Ceramics International 26 (2000) 485±493

Utilization of bauxite waste in ceramic glazes

Nevin YalcËõn*, Vahdettin SevincË
Sakarya University, Arts and Sciences Faculty, Chemistry Department, Serdivan, Sakarya 54180, Turkey

Received 15 June 1999; received in revised form 26 June 1999; accepted 1 September 1999

Abstract
Red mud (bauxite waste) emerge as by-product from the caustic leaching of bauxites to produce alumina and it causes serious
problems such as storing and environmental pollution. In this study, red mud, which is the industrial waste of SeydisË ehir Alumi-
nium Plant (Turkey), was investigated for use in the making of ceramic glazes in the ceramic industry. The chemical and the
mineralogical investigations indicated that major constituents of the red mud were hematite (a-Fe2O3) and sodium aluminium sili-
cate hydrate (1.01 Na2O.Al2O3.1.68 SiO2.1.73 H2O). The production of the porcelain, vitreous (sanitary ware glazes), tile and
electroporcelain glazes was done using the red mud. The glazes, which contain di€erent compositions and properties, were exam-
ined. Their surface properties, the chemical strength of glazes in 3% HCI and 3% NaOH and abrasion resistance were investigated
experimentally. It was found that the addition of up to 37 wt% of the red mud waste was possible in the production of the glazes.
# 2000 Elsevier Science Ltd and Techna S.r.l. All rights reserved.
Keywords: A. Firing; B. X-ray methods; D. Traditional ceramics

1. Introduction mud is the biggest problem in producing alumina. This

waste present serious problems of storing and environ-
Aluminium can be extracted from bauxite, which is a mental pollution. Although studies in this area have
compound of aluminium hydroxide, iron dioxide, sili- been done since 1950, improved processes have mostly
con dioxide, kaolin and titanium. The ®rst stage is to not been put into practice because of economic reasons
extract alumina (Al2O3) from the ore through the Bayer [3±6]. There were nearly 3 million tons of red mud waste
process, which is used with one or two exceptions, accumulated at the SeydisË ehir Aluminium Plant (Tur-
throughout the world. In this process, ground bauxite is key) between 1973 and 1996. There is not yet an eco-
reacted with sodium hydroxide under heat and pressure nomic way or an application of plant scale to utilize this
forming sodium aluminate [NaAl(OH)4], residue which red mud.
is then puri®ed and decomposed. As a result of decom- Much has been said about the possibility of using the
position, the aluminium hydrate is calcined at 950± red mud as a cheap source of raw material for the
1200 C, thus yielding alumina. The second stage is the manufacture of low-cost ceramic products [4,6]. How-
electrolysis process. In the electrolysis cells, with the aid ever, there are very few studies on using the red mud for
of a direct current, liquid aluminium is obtained from producing ceramic glazes. Hence, very little useful data
alumina. The liquid aluminium, being alloyed when are available to aid in an assessment of the potential of
required is then cast into the desired molds [1,2]. red mud ceramic glazes.
Red mud emerges as by-product from the caustic From earlier researches it was seen that red mud con-
leaching of bauxites to produce alumina, and its major sists of several oxides which can form a glassy phase after
constituents are Fe2O3, Al2O3, SiO2, Na2O and CaO, sintering. SiO2, CaO and Na2O may be responsible for the
with little amounts of Zr, Y, Th, U and rare earth ele- glassy phase. Because of this, red mud is a potential raw
ments as trace constituents. Approximately 35±40% of material for the production of ceramic glazes.
the processed bauxite goes into waste as red mud. Red Most commercial glazes have a large number of con-
stituents. It is therefore desirable to have a system of
* Corresponding author. Fax: +90-264-276-2059. representing composition that permits easy compar-
E-mail address: [email protected] (N. YalcËõn). isons. The method of the presenting molecular formulas
0272-8842/00/$20.00 # 2000 Elsevier Science Ltd and Techna S.r.l. All rights reserved.
PII: S0272-8842(99)00083-8
486 N. YalcËõn, V. SevincË / Ceramics International 26 (2000) 485±493

