Chemical Engineering Journal 443 (2022) 136522

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Chemical Engineering Journal

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Development feasibility of TLD phosphors and thermoluminescent

composite materials for potential applications in dosimetry: A review
S.A. Sinclair, M.I. Pech-Canul *, 1
Cinvestav IPN-Saltillo, Av. Industria Metalúrgica No. 1062, Parque Industrial Saltillo-Ramos Arizpe, Ramos Arizpe, Coahuila 25900, Mexico

A R T I C L E I N F O A B S T R A C T

Keywords: The present is a review on the development of TLD phosphors and composite materials for possible applications
Thermoluminescence in dosimetry using thermoluminescence (TL) as a measuring technique for ionizing radiation doses. The various
Dosimetry methodologies for the synthesis/preparation of thermoluminescent composites from both natural and synthetic
Dosimetric composites
precursors and of chemically doped and co-doped materials with oxides and rare-earth elements are considered.
Activated material
Chemically doped
The essential characteristics and properties of a material for its prospective use in solid-state dosimetry are re­
Co-doped ported, discussed, and compared the different thermoluminescent responses in different dose ranges. Natural
materials considered for dosimetry include sand beach and topaz minerals, although more recently, synthetic
topaz and topaz composites are in the spotlight. Although Eu and Ce are amongst the most sensitive rare earths
tested in dosimetric phosphors, it is crucial to continue researching the development of new composite materials,
doped and co-doped, to remarkably improve the sensitivity, fading, and the TL response as a function of the
absorbed dose, as well as affordable and viable new processing routes.

1. Introduction chemical vapor deposition (HYSY-CVD) method developed at

The increasing use and demand for radiation in many fields have
motivated the investigation of new dosimetric materials [1]. Natural
and synthetic dosimetric materials have been used to determine the
radiation dose received in the environment, in medical and industrial
activities. Synthetic dosimeters have the benefit of a controlled prepa­
ration process and precise chemical composition, exhibiting high
reproducibility levels. On the other hand, natural dosimeters are a
lower-cost alternative, and are available in large quantities [2]. Ther­
moluminescent/optically stimulated luminescence dosimeters (TL/OSL)
can store the radiation dose information in the form of charged particles
trapped by impurity sites and created during irradiation with ionizing
radiation like alpha, beta or gamma radiations.
The topaz Al2SiO4(F,OH)2 will be considered as a constituent for
composite materials in this review article. Topaz is a mineral belonging
to the group of aluminosilicates, formed in pneumolitic (400–500 ◦ C) or
hydrothermal (100–400 ◦ C) stages of igneous activity in acid rocks
(greater than 65% SiO2). It has a hardness of 8 on the Mohs scale, a
density of 3.5 g/cm3 and high chemical durability, even to hydrofluoric
acid [3,4]. Topaz has also been synthesized by the hybrid system
CINVESTAV-Saltillo using Na2SiF6 as a solid precursor and Al(OH)3 as a
reactant substrate [5,6]. Because both mineral and synthetic topaz have
shown good luminescent results, the thermoluminescent properties of
composites made with a mixture of topaz-Teflon, topaz-glass, topaz-
corundum have been studied since the year 2000 [7–9]. Wollastonite-
Teflon, citrine-Teflon, alexandrite-fluorinated polymer, and beach
sand-Teflon compounds are other materials considered thermolumi­
nescent composites for dosimetry.
To manufacture efficient dosimeters comprising a broad range of
radiation doses, research groups worldwide are developing new com­
posite materials. A solid-state composite material is defined as one that,
after processing, results in the consolidated combination of two or more
macro, micro, or nano constituents that differ in geometry/morphology
(particles, fibers, flakes, platelets, etc.) and chemical composition. One
of the constituents, which can be ceramic, metal, or polymer, plays the
role of the matrix, and the other constituents, which can be both of in
situ or ex situ origin and that may vary in size and distribution, can act as
strengthening, thermal and/or functional phases [10].
The primary motivation in proposing composites in dosimetry is the
development of materials with thermoluminescence characteristics

* Corresponding author.
E-mail addresses: martin.pech@cinvestav.edu.mx, martin.pech@cinvestav.mx (M.I. Pech-Canul).
1
ORCID: 0000-0002-0449-1981.

