International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014]

Effect of Addition of Nano Zirconia in Ceramic

Glazes
G.Venkatesh

D.Thenmuhil

Dept. of Metallurgical Engineering,

PSG College of Technology
Coimbatore, India
venkih07@gmail.com

Dept. of Ceramic Technology,

Anna University
Chennai, India
thenmuhil@annauniv.edu

S.Manisha Vidyavathy

R.Vinothan

Orient Bell Limited

Bangalore, India
vinothan.r@orientbell.com

Dept. of Ceramic Technology,

Anna University
Chennai, India
manisha@annauniv.edu
Abstract In this present study zirconia particles of nano metric
dimensions were synthesized using sol-gel method via the starting
precursors
of
zirconium
oxy-chloride
octa-hydrate
(ZrOCl2.8H2O) and oxalic acid {(COOH) 2.2H2O}. A transparent
sol obtained was dried at 110 C for 12 hours and the dried gel
was subjected to calcination at 1000C respectively for 3 hours in
order to obtain nano-zirconia particles. XRD characterization
reveals the presence of single phase tetragonal ZrO2 and SEM
morphological characterization reveals the presence of nano size
ZrO2 particles .The particle size distribution also confirms the
nano metric size range of ZrO2 particles. The obtained nano
particles was incorporated in the glaze composition which
generally is defined as a thin glassy layer on a ceramic body that
results by applying a special admixture on ceramic body and by
fusing at high temperature. This glaze formulation is well
bounded for dry tile manufacturing process .The incorporation
of the prepared nano zirconia in a typical glaze composition are
well established for its excellent mechanical, thermal and good
resistance to chemical attack. Addition of zirconia increases the
opacity of the tiles and also enhances the brightness .In this study
with the comparison of standard conventional zircon it is bound
to say that particle size decreases. Moreover glaze
characterizations i.e.TG-DTA, Spectrophotometer, Abrasion
resistance, crazing resistance tests was studied which shows the
improvement of surface characteristics which has been enhanced
by using the nano particles. The opacity is also increased with
lower dose of usage of zirconia nanoparticles.

properties of zirconia applied in glazes acts as an opacifier i.e

enhances the opacity depending on the dose of usage. Ceramic
particles in a colloidal state are charged to become dispersed
in a repulsive manner by forces developed on the surface of
particles [4,5] can be said as electrosteric stabilization[5].
Studies upon nano glazes development have a prominent
interest over the industry scale. The effects conveys to its
microstructural features, mechanical durability and its physiothermal properties.
Nano characteristics of the glaze are to produce a clean,
bright and attractive surface, antibiotic and activate the
substance present in the glaze. The constituents of the glaze
consists of various kinds of raw materials in which one or
more of them are converted to nano particles and are used in
the glaze composition[8,9]. Zirconia has a high covalence and
seven Co-ordination bonding characteristics which are rare in
other transition metals [6] . ZrO2 has three crystal forms which
are closely related to the cubic fluorite structures .the practice
of using nano zirconia with monoclinic phase with larger
surface area yields a better catalyst and reactant. Nanozirconia exhibits more excellent chemical and physical
properties as compared to normal or coarse zirconia powder,
which aims through this study. Due to the small particles
diameter result in a better sintering ability pertains to more
efficient coating over a tile substrate..

Keywords Nano zirconia, glaze, surface characteristics.

II. EXPERIMENTAL PROCEDURE

I. INTRODUCTION
The prime focus upon the ceramic glaze research is
drastically increasing in recent days over the white wares and
sanitary wares. In general typical constituents consists mixture
of several vitrified oxides and inorganic additives, termed as
glaze [1]. Glazes with high gloss, reflect light strongly [2].An
improvement of the mechanical properties of the ceramic
glaze is observed [3] by addition of monoclinic nano zirconia.
Since zirconia exists as polymorphs certainly tetragonal
zirconia seems to be unstable for the firing temperature.
Nanometric particle suspension was developed in the typical
glaze system for innovative surface characteristics in floor and
wall tile industry. So imparting of nano particle technology
adheres a greater attention to ceramic products via yielding
outstanding properties [4]. The major property of zirconia is
basically a refractory material with a higher thermal stability
confines to its commercial usage. One of the most extensive

A. Nano Zirconia Synthesis and Characterization

At first the sol gel method has been adopted for the
synthesizing zirconia with the starting materials zirconium
oxy-chloride octahydrate (ZrOCl2.8H2O) and oxalic acid
((COOH)2.2H2O) and 1 M solution were prepared using
distilled water. With the aid of constant stirring upto a ratio of
1:0.7 forms a transparent sol. The formation of zirconium
oxalate can be expressed as
2ZrOCl2.8H2O+(COOH)2H2O
10H2O (Eq. 1)