of glazes in general use is that originated by Seger, but form a glassy phase after sintering. From this point of
somewhat modi®ed. The oxides are listed in three or view, the objective of the present work is the use of the
more columns, the ®rst containing those of monovalent red mud for producing ceramic glazes.
and divalent elements, the second those of trivalent and
the third those of tetravalent elements. The sum of the
®rst column is brought to one [10]. This classi®cation is 2. Experimental procedure
rigidly required by the structure of the empirical for-
mula, which is consistently expressed in the following 2.1. Materials and methods of characterization
form:
The red mud sample was supplied by SeydisË ehir Alu-
RO R2O3 RO2 minium Plant (Konya, Turkey, producing 200 000 tons
mols of mols of neutral mols of acid of alumina per year) [2]. At the raw glazes, the red mud
bases=1.00 (amphoteric) oxides oxides was used after calcined at 500 C for 4 h using a heating
rate of 3 C/min. Kaolin, K-feldspar and bentonite were
R is the general symbol for the metallic atoms and O obtained from Mihaliccik, Cine and KuÈtahya regions of
for oxygen [8]. It is found that all the network modi®ers Turkey, respectively. Other raw materials were SiO2,
fall in the ®rst column and the network formers in the ZrSiO4, MnO2, Cr2O3, ZnO, MgO, H3BO3, Na2B4O7
second, third and fourth columns [10]. In this study, (calcined at 350 C), PbO, CaCO3, KNO3, Na2CO3.
Seger formulas of the glazes were calculated by using These were used at analytical purity.
the red mud and other raw materials. The chemical analysis of the samples were done using
Red mud consists of SiO2, Na2O, CaO, Al2O3, Fe2O3, an atomic absorption spectrophotometer (Rank Hilger,
MgO, K2O, TiO2. These oxides are very important Atom Spek H-1580), a digital photometer (Dr. Lange
constituents of several types of glazes. Na2O, K2O, LP 2 W) and wet chemical methods. The loss on igni-
CaO, MgO are the network modi®ers. SiO2, Al2O3, tion of the red mud was measured gravimetrically in a
Fe2O3, TiO2 are the network formers. The red mud mu‚e furnace (Heraeus) at 1100 C. Thermal analysis
contains 30±60 wt% Fe2O3 [6]. The e€ect of iron com- measurements (TG and DTG), using a simultaneous
pounds in glazes is also a matter of colour. Various thermal analysis instrument (Netzsch-429) were per-
colours are imparted to glazes by iron. Ferric oxide formed. Sample weight was 100 mg and the heating rate
(ferric ions, Fe3+) as a network former with a four-fold was 10 C/min under air atmosphere with Al2O3 powder
coordination produces a brownish colour. When the as reference material. The temperature limits were 20
same ferric ions are in six-fold coordination and are a and 1200 C. X-ray di€raction (XRD) studies on the
network modi®er, a weak yellow±pink appears. Ferric samples were undertaken using a Philips X-ray di€rac-
iron in glass produces reddish colours. A wide variety of tion unit (Model PM 9901/00). The particle size of the
colours is possible from minor amounts of iron present. materials was measured by using a sedigraph (5000 D
Ferric oxide is not so strong a ¯ux and its solubility in Micromeritics). Baume degrees of the glazes were mea-
the glaze is moderate to low [8]. In the present work, red sured with an areometer.
mud was used as a raw material for the preparation of
the glazes. The amounts of the included oxides of the 2.2. Formulation and processing of the glazes
red mud were determined. In the glaze compositions
that were chosen, insucient amounts of the oxides The ceramic bodies were chosen as tile, porcelain,
after using the red mud were completed from the other sanitary ware (vitreous) and electrical porcelain (elec-
raw material. Red mud was used as a main raw material troporcelain). The clay body for tile was assured from
in these glazes. As the glaze types, tile, porcelain, vit- BozuÈyuÈk Ceramic Works of Turkey. Other clay bodies
reous and electroporcelain glazes were chosen. From the were obtained from Yarõmca Porcelain Works of Turkey.
literature, the composition of these glazes was ®xed and The clay body muds were moulded into square bars
their Seger formulas and physical properties calculated. with dimensions 11010 cm at the factories. From
The production of these glazes was done using the red these bars, biscuits with dimensions 155 cm were
mud and other raw materials. Thermal shock test, che- prepared.
mical resistance test and resistance to abrasion test were As the glaze types tile, porcelain, vitreous chine sani-
applied to the glazed samples. Because of the insucient tary and electroporcelain (high-voltage insulators) gla-
literature data, it seemed necessary to undertake an zes were chosen. From literature the composition of
experimental study directed especially at the red mud these glazes were ®xed and calculated their Seger for-
ceramic glazes to determine their potential of the cera- mulas (empirical ceramic formula). Afterwards, percent
mic glazes. and batch compositions of these glazes from empirical
In this study, from earlier researches it was seen that formulas were calculated by using the red mud and
Turkish red mud consist of several oxides which can other raw materials [7±11]. From every type of glazes,
 N. YalcËõn, V. SevincË / Ceramics International 26 (2000) 485±493 487