https://doi.org/10.1016/j.cej.2022.136522
Received 23 December 2021; Received in revised form 12 April 2022; Accepted 18 April 2022
Available online 21 April 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
S.A. Sinclair and M.I. Pech-Canul
superior to those obtained with materials of a single constituent. In
contrast to the latter, it is possible to improve and/or increase the
behavior, either mechanical, thermal, or luminescent, by combining the
characteristics of two or more constituents in the compound. With the
composités design philosophy, a material with exceptional properties,
not attainable by the constituents alone, is expected to result. For
example, beach sand from Rajasthan, India, exhibits a linear TL response
up to 20 Gy. Compared with the composites prepared from the sand of
the different Brazilian beaches with Teflon, the TL response notably
improves when forming the composite, with linearity in a dose range
from 10 Gy to 1 kGy.
With the objective of developing new solid-state thermoluminescent
dosimeters (TLD), thermoluminescence (TL) has proven beneficial to
evaluate the dose to which a material is exposed to alpha, beta, and
gamma rays. Thermoluminescent materials, namely semiconductors and
insulators, can store the information of radiation dose in the form of
charged particles trapped by impurity sites at localized energy levels in
the bandgap. Subsequent stimulation of the materials by heat will
prompt the displacement of charge carriers from their capture centers,
giving place to the emission of light (luminescence) after recombination
[11]. The light’s intensity of emission by the material when heated is
related to the dose of radiation administered [12]. The temperature at
which it occurs is related to the properties of the defects responsible for
the traps and the recombination centers [13]. The imperfections of the
crystals act as traps for the charge carriers (free electrons and holes) and
vary in depth since there are levels of traps responsible for the phe­
nomenon. Therefore, the sensitivity of the material is related to the
density of the recombination centers [14].
The unprecedented interest in TL as a technique for radiation
dosimetry in environmental, personal, and clinical applications prompts
research to produce new, high-performance TL materials [15]. Dosim­
etry represents a fundamental part of quality programs, ensuring that
the irradiation procedure is carried out with standard specifications.
According to Souza & col. [7], the characteristics that are desirable for a
solid-state TL dosimeter are (i) sensitivity of TL in the dose range of
10− 4–100 Gy (doses typically involved in personal dosimetry and
radiotherapy), (ii) the possibility of manufacturing a small and easy-to-
use dosimeter, (iii) mechanical resistance under normal handling con­
ditions (temperature, ambient light, and humidity), (iv) low cost, (v)
dependence on the response of the type and energy of radiation, (vi)
independence of the TL response from the orientation of the dosimeter,
(vii) independence of the response from the time elapsed between
irradiation and reading.
This article considers the synthesis and comparison of thermolumi­
nescent properties of two types of materials: composite materials from
the natural and artificial origin and those activated or chemically doped
with oxides and rare earth elements. Commercial glass composites
[16,17], sand [18,19], topaz [7], and jade [20] have recently been
studied using the thermoluminescent technique, and the results have
shown potential applications for high-dose dosimetry. High-dose radi­
ation treatment offers several advantages in the industry (water purifi­
cation, pasteurization), medicine (sterilization), and agriculture
(disinfestation, inhibition of sprouting) [21].
Some standard commercial dosimeters are currently available, the
most famous being LiF: Mg, Ti (TLD-100), LiF: Mg, Cu, P (TLD-700H),
Al2O3 (TLD-500), CaSO4: Dy (TLD-900) y CaF2: Dy (TLD-200). However,
each of these dosimeters is only applicable within a specific radiation
range and cannot be used for all doses; they depend on factors such as
linearity, fading, and reproducibility [22]. It is thus important to
continue researching the development of new composites and incorpo­
rate elements for doping the matrix of the materials considered. There is
an open-ended area with scope for research on the properties such as
efficiency for different radiation doses, sensitivity, fading, and thermo­
luminescent response as a function of the absorbed dose encompassing a
broad range of doses to serve as potential replacement candidates for
those commercially available.
2
Chemical Engineering Journal 443 (2022) 136522
The CINVESTAV-Saltillo research group has studied and is currently
developing sintered synthetic topaz-corundum composites and their
main thermoluminescent properties [6]. Furthermore, it is crucial to
investigate new economic and viable synthesis routes. For the synthesis
of topaz, a new route developed in the working group has been
considered, called hybrid-system chemical vapor deposition or HYSY-
CVD [23–25]. The HYSY-CVD pathway is a modified / hybrid in situ
CVD process that uses the thermal gradients of the reaction chamber to
generate the reactive gas silicon tetrafluoride (SiF4) – from the decom­
position of sodium hexafluorosilicate (Na2SiF6) at 550 ◦ C – to subse­
quently react with different substrates, i.e., Al2O3, Al(OH)3 or Al2Si2O5
(OH)4 [26]. The results showed the viability of topaz formation using the
three types of reagents, in amounts of 60%, 100%, and 47%, respec­
tively. The optimal processing conditions for topaz single phase forma­
tion (temperature 750 ◦ C, time 90 min, atmosphere without gas in the
permanence stage and position 0◦ ), the reactions involved, and its
structural characteristics have been reported in addition to its optically
stimulated luminescence, thermoluminescent and radioluminescent re­
sponses [5,26–29]. The low pressures (slightly above atmospheric
pressure), short processing times, relatively low processing tempera­
tures, and low-cost reagents make the HYSY-CVD processing route
attractive for synthetic topaz and topaz composites production [27].
The objective of this review is to discuss the potentials of the
different natural and artificial composite and chemically doped and co-
doped materials with prospective applications in dosimetry through the
comparative study of the main thermoluminescent characteristics,
providing criteria for selecting them depending on the dosimetric needs,
and comparing with the different dosimeters offered in the current
market.
2. TLD phosphors and methods for preparation of chemically
doped and co-doped dosimetric materials
In a crystalline solid, the atoms occupy ordered positions in a peri­
odic structure, so the alteration in the structure constitutes a defect. By
introducing dopants in the crystal lattice, defects are formed, which
disturb the energy diagram of the crystal, creating metastable energy
levels in the bandgap. Metastable energy states are susceptible to play­
ing the role of trap or recombination centers. Doping is the most
frequently applied method of creating such traps because it allows
reproducible experiments [30].
The sol–gel method has been used successfully to prepare chemically
doped dosimetric materials. Trifluoromethanesulfonate of copper [Cu
(O3SCF3)2], zirconia propoxide, and isopropanol were used to synthesize
Cu-doped ZrO2. First, the chloride salts of zirconia were dissolved in
double-distilled deionized water at room temperature (RT). A reaction
ratio of 1:131.66 was used to add the water-soluble copper salt to the
zirconia solution. 0.15 wt% of this resultant solution was added to the
isopropanol used in the polycondensation process. The mixture was
stirred for 5 min until a homogeneous solution was obtained and placed
in a dark place for 30 days. After that time, a transparent xerogel is
obtained to subject the samples to a heat treatment at 1000 ◦ C for 24 h
[15]. In another investigation, other authors have also reported the
thermoluminescent properties of ZrO2 doped with europium, using
europium chloride, zirconia propoxide, or zirconia, and propanol as raw
materials. Zirconia chloride salts were dissolved in double-distilled
deionized water. Water-soluble chloride salt of europium was added to
the zirconia solution. The additives were added at 0.5% by weight in
propanol. The mixture was stirred for 5 min to get a uniform and ho­
mogeneous solution until a clear solution was attained, placing the so­
lution in a dark place for 30 days until a xerogel was obtained. Finally,
the samples were subjected to heat treatment at 1000 ◦ C [12].
Furthermore, Cr2O3-Al2O3 nanoparticles have been prepared by the
sol–gel method. Aluminum propoxide and chromium sulfate dissolved
in isopropanol were mixed to obtain oxides with various compositions of
Cr2O3 (0.1–5% by weight). Octadecylamine was added to the above
S.A. Sinclair and M.I. Pech-Canul
mixture with constant stirring for 1 h. Then, ammonia solution (1 N)
drops were added to the mixed salt solution until a sol was formed,
stirring the mixture vigorously for 2 h. The sol particles are subjected to
condensation for two days until they condense into solid gel particles.
The filtrate is washed with distilled water to remove foreign material.
The solid is dried at 100 ◦ C and then heated at 800 ◦ C for 2 h at 10◦ /min
[31].
Mn-doped BaSO4 powders have been prepared by the recrystalliza­
tion method, for which, BaCO3 and concentrated H2SO4 were mixed in
stoichiometric proportion, adding MnCl2. The mixture was heated at
650–700 ◦ C for 30 min under normal atmosphere and cooled to room
temperature. The sample was then ground and sieved to fine powders
[32].
TiO2 and MgO codoped lithium potassium borate (LKB) glasses were
prepared using the melt quenching technique. Boric acid was used as a
glass former, where lithium and potassium carbonate were added as
glass modifiers. Initially, the mixture was activated with titanium oxide
(0.3–1.0 mol%). Then, magnesium oxide was added as a coactivator in a
concentration between 0.05 and 0.50 mol%. The material was mixed for
40 min and then kept in an alumina crucible in an electric furnace at
1200 ◦ C for 45 to 60 min. The melt was poured into a steel mold (400 ◦ C)
and kept for 3 h to reduce mechanical stress [33].
The synthesis of silver nanoparticles consists of dissolving the pre­
cursor agent AgNO3 in ethylene glycol, followed by the slow addition of
a reducing agent (NaBH4).CaSO4:Eu, CaSO4:Eu, Ag, and CaSO4:Eu, Ag
(NP) crystals were produced by Yamashita’s method. To produce CaSO4:
Eu, a mixture of calcium carbonate (CaCO3) and europium oxide
(Eu2O3) was added to excess sulfuric acid (H2SO4) and dried at 375 ◦ C.
Preparations of CaSO4:Eu, Ag, and CaSO4:Eu, Ag(NP) followed the same
steps used to produce CaSO4:Eu, with the addition of silver oxide (Ag2O)
and silver nanoparticles (Ag(NP)), respectively. The dopants were
incorporated at a concentration of 0.1 mol%. After the growth process,
the doped crystals were washed with hot and cold distilled water,
calcined at 600 ◦ C for 1 h, and washed again to select crystals with grain
sizes between 75 and 180 μm. The granules were prepared using a 2:1
(by weight) mixture of the phosphor and powdered glass (silicon oxide)
or Teflon. Then, they were compacted at a uniaxial pressure of 100 kgf,
resulting in granules with a diameter of 6 mm, a thickness of 1 mm, and a
weight of 20 mg. The glass-added pellets were sintered at 600 ◦ C for 6 h,
and the Teflon-added pellets were sintered at 400 ◦ C for 1 h [34].
Dysprosium-doped sodium and magnesium glass materials have
been prepared by the melt quenching method. Oxides of H3BO3,
Na2CO3, MgO, SiO2, and Dy2O3 (stoichiometric amounts of 99.99%
purity) were mixed, grounding the materials in an agate mortar for 30
min until obtaining a uniform mixture. A melt was prepared at 1200 ◦ C
in an alumina crucible in 30 min. Furthermore, the melt was poured into
a graphite mold to cool, then annealed in a furnace at 400 ◦ C for 2 h, and
subsequently, the prepared samples were ground into powders [35].
ZrO2 phosphors doped with Sm3+ (1 mol%) have been synthesized
by the solution combustion technique. Hydrated zirconium (IV) oxy­
nitrate (99%), carbohydrazide (98%), and samarium (III) nitrate hexa­
hydrate (99.9%) are used as precursors. 4.624 g of zirconium (IV)
oxynitrate hydrate and 2.252 g of carbohydrazide were dissolved in 50
ml of double-distilled water in a cylindrical Pyrex dish of 300 ml. The
redox mixture of the aqueous solution containing dish was placed into a
muffle furnace preheated at 350 ± 10 ◦ C. Initially, the solution was
boiling, and it underwent thermal dehydration followed by decompo­
sition with a large number of gases evaporated. Finally, voluminous
zirconium oxide powder is obtained. Polycrystalline ZrO2 powder was
grained using agate mortar and pestle into a fine powder. The pellets of
approximately 5 mm diameter and 1 mm thickness of as-synthesized
powder (35 mg) were prepared using a homemade pelletizer with the
optimized applied pressure of 20 MPa. A series of pellets were annealed
at 600 ◦ C for 2 h [11].
The solid-state diffusion method has been used in several in­
vestigations to prepare dosimetric phosphors. The SrDy2O4 doped with
3
Chemical Engineering Journal 443 (2022) 136522
europium ions (Eu) has been synthesized by the solid-state diffusion
method, for which an amount of SrCO3 and Dy2O3 was placed in an
agate mortar and ground until obtaining a uniform mixture. A concen­
tration “x” mol% (x = 0, 0.5, 1, 1.5, 2, 2.5, 3) of Eu2O3 was added as
dopant, and ground for half an hour. Subsequently, the mixture was
sintered at 900 ◦ C/3h, annealed at 1350 ◦ C/10 h, and allowed to cool,
obtaining a resulting powder of SrDy2O4: Eu [36]. The Ce-doped phos­
phorus BaB4O7 was also prepared by solid-state diffusion, with a Ce
concentration of 0, 0.5, 1, 1.5, 2, 2.5, and 3 mol%, for which it was used
as precursor high purity barium carbonate (BaCO3) (99.9%) and boric
acid (H3BO3) (99.9%). Cerium oxide (99.99% Sigma Aldrich) was
added, and the mixture was ground for several hours. At ambient con­
ditions, the ground material was sintered at 500 ◦ C for 3 h, ground again,
and annealed at 700 ◦ C/8h in a muffle [37].
The polycrystalline samples of LiSrBO3:RE3+ (RE = Dy, Tb, Tm and
Ce) were obtained by solid-state reaction at high temperature, using as
raw material Li2CO3 (AR), SrCO3 (AR), H3BO3 (GR), Dy2O3 (99.99%) 1
mol% fraction, Tb4O7 (99.99%) 1 mol% fraction, Tm2O3 (99.99%) 0.5,
1, 2, 4, 6, 8 mol% fraction, CeO2 (99.99%) 1 mol% fraction, which were
mixed and ground in an agate mortar to heat the mixture at 450 ◦ C for 3
h. The samples were then fired at 700 ◦ C/10 h in a CO atmosphere (for
samples doped with Tb3+ and Ce3+) to prevent oxidation and in an
ambient atmosphere (for samples activated with Dy3+ and Tm3+) [38].
NaGdF4:Tb3+ phosphors were synthesized by the hydrothermal route
assisted by trisodium citrate, using rare earth oxides, gadolinium oxide
(Gd2O3) (purity ≥ 99.89%), and terbium oxide (Tb2O3) (purity ≥
99.89%). Rare earth nitrate solutions were prepared by dissolving the
oxides of Gd2O3 and Tb2O3 in nitric acid at ~ 80 ◦ C. To form the metal-
citrate complex, an aqueous solution of Gd(NO3)3 and Tb(NO3)3 (0.2 M)
were mixed in 30 ml of an aqueous solution containing 2 mmol of tri­
sodium citrate dihydrate (Na3C6H5)7 2H2O (0.5882 g). It was stirred,
and 2 M NaF solution was added to the solution to transfer it to an
autoclave and heated at 180 ◦ C for 24 h. The resulting product was
separated by centrifugation and washed several times with distilled
water and ethanol to dry under vacuum at 80 ◦ C/8h [39].
BaF2:Ce phosphor powder was synthesized by the chemical copre­
cipitation method. 5.71 g of BaCl2 and 1.74 g of NH4F were separately
dissolved in 20 ml (99.9% purity, grade A.R) and 30 ml double distilled
water (DDW) with continuous stirring for 30 min, respectively. Subse­
quently, 1 mol% cerium oxide (CeO2) was dissolved in a BaCl2 solution
with continuous stirring, adding 25 ml of ethanol. Stoichiometric com­
positions of NH4F solution were added drop by drop to the BaCl2 solu­
tion under continuous stirring conditions until the reaction continued
for 2 h and 30 min to generate precipitation. The precipitate was filtered
out and dried at 120 ◦ C/5h [40].
The acid recrystallization method was used to prepare Dy-activated
CaSO4 (0.1 mol%). The CaSO4⋅2H2O and Dy2O3 were dissolved in sul­
furic acid. The acid was distilled in a flask connected to a condenser,
heating the solution to about 337 ◦ C (boiling point of H2SO4) to evap­
orate the acid completely. It was cooled, and the phosphorus in its
microcrystalline form was washed with double-distilled water to remove
the acid traces and dried at 100 ◦ C for 4 h. The microcrystal was crushed
and sieved into grains of 100 to 200 μm in size to be annealed at 700 ◦ C/
2h [41].
Lithium fluoride doped with Mg and Dy was synthesized by the
fusion method. The precursors used were LiF (99.99% purity), MgCl2
(anhydrous of 98% purity), and Dy(NO3)3⋅5H2O (99.9% purity). The
raw materials were mixed and placed in a platinum crucible within a
specific reactor for the melting and cooling process under a controlled
nitrogen atmosphere (99.9995% purity). Doping was performed by
melting LiF at 1050 ◦ C in the presence of activators in a nitrogen at­
mosphere (in heating and cooling steps) for 30 min. The cooled material
was ground and annealed for 10 min at 300 ◦ C and then cooled to room
temperature at 75 ◦ C/min in a dark environment [42].
The sintering method has been used in several investigations for the
synthesis of various phosphors. MgSO4⋅7H2O, CuSO4⋅5H2O, and
S.A. Sinclair and M.I. Pech-Canul Chemical Engineering Journal 443 (2022) 136522

