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J. Am. Ceram. Soc.

, 86 [1] 183 85 (2003)

journal
Role of -Fe2O3 Morphology on the Color of
Red Pigment for Porcelain
Hiroaki Katsuki*
Saga Ceramics Research Laboratory, 3037-7, Arita-machi, Saga 844-0024, Japan

Sridhar Komarneni*
Materials Research Institute and Department of Crop and Soil Sciences, 205 Materials Research Laboratory,
The Pennsylvania State University, University Park, Pennsylvania 16802
FeCl36H2O and 0.01M HCl solutions. The formation kinetics
of -Fe2O3 powders via the microwave-hydrothermal ractions
appeared to increase with increased reaction temperature due to
the rapid heating time compared with that of the conventionalhydrothermal reaction.11 Furthermore, it is suggested that the
localized superheating in the solution via the microwavehydrothermal reaction12 causes the formation of smaller
-Fe2O3 particles because the nucleus formation can be promoted.
In this communication, the effect of morphology and aggregation of some -Fe2O3 powders on the tone of red color for
porcelain pigment was investigated.

To produce a new red pigment for Japanese porcelains,


some hematite (-Fe2O3) powders produced by different
methods were investigated by mixing them with lead-free
frit powders and firing them on white porcelain plates at
800C. Commercial hematite powders and uniform -Fe2O3
powders 155 and 53 nm in diameter which were prepared
using conventional- and microwave-hydrothermal reactions, respectively, were used as sources of red pigments.
The morphology and dispersion of the above -Fe2O3
powders were found to have a significant effect on the tone
of red color for porcelain pigment.
I.

Introduction

II.

such as FeO, -Fe2O3, -Fe2O3, and Fe3O4 are


widely used as electronic materials, pigments, cosmetics,
coatings, abrasives, etc.1,2 -Fe2O3 powders for some pigments
are commercially produced by either forced hydrolysis or
calcination of FeSO4, FeCl3, and Fe(NO3)3.3 Many -Fe2O3
powders are available for use as red pigment for Japanese
porcelain enamel, but the morphology and color of commercial
-Fe2O3 powders are different because of different raw materials and production systems.3 Most of the commercial -Fe2O3
powders for red pigments are composed of elongated crystals,
80 230 nm long and 40 100 nm thick, and these crystals are
strongly aggregated. It takes a long time to disperse these
powders well in water under ultrasonic treatment. Dispersion of
these powders in lead-free frit powders is an important factor to
produce a beautiful red color pigment. The tone of the red color
is strongly influenced by the aggregation, morphology, and the
amount of -Fe2O3 powders in the frits. However, the effects of
the morphology and dispersion of -Fe2O3 powders on the
color of red pigment on Japanese porcelain have not been
investigated. The preparation of monodispersed -Fe2O3 powderswhich have cubic, spherical, ellipsoidal, and rodlike
morphologies has been studied extensively.4 10 In our previous study,11 highly monodispersed and uniform -Fe2O3 powders, 50 60 nm in diameter, were formed at 120160C for
2 h via the microwave-hydrothermal reactions of 0.018M