18 pieces which contain di€erent compositions and magnetic stirring for preparation of a homogeneous
properties were prepared (total of 72 pieces). Their mixture of the glaze constituents and water, free from
physical properties were also determined. coarse particles and lumps. The characteristics concern-
On the basis of the dependence of the properties of ing the mud at 50  Be are given as follows:
glasses upon composition, it is possible to compute
physical properties, e.g. density, coecient of thermal Speci®c gravity (g/cm3) 1.529
expansion, tensile strength, compressive strength, hardness Solid quantity (g/l) 856.557
factor, coecient of surface tension and heat (thermal) Water quantity (g/l) 672.443
conductivity, according to the general formula:
A dipping method was used for the glaze application.
P ˆ c1 x1 ‡ c2 x2 ‡ c3 x3 ‡ . . . ‡ cn xn …1† For tile, porcelain and vitreous glazes, the clay bodies
were ®red at 900 C for 3 h in a mu‚e furnace (Heraeus
in which P is the property, c is the percentage weight of model) and the biscuits were cooled naturally in the
an oxide component, and x1 , x2 , x3 and xn are their furnace. Then the biscuits were washed with a brush for
appropriate factors [8]. removing powders and were dried at 105 C in the oven.
The ratio of the acid to the base is shown like that Glazed biscuits were ®red as follows. Porcelain (1050±
1400 C), vitreous (1050±1280 C) and electroporcelain
Sum of the mol of the (1050±1380 C) glazed biscuits were ®red in the oxidative
acid oxides tunnel kiln at Yarõmca Porcelain Works of Turkey. Tile
Acid=base ratio ˆ
Sum of the mol of the glazed biscuits were ®red at 1000±1250 C for 3 h in the
base oxides electrical furnace in our laboratory.

Fe, Co, Ni, Mn, and Cu oxides as the basic oxides, and 2.4. Experiments for the ®tting of the glaze to the body
Sn, Ti, As, Si and B oxides as the acid oxides are used at
the calculations [7]. 2.4.1. Determination of the crazing
The coecient of melting computes from that rela- Crazing is recognized as due to di€erences in thermal
tions [13]: expansion between body and glaze. Stresses in the glaze
layer will always result when the reversible thermal
100x expansions of the glaze and body are not identical. If
Fˆ …2†
x‡y the coecient of expansion of the glaze is greater than
  that of the body (below the softening temperature of the
20 glaze) then, during initial cooling, the glaze layer will
xˆ …Al2 O3 ‡ ZrO2 † ‡ SiO2 0:38 …3†
17 develop tensile stress. Because glazes are character-
istically weak in tension, glaze layers subjected to tensile
y ˆ RO ‡ B2 O3 ‡ Sb2 O3 …4† stress will rupture (craze) [8]. This may cause it to break
in ®ne irregular cracks known as crazing. This tension
where F=the coecient of melting, RO=mol of the was commented according to type, number and size of
basic oxides. the crazes.
The formula used for the oxygen ratio is:
2.4.2. Harkort test (thermal shock test)
2S ‡ 3B In this test method, the glazed sample was heated to
Oxygen ratio ˆ …5†
3Al ‡ 1 100 C and plunged into water at room temperature
(17.6 C), then examined for craze lines. When none was
where S, B, Al are mol of SiO2, Bi2O3 and Al2O3, respec- found, the temperature was raised another notch and
tively [7]. Also, the mol ratio Al2O3/SiO2 was calculated the sample requenched. The procedure was repeated
for the each glaze formula. Factors and formulas for until a temperature was found where the glaze crazes.
computing some properties of glazes from composition The resistance to crazing was then reported as the max-
and the limit values of the physical properties have been imum temperature from which the quench could be
taken from the literature [7,8,10,12,13]. made without creating crazing [8]. The relation between
the temperature and the resistance time against crazing
2.3. Glaze application and ®ring is given in Table 1.