Na2O.2SiO2⋅9H2O were mixed with LiF powder, with different concen­
trations of dopants Mg (0–0:25 mol%), Cu (0–0:07 mol%), Na, and Si
(0–1:5 mol%). The samples were dried and heated in an oven for 30 min
under a controlled nitrogen atmosphere, cooled, and pulverized into
granules 4.5 mm diameter and 0.88 mm thickness by pressurization with
a mechanical press at room temperature. The pressed pellets were sin­
tered at temperatures from 785 ◦ C to 832 ◦ C in an electric furnace under
a controlled nitrogen atmosphere. The cooled pellet was finally
annealed in a furnace at 250 ◦ C [43]. The NaCl:Cu phosphor was pre­
pared from a high purity powder mixture of NaCl and CuCl. 0.5 wt CuCl
was added to NaCl and mixed in an agate mortar, and the mixed powder
was placed in a 7 mm diameter cylindrical mold and pressed at 0.5 tons
for 1 min. The granules obtained were sintered at 650 ◦ C for 10 h in an
air atmosphere [44].
For the preparation by the sintering method of CaF2:Tb: CaF2, Tb4O7
(99.99% purity) and/or Sm2O3 (99.99% purity) were mixed. The
mixture was pressed into 6 mm diameter and 0.7 mm in thickness plates
and sintered at 1100 and 1254 ◦ C for 2 h, followed by cooling to room
temperature [45]. It was also prepared, by the CaB4O7:Eu sintering
method. EuCl3 (0.06% by weight) was mixed with an ethanol solution.
The mixture was stirred, dried, and sintered at 960 ◦ C for 1.5 h, followed
by cooling to room temperature [46].
Table 1 summarizes the methods, materials, and experimental con­
ditions for preparing materials activated by incorporating certain
dopants.
3. Thermoluminescent properties of doped and co-doped
materials for dosimetry
The luminescence efficiency of materials and other thermolumines­
cent properties (sensitivity and TL response) can be increased with the
addition of dopants or impurities that will be forming part of the ma­
terialś structure [47]. The dopant directly affects activation centers and
capture levels, in turn improving luminescence properties [36]. CaSO4 is
one of the most common dosimetric materials and is widely used in
dosimetry applications [48,49].
Recent research [50,51] has proposed incorporating new elements as
co-dopants of dosimeters known as CaSO4: Dy, CaSO4: Eu, and CaSO4:
Tb. Rare earth elements have been used as dopants in various in­
vestigations. The concentration of the dopants plays a vital role in
generating the trapping centers or defects in the materials. The shape of
the glow curve, the thermoluminescence efficiency, and the sensitivity
are strongly influenced by the concentration of impurities/dopants [36].
Nunes and Campos [52] studied the element cerium as a CaSO4: Eu
coactivator, obtaining a low-cost alternative dosimeter as the main
advantage over the already used CaSO4: Dy (TLD-900) and LiF: Mg, Ti
(TLD-100).
The CaSO4-glass and CaSO4-Teflon have been activated with Eu, Eu
and Ag and Ag nanoparticles (NP), the CaSO4: Eu, Ag (NP) having a
higher emission intensity TL, approximately five times greater than the
composites containing only Eu and Ag, suggesting that Ag nanoparticles
can alter the material’s crystal lattice, creating new defects and traps for
electrons and linear response with a dose range of 0.1 Gy to 1 Gy.
Therefore, CaSO4: Eu, Ag (NP) has more significant potential as a TLD
dosimeter [34]. For Tb and Eu activated CaSO4, there are three
recombination centers. The peak at 170 ◦ C is associated with defects
generated by europium and is characteristic of the recombination cen­
ters of Eu2+ ions. The peaks at 270 ◦ C and 340 ◦ C are related to defects
caused by the insertion of terbium in the CaSO4 matrix, and their
luminescent intensities are associated with the recombination centers
Tb3+ ions. According to the dose–response curve, it has been reported
that these composite materials present a linear TL response in the dose
range of 0.1 to 1 Gy with exposure to beta radiation (90Sr/90Y). The
samples were also exposed to gamma radiation (60Co) with a dose of 1 to
100 Gy, which showed linearity from 1 Gy to 30 Gy and supralinearity
from 30 Gy to 100 Gy [53]. For investigating its TL response, Cr-doped
Al2O3 was exposed to doses in the range of 3 to 700 mGy, exhibiting a
linear behavior in the range between 3.5 and 350 mGy and sublinearity
for doses higher than 350 mGy [31].
Within the considered literature, new microcrystalline phosphors
with higher sensitivity and dosimetric properties have been investi­
gated. Lakshmanan et al. [54] developed CaSO4: Dy as a micro-
phosphorus for gamma dosimetry synthesized by co-precipitation
technique. Mahesh S. Bhadane et al. [41] synthesized a Dy-activated

Table 1
Summary of methods and experimental conditions of doped materials for dosimetry.
Preparation method Precursors Temperature Time Reference
(◦ C) (min)