ZrO(COO)2 + 2HCl +

Zirconium oxalate sol obtained was kept at room

temperature for a very short time to achieve gelation. The gel
was dried at 110 C for 12 hours and thus zirconia powders
were obtained. The as prepared samples obtained from drying

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of gel is been calcined. The calcination was done at 1000 C

for 3 hours at the heating rate of 10C/s. The crystallinity of
nano ZrO2 was observed at the temperatures higher than
800C. Finally the fine powders obtained after calcination
yields a nano metric range of ZrO2.
The X-ray diffraction studies ( BRUKER D-2,Ni filter,
CuK radiation) were done in order to determine the phase
purity , crystal structure of Powder samples ,Crystallite size
using Scherer method and last In order to assess the stability
behavior of crystalline behavior of zirconia .The as
synthesized powder samples were characterized using
TG/DTA for its thermal behavior .Further information was
revealed by scanning electron microscope (SEM) for its
powder morphology and its particle size determination .for the
ultimate particle size determination was done by laser particle
size analyser (Malvern).
B. Glaze Formulation and Characterization
The typical raw materials used in industrial grade for glaze
formulation is shown in Table 1 with their weighing ratios.
TABLE I
THE COMPOSITION OF GLAZE AND ENGOBE

Composition
Carboxy Methyl Cellulose
Talc Powder
Sodium Tri Poly phosphate
Quartz Powder
Clay
Alumina
Calcite Powder
Feldspar
Wollastonite
Frit (Opaque + Transparent)
White Aluminium Oxide
Zirconium Silicate
Drain Glass Scrap

Percentage [%]
Engobe
Glaze
<0.2
<0.2
<3.5
<0.2
<5.2
<5.2
<2.3
<14
<20
<4.3
<23
<2.2
12.4-13.4
<5.8

This engobe is applied over to the dried tile surface and

again pre dried before applying a glaze. The benefits of
applying engobe is it acts as an interface between body and
glaze followed by fast firing technology using roller kiln at 40
min cycle. The similar procedure was trailed for the second
optimisation with the following ratio 0.5, 1, 1.5, 2, 5 and 10 %
with reference to standard composition devises different cycle
rate and firing temperature.
The glaze characterisations traverse with the examination
of visual appearance which reveals the surface texture, gloss
and smoothness. With rid of visual quality the colour tree i.e
spectrophotometer
(MinoltaCM-2002spectrophotometer)
divulges any single colour position of a dot or point on this
form, which is recorded in the order of hue, value or Chroma
(H.V.C.), and L*, a*, b* values [3]. Since every property of
ceramic tile has a resistance to abrasion, the abrasion
resistance of various ratios were examined. The crazing of all
the tiles is tested using auto clave with 5.2 Kg/cm2 for two
hours per cycle to ensure the life of the tiles in application.
Chemical resistance of the tile surface were inspected using
hydrochloric acid and potassium permanganate as alkalis to
confines the results. Solar reflective index of the coated tile
was tested which shows the reflectance of sunlight over the
tile glazed with nano materials.
III. RESULTS AND DISCUSSION
A. Powder Characterization

<0.4
<6.4
<54.0
<3.2
<18.0

<19.0

<11.0

Above composition is weighed and batched accordingly

and set as a standard conventional zircon composition for a
industry grade. In this above formulation Instead of using
zircon the prepared nano zirconia is imparted at various ratios
to study its technological benefits over the usage of
conventional zirconium silicate .To proceed with the first
standardization of the nano zirconia composition first
optimization procedure was taken by adding 13.4, 6.7, 5.0,
3.4, 1.7 and 0.134 % ratios of nano ZrO2 accordingly . The
procedure for preparing glaze is done using weighing of raw
materials and mixing it .Allowing water percentage from 4550% for each composition was held in porcelain jar and
likewise grinding media was added milled together for 30
minutes .the completion of milling obtains the glaze slip that
was eventually undersized using 240 mesh. The prepared
glaze slip was stripped over the engobed tile surface for
obtaining a uniform glaze coating .the tile using here is a
industry grade tile manufactured from Orient Bell Ceramics
Pvt. Ltd. However the current focus is on the glaze
formulation not on the tile substrate. The engobe (refer Table
1) is applied on a tile before applying a glaze. Another set of
emblematic industrial engobe composition is shown below.