RON OXIDES

Experimental Procedure

Based on our previous study,11 monodispersed and uniform


-Fe2O3 powders 155 nm in diameter were prepared at 100C for
72 h via the conventional-hydrothermal reaction of 0.018M
FeCl36H2O and 0.01M HCl solutions. Furthermore, monodispersed and uniform -Fe2O3 powders 53 nm in diameter were
prepared at 140C for 2 h via the microwave-hydrothermal
reaction of 0.018M FeCl36H2O and 0.01M HCl solutions. A
commercial -Fe2O3 powder (Nishiki Ryu 1, Meihindo Co., Arita,
Japan) was used to compare with the result of synthesized -Fe2O3
powders. This commercial powder was produced by the calcination of FeSO47H2O in the temperature range of 700750C and
then finely pulverized. To characterize the stability and dispersion
of these powders in water, 0.3 g of each powder was mixed well
with 50 mL of deionized water using an ultrasonic cleaner (Model
B12, 40W, Yamato Co., Japan) for 5 to 60 min, and left to settle
for 8 h. The morphology of these powders was observed using
transmission electron microscopy (TEM; Model 2010, JEOL,
Tokyo, Japan). Some -Fe2O3 powders were mixed with a
commercial lead-free frit (F50, Excel Co., Arita, Japan) to prepare
red pigments. The chemical composition of the frit was as follows
(wt%): SiO2, 52.48; B2O3, 21.52; Al2O3, 5.92; CaO, 0.7; Na2O,
10.01; K2O, 2.07. The density and particle size were 2.6 g/cm3 and
1.8 m, respectively. The softening point of the frit was 589C and
it melted above 740C. The coefficient of thermal expansion was
6.9 106/C from 25 to 600C. Figure 1 shows a flow chart for
the preparation of red pigment. Five grams of -Fe2O3 powders
was mixed with 100 g of water and dispersed well using an
ultrasonic treatment. Times of ultrasonic treatment were 5 and 60
min for the commercial -Fe2O3 powder and 5 min for the
hydrothermally synthesized powders. The dispersed suspension
was added to the frit, and milled in a porcelain mortar for 4 h. After
drying, the mixture of -Fe2O3 powders (20 wt%) and frit (80
wt%) was mixed with a printing oil as an organic binder by using
a three-roll mill, to give paste stuffs with good homogeneity and

D. W. Johnson Jr.contributing editor

Manuscript No. 186954. Received May 23, 2002; approved October 14, 2002.
This work received financial support from the Kazuchika Ohkura Memorial
Foundation in 2001 and the Saga Ceramics Research Laboratory.
*Member, American Ceramic Society.

183

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Communications of the American Ceramic Society

Vol. 86, No. 1

Fig. 2. Stability of some -Fe2O3 powders in water after 8 h: (a)


commercial powders treated in an ultrasonic cleaner for 5 min, (b)
commercial powders treated in an ultrasonic cleaner for 60 min, (c)
nanosized powder 155 nm in diameter treated in an ultrasonic cleaner for
5 min, and (d) nanosized powder 53 nm in diameter treated in an ultrasonic
cleaner for 5 min.

Fig. 1. Preparation of red pigments containing -Fe2O3 powders and the


evaluation of color and color differences on porcelain.

viscosity suitable for screen printing. The paste stuffs of red


pigment were screen printed using a 100 mesh screen on a sheet of
mount paper with gum which was dextrin, soluble in water.
Pigment films (40 mm 40 mm) were separated from the
slide-off transfer sheets by soaking them in water. The films were
then transferred onto white Japanese porcelain plates that were
fired with translucent glaze under a reducing atmosphere at
1300C. The pigment films transferred onto a porcelain plate were
finally fired at 800C for 1 h in air. After firing, the tone of red
color was analyzed using a color and color difference meter (X
Rite 528, Nippon Lithograph, Inc., Osaka, Japan) based on the L*
(lightness), a* (hue), and b* (saturation) test.12

III.

Results and Discussion

Figure 2 shows the stability of different -Fe2O3 powders in


water after 8 h. Before the stability experiment, samples (a), (b),
(c), and (d) were dispersed using ultrasonic treatment for 5, 60,
5, and 5 min, respectively. Figure 3 shows the morphologies of
the different -Fe2O3 powders after ultrasonic treatment. Commercial powder tends to easily settle after ultrasonic treatment
for 5 min (Fig. 2(a)), but the sedimentation of this powder in
water was slightly depressed after longer ultrasonic treatment
time (Fig. 2(b)) because of better powder dispersion (Fig. 3(b)).
It can be seen from Figs. 3(a) and (b) that commercial -Fe2O3
powders are composed of elongated crystals, 100 150 nm long
and 50 70 nm thick. Commercial -Fe2O3 powders were
strongly aggregated and it was very difficult to disperse them
well in water under ultrasonic treatment for 5 min (Fig. 2(a)) or
60 min (Fig. 2(b)). However, -Fe2O3 powders prepared from
0.018M FeCl36H2O and 0.01M HCl solutions via conventional
and microwave hydrothermal reactions at 100 and 140C were
well dispersed in water and did not settle after ultrasonic
treatment for 5 min (Figs. 2(c) and 2(d)).