Sol-gel Copper trifluoromethanesulfonate Cu(O3SCF3)2, Zirconium propoxide and isopropanol, ZrCl4 1000 1440 [15]
Sol-gel Europium chloride (EuCl3), Zirconium propoxide Zr(C3H7O)4 and propanol (C3H8O) 1000 – [12]
Sol-gel Aluminum propoxide and chromium sulfate Cr2(SO4)3 dissolved in isopropanol (C3H8O), 800 120 [31]
Octadecylamine, ammonia (NH3)
Recrystallization BaCO3, H2SO4, MnCl2 650–700 30 [32]
Melt quenching technique Boric acid (H3BO3), lithium carbonate (Li2CO3), Potassium carbonate (K2CO3), Titanium dioxide 1200 ◦ C 60 [33]
(TiO2), magnesium oxide (MgO)
Yamashita’s Method* Calcium carbonate (CaCO3), europium oxide (Eu2O3), sulfuric acid (H2SO4), silver oxide (Ag2O) y Glass: 600 Glass: [34]
silver nanoparticles (Ag (NP))- Powdered glass (silicon oxide) and teflón Teflon:400 360
Teflon:
60
[Melt quenching technique H3BO3, Na2CO3, MgO, SiO2 y Dy2O3 1200 30 [35]
Solution combustion Zirconium (IV) oxynitrate hydrated (99%) ZrO(NO3)2*xH2O, carbohydrazide (98%) (CH6N4O) 600 120 [11]
and samarium (III) nitrate hexahydrate (99.9%) Sm(NO3)3*6H2O
Solid-state diffusion SrCO3, Dy2O3 and Eu2O3 900 180 [36]
Solid-state diffusion BaCO3, H3BO3 and CeO2 500 180 [37]
Solid state reaction Li2CO3, SrCO3, H3BO3, Dy2O3, Tb4O7, Tm2O3 and CeO2 700 600 [38]
Hydrothermal route assisted by Gd2O3 and Tb2O3 180 1440 [39]
trisodium citrate
Chemical coprecipitation BaCl2, NH4F and CeO2 120 300 [40]
Acid recrystallization CaSO4⋅2H2O, Dy2O3 and H2SO4 337 – [41]
Fusion method LiF, MgCl2 and Dy(NO3)3⋅5H2O 1050 30 [42]
Sintering MgSO4⋅7H2O, CuSO4⋅5H2O, Na2O.2SiO2⋅9H2O and LiF 785 ◦ C to – [43]
832 ◦ C
Sintering NaCl and CuCl 650 600 [44]
Sintering CaF2, Tb4O7 and Sm2O3 1100 and 1254 120 [45]
Sintering EuC13 960 90 [46]

