Sulfur-enhanced thermoluminescence of γ-radiated zirconia
Sulfur-modified zirconia with various S contents have been characterized and analyzed for potential applications in dosimetry. The thermoluminescent signal induced by gamma radiation in pure zirconia and sulfated zirconia in the tetragonal phase has been considered. Experimental results show that th...
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Інститут надтвердих матеріалів ім. В.М. Бакуля НАН України
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| Цитувати: | Sulfur-enhanced thermoluminescence of γ-radiated zirconia / E. Rubio, D. Mendoza, V. Rodríguez, V.M. Castaño // Сверхтвердые материалы. — 2015. — № 5. — С. 55-61. — Бібліогр.: 20 назв. — англ. |
Репозитарії
Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1859928536242978816 |
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| author | Rubio, E. Mendoza, D. Rodríguez, V. Castaño, V.M. |
| author_facet | Rubio, E. Mendoza, D. Rodríguez, V. Castaño, V.M. |
| citation_txt | Sulfur-enhanced thermoluminescence of γ-radiated zirconia / E. Rubio, D. Mendoza, V. Rodríguez, V.M. Castaño // Сверхтвердые материалы. — 2015. — № 5. — С. 55-61. — Бібліогр.: 20 назв. — англ. |
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| description | Sulfur-modified zirconia with various S contents have been characterized and analyzed for potential applications in dosimetry. The thermoluminescent signal induced by gamma radiation in pure zirconia and sulfated zirconia in the tetragonal phase has been considered. Experimental results show that the thermoluminescent glow peak depends on both the crystalline structure and sulfate concentration and that the response is linear for an ample range of irradiation.
Зразки модифікованої сірого двоокису цирконію з різним вмістом сірки охарактеризовано і проаналізовано з точки зору потенційного застосування в дозиметрії. Розглянуто термолюмінісцентний сигнал, викликаний гамма-випромінюванням в чистому і сульфатованому двоокису цирконію в тетрагональної фазі. Експериментальні результати показують, що пік термолюмінісцентного світіння залежить як від кристалічної структури, так і від концентрації сульфату. Ця характеристика лінійна для великого діапазону опромінення.
Образцы модифицированной серой двуокиси циркония с различным содержанием серы охарактеризованы и проанализированы с точки зрения потенциального применения в дозиметрии. Рассмотрен термолюминисцентный сигнал, вызванный гамма-излучением в чистой и сульфатированной двуокиси циркония в тетрагональной фазе. Экспериментальные результаты показывают, что пик термолюминисцентного свечения зависит как от кристаллической структуры, так и от концентрации сульфата. Эта характеристика линейна для большого диапазона облучения.
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ISSN 0203-3119. Сверхтвердые материалы, 2015, № 5 55
UDC 535.377:661.883.1
E. Rubio (Puebla, México)
D. Mendoza (Estado de México, México)
V. Rodríguez (Pachuca, Hidalgo, México)
V. M. Castaño* (Santiago de Querétaro, México)
*meneses@unam.mx
Sulfur-enhanced thermoluminescence
of γ-radiated zirconia
Sulfur-modified zirconia with various S contents have been
characterized and analyzed for potential applications in dosimetry. The
thermoluminescent signal induced by gamma radiation in pure zirconia and sulfated
zirconia in the tetragonal phase has been considered. Experimental results show that
the thermoluminescent glow peak depends on both the crystalline structure and sulfate
concentration and that the response is linear for an ample range of irradiation.
Keywords: thermoluminescence, gamma radiation, pure zirconia,
sulfated zirconia, crystalline structure.
