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General Review of Application of Phosphorescence Pigments in Ceramic

Industry

Conference Paper · January 2009

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
GENERAL REVIEW OF APPLICATION OF
PHOSPHORESCENCE PIGMENTS IN CERAMIC INDUSTRY

Selvin Y. KAYA1, Bekir KARASU2, Erkul KARACAOĞLU3

1
Anadolu University, Glass Department, Eskişehir, Türkiye
2
Anadolu University, Materials Science and Engineering Department, Eskişehir,
Türkiye
3
Anadolu University, Graduate School of Sciences, Department of Ceramic
Engineering, Eskişehir, Türkiye

ABSTRACT

In the world ceramic industry develops new materials which emit light as a phoshor,
possess high phosphorescence brightness, and become resistant to heat, atmospheric
effects and chemicals.
In recent years, as a new generation of long afterglow phosphors, rare-earth-doped
alkaline earth silicates and aluminates have been researched extensively due to a
growing market for their application in ceramic glazes, resins, and coating of brick
and roof tiles. In this study, detailed information about phosphorous materials that
used in ceramic industry and their applications are given.
The use of phosphorescence glazes on brick and roofing tile supplies high quality
and also attracts costumer’s attention. It is thought that such application will result in
a breakthrough for national relevant industries. It was determined that newly
developed, low temperature, fluorescence ability bearing glazes can be easily
employed by brick and roof tile producers for various purposes.
Produced pigments were also mixed with epoxy resin and applied on a wooden
hardboard. In conclusion either decorative or functional new epoxy coating products
were produced.

Keywords: Phosphor, Phosphorescence, Pigment, Glow glaze.

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1. INTRODUCTION

1.1. Past and Present Phosphor Research

The scientific research on phosphors has a long history going back more than 100
years. A prototype of the ZnS-type phosphors, an important class of phosphors for
television tubes, was first prepared by Théodore Sidot, a young French chemist, in
1866 rather accidentally. It seems that this marked the beginning of scientific
research and synthesis of phosphors [1].
From the late 19th century to the early 20th century, Lenard et al. in Germany
performed active and extensive research on phosphors, and achieved impressive
results. They prepared various kinds of phosphors based on alkaline earth
chalcogenides (sulfides and selenides) and zinc sulfide, and investigated the
luminescence properties [1].
They established the principle that phosphors of these compounds are synthesized by
introducing metallic impurities into the materials by firing. The metallic impurities,
called luminescence activators, form luminescence centers in the host. Lenard and
coworkers tested not only heavy metal ions but various rare-earth ions as potential
activators. Alkaline chalcogenide phosphors developed by this research group are
called Lenard Phosphors, and their achievements are summarized in their book [1].
Pohl et al. in Germany investigated Tl+ activated alkali halide phosphors in detail in
the late 1920s and 1930s. They grew single-crystal phosphors and performed
extensive spectroscopic studies. They introduced the configurational coordinate
model of luminescence centers in cooperation with F. Seitz in the U.S. and
established the basis of present day luminescence physics [1].
Leverenz et al. at Radio Corporation of America also investigated many practical
phosphors with the purpose of obtaining materials with desirable characteristics to be
used in television tubes. Detailed studies were performed on ZnS-type phosphors.
Their achievements are compiled in Leverenz’s book [1].
Since the end of World War II, research on phosphors and solid-state luminescence
has evolved dramatically. This has been supported by progress in solid-state physics,
especially semiconductor and lattice defect physics; advances in the understanding of
the optical spectroscopy of solids, especially that of transition metals ions and rare-
earth ions, have also helped in these developments [1].
Research on phosphors and their applications requires the use of a number of fields
in science and technology. Synthesis and preparation of inorganic phosphors are
based on physical and inorganic chemistry. Luminescence mechanisms are
interpreted and elucidated on the basis of solid-state physics. The major and
important applications of phosphors are in light sources, display devices, and
detector systems. Research and development of these applications belong to the
fields of illuminating engineering, electronics, and image engineering. Therefore,
research and technology in phosphors require a unique combination of
interdisciplinary methods and techniques, and form a fusion of the above mentioned
fields [1].