1) XRD Analysis : It is well known that calcination

temperature has a strong influence on the morphology of the
powders and the occurrence of pure single crystalline phase
(Hernawan, RifkiSeptawendar et al 2011 and 2012). Fig. 1
shows the X-ray powder diffraction patterns for the calcined
powders in addition to that crystallite size were determined
using Scherer formula. The wavelength of X-ray source used
is ( = 1.54 A ). It was observed that increasing temperatures
to 1000 C the crystallinity nature also increases i.e more
crystalline peaks were observed. In 1000 C only monoclinic
structure are matched with standard reference pattern .Both the
pattern matches with zirconia (ZrO2) .thus the diffraction
studies also elucidates the crystallite size behaviour due to the
line broadening effect seen. The crystallite size is found to be
as 50 60 nm by using Debye Scherer method.

Fig. 1 XRD pattern of Zirconia synthesised at 1000C

2)Microstructural Observation : Fig. 2 shows the SEM

image of zirconia powder samples calcined at 1000C. It can
be inferred that the particle size range is in order of 50nm
200nm .It is evident from the SEM image the particle size

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greatly influence the morphological characteristics and steric

behavior in the glaze slip.

Fig. 4 Shows the TG-DTA curve for nano zirconia powders

Fig. 2 SEM image of Zirconia at 1000C

3)Particle Size Analyser: The particle size distribution is in the

range of 100-150 nm for nano zirconia (refer with Fig. 3 a)
whereas the standard conventional zircon (refer with Fig. 3 b)
is of 685 nm.

630 C range. Suddenly, in a narrow range of temperatures,

which corresponds to the endothermic peak at 630C, all
tetragonal phase starts to transform to monoclinic. Above this
temperature, there are no more weight losses i.e constant.
B. Glaze Characterization
1) Spectrophotometer: It is otherwise known as the
Colour Tree. It is cylindrical or sometimes spherical in shape,
which is a representative form of any single colour (refer
Fig.5).

Fig. 5 Shows the general colour

representation
in
spectrophotometer

Fig. 3 a Particle size distribution for nano zirconia

TABLE II
SPECTROPHOTOMETER RESULT FOR STANDARD ZIRCON

Fig. 3 b Particle size distribution for

Conventional zircon

4)TG-DTA Analysis: A TGA and DTA of the synthesized

nano zirconia powders where recorded as a graph with
temperature and weight (refer Fig. 4). It was observed from
the TGA curve (refer Fig. 4) the weight loss occurring over a
range of temperatures with followed by reaction occurring in
various temperatures. At first a substantial weight loss
happens in the temperature range from 294 C to 372 C
associated with evaporation of organics and volatile
substances as observed on the TGA curve.
The large weight loss in the 290.08373.88 C range has
been attributed to the vaporization of the by-products of the
reactions, evolution of carbon as a gas and condensation
polymerization. The exothermic peaks on the DTA curve
(refer Fig. 4) at same temperatures and 490 C confirm this
fact. On the other hand, the exothermic peak which occurs at
490 C on the DTA curve is attributed to the decomposition of
the amorphous phase into a tetragonal one. The weight losses
observed in this range are due to evolution of remained carbon
and tetragonal and amorphous phases both coexist in the 490

STD zircon

L*

a*

b*

13.4

92.3

-1.8

3.5

TABLE III
SPECTROPHOTOMETER RESULT FOR FIRST SET OF
OPTIMIZATION FOR NANO ZIRCONIA

Nano zirconia
13.4
6.7
5.0
3.4
1.7
0.134

L*
94.6
91.9
89.6
88.6
86.4
85.7

a*
-2.1
-2.0
-1.7
-2.0
-1.8
-1.7

b*
2.1
2.0
3.2
4.4
6.3
6.0

From the above results addition of nano zirconia in varying

percent shows that less than of 6.7% gives the almost close
results with the standard composition. It is observed by the
texture and color appearance. Hence the first optimization
confines that less than 6.7% of nano ZrO2 matches the
standard value.

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International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014]

TABLE IV
SPECTROPHOTOMETER RESULT FOR SECOND SET OF
OPTIMIZATION FOR NANO ZIRCONIA

Nano zirconia
L*
a*
b*
0.5
82.3
5.0
4.9
1
83.5
5.0
4.8
1.5
84.9
5.2
4.7
2
86.8
4.9
4.0
5
88.3
3.6
2.9
10
90.5
2.9
1.8
STD
86.9
5.2
3.6
The second set of optimization quantifies that 2 % of Nano
zirconia matches the standard value . Hence from the above
results it can be said that 2% of nano zirconia replaces the
standard conventional zircon property.
2) Abrasion Resistance: For nano zirconia over 1500
Revolutions it is inferred that very less surface erosion and
thereby increases surface hardness compared with the standard
composition .comparatively for standard composition from fig
infers that Surface hardness is less also surface is eroded
slightly .It is also can be said as that increasing the percentage
0.5-13.6% of nano zirconia directly increases the abrasion
resistance of material (refer Table 5 & Table 6).