The glaze materials were weighed, the mixture was 2.4.3. Chemical resistance test (resistance to acids and
ground in a ball mill and screened through a 75 mm (200 bases test)
mesh) screen. Enough water was added to reach a The glazed surfaces of the samples were washed with
pouring consistency (50  Be) and was mixed with the methyl alcohol. Then they were treated in 3% HCl
488 N. YalcËõn, V. SevincË / Ceramics International 26 (2000) 485±493

Table 1 Table 2
The relation between the temperature and resistance time against Chemical analysis of red mud and calcined red mud
crazing for the glazed samples [14]
Compounds Composition (wt%)
Temperature ( C) Resistance time against crazing
Red mud Calcined red mud
120 First 8 days
150 3±4 months Fe2O3 35.73 37.07
160 15 months Al2O3 23.29 25.61
180 2±3 years SiO2 12.08 13.83
200 Continuously TiO2 4.08 6.50
Na2O 7.40 7.62
K2O 0.28 0.34
CaO 2.81 3.16
solution for 7 days at 20 C and were treated in 3% MgO 0.76 1.77
NaOH solution for 7 days at 20 C. Afterwards, the CO2 2.40 2.80
SO3 1.34 1.03
glazed surfaces were inspected visually and with a hand
Loss on ignition (1100 C) 8.66 ±
lens for colour, gloss, crazing, bubbles, orange peeling,
etc. [15].

2.4.4. Resistance to abrasion test (sand blast test) Table 3

In this test method, the glazed sample in the form of a The weight losses of the red mud and the calcined red mud
plate was mounted at an angle of 22.5 and subjected to Temperature ( C) Weight losses (%)
a blast of 80 mesh silica sand. Fixed quantities of 30 kg
per blast were employed at 15 min. Sands were poured Red mud Calcined red mud
to samples from an interval 47 mm length and 185 mm 110 0.97 0.24
height. The samples were weighed before and after the 290 2.72 1.38
experiments to discover the weight loss [10,14]. A mea- 530 4.77 2.26
750 6.10 3.14
sure of the abrasion resistance was taken as the amount
900 7.07 4.16
of glaze removed by the blast.

3. Results and discussion An X-ray di€raction diagrams of red mud and cal-
cined red mud are given in Fig. 2. X-ray di€raction
The chemical analyses of the mud and the calcined results of red mud and calcined red mud showed that
red mud are given in Table 2. the phases were found as hematite (/-Fe2O3), sodium
The particle size analysis of the red mud and the cal- aluminium silicate hydrate (1.01 Na2O. Al2O3. 1.68
cined red mud revealed a size distribution between 5 and SiO2. 1.73 H2O), sodalite [Na4Al3Si3O12(OH)], sodium
35 mm in all samples. 88% of the particles are ®ner than silicate (Na2SiO3), sodium aluminium oxide (NaAlO2),
10 mm in the red mud and 80% of the particles are ®ner iron titanium oxide (Fe2TiO5), calcium silicate
than 10 mm in the calcined red mud [16]. From the (CaSiO3), sodium titanium oxide (Na2Ti3O7), sodium
thermal gravimetric analysis curves (TG and DTG) for carbonate (Na2CO3) and sodium iron oxide (NaFeO2)
the samples, weight losses are measured and are given in except for red mud [16]. Table 4 shows the results
Table 3. Also, Fig. 1 shows the thermal gravimetric obtained from the XRD analysis of the red mud and
analysis diagrams for the samples. calcined red mud. The X-ray di€raction and chemical
The red mud dehydrates free water absorbed on the analysis studies of the red mud showed that the red mud
surface of the particles between 240 and 350 C, and was mainly consisted of SiO2, Na2O, CaO, Al2O3,
bound water between 460 and 590 C. Weight losses Fe2O3, MgO, K2O and TiO2. These oxides are very
were observed between 700 and 780 C and between 850 important constituents of several types of glazes.
and 940 C for SO3 and CO2, respectively. The DTG Because of this property, red mud may be used as a
peak temperatures 290, 530, 750 and 900 C represent glaze raw material.
the temperatures at which the rate of mass-change is at
a maximum and are clearly not the temperatures at 3.1. Utilization in the ceramic glazes of red mud
which the sample begins to lose mass or the ®nal tem-
perature, which is the temperature at which the sample Computed Seger formulas and physical properties of
completes reaction. The organic matter in red mud also the red mud and the calcined red mud samples are given
burns at 370 C [17]. The free water, the bound water in Tables 5±7.
and the organic matter in the red mud were removed by From Table 7 it can be seen that the physical proper-
being calcined at 500 C. ties of the red mud and the calcined red mud were not
 N. YalcËõn, V. SevincË / Ceramics International 26 (2000) 485±493 489