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1.2. Mechanism of Phosphorescence

In fluorescent materials electrons have energies in the impurity state band for a very
short time (10-9 to 10-6 seconds). Then, they emit light as their energy changes to
energy in the valence band. As a result, fluorescent materials will only glow while
light of sufficient energy shine on them. In phosphorescent objects, the electrons
remain in the impurity band for a while. After this time delay the electrons emit light
as their energy changes [2]. Thus, phosphorescent substances have the ability to store
up light and release it gradually. The notion of a metastable state explains this. If the
molecules of the substance can get from the ground state to a metastable state, and if
the metastable state can slowly decay back to the ground state via photon emission,
then we have phosphorescence. Typically, the metastable state is a triplet state, and
the ground state is a singlet one. Ground state molecules absorb photons and go to
excited singlet states. Most of them immediately hop right back to the ground state,
emitting a photon, but non-radiative processes take a few to a less energetic triplet
state. Once these molecules get to the lowest triplet state, they are stuck there, at least
for a while. Some low probability process accomplishes the triplet-singlet
conversion, and the molecules slowly leak out light (Figure 1) [3].
The electrons remain with energy in the impurity band because the physical situation
“forbids” a direct transition from impurity to valence band. To change energy to that
of the valence band the electrons must first gain back the thermal energy that they
lost when they made the transition to the impurity band. Because the energy is small,
it can generally be provided by the ambient energy in the air [2].

Figure 1. Phosphorescence mechanism [3].

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2. PHOSPHORESCENT PIGMENTS

2.1. Phosphor Pigments with the Ability of Luminescence

Phosphorescent pigments, after being excited by a light source, will continue to emit
light when excitation ceases. Long lasting phosphors can be divided two subgroups
which are sulphuric phosphor symbolize with ZnS: Cu and earth alkaline metal
aluminates activated with Eu2+: ROa+ (Al1-xGax)2 O3b+ (Y1-y Scy)2O3c+B2O3d+Eu2e+Mn+
(R; Ba, Sr, Ca, Mg, Zn and M; Nb, Zr, Bi, Mn, Sn, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy,
Ho, Er, Tm, Yb, Lu) [4]. Phosphors with long afterglow properties and radioactive
type phosphors should not put in the same category. Radioactive type of phosphors
can continue its radiation for years. However, mechanism of this type of phosphors
operates by using the nuclear radiation energy as excitant source. Consequently, they
are different from safe and long persistent phosphors [3].

2.2. The Phosphorescence Pigments Development in the World

It is known for a long time that ZnS: Cu materials have green light emission with
unfortunately limited brightness and duration (just a few hours) in the applications
[4]. To eliminate this kind of disadvantage, SrAl2O4: Eu2+, Dy3+ system which
indicates the emissions of blue, green, bluish-green, yellowish-green color was
developed.
Earth alkaline aluminate systems doped with rare earth elements are long persistence
phosphorescent pigments. Because of their crsytal structures they have a very
powerful absorbing, storing and emission of light properties. As a result of this the
most important property of these systems is showing high brilliancy and long lasting
emission. Their brilliancy and glowing time is ten times more than zinc sulphate
systems that means they display effect of longevity (permanently keeping the feature
without broken the crystal structure). Earth alkaline aluminate systems are not
harmful for human health because they do not contain radioactive component. Also,
in contrast to zinc sulfate systems earth alkaline aluminate systems are more stable
and resistant to atmospheric conditions. Light absorbtion and emission continues
without interruption [5-6].Recent studies have brought out many such phosphors like
Eu2+, Dy3+ -doped alkaline earth aluminates [7-9], Tb3+, Ce3+-doped alkaline earth
aluminates [10], Eu2+, Dy3+ and Eu2+, Ce3+ -doped alumino silicates [11-14], Dy3+-
doped strontium silicate [15], Eu2+, Pr3+-doped calcium sulfide [16], Pr3+, Li+ -doped
calcium zirconate [17], etc. However, among all these phosphors the Eu2+, Dy3+ -
doped alkaline earth aluminates are the most suitable phosphors due to their long
persistence time and bright afterglow. These Eu2+, Dy3+/Nd3+ -doped alkaline earth
aluminate phosphors exhibit afterglow which is visible to the naked eye for more
than 10 h in the dark after exposure to fluorescent light or sunlight. The prominent
aluminate persistent phosphors are SrAl2O4:Eu2+, Dy3+ [13], CaAl2O4:Eu2+, Nd3+ [18]
and Sr4Al14O25:Eu2+, Dy3+ [19].To explain the persistent luminescence process, many
mechanisms have been put forth involving filling of traps by UV irradiation and
subsequent thermal bleaching of traps resulting in emission from the Eu2+ sites.
Matsuzawa et al. [8] in their study of SrAl2O4:Eu2+, Dy3+ proposed a mechanism
based on photoconductivity.

