taken from “D” (Diopside) cyrstal.
Figure 2. (a) SEM micrographs of the MOF1, (b) EDX
analyses taken from “Z” (Zircon) cyrstal and (c) EDX
analyses taken from “D” (Diopside) cyrstal.
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(c)
18 th International Metallurgy & Materials Congress
Bildiriler Kitabı
TMMOB Metalurji ve Malzeme Mühendisleri Odası
Using of borax wastes by not changing the Seger formulas
of standard glazes does not affect the crystallization and
microstructure of the glaze and not deteriorate the desired
matte surface texture. Similar results have been reported in
the literature. [3-4]
4. Conclusion
Boric acid that is used in MOF1 recipe source of B 2O3,
was removed in MOF1-A5 and MOF1-A6 frits recipes.
The whole amount of B2O3 in the recipes were provided
from wastes Furthermore, the amount of dolomite that
used as source of CaO and MgO, were decreased by 66.67
% in MOF1-A5 recipe and by 41.3 % in MOF1-A6 recipe
and some amount of the CaO and MgO requirements is
provided from wastes.
Using of boron wastes by not changing the Seger formulas
of standard frits does not affect the crystallization and
microstructure of the glaze. Even though there have been
increases in the brightness values, decreases in the surface
roughness and whiteness values of the glazes obtained by
the use of MOF1-A5 and MOF1-A6 frits, these differences
do not have a negative effect on usage of frit in glazes.
Finally, it can be understood that frits prepared with
colemanite wastes in the ZrCMS glass ceramics system
can be easily used without leading to any surface failure or
fault.
Acknowledgment
The authors would like to thank to BOREN (National
Boron Research Institute) for the financial support to the
Project numbered 2015-31-07-15-002.
References
[1] http://www.etimaden.gov.tr/ Dated: 02.05.2016
[2] B. CÕcek, L. EsposÕto, A. TuccÕ, E. Bernardo, A. R.
BoccaccÕnÕ and P. A. BÕngham, Microporous Glass
Ceramics From Combination Of Silicate, Borate and
Phosphate Wastes, (2012).
[3] B. Karasu, Use of Borax Solid Wastes in Ceramics’
World, Anadolu University, Faculty of Engineering and
Architecture, Department of Materials Science and
Engineering, (2007).
[4] B. Karasu, G. Kaya, A. ÇakÕr, and S. Yeúilay,
UtÕlÕzatÕon Of Borax SolÕd Wastes In Fast SÕngle-FÕrÕng
PorcelaÕn TÕle Glass-CeramÕc Glazes Under IndustrÕal
WorkÕng CondÕtÕons, Anadolu University; Department of
Materials Science and Engineering, (2008).
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