4
S.A. Sinclair and M.I. Pech-Canul
CaSO4 microphosphor by the acid recrystallization method and studied
the structural, morphological and thermoluminescent characteristics by
irradiating the material with thermal neutrons, where a deconvolution
was performed by the computerized glow curve deconvolution method
(CGCD) to obtain parameters such as trap depth, order of kinetics, fre­
quency factor and maximum peak temperature. The microphosphor
presents a diffraction pattern with an intensity that decreases with
increasing neutron fluence from 6 × 1011 n/cm2 to 52 × 1011 n/cm2
with no modifications in peak position, since thermal neutrons produce
prompt alpha particles that can be responsible for introducing phos­
phorus defects. The material presented a glow peak at 240 ◦ C with an
intensity that increases with neutron fluence and a linearity up to 52 ×
1011 n/cm2.
The thermoluminescent response of cerium has also been studied as a
dopant in BaB4O7, in different molar concentrations (0.5 to 3 mol%)
when exposing the material to gamma rays in a range of 1 Gy-3 kGy
[37]. Structural and morphological characteristics were analyzed by X-
ray diffraction (XRD) spectroscopy and scanning electron microscopy
(SEM), revealing a monoclinic crystalline structure and an average
particle size of 2 μm. BaB4O7 phosphor is one of the borate phosphors
that has shown efficient properties, being a promising material for
possible dosimetric applications. For example, Na and Dy doped on
borate phosphors have been used for TL studies [55–57] and BaB4O7: Eu
for temperature sensing [58].
Borates are materials of interest due to their nearly tissue-equivalent
absorption coefficient, high sensitivity, low cost and easy preparation. In
1967 Schulman et al. [59] began studies of the TL phenomenon in bo­
rates. Furetta et al. [60] reported in 2001 the main dosimetric charac­
teristics of Li2B4O7: Cu, In and Li2B4O7: Cu phosphors. Also, the TL
properties of LiSr4(BO3)3 doped with Ce, Ba2Ca(BO3)2 doped with Tb
and Zn(BO2)2: Tb have been investigated [61–66].
On the other hand, cerium is one of the most sensitive rare earth
elements that acts as an efficient dopant in the thermoluminescent
phenomenon [67–69]. The highest TL intensity in the glow curves was
obtained with a Ce concentration of 2 mol%, with a decrease in intensity
with dopant concentrations greater than 2%, observing two main peaks
at 176 ◦ C and 311 ◦ C. The intensities of these peaks increase linearly
with increasing gamma doses from 1 Gy to 3 kGy, saturating at doses
greater than 3 kGy. Phosphor reproducibility remains constant after 7
replicates and fading was 7% up to 6 months. A study of the TL glow
curve was also carried out to know the levels of the traps, by means of
the activation energy method -Tstop in combination with the initial rise
Method (IRM), revealing five activation peaks with centers at 1.1, 1.5,
and 1.8 eV [37].
For the last two decades, BaF2 doped with rare-earth impurities has
been used in thermoluminescence and radioluminescence applications
due to its good sensitivity to ionizing radiation and high effective
number (Zeff = 50.96) [70,71]. Dy-doped BaF2 has been reported to
show an excellent linear dose–response of 1 Gy to 3 kGy [37]. BaF2: Ce
phosphor powder synthesized by the chemical coprecipitation method
shows excellent properties for high gamma dose measurement applica­
tions. The correlation of the different molar concentrations of Ce (0.5, 1,
1.5, and 2 mol%) with its structural, morphological, and luminescent
properties was studied [40]. According to the X-ray diffraction pattern, a
cubic structure without impurity peaks was obtained due to the small
amount of added dopant. The shape of the particles indicated a cubic
and uniform form with an average particle size of 99 nm. BaF2: Ce 1 mol
% showed the highest intensity with two main peaks, 175 and 275 ◦ C.
The glow curves of the other concentrations presented inconsistent and
lower intensity temperature peaks. The 1 mol% BaF2: Ce phosphorus
was then annealed at 500 ◦ C for time intervals from 0.5 h to 4 h, showing
the maximum intensity at 2 h. The intensity of the glow peak increased
linearly with increasing dose from 1 Gy to 3 kGy with sensitivity
remaining constant, fading 6.83% over 2 months, and good
reproducibility.
Another material of interest is MgB4O7 doped with rare earth
5
Chemical Engineering Journal 443 (2022) 136522
elements. Different dopant concentrations have been found to be asso­
ciated with TL peaks at different temperatures and with different
entrapment mechanisms [72,73]. BaSO4 has also been doped with im­
purities (Dy, Eu, P), being able to find an application as an X-ray storage
dosimeter due to its high sensitivity [74]. It has been reported that the
applications of highly sensitive dosimeters based on sulphates doped
with alkaline earth elements are restricted by a number of factors, one of
which is anomalous fading. The sensitivity of BaSO4: Eu has been re­
ported to be comparable to that of CaSO4:Dy. However, the TL peak
occurred at a lower temperature, with a 13% fading over a 30-day period
at room temperature, with a minimum measurable dose of 50 Gy [75].
The influence of different rare-earth dopants Dy3+, Tb3+, Tm3+, and
Ce3+ on the thermoluminescence of LiSrBO3 phosphor has been dis­
cussed. These materials were synthesized by solid-state reaction at high
temperature. The glow curves showed that, for a concentration of 1%
Dy3+, a single peak was obtained at 107 ◦ C, a peak at 132 ◦ C with two
weak shoulders at 94 and 207 ◦ C for 1% Tb3+, two TL peaks located at
123 and 193 ◦ C for 1% Tm3+ and two peaks around 118 and 272 ◦ C for
1% Ce3+. Of the four phosphors analyzed, the highest TL intensity was
obtained for LiSrBO3 doped with Tm3+. The effect of Tm3+ concentra­
tion on TL intensity was investigated, and the result showed that the
intensity of the TL peak increases with increasing Tm3+ concentration
from 0.5% to 1% and reaches the maximum value at 1%, and then de­
creases with further increase in Tm3+ concentration. Therefore, the
optimal molar fraction was 1%. The dose–response of LiSrBO3: 1% Tm3+
to gamma rays was linear in the range of 1 to 400 mGy [38].
Albeit BeO was proposed as an OSL dosimeter in the 1970 s, it was
not until the late 1990 s when more in-depth studies of its properties
were conducted [76]. The material has been used in photons and beta
rays dosimetry, exhibiting sensitivity to ionizing radiation with a linear
dose–response in a wide range from 1 μGy to 5 Gy and a fading less than
1% in 6 months [77,78]. It has a low effective atomic number (Zeff =
7.14 [79], 7.21 [77]) nearly equivalent to that of tissue, allowing
medical applications. Magnesium borate (MgB4O7) doped with rare
earth elements is another relevant material in the dosimetry of ionizing
radiation. Some of the properties that make MgB4O7 attractive as a
dosimeter are its low effective atomic number, low dependence on
photon energy and the possibility of developing neutron dosimeters
[80,81].
Li2B4O7 lithium borate dosimeters show promising TL properties for
both medical and environmental fields. Although manganese has been
used as an activator, where favorable thermoluminescence characteris­
tics have been obtained, the sensitivity to radiation is low. However, by
substituting copper for manganese, sensitivity is improved [59]. A study
by Wall et al. [82] showed that the sensitivity of Li2B4O7: Cu was almost
eight times higher than the sensitivity of L2B4O7: Mn. Its sensitivity to
137
Cs radiation was two-fold compared to that of TLD-100, and the
signal fading in three months was 11% [83]. Lithium borate with copper
as dopant and indium as co-dopant has been used, showing greater
sensitivity, with a minimum detectable dose of up to 10 μGy and a
slower fading of 10% in 3 months. The dose responses of both Li2B4O7:
Cu, In and Li2B4O7: Cu was linear in the range of 10− 4–103 Gy (60Co)
[60]. In another study, the properties of lithium borate co-doped with
Cu, In; Cu, In, Ag and Mg, Cu, O, exposed to 60Co gamma radiation with
a dose of 10− 4 − 3 × 103 Gy, were reported. Results revealed a glow
curve for Li2B4O7: Cu, Ag, P with a TL peak between 185 and 190 ◦ C and
sensitivity to radiation five times that of LiF: Mg, Ti. The signal of
Li2B4O7: Cu, In faded 6% in 3 months, while the fading of the dosimeter
doped with Cu, In, Ag was 10% in 3 months, with a minimum dose of 10
µGy [84]. Moreover, owing to its attractive properties, lithium tetra­
borate, Li2B4O7, has been proposed as a multifunctional material for
personal dosimetry [85].
Lithium and magnesium borate glasses with different oxides have
been activated to study their thermoluminescent characteristics. The
response to the dose was linear in the range of 10− 2–103 Gy, showing a
behavior independent of the concentration of the activators; these
S.A. Sinclair and M.I. Pech-Canul
impurities are related to intrinsic defects, showing an increase in in­
tensity with an increment MgO concentration (0.25 mol%), thus
creating deep traps [84]. Furthermore, this material did not present the
typical supralinearity of the response that different materials studied
have shown, with doses greater than 10 Gy [33]. Sodium and magne­
sium borosilicate glasses activated with dysprosium oxide have shown a
single prominent TL peak, with variations in the intensities of the glow
curves as the Dy concentration increases and the maximum peak tem­
perature shifts towards higher temperatures. This is due to the increase
in the density of the electron traps with the increase in the concentration
of Dy3+, with the presence of linearity in a dose range of 50 to 10000 Gy
[35]. It has been reported that as a doping agent into BaSO4, Mn in­
teracts strongly with intrinsic defects and leads to an increase in the
glow curves intensities with increasing irradiation dose, being the
magnitude of such TL intensity, three-fold compared to that of the
undoped samples. Due to the steady increase in the TL signal by its
incorporation as an impurity, Mn is well known as an efficient activator
in many materials [32].
In recent years, ZrO2 has been doped with rare-earth elements,
resulting in a promising TL dosimeter that has received significant
attention given its dosimetric applications. ZrO2 was first proposed in
1990 as a material that shows good dosimetric performances under ul­
traviolet and visible light [86]. Excellent characteristics such as sensi­
tivity, low fading, reuse, and linear dose–response to X-rays and gamma
radiation have been reported [87]. Furthermore, it was observed that
the position of the TL peak changes at higher temperatures in samples
doped with europium [12]. It has been reported that in addition to the
use of rare earth elements as dopants, Ag particles improve the ther­
moluminescent characteristics of some materials. The development of a
new double doped TL material KMgF3: Eu, Ag, which has enhanced
thermoluminescent features compared to KMgF3: Eu, has also been re­
ported [88].
The TL properties of ZrO2 doped with Sm and Eu have been dis­
cussed, reporting a linear TL response in the range of 2 to 90 Gy with
increasing exposures to beta radiation doses. The introduction of Eu3+
produces defects in the crystalline lattice. It induces metastable energy
states, which act as recombination centers, affecting the TL response of
ZrO2 since Eu-doped material is 1.9 times more sensitive to beta radia­
tion than non-doped ZrO2 [12]. ZrO2: Cu also shows adequate dosi­
metric properties, showing a broad peak at 180 ◦ C with a prominent
shoulder at 130 ◦ C on the glow curve [15].
In the year 2020, the dosimetric properties of SrDy2O4 activated by
Eu3+ ions for high doses of gamma radiation were reported for the first
time, where the concentration of Eu ions varied from 0% to 3%. The
material was successfully synthesized by the solid-state reaction method
[36]. The glow curves were measured from room temperature to 400 ◦ C
at a heating rate of 5 ◦ C/sec after irradiating the samples with 60Co,
observing that initially, from 0.5% to 1% concentration of Eu, TL in­
tensity increased. However, above 1% Eu, TL intensity gradually
decreased. SrDy2O4 doped with 1% mol Eu showed the most prominent
glow curve response, with two peaks, at 125 ◦ C, and 203 ◦ C. The TL
dose–response of the glow curve increased linearly from 1 Gy to 4 kGy. A
fading and reproducibility study of the doped material was carried out
with gamma irradiation at a dose of 1 kGy, obtaining a fading of 9% up
to 50 days and a constant TL response reproducibility of at least 7 cycles.
In that same year, Kulkarni et al. [39] studied the effect of optimal
concentrations of impurities (0, 0.5, 1, 2, 3, 4, 5%) and heat treatment
(200–800 ◦ C for 2 h) on the structural, morphological, photo­
luminescent and thermoluminescent properties of NaGdF4 doped with
Tb3+ synthesized via tri-sodium citrate assisted hydrothermal route.
NaGdF4, doped with a concentration of 3% Tb3+ and annealed at 700 ◦ C
produced a glow curve of higher intensity, with a single peak at 230 ◦ C
with a small shoulder at 145 ◦ C. Therefore, it is possible to assure that
the presence of Tb3+ dopant ions increases the number of luminescent/
capture centers in the host system. The material also showed a linear
response over a very wide gamma dose range from 100 Gy to 20 kGy
6
Chemical Engineering Journal 443 (2022) 136522
with less than 10% fading over 90 days and reasonable reproducibility,
revealing that NaGdF4: Tb3+ is suitable for high-dose dosimetry.
Another of the materials studied is corundum or α-alumina. It has
excellent mechanical, electrical, thermal, and optical properties due to
the closed hexagonal packing of oxygen ions [89,90]. Studies have been
carried out on the doping of Al2O3 with Cr, anticipating that the modi­
fication of alumina with transition elements increases the number of
defects in the structure of alumina, improving some TL properties such
as its absorption capacity. In various investigations, the authors have
focused on preparing corundum powders using multiple chemical routes
to obtain a thermally stable α-Al2O3 without changes in the preparation
conditions [31].
LiF-based TL materials are widely used in personal monitoring due to
chemical stability, low energy dependence, and close tissue equivalence
(Zeff = 8.14). The intensity, sensitivity and TL emission of LiF phosphors
depend on the synthesis method, the type, and amount of dopant used
[43]. Mg has been reported to be one of the most effective dopants for
increasing the TL response, because Mg-related defects act as electron
traps by forming impurity-vacancy dipoles in LiF [80]. In 2018, E.
Sadeghi et al. [42] manufactured the Mg and Dy doped LiF for the first
time by the fusion method, where they studied impurity concentrations
and heat treatment (240, 300, 350 and 400 ◦ C for 10 min) to achieve
high sensitivity to thermoluminescence. Initial rise, isothermal decay
and computerized glow curve deconvolution (CGCD) methods were
applied to obtain kinetic parameters of the prepared TL materials as well
as the Tm-Tstop technique to identify the number of overlapping TL
peaks. Glow curves were analyzed at different Dy concentrations of 0.05,
0.1, 0.3, 0.5, 1 mol% with a fixed Mg concentration of 0.2 mol% and Mg
concentrations of 0.1, 0.2, 0.4, 0.5, 0.6, 0.7, 0.8 and 1 mol% with an
optimal amount of 0.1 mol%. The highest TL peak intensities obtained
occurred with 0.1 mol% Dy and 0.7 mol% Mg. LiF: Mg, Dy exhibits a
sharp dosimetry peak at 237 ◦ C and lower temperature peaks at 122 ◦ C
and 175 ◦ C. The best heat treatment for the annealing regime was 300 ◦ C
for 10 min, resulting in a marked increase in TL sensitivity. Linearity of
the TL dose–response occurred in the range of 1 mGy to 10 Gy. To
evaluate the fading of the TL signal, the LiF: Mg, Dy powder was exposed
to a gamma dose of 500 mGy to record its TL signals after 0, 1, 4, 7, 14,
and 30 days. Therefore, the prepared phosphor offers potential appli­
cations for personal and environmental dosimetry because of its
adequate TL sensitivity, low fading, good reusability, and tissue
equivalence.
Nam et al. [91,92] doped LiF: Mg, Cu, Na, Si with four different
activators. They found that the optimal composition of the powder
dopants is Mg: 0.6 mol%, Cu: 0.8 mol%, Na: 1.8 mol%, and Si: 1.8 mol%.
However, by sintering the powders, the sensitivity of the material
decreased, exhibiting poor reusability. To improve the sensitivity of TL
detectors, the structure of the glow curve of LiF: Mg, Cu, Na, Si was
studied as a function of the concentrations of dopants, Mg (0–0.25 mol
%), Cu (0–0.07 mol%), Na and Si (0–1.15 mol%), and the sintering
temperature. Results showed that the structure of the glow curve and the
luminescent efficiency are highly dependent on the sintering tempera­
ture. The glow curves obtained showed a main TL peak intensity with a
concentration of 0.2% in moles of Mg by varying the concentrations of
Mg in 0, 0.05, 0.15, 0.20 and 0.25 mol% with a concentration of 0.05
mol% Cu and 0.9 mol% of Na, Si. For the different concentrations of Cu
0.00, 0.05, 0.10, 0.15, 0.20, 0.25 mol% and Mg concentration of 0.2 mol
% and Na, Si of 0.9 mol% a glow curve with main peak was shown for
0.05 mol% Cu. With the increase of Cu concentrations, the intensity of
the main peak rapidly intensified, and the high-temperature peak
rapidly decreased. The maximum intensity of the main peak for con­
centrations of Na, Si with a concentration of Mg 0.2 mol% and Cu 0.9
mol%, was observed with 0.9 mol%. The central maximum intensity of
the sintering temperature was shown in a pronounced peak at 830 ◦ C.
The high-temperature peak decreased rapidly with increasing sintering
temperature [43].
There are also research reports involving the sintering of materials
S.A. Sinclair and M.I. Pech-Canul Chemical Engineering Journal 443 (2022) 136522