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They have suggested the reduction of Eu2+ to Eu+ under UV irradiation due to
electron capture and oxidation of Dy3+ to Dy4+ due to hole capture. Aitasalo et al.
[20] have contested this process as the reduction of Eu2+ to Eu+ or oxidation of Dy3+
to Dy4+ under UV excitation in oxide materials requires higher energy. Instead, they
explained this based on the occurrence of energy transfer to Eu2+ through a host of
processes involving cation/anion vacancies.
Recently, Clabau et al. [21] have proposed that on UV irradiation some Eu2+ ions are
oxidized to Eu3+ and the released electrons are trapped at the oxygen vacancy levels
located in the vicinity of the photo-generated Eu3+ cations. The phosphorescence
arises from the recombination of these trapped electrons around the photo-generated
Eu3+ sites. However, no general agreement has been arrived on the detailed
mechanisms as the trapping dynamics is very complicated. Katzumata et al. [22]
have reported that only three phases of strontium aluminates such as SrAl2O4,
SrAl4O7 and SrAl12O19 doped with Eu2+ and Dy3+ exhibit afterglow. Later it was
reported [23] that Sr4Al14O25:Eu2+, Dy3+ exhibits strong afterglow with high quantum
efficiency of 90 %. The non-stoichiometry of metal ions in the phosphor is expected
to influence the luminescence properties of phosphors like luminescence spectrum
and quantum efficiency [24]. In this report, the luminescence characteristics of Eu2+,
Dy3+ -doped Sr4Al14O25 and the effects of non-stoichiometry of metal ions are
presented.

2.3. Phosphorescence Pigment Studies in Türkiye

Phosphorescent studies in Türkiye have been done by the Karasu [25-28] and his co-
workers. The studies include production of the phosphorescent pigments and their
applications in ceramic materials.
One of the studied subject was “Production of Long Duration Phosphorescence
Pigment in the SrAl2O4:Eu2+, Dy3+ System”. In this study, effects of variations in
milling time, concentrations of dominant (Eu2O3), auxiliary activators (Dy2O3) and
Y2O3 and gas flow rate on the brightness and afterglow properties of phosphorescent
pigments were examined. The results showed that; milling time of mixed batches and
the amount of dominant and auxiliary activators are important for brightness and
afterglow of phosphor pigments. Also, The flow rate of gas which was used during
the firing the pigments did not change the phosphorescnet pigment’s luminescent
intensity and afterglow [25].
Another studied subject was “Improvement of Process Parameters in the Production
of Yellowish-Green Colour Phosphorescence Pigments”. In this study, for
determining phosphorescence characteristics of the yellowish-green phosphorescent
pigments effects of variations in milling time, concentrations of dominant and
auxiliary activators (Eu2O3, Dy2O3), amount of Y2O3 and different raw material
compositions on the brightness and afterglow properties were examined. The results
presented that; mixed batches had the milling time limitation. Although the amount
of Y2O3 was important fort the afterglow and brightness of the pigments, There was
no change on the phosphor brightness while the Dy2O3 amount was changed. Also,
the increasing firing temperature improved the pigment’s brightness and afterglow
[26].