suitable for using as the glaze raw material alone. Their 3.2. The appearance properties of the ®nished glaze
values were not within the limit values of the physical
properties given in the literature [13,16] for the successful 3.2.1. Porcelain glazes
glaze types. Therefore, these properties must be corrected The glazes which were prepared with the calcined red
with other raw material additives. mud and named as the raw porcelain glaze, with nota-
This result was veri®ed experimentally. A glaze was tion P1±P10, were successful except for P8. These glazes
prepared using the red mud alone and applied to the tile have di€erent equivalent values of the oxides at the
body. The tile glazed body was ®red at 1100 C for 3 h in Seger formulas. The equivalent values of the oxides were
the electrical furnace. The glaze surface was matt and at these intervals: Na2O (0.01±0.20), K2O (0.14±0.30),
had large crazes. It has not shown glaze properties. This MgO (0.05±0.10), CaO (0.45±0.63), ZnO (0.00±0.25),
structure is given in Fig. 3. Al2O3 (0.30±0.50), Fe2O3 (0.00±0.30), B2O3 (0.00±0.35),
SiO2 (2.37±6.00), TiO2 (0.00±0.05) and ZrO2 (0.00±0.20).
All of them have a glossy surface known as bright
glazes. Colours of these glazes were observed as yellow,
mustard, brick red, dark brown. P11±P15 glazes which
prepared with addition calcined red mud at the amounts
increase gradually to a glaze composition that chosen
were successful outside P15. The calcined red mud wt%
using at these glazes were 0.00, 11.81, 21.58, 29.57,
36.95, respectively. The amount of the ferric oxide var-
ied from 0.00 equivalent to 0.40 equivalent at these
glazes (0.00, 0.10, 0.20, 0.30, 0.40); other oxide equiva-
lents were the same. Increasing the amount of calcined
red mud in the formula, the glazes were matt, dark
colour, burn and with pore. P16, P17 and P18 fritted
glazes have a glossy surface and obtained a range of
colours from mustard to brown. In these fritted glazes
a part of the materials and the remaining raw materials
were added on. These frit and raw mixture glazes were
successful. The amounts of the ferric oxide were 0.10,
Fig. 1. TG and DTG analysis curves of red mud and calcined red 0.15 and 0.20 equivalents at the fritted glazes, respec-
mud. tively.

Fig. 2. XRD diagrams of red mud and calcined red mud.

490 N. YalcËõn, V. SevincË / Ceramics International 26 (2000) 485±493

Table 4
XRD analysis of samples

Mineral names Formulas Peak no.

Red mud Calcined red mud

Hematite a-Fe2O3 8, 10, 13, 14, 18, 19, 20, 21, 23 7, 9, 11, 12, 16, 18, 19, 21, 22, 25
Sodium aluminium silicate hydrate 1.01 Na2O.Al2O3.1.68 SiO2.1.73H2O 2, 3, 4, 5, 6, 9, 14, 17 2, 4, 5, 8, 13, 17
Sodalite Na4Al3SiO3O12 (OH) 1, 5, 9 1, 4, 8
Sodium silicate Na2SiO3 7, 9, 11 6, 8, 10, 17
Sodium aluminium oxide NaAlO2 8, 9, 19, 20, 21 7, 8, 19, 21, 22
Iron titanium oxide Fe2TiO5 13, 16, 17, 22 12, 23, 24
Calcium silicate CaSiO3 12, 13, 16 12, 13, 16
Sodium titanium oxide Na2Ti3O7 7, 11, 15 6, 14
Sodium carbonate Na2CO3 7, 9, 11 6, 8, 10
Sodium iron oxide NaFeO2 ± 12, 20

Table 5 Table 7
Computed Seger formula of the red mud Computed physical properties of the red mud and the calcined red
mud
0.623 Na2O 1.051 SiO2
0.016 K2O 1.192 Al2O3 0.313 TiO2 Physical properties Red mud Calcined red mud
0.262 CaO 1.166 Fe2O3 0.285 CO2
0.099 MgO 0.088 SO3 Coecient of thermal expansion 3.79 4.09
10ÿ5 (mm3  Cÿ1)
Coecient of surface tension 390.287 425.43
(dyn cmÿ1)
Thermal conductivity 0.9859 1.091
Table 6 (kcal mÿ2  Cÿ1 sÿ1)
Computed Seger formula of the calcined red mud Density (g cmÿ3) 2.85 2.47
Tensile strength (kg mmÿ2) 2.972 3.331
0.541 Na2O 1.015 SiO2
Compressive strength (kg mmÿ2) 43.368 49.179
0.016 K2O 1.105 Al2O3 0.358 TiO2
Hardness factor 239.114 265.802
0.195 CaO 1.020 Fe2O3 0.279 CO2
Acid/base ratio 0.212 0.231
0.248 MgO 0.057 SO3
Coecient of melting 61.99 47.956
Al2O3/SiO2 ratio 1.134 1.089
Oxygen ratio 0.46 0.47
Molecular weight (g mol) 518.70 439.02
3.2.2. Vitreous glazes