thermal emittance (E) .It is observed that for the tile coated
with conventional standard zircon has SRI of 96 and
comparatively the usage of nano zirconia about 2% shows the
SRI as 103 . This drastic increase in SRI elucidates that the
withstand of surface roof temperature can go more than 55-60
C .Hence overall it can be said as the usage of nano zirconia
enhances the reflectance more than a commercial conventional
glaze and it creates a unique behaviour in tile industry.
IV. CONCLUSIONS
Thus from the above results it can be concluded that the
behavior of nano zirconia addition to a typical glaze shows a
promising results over industrial scale .the uniqueness of
using 2% nano zirconia reduces the raw material consumption
by nearly 75% and also enhances some extensive properties
such as opacity i.e surface appears to be much glossy with
much brightness. Lower dosage of nano zirconia enhances the
surface roughness and higher the usage pertains the surface to
be harder. The abrasion resistance of 2 % ZrO2 matches the
standard industry optimization. Finally obtaining a solar
reflectance of 103 for 2% ZrO2 it is obviously can be used for
cool roofing purpose at a greater extent.
REFERENCES

TABLE V
ABRASION RESISTANCE RESULTS FOR NANO ZIRCONIA

Nano zirconia
0.5-1%

[1]

BijanEftekhariYekta, ParvinAlizadeh, Leila Rezazadeh, Floor tile

glass-ceramic glaze for improvement of glaze surface properties, J.
European Ceram. Soc. 26 (2006) 38093812.

[2]

M. Llusara, G. Monrosa, C.M. Rodriguesb, J.A. Labrinchac,

Study of zircon or zirconia crystals addition in ceramic glazes by
impedance spectroscopy, Ceramics International 31 (2005) 181
188.

[3]

J.K. Nsiah, Ceramics Effect Of Different Glaze-Base Systems On

Generation Of Colour, Quarterly Science Vision, Vol.9 No.1-2 (Jul
- Dec, 2003) & 3-4 (Jan - Jun, 2004)

[4]

B. EftekhariYekta, P. Alizadeh, L. Rezazadeh, Synthesis of glassceramic glazes in the ZnOAl2 O3 SiO2ZrO2 system, J. European
Ceram. Soc. 27 (2007) 23112315.

[5]

K. Pekkana, B. Karasu, Zircon-free frits suitable for single fastfiring opaque wall tile glazes and their industrial productions, J.
European Ceram. Soc. 29 (2009) 15711578.

[6]

Michael W. Pitcher.W Sergey V. Ushakov, and Alexandra

Navrotsky,Energy Crossovers in Nanocrystalline Zirconia, J. Am.
Ceram. Soc. 88 [1] 160167 (2005).

[7]

Linda Froberg, LeenaHupa, Topographic characterization of

glazed surfaces, J. Applied Surface Science 254 (2008) 1622
1629.

[8]

K.J. Hong, J.M. Kim, H.S. Kim, Microstructure and properties of

CaOZrO2SiO2 glassceramics prepared by sintering, J. European
Ceram. Soc. 23 (2003) 21932202.

[9]

M. Llusara, G. Monrosa, C.M. Rodriguesb, J.A. Labrinchac,

Study of zircon or zirconia crystals addition in ceramic glazes by
impedance spectroscopy, Ceramics International 31 (2005) 181
188.

[10]

Robert J. Castilone, Dattaguru Sriram, and William M. Carty,

Robert L. Snyder, Crystallization of Zircon in Stoneware Glazes,
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Grade
Class II

1.5-2%

Class III (1500 revolutions)

5-10%

Class IV

TABLE VI
THE STANDARD INDUSTRY ABRASION OPTIMISATION

S.No

Revolutions passed

Class

300

600

II

1500

III

12000

IV

25000

Fig. 6 Shows the Abraded Surface of Standard Zircon

3) Chemical Durability: With reference to standard

composition the effect of hydrochloric acid and potassium
permanganate (alkali) doesnt affect the surface characteristics
and its texture .hence the property does not change over the
attack of acids and alkalis .So chemical durability is likely
increasing when addition of nano zirconia .
4) Solar Reflective Index: Solar reflectance isn't the only
property to look for in a roofing material. It should also have a
high infrared emittance to help the roof shed heat by reradiation. It is computed by solar reflectance (R) and the

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[11] Hand book Sol Gel Processing and Technology, Volume I ,

Sumiosakka .