INTRODUCTION
Zirconia is, perhaps, one of the more versatile ceramic materials in
today´s industry. Indeed, this important material, one of the hardest known, has
already found important commercial applications [1–6], ranking from abrasives
and jewelry (as a Diamond-like stone) to lasers, automobile, aerospace, and even
music technology (i.e., Panasonic´s low distortion headsets), through its various
crystallographic phases [2–7]. Among the reasons for this, one can mention the
interesting chemical and physical properties of zirconia, which can be somehow
taylored by adding impurities or by using different phases since, for example, the
electronic band gap is dependent on whether cubic, tetragonal, monoclinic, or
amorphous structures are present. The other attractive characteristic of zirconia is
that it is readily available in nature and/or can be synthesized by using various
techniques, including low temperature routes [7–10], which make this mineral
suitable for many industrial uses.
Given the very high thermal, electrical, and mechanical stability of zirconia, its
use for dosimetry of ionozing radiation seems extremely attractive, as most com-
mercially available dosimeters are made out of rather weak materials, mainly al-
kaly halides [12–15], which can also become an environmental hazard, when dis-
posed, whereas zirconia is currently employed for bioengineered devices in situ.
One important requirement for an ionizing radiation thermoluminescent (TL)
dosimeter, however, is the need of reproducibility, linear behavior within the radia-
tion range required for, as an example, biomedical uses, and, very relevant, the
capability of controlling the TL response depending on the operation conditions of
the dosimeter [15–20].
Accordingly, in previous works we have reported the suitability of zirconia for
TL applications [13–18, 20] for as-prepared specimens, including different synthe-
sis routes. In the present manuscript we describe how a very simple sulphurization
of zirconia can control, to a great extent, the TL response of zirconia.
© E. RUBIO, D. MENDOZA, V. RODRÍGUEZ, V. M. CASTAÑO, 2015
www.ism.kiev.ua/stm 56
EXPERIMENTAL
Commercial ammonia zirconium carbonate white paste (Magnesium Electron Inc.),
formed by 40 % zirconium compounds and 7 % CO2 was utilized, as purchased. A
zirconium sol was prepared according to the following reaction [14–16]:
2[Zr2(CO3)(OH)2O2] + 2NH3 + 6H2O → (NH4)2Zr(OH)2(CO3)2 + 3Zr(OH)4,
using ammonia (Baker) with 7.6 % of NH3.
Then, 616.9 g of zirconium carbonate were mixed with 1261.3 ml of NH4OH
1.58 M. To ensure full dispersion of the paste, alumina balls were added and
refluxed for 24 h, obtaining an aqueous solution of ammonia zirconium carbonate
(NH4)2Zr(OH)2(CO3)2.
Aging at room temperature leads to evaporation of humidity and ammonia, thus
increasing viscosity. After a week, a transparent monolith is obtained, which was
characterized in a TGA-DTA instrument SDT 2960 TA in the range of 50 to
1100 °C. X-ray diffraction of samples calcined at 300, 450, 600 and 800 °C for 1 h
was carried out in a Siemens D-5000 equipment.
The sulfated zirconia was obtained by preparing three 50 ml aqueous solutions
with 0.5, 1, and 2 ml sulfuric acid, respectively, which led to CO2 liberation and a
white powder precipitates, which were filtered and dried at 60 °C for 24 h. These
samples were calcined at 600 °C for 1 hour. Sulfur concentration was determined
by EDS in a JEOL 5900 LV SEM.
Samples were irradiated with a 60Co source, which emits 1.31 MeV gamma
radiation, with a half life time of 5.3 years and a dose rate of 0.59 Gy/min. The
range of radiation utilized was 4.16 to 100 Gy.
TL was characterized in a Harshaw 4000 as follows: preheating at 30 °C, then
heated in the range 50 to 300 °C at a rate of 10 °C/s and acquisition time of 30 s,
under N2 atmosphere.
RESULTS AND DISCUSSION
Full physicochemical characterization of the sulfur-modified zirconia has been
described previously [17–19]. The table summarizes the EDS characterization of
the S content of the samples prepared. The TL behavior is illustrated in Figs. 1, 2
and 3, in terms of exposure to gamma irradiation, from 7.5 up to 240 min, for
sulfated zirconia samples corresponding to1.3, 2.4, and 4 wt % sulfur content,
respectively.