for their characterization by thermoluminescence. Among these mate­
rials are doped alkaline halide crystals such as NaCl, which have
revealed dosimetric characteristics that make them suitable for devel­
oping detectors in different radiation fields. NaCl: Cu glow curves
showed five peaks centered at 121, 162, 233, 308, and 400 ◦ C. One of
the main advantages over TLD-100 is that the position of the principal
peak occurs at a higher temperature. TL intensity increased regarding
radiation dose from 0.417 to 25.0 Gy with a linear response for doses
below 10 Gy, suitable for personal and environmental dosimetry doses.
The fading of the TL signal occurs only for the low-temperature peaks in
less than 3 min after irradiation, while the primary peak does not show
significant changes, presenting good thermal stability. The relative
sensitivity of the material obtained compared to the TL signal of the
commercial dosimeter TLD-100 was 0.18; being an encouraging result
because it represents less than an order of magnitude below TLD-100,
and this could be optimized by varying the Cu concentration, co-
doping it with other impurities, as well as changing the sintering tem­
perature [44].
A study of sintered CaF2 doped with Tb4O7 and Sm2O3 was reported,
where the TL properties at a UV radiation dose to achieve higher
sensitivity. CaF2 was co-doped and sintered with Tb4O7 (0.06 wt%),
Sm2O3 (0.03 wt%) at 1254 ◦ C and doped with 0.06 wt% at 1200 ◦ C and
0.06 wt% at 1100 ◦ C. For CaF2 doped, only with Tb4O7, it was possible to
observe three TL peaks at 80, 105, and 185 ◦ C. On the other hand, a TL
peak was observed at 105 ◦ C for the sample doped with Tb4O7 and
Sm2O3. The 185 ◦ C peak intensity of TbO4 sintered at 1200 ◦ C was 1.9
times higher than that of the 1100 ◦ C sintered sample, and the 105 ◦ C
peak intensity of the co-doped sample was 12.9 times higher than that of
the doped sample 185 ◦ C sintered at 1200 ◦ C. The intensity of the 105 ◦ C
peak of CaF2:Tb was intense with the addition of Sm2O3 [45].
The TL response of sintered CaB4O7 doped with europium ions has
been investigated, where the authors performed a comparison of glow
curves between undoped and doped CaB4O7. The peak positions are
similar to each other from 90 to 100 ◦ C and from 180 to 190 ◦ C with
additional peaks at 140 and 240 ◦ C for the doped material and with
lower TL intensities for the undoped CaB4O7, suggesting that the Eu ions
play the role of luminescent centers [46].
Table 2 summarizes the conditions used in different activated or
doped materials for the analysis of the glow curves (number and location
of peaks).
4. Composite materials for potential applications in dosimetry
In the last 50 years, the thermoluminescent properties of mineral
topaz have been investigated, showing that this material exhibits
promising dosimetric features. Since 2000, the thermoluminescent
properties of composites from topaz-Teflon and topaz-glass mixtures
have been studied to develop new solid-state dosimeters [7–9]. These
results showed that topaz composites are up-and-coming candidates for
thermoluminescent applications. They have demonstrated adequate
dosimetric characteristics such as a wide range of dose–response line­
arity, homogeneity, acceptable reproducibility, and slow fading of the
glow curves. For high doses, they can be used in consecutive irradiation-
reading-annealing cycles with no change in their sensitivity. However,
there is a limitation to this type of composite since Teflon volatilizes at
temperatures above 300 ◦ C, and the TL peak of topaz used in dosimetry
occurs between 150 and 400 ◦ C [7,13]. Measurements of TL and thermal
annealing should be performed up to 400 ◦ C to provide the complete
integration of the emission curve because heat treatment at 400 ◦ C is
more efficient for depopulating TL traps by completely removing the
signal before its use [9]. The topaz-glass composites showed a linear
response for gamma rays from 10 mGy to 1 Gy, with a saturation of the
TL signal that occurs with gamma doses greater than 2 kGy [93]. A study
of synthetic topaz composites with corundum obtained in situ with
sintering of the material with increasing temperature has also been re­
ported, exhibiting favorable thermoluminescent characteristics, such as
a maximum TL peak intensity in the glow curves between 150 and
250 ◦ C (appropriate range for dosimetric applications) and mechanical
stability, with a microhardness of 54.560 HV with 90% corundum phase
[6].
The thermoluminescent characteristics of beach sand from different
locations in Brazil have also been studied, proving suitable for high-dose
dosimetry [19]. Vaujapurkar and Bhatnagar [94] studied sand from
Rajasthan, India, presenting two TL peaks at 80 and 220 ◦ C. The first
peak is not helpful for dosimetry due to its rapid thermal decay at room
temperature (fading), while the second has an adequate response
depending on the absorbed dose. Thus, suggesting that sand could be
used as a dosimeter for gamma radiation and X-rays with doses up to 20
Gy.
Currently, researchers worldwide are devoted to studying and
modifying the properties of graphene. Owing to its good electronic,
thermal, and mechanical properties for technological applications, the
usefulness of graphene is growing in materials science and engineering
[95–97]. Graphene oxide (GO) has been synthesized by the Hummer
method, being reduced to graphene (RGO) by hydrazine hydrate and
graphene-nano ZnS compound by in situ reduction of graphene oxide
(GO) and zinc nitrate [Zn(NO3)2] by sodium sulfide (Na2S). Reduced
graphene oxide (RGO) did not display any thermoluminescence emis­
sion. The GO glow curve has only one wide peak at a position between
227 and 277 ◦ C with an absorbed dose increasing from 1 Gy to 5000 Gy,

Table 2
Types of radiation, number and location of TL peaks of doped materials.
Material Activator or dopant Radiation source Number of peaks Peak location TL Reference

Li2B4O7, K3BO3 glasses TiO2 and MgO γ-rays 60Co 1 240 ◦ C [33]
Na and Mg borosilicate glasses Dy2O3 γ-rays 60Co 1 116.85–161.85 ◦ C [35]
BaSO4 Mn X-rays 2 147 ◦ C [32]
225 ◦ C
ZrO2 Sm β-rays 90Sr/90Y 1 186.85 ◦ C [11]
ZrO2 Eu β-rays 2 204 ◦ C [6]
90
Sr / 90Y 292 ◦ C
ZrO2 Cu UV radiation 2 130 ◦ C [15]
180 ◦ C
CaSO+4 -Glasses Eu, Ag, Ag (NP) β-rays 1 230 ◦ C [34]
90
CaSO+4 -Teflon Sr/90Y 1 200 ◦ C
CaSO4 Tb, Eu β-rays 3 170 ◦ C [53]
90
Sr / 90Y 270 ◦ C
340 ◦ C
Al2O3 Cr β-rays 5 109.45 ◦ C [31]
90
Sr/90Y 181.65 ◦ C
236.65 ◦ C
298.45 ◦ C
362.65 ◦ C