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In the search of “Application of Phosphorescence Glazes on Bricks and Roof Tiles”
it was studied that newly developed, low temperature, fluorescence ability bearing
glazes can be easily employed by brick and roof tile producers for various purposes.
This study indicated that; the bircks and roof tiles red colors could be covered by the
appropriate glaze which included different colors of phosphor pigments composition
by the single firing. It could be told that the cheaper roof tiles and bricks could have
increased cost covered with these glazes, but their attractiveness and charm were also
the advantage to attract the interest of people [27].
The other research on “The Production of Long Afterglow Blue and Blueish-Purple
Phosphor Pigments” showed that; the sensibility during weighing of powders,
milling time, the particle size and distribution, the purity of raw materials, type and
amount of gas were very important parameters during the production process of
phosphorescence pigments. Especially, firing process at different gas atmospheres
was very important for hole formation mechanism of the luminescence properties.
Also the samples which were fired under nitrogen-hydrogen gas atmosphere had the
dark gray color but, under the other gas atmospheres the samples had white or close
to white color [28].
In the subject on “Production of Yellowish-Green and Bluish-Green
Phosphorescence Pigments and Applying into Epoxy Resin Coatings”,
phosphorescence pigments in the SrAl2 O4:Eu2+, Dy3+ system were produced and
mixed with epoxy resin and applied on a wooden hardboard. In conclusion either
decorative or functional new epoxy coating products were achieved.

2.4. Photoluminescent (Luminescent, Luminous, Glow in Dark) Ceramics

Photoluminescent (Luminous, glowing in the dark) ceramics and photoluminescent

glass are produced by adding photoluminescent pigment in the producing process of
common ceramics and glass. The photoluminescent glaze is composed of basic glaze,
photoluminescent pigment as well as little additives and can be directly used to
produce luminous products after complete blend.
Compared to the common ceramics and glass, the products can glow in the dark after
absorbing the visible lights, this feature makes ceramics and glass used more widely.
The material of the photoluminescent ceramics and glass can absorb various visible
lights until saturated, then can glow in the dark constantly, unlimited recycle use with
a long time after-glow, ten times brighter light than that of the traditional
luminescent material (sulfate). The material is free from radioactivity, nontoxic and
harmless. The certain level bright emergency lighting can guide people evacuate
orderly under emergency and reduce confusion other than energy-saving.
The application of photoluminescent ceramics and glass in the domestic houses and
public buildings can not only decorate and beauty the houses and working
environment, but also can bring more conveniences to residents with its glow in the
dark (Figures 2-5).
Photoluminescent ceramics and glass can release a certain length light wave, which
can restrain some kinds of mildews and diseases. This characteristic meets the
fashionable and healthy living ideology for modern people by application of the
products into kitchen and bath room. Photoluminescent ceramics and glass are
corrosive-proof, friction resistant, fire retardant, aging resistant and free from
radioactivity compared to other organic luminescent materials, which make it widely
used in domestic houses and public buildings [29].
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Figure 2. Photoluminescent floor tiles.

Figure 3. Photoluminescent internal tiles.

Figure 4. Photoluminescent outdoor ceramic.

Figure 5. Photoluminescent artistic mural.

3. SUMMARY

Since the synthesis of the strontium aluminate phosphor, a phosphor far exceeding
the traditional sulfide phosphor in brightness, persistent time, and chemical
durability, new non-radioactive long lasting phosphor materials received rapidly
growing interest, especially the rare-earth-doped alkaline-earth aluminates. These
compounds can formulate (unlike zinc sulphide compounds) to produce a range of
colors. Until now, intense green and blue emitting persistent oxide phosphors have
been commercially available with beter chemical stability over sulfides. Strontium
aluminate and other proprietary compounds represent a revolution in the
photoluminescent industry, which has relied on zinc sulphide pigments for the better
part of a century.

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The following are taken up as application of rare earth phosphor: incandescent
electric lamp and fluorescent lamp, albedo light emitting diode, phosphor for plasma
display, long persistent phosphor. Furthermore, recent development trends such as
nano phosphor and stress phosphor, the combinatorial synthesis method are referred.
There will undoubtedly be new and better photoluminescent pigments and products
introduced in the near future, including those with different emission colors.

4. REFERENCES

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