S content of sulfated samples (by EDS)
Sample S content, wt %
1 0
2 1.3
3 2.4
4 4.0
Exposure to gamma irradiation produced very interesting TL spectra, since the
maxima, at 118, 135, and 110 °C, depend on the sulphur content (1.2, 2.4, and 4 wt %,
respectively). It is known that the degree of crystallinity is a factor that largely
determines the presence and intensity of the TL signal in many cases and one could
think this is the present case. However, Fig. 4 shows typical X-ray diffraction patterns
of the pure and S-containing zirconia, revealing the presence of the tetragonal zirconia
phase. The same pattern is observed for the samples with different concentrations of S.
ISSN 0203-3119. Сверхтвердые материалы, 2015, № 5 57
0
50
100
150
200
50 100 150 200 250 300
Temperature, °C
In
te
ns
it
y,
a
rb
. u
ni
ts
1
2
3 4
5
6
7
Fig. 1. TL behavior of 1.3 wt % content S of zirconia for gamma irradiation for 7.5 (1), 15 (2), 22
(3), 30 (4), 60 (5), 120 (6), 240 (7) min.
0
50
100
150
200
250
300
350
50 100 150 200 250 300
Temperature, °C
In
te
n
si
ty
,
ar
b.
u
ni
ts
1
2
3 4
5
6
7
Fig. 2. TL behavior of 2.4 wt % content S of zirconia for gamma irradiation for 7.5 (1), 15 (2),
22.5 (3), 30 (4), 60 (5), 120 (6), 240 (7) min.
0
200
400
600
800
1000
1200
1400
1600
50 100 150 200 250 300
Temperature, °C
In
te
n
si
ty
,
ar
b.
u
ni
ts
1
2 3
4
5
6
Fig. 3. TL behavior of 4 wt % content S of zirconia for gamma irradiation for 7.5 (1), 15 (2), 30
(3), 60 (4), 120 (5), 240 (6) min.
www.ism.kiev.ua/stm 58
In
te
n
si
ty
, a
rb
. u
ni
ts
2θ, deg
Fig. 4. X-ray powder diffraction of zirconia with different contents of S: 0 (1), 1.3 (2), 2.4 (3),
4 (4) wt %; T – tetragonal zirconia.
Figure 5 shows the TL response of the 2.4 wt % content of S to various doses of
gamma irradiation, where two main peaks, located at 274 and 147 °C are clearly
observed for the S-containing samples, whereas the pure zirconia specimen shows
no evidence of the higher temperature peak, indicating that deeper electron traps
are formed by the incorporation of S, thus demonstrating that the electronic struc-
ture of zirconia can be controlled by adding S, as indicated.
Figure 6 summarizes the results of the present investigation, for it shows the
plots of the TL intensity vs. the gamma irradiation period, for selected S-containing
samples, as compared to the pure zirconia case. Two features are to be noticed in
this figure, first, the clear dependence on the S content, as mentioned above and,
second, the highly linear behavior found.
The TL response generally comprises four regions, namely supralinear, linear,
sub-linear, and saturation. The linear region is the most important, both from the
ISSN 0203-3119. Сверхтвердые материалы, 2015, № 5 59
dosimetry and electronic devices points of view. Generally speaking, in this region,
the TL sensitivity increases with dose, but this has also been observed at low doses.
The origin of this phenomenon is still not well understood and it has been
suggested that seems associated to surface states, which would correspond to the S-
modified zirconia. Indeed, since the TL response depends on imperfections of the
crystal lattice and of the impurities in the zirconia, greater sensitivity would be
expected for higher concentrations of S.