7
S.A. Sinclair and M.I. Pech-Canul Chemical Engineering Journal 443 (2022) 136522

with a more intense TL peak located at 250.45 ◦ C for a dose of 10 kGy, was provided in 1978 [102]. Azorín et al. [103] reported the sensitivity
showing linearity only at low doses up to 100 Gy. The glow curves of the of the mineral topaz, finding two prominent TL peaks, while Lima et al.
G-ZnS compound show a single peak located between 219 ◦ C and 254 ◦ C [104] reported four TL peaks of topaz extracted from Minas Gerais,
over the entire irradiation range, with a variation in dose from 1 Gy to Brazil. They also noted that the number and positions of the TL peaks
50 kGy. G-ZnS shows the most intense TL glow curve for a dose of 50 kGy depend on the time between irradiation and measurement.
with a linear TL response from 1 Gy to 50 kGy [98]. The advent of Topaz has been synthesized using different methods and precursors
carbon nanotubes (CNT) motivated the improvement of the properties of [105], including thermal hydrolysis, where Al2O3, SiF4, SiO2 were used,
polymer-matrix composites for structural and multifunctional applica­ with temperatures between 750 and 950 ◦ C [106]; high-pressure pro­
tions [99,100]. The dosimetric characteristics of polymer-carbon cessing methods with AlF3, Al(OH)3, SiO2, 900 ◦ C at a pressure of 1960
nanotube nanocomposites have been evaluated and compared by vary­ MPa [107]; hydrothermal processes using AlF3, Al2O3, SiO2 at temper­
ing the weight percentages of nanotubes for different polymeric matrices atures greater than 800 ◦ C at 196 MPa and <800 ◦ C at 49 MPa [108];
including high-density polyethylene (HDPE), polycarbonate (PC), sintering with NH4F, Al2Si2O5(OH)4 at temperatures between 725 and
polyethylene terephthalate (PET), polymethyl methacrylate (PMMA) 750 ◦ C [109], Al2O3, SiO2 and AlF3 at 770–800 ◦ C [110]; chemical vapor
and polystyrene (PS). The authors evaluated the current density of the deposition (CVD) with Na2SiF6, Al2O3, Al(OH)3, Al2Si2O5(OH)4 at
polymer–carbon nanotube nanocomposites over the radiation absorbed 700–750 ◦ C and times between 60 and 90 min [5] and Na2SiF6, Al(OH)3
dose under a fixed DC voltage. It was found that the type of polymer with at a temperature of 750 ◦ C, time of 90 min and compaction pressure of
different relative permittivity and heat capacity may influence the 30 MPa [6].
sensitivity and the working dose range as a dosimeter [101]. Fig. 1 presents a graphic summary of the experimental procedures
used by the various authors to obtain composite materials for dosimetry.
5. Processing routes for thermoluminescent dosimetric For topaz-Teflon and topaz-glass, the same preparation route has been
composites followed. The topaz crystals were pulverized to a size between 0.075 and
0.150 mm and were treated at 300 ◦ C for 30 min. The heat-treated
In the last 18 years, various authors have reported the thermolumi­ powder was mixed with Teflon in a 1:2 ratio (by weight) and uni­
nescent characteristics of composite materials for potential applications axially pressed, producing pellets of 6 mm in diameter and 1 mm thick
in dosimetry, using different manufacturing methods, under different [7,13,93,113]. The topaz-glass composites were prepared as follows:
processing conditions, and natural and synthetic precursors. The topaz crystals in size range between 0.045 and 0.075 mm were pulver­
following tables condense the routes used in the investigations ized and mixed with glass powder in a 1:1 ratio (by weight), using
mentioned above. Table 3 lists the composites types that have been polyvinyl alcohol with a concentration of 0.1 g/mL, as a binder. The
made with minerals extracted from different geographical regions, as mixture was pressed uniaxially until obtaining samples of 6 mm in
well as those prepared with synthetic materials. Topaz is the most diameter and 1 mm thick, after which they were heat-treated at 750 ◦ C
widely used mineral in this type of composite since previous studies for 180 min [7,13].
have shown excellent results for dosimetry. The first TL report of topaz Recycled window glass classified as transparent for industrial use has
been used to prepare composites, for which topaz crystals were pul­
Table 3 verized to a size between 45 and 65 μm. The glass sample was crushed to
Methods and experimental conditions used in the manufacture of composites a diameter of 0.55 mm. After grinding, the glass powder was dried and
reported by various authors. mixed with topaz crystals (50% by mass), and samples of 6 mm in
Preparation Precursors Temperature Time Reference
diameter and 2 mm in thickness were formed by uniaxial pressing [93].
method (◦ C) (min) Topaz samples were collected from the Sabser mine in Skardu, Pakistan,
with crystal sizes between 1.5 and 3.5 cm. The topaz crystals were
Sintering Natural topaz-Teflon 300 and 30 and [7]
Natural topaz-glass 400,750 90,180 cleaned with 50% water and 50% Regia solution ((3HCl + HNO3) to
remove dirt and other material particles. The topaz was crushed and
Sintering Natural colorless topaz- 300 and 30 and [13] mixed uniformly (2% by weight) and glass (1% by weight) until
Teflon 400,750 90,180
obtaining samples with dimensions of 6 mm in diameter and 1 mm in
Natural colorless topaz-
glass
thickness, after compacting with a hydraulic press [1]. The topaz from
Sintering Beach sand-Teflon 300 and 400 60 and [18] Minas Gerais, Brazil, has also been studied, where the crystals were
90 crushed in an agate mortar and sieved to sizes between 45 and 65 μm.
Sintering Natural colorless topaz- 400 60 [9] The glass was crushed to 0.5 mm in diameter and ground for 100 h with
glass
isopropyl alcohol in a volumetric ratio of 10:60:30. The glass was dried
Sintering Natural topaz-Teflon 300,400 30 [93]
Natural topaz-window 90 and mixed with topaz crystals and a binder solution of polyvinyl alcohol
glass with a concentration of 0.1 g/mL. Samples of size 6 mm in diameter and
Sintering Beach sand-Teflon 300 and 400 60 and [19] 2 mm in thickness were formed by uniaxial pressing [9]. Based on a
90 Taguchi L8 experimental design and analysis of variance (ANOVA), the
Sintering Wollastonite-Teflon 300 and 400 30 and [111]
90
sintering of topaz powders synthesized by the HYSY-CVD method has
Sintering MnSiO3, CaMg(Si2O6), 300 and 400 60 and [112] been reported. The feasibility of its sintering by in situ forming
Ca2Mg5 (Si4O11)2(OH)2, 90 corundum in the topaz matrix and the control in the amount of
Ca2Fe5 (Si4O11)2 (OH)2- corundum phase with increasing temperature was verified, obtaining
Teflon
the topaz/corundum composite, with an average density of 2.906 g/
Sintering Natural topaz-Teflon 300 and 400 30 and [113]
90 cm3. Topaz/corundum composites have favorable thermoluminescent
Sintering Mineral topaz-glass 900 60 [1] characteristics, with peak intensity in the glow curves at temperatures
Sintering Mineral citrine (SiO2) 300 60 [114] between 150 ◦ C and 250 ◦ C (appropriate temperature range for dosi­
-Teflon metric applications). It has also been found that the presence of the
Patented Alexandrite (BeAl2O4)- 400 60 [115]
technique fluorinated polymer
corundum phase in the composite is beneficial for thermoluminescent
(Brazil) properties, as a higher peak intensity is reached with a 30.7% corundum
Sintering Synthetic topaz 850–1000 30–60 [6] phase [6].
Al2SiO4F1.44(OH)0.56- Wollastonite and citrine have also been extracted from Minas Gerais,
corundum (Al2O3)
Brazil, for the manufacture of the wollastonite-Teflon and citrine-Teflon

8
S.A. Sinclair and M.I. Pech-Canul Chemical Engineering Journal 443 (2022) 136522

Fig. 1. Graphical summary of processing routes and experimental conditions for the development of composite materials for dosimetry.

composites. The mineral is cleaned and crushed until obtaining powders
with diameters between 0.074 and 0.177 mm, and the powdered
wollastonite was heat-treated at 300 ◦ C for 30 min, followed by another
heat treatment at 400 ◦ C for 90 min. The powder was mixed with Teflon
in a 1:2 ratio (by weight) and pressed to produce pellets of 6 mm in
diameter and 1 mm thick [111]. For citrine, the extracted samples were
washed and pulverized until obtaining particles between 0.075 and
0.180 mm in diameter, to be subjected to a heat treatment of 300 ◦ C for
1 h. The composite was prepared using Teflon-citrine in a 2:1 ratio (by
weight) [114].
Sand samples from various beaches in Brazil have been studied. To
remove organic impurities, the sand was washed with a 1 N hydrochloric
acid solution and rinsed with distilled water to remove HCl, dried in an
electric oven at 75 ◦ C for 1 h. Magnetic particles (iron) were removed
using a magnetic separator, and sintered sand pellets were prepared
using Teflon as a binder [18,19]. Fig. 2 shows a graphical summary of
the experimental methodology for the preparation of these composite
materials.
6. Emission and thermoluminescence response of different
composite materials
For a material to be considered a thermoluminescent dosimeter
(TLD), it must show in the glow curves a thermoluminescent peak at a
high temperature not to be affected by ambient temperature and suffi­
ciently low to avoid interference with the emission of the black body of
the heating plate of the thermoluminescence equipment that occurs at
approximately 400 ◦ C. The results of the thermoluminescent emission of

Fig. 2. Experimental methodology for obtaining wollastonite-Teflon, citrine-Teflon and sand-Teflon composite for dosimetry.

