SYNTHESIS AND CHARACTERIZATION OF ZIRCON

CERAMIC PIGMENTS WITH RARE-EARTH

ELEMENTS
Tsvetan Dimitrov, Dragostin Marinov
Ruse University Angel Kanchev - Razgrad Branch, Aprilsko Vastanie str. 47,
7200 Razgrad, Bulgaria, e-mail: tz_dimitrow@abv.bg

Abstract
Experiments have been carried out on the solid state synthesis of zircon ceramic pigments with different chromophore rareearth elements Pr, Nd and Er. Zircon ceramic pigments are used mainly because of their high-temperature stability combined
with pleasant color. The main raw materials for synthesis of pigments are SiO 2.nH2O and ZrO2. The raw material SiO2.nH2O used
for introducing SiO2 into the mix for obtaining pigment is much more reactive than the ordinary quartz sand. Pr6O11, Nd2O3 and
Er2O3 were used as the raw material for introducing the chromophore elements.

INTRODUCTION
The use of rare earth elements as chromophores dates back to 19 th century when
Le Chatelier first observed permanent of the color of the pigments obtained
determined by the f-f transitions of electrons.
The wide use of zircon ceramic pigments is based mainly on their high temperature
stability and resistance to the effect of silicate melts, combined with pleasant colors.
1,2
.
Since Seabright3 first obtained them in 1947, researcher have done incessant and
intense studies on zircon pigments, as the strong crystal lattice of zircon - ZrSiO 4 is
extremely favorable for designing pigments of new colors.
Except for the well known zircon pigments xontaining vanadium, iron,
praseodymium1,4,5, attempts have been made to obtain pigments including other
elements like chromium, manganese, copper, etc 6,7.
Many researchers 8-11 have focused their efforts on elucidating the mechanism of
zircon pigment formation, the role of the mineralizers, as well as the possibility to
use various raw materials for their preparation.

Table1. Compositions of the pigments synthesized, mass %

PIGMENT

ZrO2

SiO2.nH2O

NaF

Pr6O11

Nd2O3

Er2O3

Pigment 1 - 5% Pr4+

54,7

35,3

5,0

5,0

Pigment 2 - 5% Nd3+

54,7

35,3

5,0

5,0

Pigment 3 5% Er3+

54,7

35,3

5,0

5,0

EXPERIMENTAL
Materials and synthesis of pigments
The basic materials used to synthesize pigments by the metjhod of solid phase
sintering were SiO2.nH2O and ZrO2. The material used to introduce SiO2 SiO2.nH2O is quite more reactive than common quartz sand and its particle size
was in the range 2-7m.
The cromophore oxides used to impart color to the pigments Pr 6O11, Nd2O3, Er2O3
were pure. The optimal amount of chromophore element is different for the
different pigments. Since the contents of chromophore element above 5% did not
produce more intense colors (in some cases had even adverse effect), the
pigments in the present work were synthesized with 5 mass% content of
chromophore elements.
The amount of mineralizer introduced NaF was 5 mass%. The compositions of the
pigments synthesized are presented in Table 1.
RESULTS AND DISCUSSION
X-ray phase analysis
The diffractograms of the ceramic pigments synthesized are presented in Fig.2. For
the pigments containing 5% Pr4+, the main phase ZrSiO4 appeared at temperatures
as lo as 800 but the prevailing phase was still ZrO2(monoclinic). The full
synthesis of ZrSiO4 was observed at 900 whre the presence of ZrO2(monoclinic)
was negligible.
During the synthesis of the yellow praseodymium pigment, Pr 6O11 reacted with the
mineralizer and the main ingredients which made it easier to obtain the end product
colored zircon. The reaction of ZrSiO4 synthesis was preceded by the formation
of compounds with characteristics of intermediate products which have been
thoroughly studied by a number of researchers: PrOF, Na2Pr8(SiO4)6F2, Na2ZrO3
Na2Si2O5.[?]
Initially, a reaction takes place between SiO2 and the mineralizer to produce volatile
SiF4 which reacts with ZrO2 abnd Pr6O11 in the reaction zone. The optimal
temperature for synthesis of zircon-praseodymium pigments with mineralizer was
found to be 900
Similar phases were observed for the pigments containing 5%Nd3+ and 5%Er3+.
As can be seen from the X-ray patterns of the pigments synthesized with
minerilzers in the initial; blend, there is an excess of ZrO 2. The lack of SiO2 can be
caused either by the reaction of SiO2 with NaF which gives the volatile halogenide
-SiF4 or by the formation of Na-silicates which are in glass state but they are in very
small amounts and cant be found in the end product.
The unit cell parameters of the pure ZrSiO4 and the pigmens contanining 5%Pr4+,
5%Nd3+ or 5%Er3+ with mineralizer NaF were determined by the X-ray analysis and
the results are presented in Table 2.
It can be seen from these results that the introduction of additives 5%Pr4+, 5%Nd3+
or 5%Er3+ did not change the basic syngony of zircon tetragonal. The increase of
ion radii in the order Pr4+, Er3+, Nd3+ obviously affected the increase of the parameter
a by the same order. A tendency of increase of the co-ordinates a and c by order of
4+
3+
Pr
,
Er
,Nd
CONCLUSIONS
1. Zircon pigments of new colors were obtained by adding rare earth elements (Pr, Nd, Er).
2. The possibility to prepare yellow praseodymium-zircon pigment was confirmed.
3. The main phase of ZrSiO4 is formead at temperatures as low as 800 but it is fully
synthesized at 1000.
4. Pigments of the following colors were obtained: Pr (yellow), Er (pink), Nd (grey).
5. The pigments synthesized had particle dispersity from 1 to 3 m.
6. The pigments synthesized can successfully be used in faience glazes.