50 100 150 200 250 300
–2000
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
24000
26000
28000
5
4
3
2
1
6
7
8
In
te
n
si
ty
T
L
, a
rb
. u
ni
ts
Temperatura, °C
Fig. 5. TL response to various gamma irradiation doses of the 2 wt % content S of zirconia:
4.16 (1), 8.25 (2), 16.5 (3), 33.0 (4), 50.0 (5), 66.0 (6), 82.5 (7), 100.0 (8).
0 20 40 80 100
0
100
200
400
500
600
700
800
3
2
1
In
te
ns
it
y
T
L
,
ar
b.
u
ni
ts
Gamma irradiation time, min
60
Fig. 6. TL intensity vs. gamma irradiation time for zirconia with 0 (1), 0.9 (2) and 2.4 (3) wt %
content of S.
It is also seen that the intensity of TL response follows a linear behavior with
respect to the dose for the UV radiation in the range of 10 to 180 s of exposure and
with gamma radiation in the range of 14.6 to 100 Gy, this indicates that the equip-
ment for detection of gamma radiation within these ranges may be used.
www.ism.kiev.ua/stm 60
TL obtained signal determines the kinetics, which can be expected in this case
is the unique characteristic of the material that TL response linearity and
dependence presents dose rate during irradiation. The structure of the peaks
indicates a continuous distribution of traps.
For use in dosimetry, the existence of TL bands, above room temperature
relatively high temperatures indicate the existence of very stable while one can
observe a strong signal fading over time with traps.
CONCLUSIONS
The addition of S to native zirconia has been found to clearly affect the TL
response of the material. In general, an excellent TL sensitivity is presented for
irradiation doses ranging from 4.16 to 100 Gy of radiation, a very broad range that
would allow readings within the range of radiation used in therapy for humans and
animals.
Зразки модифікованої сірого двоокису цирконію з різним вмістом сірки
охарактеризовано і проаналізовано з точки зору потенційного застосування в дозиметрії.
Розглянуто термолюмінісцентний сигнал, викликаний гамма-випромінюванням в чистому
і сульфатованому двоокису цирконію в тетрагональної фазі. Експериментальні резуль-
тати показують, що пік термолюмінісцентного світіння залежить як від кристалічної
структури, так і від концентрації сульфату. Ця характеристика лінійна для великого
діапазону опромінення.
Ключові слова: термолюмінісцентний сигнал, гамма-випромінювання,
двоокис цирконію, сульфатований двоокис цирконію, кристалічна структура.
Образцы модифицированной серой двуокиси циркония с различным со-
держанием серы охарактеризованы и проанализированы с точки зрения потенциального
применения в дозиметрии. Рассмотрен термолюминисцентный сигнал, вызванный гамма-
излучением в чистой и сульфатированной двуокиси циркония в тетрагональной фазе.
Экспериментальные результаты показывают, что пик термолюминисцентного свечения
зависит как от кристаллической структуры, так и от концентрации сульфата. Эта
характеристика линейна для большого диапазона облучения.
Ключевые слова: термолюминисцентный сигнал, гамма-излучение, дву-
окись циркония, сульфатированная двуокись циркония, кристаллическая структура.
1. Ward D. A., Ko E. I. One-step synthesis and characterization of zirconia-sulfate aerogels as
solid superacids // J. Catal. – 1994. – 150, N 1. – P. 18–33.
2. Yamaguchi T. Recent progress in solid superacid // Appl. Catal. – 1990. – 61, N 1. – P. 1–25.
3. Yamaguchi T., Tanabe K., Kung Y. C. Preparation and characterization of ZrO2 and SO4
2–-
promoted ZrO2 // Mater. Chem. Phys. – 1987. – 16, N 1. – P. 67–77.
4. Arata K., Hino M. Preparation of superacids by metal oxides and their catalytic action // Ma-
ter. Chem. Phys. – 1990. – 26, N 3–4. – P. 213–237.
5. Brinker C. J., Sherer G. W. Sol-gel science. The physics and chemistry of sol-gel processign. –
New York, Academic Press, USA, 1990. – 912 p.