Raw vitreous glazes prepared using calcined red mud cream, brown colours with designed. The amounts of
and named as V1±V10 glazes were successful except V7, the ferric oxide were 0.05, 0.15 and 0.10 equivalents at
V9 and V10. These glazes have di€erent equivalent the fritted glazes, respectively.
values of the oxides at the Seger formulas. The equiva-
lent values of the oxides were at these intervals: Na2O 3.2.3. Tile glazes
(0.01±0.10), K2O (0.08±0.15), MgO (0.00±0.09), CaO The glazes which prepared with the calcined red mud
(0.01±0.55), ZnO (0.15±0.27), Al2O3 (0.22±0.37), Fe2O3 and named as the raw tile glazes, with notation A1±A10
(0.00±0.30), B2O3 (0.00±0.35), SiO2 (2.60±4.50), TiO2 were successful except for A1. These glazes have di€er-
(0.00±0.05) and ZrO2 (0.00±0.18). V7 does not have a ent equivalent values of the oxides at the Seger for-
smooth surface. V9 showed crawling and V10 showed mulas. The equivalent values of the oxides were at these
pin holes. The high viscosity of glaze causes pin holes. It intervals: Na2O (0.02±0.40), K2O (0.04±0.22), MgO
is corrected with 0.1 mol SrO added to the Seger for- (0.00±0.19), CaO (0.14±0.70), ZnO (0.00±0.20), PbO
mula. V11±V15 glazes which prepared with addition cal- (0.00±0.45), Al2O3 (0.26±0.38), Fe2O3 (0.00±0.30), B2O3
cined red mud at the proportions increase gradually to a (0.08±0.80), SiO2 (2.56±3.80), TiO2 (0.00±0.05). A1 has
glaze composition that chosen were successful. The cal- the tensile crazing. Here, the expansion coecient of the
cined red mud wt% using at these glazes were 0.00, 5.92, glaze was higher than that of the body and the glaze
10.86, 20.38 and 28.14, respectively. The amounts of the showed ®ne irregular cracks known as crazing. To
ferric oxide were 0.00, 0.05, 0.10, 0.20 and 0.30 equiva- decrease its expansion coecient, the amount of silica is
lent at these glazes. These glazes have a glossy surface increased and the amounts of ¯uxing agents are
and their colours were observed as white, beige brown decreased. Alterations of glaze composition must of
and black. V16±V18 fritted glazes were matt and at course be made within limits [10]:
 N. YalcËõn, V. SevincË / Ceramics International 26 (2000) 485±493 491