Figure 4 shows the color of red pigments prepared from some


-Fe2O3 powders on porcelain plates fired at 800C, and Table
I shows color and color differences. It is said that pigments
show a high tone of red and yellow color with increasing
parameters of L*, a*, and b*.13 Figure 4 suggests that the tone
of red of pigment is very sensitive to dispersion of hematite.
Commercial -Fe2O3 powders were very difficult to disperse
well using ultrasonic treatment in water for 5 min, so L* and b*
were 27.4 and 13.2, respectively, and the color became dark
red. But L*, a*, and b* increased, and the tone of red color of
the pigment was improved with longer ultrasonic treatment time
(60 min) because of the lower aggregation of powder in water
(Fig. 2(b)), as expected. Compared with the dispersion and
stability of commercial -Fe2O3 powders, -Fe2O3 powders
prepared from conventional- and microwave-hydrothermal reactions were well dispersed in water (Figs. 2(c) and (d)) and
showed higher L*, a*, and b*. There are many factors controlling the parameters L*, a*, and b* of pigment, for example,
the particle size, dispersion, and ionization of -Fe2O3 powders
in frits, and the refractive index and surface roughness of the
pigments on porcelains. Indeed it can be seen from Table I that
smaller nanosized -Fe2O3 powders 53 nm in diameter had
higher L*, a*, and b* than those of conventionalhydrothermally prepared powders 155 nm in diameter. From
these results, it is clear that new red pigments with high
lightness and tone could be prepared using microwavehydrothermally prepared nanophase -Fe2O3 powders. Further
studies of the effect of the particle size of powder on
the lightness, the tone of red, and yellow color are now in
progress.

IV.

Conclusions

Commercial powders were strongly aggregated and had a


poor dispersion in water, but monodispersed and uniform
-Fe2O3 powders 155 and 53 nm in diameter which were
prepared using conventional- and microwave-hydrothermal reactions, respectively, showed high dispersion in water. Commercial -Fe2O3 powders composed of aggregated crystals
80 230 nm in length and 40 100 nm in thickness had a lower
lightness and tone of red and yellow colors. Smaller nanosized
-Fe2O3 powders 53 nm in diameter showed higher tone of
reddish yellow than those of powders 155 nm in diameter.
Compared with commercial -Fe2O3 powders, nanosized
-Fe2O3 powders which were hydrothermally prepared are
expected to be useful as new red pigments for Japanese
porcelains.

January 2003

Communications of the American Ceramic Society

185

Fig. 3. Morphologies of some -Fe2O3 powders after ultrasonic treatment: (a) commercial powders treated in an ultrasonic cleaner for 5 min, (b)
commercial powders treated in an ultrasonic cleaner for 60 min, (c) nanosized powder 155 nm in diameter treated in an ultrasonic cleaner for 5 min, and
(d) nanosized powder 53 nm in diameter treated in an ultrasonic cleaner for 5 min.

Table I. Color and Color Difference of White Porcelain


Plates Fired with Red Pigment Films Containing Some
-Fe2O3 Powders

-Fe2O3 powders

Crystal size (nm)

Commercial

100150 (long)
5070 (thick)
100150 (long)
5070 (thick)
155
53

Commercial
C-H
M-H

Ultrasonic
treatment
time
(min)

Color and color


difference
L*

a*

b*

27.4

26.4

13.2

60

30.5

28.5

15.9

5
5

30.0
31.5

30.7
33.1

15.6
18.4

Prepared via conventional-hydrothermal reaction at 100C for 55 h. Prepared via


microwave-hydrothermal reaction at 140C for 2 h. L*: lightness. a*: hue. b*:
saturation.

Fig. 4. Color of red pigments prepared from some -Fe2O3 powders on


porcelain plates fired at 800C: (a) commercial powders treated in an
ultrasonic cleaner for 5 min, (b) commercial powders treated in an
ultrasonic cleaner for 60 min, (c) nanosized powder 155 nm in diameter
treated in an ultrasonic cleaner for 5 min, and (d) nanosized powder 53 nm
in diameter treated in an ultrasonic cleaner for 5 min.

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