6. Chen F. R., Coudurier G., Joly, J.-F., Vedrine J. C. Superacid and catalytic properties of
sulfated zirconia // J. Catal. – 1993. – 143, N 2. – P. 616–626.
7. Limaye A. U., Helble J. J. Morphological control of zirconia nanoparticles through combustion
aerosol synthesis // J. Am. Ceram. Soc. – 2002. – 85, N 5. – P. 1127–1132.
8. Livaje J., Henry M., Sanchez C. Sol-gel chemistry of transition metal oxides // Prog. Solid
State Chem. – 1998. – 18. – P. 259–341.
9. Matijevic E. Monodispersed colloidal metal oxides, sulfides and phosphates // Ultraestructure
processing of ceramic, glasses and composites / Eds L. L. Hench, P. R. Urlich. – New York:
Wiley and Sons, 1984. – P. 334–352.
10. Mendoza-Anaya D., González Martínez P., Rodríquez-Lugo V., Castaño V. M. γ-radiation
induced termoluminescence of Fe-doped silica gels // J. Mater. Sci.: Mater. in Electron. –
1999. – 10, N 1–3. – P. 623–625.
ISSN 0203-3119. Сверхтвердые материалы, 2015, № 5 61
11. Mendoza-Anaya D., Angeles-Chávez C., Salas P., Castaño V. M. TEM and TL análisis of
silica samples with metallic impurities synthesized by sol-gel method // Acta Microscopica. –
2001. – 10, B. – P. 213–216.
12. Harani R., Hogarth C. A., Lott K. A. K. Electron spin resonance in phosphate glasses mixed
transition metal ions // J. Mater. Sci. – 1984. – 19, N 5. – P. 1420–1427.
13. Salas P., De la Rosa-Cruz E., Mendoza-Anaya D. et al. Thermo-luminescence induced by
gamma irradiation in sol-gel prepared zirconia–silica materials // Mater. Res. Innov. – 2001. –
4, N 1. – P. 32–35.
14. Rubio E. Síntesis, propiedades y aplicaciones de nuevos materiales de óxido de circonio: Ph.
D. thesis (Engineering). – Universidad Autonoma de Queretaro, 2005.
15. Pat. Mexico. Method for preparing dosimeters from sulfurated zirconia and applications
therein / E. Rubio, V. Rodriguez, V. M. Castaño. – Pat. application (under revision), 2013.
16. Rubio E., Rodriguez-Lugo V., Rodriguez R., Castaño V. M. Nano zirconia sulfated zirconia
from ammonia zirconium carbonate // Rev. Adv. Mater. Sci. – 2009. – 22. – P. 67–73.
17. Salas P., De la Rosa E., Mendoza D. et al. High temperature thermoluminescence induced on
UV-irradiated tetragonal zirconia prepared by sol-gel // Mater. Lett. – 2000. – 45, N 5. –
P. 241–245.
18. Salas P., De la Rosa E., Mendoza D. et al. Thermoluminescence induced by gamma irradia-
tion in sol-gel prepared zirconia-silica materials // Mater. Res. Innov. – 2000. – 4, N 1. –
P. 32–35.
19. Bazhanov D., Knizhnik A., Safonov A. et al. Structure and electronic properties of zirconium
and hafnium nitrides and oxynitrides // J. Appl. Phys. – 2005. – 97, art. 044108.
20. Hernandez M., Bernal R., Cruz C. et al. High dosage thermoluminescence diamond dosime-
ters // J. Superhard Mater. – 2012. – 34, N 4. – P. 234–238.