glazes which were prepared with addition of calcimined

red mud with the amounts increased gradually to a
chosen glaze composition had a matt, burnt-like
appearance except for E11 and E12. The calcined red
mud wt% used for these glazes were 0.00, 7.61, 14.69,
18.41 and 27.14. The amounts of the ferric oxide were
0.00, 0.10, 0.20, 0.30 and 0.40 equivalent at these glazes.
The wt% of the calcined red mud are used to de®ne the
glazes that show also gradual increase at the ferric oxide
amounts of the chosen compositions. Other oxide
equivalents at the Seger formulas are the same. The
increase gradually at the ferric oxide amounts was used
as the main criteria for these types of the glazes. The
fritted glazes with notation E16±E18 were unsuccessful as
expected. The amounts of the ferric oxide were 0.25,
0.20 and 0.10 equivalents at the fritted glazes, respec-
tively. These glazes were unmatured and showed a
structure with poles. Many larger electrical porcelain
pieces cannot be re®red for maturing the glaze because
of the high risk of dunting. The glaze must, therefore, be
applied to the raw piece and must not mature too
rapidly in the single ®ring.
Fig. 3. Tensile crazing of the red mud glaze.
3.3. The results of experiments for the ®tting of the
glaze to the body
ratio silica: ¯ux between 2:1 and 3:1
ratio alumina: silica between 1:4.2 and 1:5.5 All of the glaze types did not show the tensile crazing
apart from V7, V9, V10, A1, A17 and A18 glazes. This
The colours of these glazes were observed as cream± showed that the expansion coecients of the glazes and
yellow, mustard, green, brown and black. A11±A15 gla- bodies ®tted to each other.
zes were semi-matt and the range of colour from white All of the glazed samples (except for A1) resisted the
to brown. These glazes were prepared with addition of thermal shock test (Harkort test) which made at 100,
calcined red mud with the amounts increased gradually 120, 150, 160, 180 and 200 C. None of them showed the
to a chosen glaze composition. The calcined red mud tensile crazing. In this state, the prepared glazes will
weight percents of these glazes were 0.00, 6.07, 11.73, resist a long period of time against crazing.
21.30, 29.65. The amounts of the ferric oxide were The resistance to 3% HCI solution of the glazed
0.00, 0.05, 0.10, 0.20, 0.30 equivalents at these glazes. samples are positive except V3, A9, A14 and A15. These
All of them were successful. The fritted glazes known glazes have a surface with knobs. Other glazes protected
as A16±A18 were unsuccessful except for A16. A17 has their colours and glosses. All glazes are resistant to a
the peeling and A18 did not mature. The amounts of the test made with 3% NaOH solution. No change was
ferric oxide were 0.15, 0.25, 0.10 equivalents at the frit- observed in their colours and glosses. The results of
ted glazes, respectively. resistance to abrasion test measured using the system
developed by Scott are illustrated in Table 8.
3.2.4. Electroporcelain glazes From Table 8, it was seen that P8, P14, P15, P17 and
Raw electroporcelain glazes were prepared with addi- P18, namely porcelain glazes, showed larger abrasion
tion calcined red mud and named as E1±E10. These gla- values. These glazes have more red mud content from
zes were successful except E4, E5, E9 and E10. These others. When the Fe2O3 content of the glazes was too
glazes have di€erent equivalent values of the oxides at high (larger than 0.30 equivalent) the appearance began
the Seger formulas. The equivalent values of the oxides to spoil.
were at these intervals: Na2O (0.05±0.13), K2O (0.11±0.32), V9 and V18, namely vitreous glazes, showed larger
MgO (0.00±0.35), CaO (0.20±0.70), ZnO (0.00±0.35), abrasion values. These glazes have too high PbO values.
Al2O3 (0.39±0.71), Fe2O3 (0.06±0.45), B2O3 (0.00±0.10), PbO values are 0.90 equivalent at V9 and 0.30 equiva-
Cr2O3 (0.00±0.15), SiO2 (2.00±6.28), TiO2 (0.01±0.08), lent at V18. It has been said that the abrasion resistance
ZrO2 (0.00±0.10), MnO2 (0.00±0.40). Unsuccessful glazes of the glaze is decreased importantly as the content of
were matt and had a burnt-like appearance. All of the lead rises. Also, high B2O3 and alkali values decrease
glazes were observed as brown and black colours. E11±E15 the abrasion resistance of the glaze. Al2O3, SiO2 and
492 N. YalcËõn, V. SevincË / Ceramics International 26 (2000) 485±493

Table 8
The results of resistance to abrasion test of the glazes

Porcelain glazes Abrasion (mg) Vitreous glazes Abrasion (mg) Tile glazes Abrasion (mg) Electro porcelain glazes Abrasion (mg)

P1 0.40 V1 6.20 A1 10.62 E1 2.48

P2 1.84 V2 1.22 A2 13.48 E2 1.34
P3 6.96 V3 9.92 A3 1.22 E3 4.66
P4 2.14 V4 4.80 A4 6.82 E4 17.9
P5 2.82 V5 0.86 A5 0.36 E5 4.96
P6 5.96 V6 5.32 A6 4.44 E6 25.48
P7 3.12 V7 5.34 A7 8.14 E7 3.98
P8 23.44 V8 2.76 A8 0.32 E8 6.60
P9 4.08 V9 65.41 A9 3.98 E9 29.52
P10 1.96 V10 9.94 A10 9.18 E10 57.62
P11 2.78 V11 0.52 A11 5.32 E11 2.24
P12 1.86 V12 0.50 A12 6.26 E12 1.34
P13 2.64 V13 0.58 A13 5.18 E13 1.68
P14 12.70 V14 0.32 A14 3.96 E14 4.14
P15 10.22 V15 0.38 A15 2.56 E15 5.40
P16 3.04 V16 6.04 A16 4.48 E16 ±
P17 23.74 V17 3.98 A17 ± E17 ±
P18 25.02 V18 24.82 A18 ± E18 2.82