Fig. 2. Diffractograms of the ceramic p[igments synthesized

- ZrSiO4; - ZrO2 (monoclinic); - -SiO2

Fig.3 Color space in the system CIELab

Table 2. Results for the color co-ordinate
measurements of the pigments.

Temperature,

Chromoph
ore
5%Pr4+
800
5%Pr4+
900
5%Pr4+
1000
5%Er3+
900
5%Er3+
1000
5%Nd3+
900
5%Nd3+
1000

L*
94,86
85,15
84,95
94,76
94,94
91,68
88,4

a*
-5,31
-2,59
-2,84
4,71
1,51
1,51
-0,56

b*
16,97
81,43
82,96
0,1
-2,5
-2,5
-2,74

Fig.4 SEM micrograph of

pigment containing Nd3+

Fig. 5. SEM micrograph of

pigment containing Er3+.

Electron microscopy
The morphology of the powder pigments was observed by
scanning electron microscope.
Figure 4 and Figure 5 show SEM micrograph of pigments
sintered at 1000C containing Nd3+ and Er3+. The
pigments are monodispersed materials with unambiguous
crystal habitus and crystal size of about 3-5 m. The
neodymium and erbium ions are uniformly distributed in
the sample.

Pigment color measurements

Color is one of the most important properties of the pigments. Colored substances absorb and transform light of
certain wave length in the visible part of the spectrum. The color of the most natural and synthesized mineral
substabces is related to the presence of transition elements with with non-filled d- and f- electron orbitals which
stipulates the electron transitions.
The color co-ordinates were determined in the system CIELab where L* - brightness, L* = 0 black color, L* = 100
white color.
a* - green color (-) / red color (+);
b* - blue color (-) / yellow color (+)
Fig.3 shows the color space in the system CIELab.
Pigment colors were determined spectrally by tintometer RT 100 Color (product of Lovibont). Table 2 shows the
results obtained from tese measurements
The pigments containing Pr4+ haD yellow color and the values of L* decresed with he increase of temperature,
+b*(yellow color) sharply increased to reach 82.96 at 1000. In the temperature interval 1000 - 1100, the hue of the
yellow color was preserved.
The pigments containing Er3+ have pale-rose color with no significant differences in color and parameters (L*, a*, b*)
with the increase of sintering temperature;
The pigments with Nd3+ have light violet color. It did not change with the increase of temperature.