Centro Universitario de Vinculación, Received 14.01.15
Benemérita Universidad Autónoma de Puebla, México
Instituto Nacional de Ciencias Nucleares,
Centro Nuclear de Salazar, Estado de México, México
Universidad Autónoma de Hidalgo, Pachiuca, Hidalgo, México
Centro de Física Aplicada y Tecnología Avanzada,
Universidad Nacional Autónoma de México,
Santiago de Querétaro, México
|
| id | nasplib_isofts_kiev_ua-123456789-126213 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 0203-3119 |
| language | English |
| last_indexed | 2025-12-07T16:08:07Z |
| publishDate | 2015 |
| publisher | Інститут надтвердих матеріалів ім. В.М. Бакуля НАН України |
| record_format | dspace |
| spelling | Rubio, E. Mendoza, D. Rodríguez, V. Castaño, V.M. 2017-11-17T15:50:55Z 2017-11-17T15:50:55Z 2015 Sulfur-enhanced thermoluminescence of γ-radiated zirconia / E. Rubio, D. Mendoza, V. Rodríguez, V.M. Castaño // Сверхтвердые материалы. — 2015. — № 5. — С. 55-61. — Бібліогр.: 20 назв. — англ. 0203-3119 https://nasplib.isofts.kiev.ua/handle/123456789/126213 535.377:661.883.1 Sulfur-modified zirconia with various S contents have been characterized and analyzed for potential applications in dosimetry. The thermoluminescent signal induced by gamma radiation in pure zirconia and sulfated zirconia in the tetragonal phase has been considered. Experimental results show that the thermoluminescent glow peak depends on both the crystalline structure and sulfate concentration and that the response is linear for an ample range of irradiation. Зразки модифікованої сірого двоокису цирконію з різним вмістом сірки охарактеризовано і проаналізовано з точки зору потенційного застосування в дозиметрії. Розглянуто термолюмінісцентний сигнал, викликаний гамма-випромінюванням в чистому і сульфатованому двоокису цирконію в тетрагональної фазі. Експериментальні результати показують, що пік термолюмінісцентного світіння залежить як від кристалічної структури, так і від концентрації сульфату. Ця характеристика лінійна для великого діапазону опромінення. Образцы модифицированной серой двуокиси циркония с различным содержанием серы охарактеризованы и проанализированы с точки зрения потенциального применения в дозиметрии. Рассмотрен термолюминисцентный сигнал, вызванный гамма-излучением в чистой и сульфатированной двуокиси циркония в тетрагональной фазе. Экспериментальные результаты показывают, что пик термолюминисцентного свечения зависит как от кристаллической структуры, так и от концентрации сульфата. Эта характеристика линейна для большого диапазона облучения. en Інститут надтвердих матеріалів ім. В.М. Бакуля НАН України Сверхтвердые материалы Получение, структура, свойства Sulfur-enhanced thermoluminescence of γ-radiated zirconia Article published earlier |
| spellingShingle | Sulfur-enhanced thermoluminescence of γ-radiated zirconia Rubio, E. Mendoza, D. Rodríguez, V. Castaño, V.M. Получение, структура, свойства |
| title | Sulfur-enhanced thermoluminescence of γ-radiated zirconia |
| title_full | Sulfur-enhanced thermoluminescence of γ-radiated zirconia |
| title_fullStr | Sulfur-enhanced thermoluminescence of γ-radiated zirconia |
| title_full_unstemmed | Sulfur-enhanced thermoluminescence of γ-radiated zirconia |
| title_short | Sulfur-enhanced thermoluminescence of γ-radiated zirconia |
| title_sort | sulfur-enhanced thermoluminescence of γ-radiated zirconia |
| topic | Получение, структура, свойства |
| topic_facet | Получение, структура, свойства |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/126213 |
| work_keys_str_mv | AT rubioe sulfurenhancedthermoluminescenceofγradiatedzirconia AT mendozad sulfurenhancedthermoluminescenceofγradiatedzirconia AT rodriguezv sulfurenhancedthermoluminescenceofγradiatedzirconia AT castanovm sulfurenhancedthermoluminescenceofγradiatedzirconia |