ZrO2 increase the abrasion resistance of the glaze [8]. A1 The calcined red mud wt% used at the successful
and A2 tile glazes have a little higher abrasion values vitreous glazes ranged between 6 and 29. At the fritted
than others. A1 has the tensile crazing anyway and A2 glazes these values were at the interval 9±24 wt%. The
has high PbO value. E4, E6, E9 and E10 electroporcelain limit equivalent values at the Seger formulas of the oxi-
glazes showed larger abrasion values. Fe2O3 values of des which founded at the successful vitreous glazes are
these glazes are 0.20, 0.35, 0.40 and 0.45 equivalent, as follows:
respectively.
These values found for unsuccessful glazes are smaller Na2O 0.01±0.10
than the values quoted in Turkish Standards TS 3451 K 2O 0.08±0.15 Fe2O3 0.00±0.30
for the abrasion of tile glazes [18]. According to these MgO 0.00±0.09 B2 O 3 0.00±0.35
standards, the average abrasion value is 80 mg. In the CaO 0.44±0.55 SiO2 2.60±4.00
examinations, for all of the glaze types the average ZnO 0.15±0.27 TiO2 0.00±0.05
abrasion value was accepted as 10 mg. Some changes Al2O3 0.22±0.35 ZrO2 0.00±0.18
occurred in the glazes which showed values more than
10 mg, for example, becoming dull with impaired gloss The calcined red mud wt% used at the successful tile
on the abraded surfaces. From the total of 72 glazes, glazes ranged between 5 and 30. It was found that the
only 13 pieces exceeded 10 mg value. This shows that addition of up to 23 wt% of the red mud waste was possi-
the prepared glazes are resistant to abrasion. According ble in the production of the fritted tile glazes. The limit
to the results of experiments for the ®tting of the glaze equivalent values at the Seger formulas of the oxides which
to the body, the number of the unsuccessful glazes is founded at the successful tile glazes are the following:
only 29.
The calcined red mud wt%, which were used at the Na2O 0.04±0.29 Fe2O3 0.00±0.30
successful porcelain glazes, ranged between 7 and 23. On K 2O 0.04±0.18 B2O3 0.08±0.80
the fritted glaze, the founded red mud increased more than MgO 0.00±0.19 SiO2 2.56±3.60
17 wt% the abrasion values. The limit equivalent values at CaO 0.20±0.70 TiO2 0.00±0.05
the Seger formulas of the oxides which founded at the ZnO 0.00±0.20
successful porcelain glazes are as follows: PbO 0.00±0.45
Al2O3 0.26±0.38
Na2O 0.01±0.20
K 2O 0.14±0.24 Fe2O3 0.00±0.30 The calcined red mud wt% used at the successful
MgO 0.05±0.10 B2O3 0.00±0.35 electroporcelain glazes ranged between 5 and 37. The
CaO 0.45±0.63 SiO2 2.37±4.60 fritted electroporcelain glazes were unsuccessful. These
ZnO 0.00±0.25 TiO2 0.00±0.04 glazes were containing to the red mud at interval 17±32
Al2O3 0.30±0.45 ZrO2 0.00±0.20 wt%. The limit equivalent values at the Seger formulas
 N. YalcËõn, V. SevincË / Ceramics International 26 (2000) 485±493 493

Table 9
The limit values of the physical properties for the successful glazes

Properties Types of glazes

Porcelain Vitreous Tile Electroporcelain

Coecient of thermal expansion 10ÿ5 (mm3  Cÿ1) 2.20±2.52 2.13±2.35 1.99±2.60 1.93±3.06
Coecient of surface tension (dyn cmÿ1) 352±378 348±384 287±373 369±385
Thermal conductivity (kcal mÿ2  Cÿ1 sÿ1 1.84±2.01 1.85±2.06 1.61±2.12 1.54±1.96
Density (g cmÿ3) 2.33±2.73 2.34±2.78 2.41±4.73 2.14±2.35
Tensile strength (kg mmÿ2) 2.75±8.63 7.89±9.06 6.42±9.18 6.50±7.86
Compressive strength (kg mmÿ2) 87±96 86±98 80±102 69±103
Hardness factor 265±340 253±301 255±313 260±350
Acid/base ratio 0.86±1.29 1.05±1.39 0.92±1.36 0.62±1.67
Coecient of melting 30.96±50.26 32.07±48.04 39.46±57.26 19.32±50.28
Al2O3/SiO2 ratio 0.09±0.13 0.08±0.15 0.09±0.10 0.11±0.19
Oxygen ratio 2.65±4.18 3.20±4.13 3.01±4.67 2.65±4.13
Molecular weight (g mol) 286±428 273±400 331±411 315±563

References
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K 2O 0.12±0.26 B2O3 0.00±0.10 [2] Etibank, SeydisË ehir, Aluminium Plants Introducing Catalogue,
MgO 0.03±0.35 Cr2O3 0.05±0.15 SeydisË ehir, Turkey, 1984.
[3] R.S. Thakur, B.R. Sant, Utilization of red mud, Journal of Sci-
CaO 0.30±0.48 SiO2 2.00±6.28
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1983 (in Turkish).
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