9
S.A. Sinclair and M.I. Pech-Canul Chemical Engineering Journal 443 (2022) 136522

manufactured composites have been reported by various authors (see
Table 4).
A comparison of the emission intensities of the topaz-Teflon, topaz-
glass composites was made with the commercial dosimeter TLD-100,
which corresponds to LiF: Mg, Ti, obtaining approximately the same
intensities. However, peak positions vary, showing TL peaks at higher
temperatures, with almost 50% of the total TL emission area above
220 ◦ C. Therefore, in terms of dosimetric applications, the composite
materials have a more significant advantage over the commercial
dosimeter TLD-100, since the highest temperature peaks are more stable
at room temperature than those at low temperatures [7]. This result is
essential for environmental dosimetry applications, where the TL
emission is measured long after the sample is irradiated [13]. However,
topaz-Teflon composites have an intensity TL 80% higher compared to
the intensity of topaz-glass. This difference in intensities is the result of
the temperature applied to both materials since the topaz-Teflon was
thermally treated at 400◦ C and the topaz-glass at 700◦ C. It is possible to
assure that the TL intensity of topaz is reduced if the temperature of the
pre-irradiation treatment is increased [9].
The TL response to the dose of the topaz-Teflon composite irradiated
with 60Co gamma rays has also been studied, observing a sublinear dose
dependence for low doses (10− 4–10− 2 Gy), linear from 10− 2 to 20 Gy,
supralinear and again sublinear, reaching saturation between 2 and 3
kGy. For topaz-glass composites, linearity of the TL response was
observed with the dose when the material was irradiated with γ rays of
0.11 Gy–14.6 Gy (137Cs), 0.1 to 6.0 Gy (60Co), and X-rays (6 MV) [9].
These results show that composites prepared from colorless natural
topaz are suitable for different applications in dosimetry [7,13], being
very promising new TL dosimeters since they are appropriate for per­
sonal dosimetry (low doses) or radiotherapy, where they use doses be­
tween 0.1 and 100 Gy, as well as for the use of quality control programs
for radiation-emitting devices, where the doses are very high [13].
In addition to thermoluminescent studies of topaz, research has been
carried out on different composite materials made from natural min­
erals, such as wollastonite and citrine stones, as well as for beach sand
from various locations in Brazil. The relationship between the dose and
TL intensities of wollastonite-Teflon was studied, showing linearity with
the absorbed dose between 1 and 10 Gy, supralinearity for doses be­
tween 5 × 102 Gy and 7 × 103 Gy, and for high doses, the maximum
Table 4
Types of radiation, number and location of TL peaks of composites reported by
various authors.
intensity presented a proportional response at an absorbed dose up to 7
× 103 Gy, suggesting that this composite may be helpful for high dose
measurements [111]. The dose–response curve of citrine-Teflon samples
irradiated at 60Co shows a linear behavior and sublinearity after 500 Gy
[114]. For sintered sand composites, linearity was observed between 10
Gy and 1 kGy, with saturation effects around 10 kGy [19].
The thermoluminescent characteristics of sands from various bea­
ches in Brazil have studied, including Barra do Sahy Beach, São Paulo
(sample A); Santinho Beach, Santa Catarina (sample B); and Ponta Negra
Beach, Rio Grande do Norte (sample C), where a comparison of the
thermoluminescent properties of the different sand samples, both nat­
ural and without iron particles, was carried out, proving them suitable
for high-dose dosimetry. The sand comprises quartz, feldspar, and some
other impurity elements in smaller quantities. Table 5 shows the
chemical composition results of the different beach sand samples per­
formed by the neutron activation analysis technique. For these com­
posites, linearity was observed between 10 Gy and 1 kGy, with
saturation effects around 10 kGy [19].
7. Comparison of thermoluminescent (TL) properties in
composites reported for the various dosimetric applications
The composite materials studied have presented specific favorable
properties for the various dosimetry applications. With the composite
materials made from natural topaz, an adequate reproducibility of the
glow curve has been obtained since they can be used in consecutive
irradiation, reading, and annealing cycles without noticeable changes in
their sensitivity [7,13]. The sensitivity of topaz-Teflon is 2.2 times less
than that of the commercial dosimeter TLD-100 (LiF: Mg, Ti), and that of
the topaz-glass composite is two times less than the sensitivity of the
TLD-100. The reproducibility of topaz-Teflon composite is better than
that of topaz-glass dosimeters, indicating that improvements in the
preparation of the latter are needed, as there is better control in the
process of obtaining topaz-Teflon. Different TL readings were taken from
the topaz-Teflon samples irradiated at 1 Gy and heat-treated at 300 ◦ C/
h, obtaining TL intensities that remain unchanged up to 10 cycles [13].
So far, no significant changes have been observed after the cycles
analyzed, so it can be ensured that the reproducibility of these composite
Table 5
Chemical composition of sand from different beaches in Brazil. They are taken
from [19] with permission.
Barra do Sahy Beach Santinho Beach Ponta Negra Beach

Composite Radiation source Number of Peak location Reference Element A1 A2 B1 B2 C1 C2

peaks TL (μg/g)

Topaz-Teflon γ-rays 60
Co 1 260 ◦
C [7] Al 7015 ± 5765 ± 4701 ± 3760 ± 8099 ± 5476 ±
Topaz-glass 2 120 and 86 86 51 51 81 70
250 ◦
C Ba 86 ± 1 75 ± 1 53.5 ± 43.3 ± 87 ± 0.7 102 ± 1
Topaz-Teflon Electron beams 8, 1 200 ◦
C [113] 0.8 0.7
10, 12 y 14 MeV Ca 4075 ± 952 ± 2999 ± 267 ± 27666 2168 ±
Topaz-Teflon γ-rays 60Co 2 150 and [13] 299 70 220 20 ± 2033 159
Topaz-glass 2 260 ◦
C Ce 92 ± 1 8.5 ± 5.70 ± 3.38 ± 31.1 ± 15.3 ±
120 and 0.1 0.07 0.04 0.4 0.2
250 ◦
C La 44 ± 1 3.9 ± 3.3 ± 2.01 ± 16.0 ± 7.3 ±
Topaz-Teflon γ-rays 60
Co 2 120 and [9] 0.1 0.1 0.06 0.5 0.2
Topaz-glass 2 220 ◦
C Mn 94 ± 3 12.8 ± 21.7 ± 5.5 ± 99,229 2.4 ±
110 and 0.9 1.3 0.6 0.2
210 ◦
C Na 322 ± 141 ± 146 ± 66 ± 10 444 ± 342 ±
Topaz- β-rays 90Sr 1 193 ◦
C [6] 66 36 15 24 10
corundum Nd 37.1 ± 3.11 ± 2.79 ± 1.24 ± 9.0 ± 6.9 ±
Wollastonite- γ-rays 60
Co 3 100–150 ◦ C [111] 0.9 0.07 0.06 0.03 0.2 0.5
Teflon 200 ◦ C Th 18.41 1.73 ± 0.83 ± 0.42 ± 17.3 ± 7.03 ±
245 ◦ C ± 0.08 0.01 0.02 0.01 0.07 0.03
Citrine-Teflon γ-rays 60
Co 2 160 ◦ C [114] Ti 1588 ± 286 ± 667 ± 134 ± 28615 461 ±
220 ◦ C 113 58 57 37 ± 1445 54
Sand-Teflon γ-rays 60
Co 2 110 ◦ C [18] Fe (%) 0.498 0.105 0.207 0.055 1.46 ± 0.039
170 ◦ C ± 0.009 ± 0.002 ± 0.004 ± 0.001 0.03 ± 0.001
60
Sand-Teflon Co 2 110 ◦ C, [19]
A1, B1 and C1: natural sand samples, cleaned with HCl (1 M); and A2, B2 and C2:
γ-rays
170 ◦ C
natural sand samples, cleaned with HCl (1 M), without Fe.

10
S.A. Sinclair and M.I. Pech-Canul
materials is adequate for the proposed application [9].
The fading of natural topaz-Teflon composite heat-treated at 400◦ C
and gamma-irradiated at 0.1 Gy is acceptable, demonstrating that reuse
is possible, with a fading of approximately 7% in 30 days, being below
the limit of 10% fading acceptable for dosimetry (CEI / IEC 1066, 1991)
[13]. For the topaz-glass samples irradiated at 1 Gy (60Co), a fading of
8% was observed after 30 days and 15% at 60 days [9]. The detection
limit is the smallest dose value that can be detected with a specific
confidence level. For composite materials prepared with sand from
Barra do Sahy, Santinho, and Ponta Negra beaches, lower detection
limits of 30, 20, and 40 mGy, respectively, have been obtained [19]. The
thermal fading of the sand samples was determined by taking daily
measurements up to 30 days after irradiation, presenting a reduction in
its TL response of 20% after 24 h post-irradiation, with a slow decay and
with constant values after 15 days [19].
For wollastonite-Teflon composites, the minimum detection limit
was 0.04 Gy, indicating that this dosimeter shows a TL response only
when irradiated with doses greater than or equal to the mentioned limit.
Five successive cycles of irradiation-reading-annealing were carried out
to determine the reproducibility, showing adequate repeatability for
dosimetric purposes without significant changes in its sensitivity, with a
dispersion of the results less than 6.3% [111]. The lower limit of
detection of the citrine composite was obtained at 150 mGy, with a
response to reproducibility attained of 3.25%, by subjecting the material
to a heat treatment at 300 ◦ C/1h, irradiation of 60Co (5 kGy), and heat
treatment at 130 ◦ C/10 min (to eliminate the peak at low temperature)
[114].
8. Prospects and conclusions
The thermoluminescent properties of the different composites and
activated materials for their application in dosimetry have been dis­
cussed. These composite materials have superior properties compared to
commercial dosimeters, such as more excellent stability of traps and
recombination centers at higher temperatures. Composite materials
processed from natural colorless topaz are very promising new solid-
state TL dosimeters, being suitable for various applications, such as
personal dosimetry, where low doses are measured, or radiotherapy,
where doses between 0.1 and 100 Gy are applied, as well as for the use of
quality control in radioactive equipment, where high doses are involved.
Sand composites can be applied in high doses in areas such as industry
(pasteurization and water purification), medicine, agriculture (insect
control and population, seed stimulation), in addition to presenting
advantages of low cost, high availability, and easy handling. The acti­
vated materials showed a general trend of stability of the traps; as the
concentration of the activators increases, the emptying temperature of
the traps shifts towards the higher temperature, because of the rise in the
population of load carriers with the introduction of the dopant. The
increase in the TL intensities in the glow curves was also verified, as well
as a greater sensitivity of the materialś response compared to the
undoped samples.
Despite the advances achieved so far, there is still room for
improvement. Investigations should not be limited to establishing the
optimal dopant concentrations with the addition of different activators.
Research areas for possible contributions include a) Explaining the
decrease in the TL intensity of a phosphor after reaching a maximum
value with the addition of a given dopant, as in the case of LiSrBO3
doped with Tm3+ and SrDy2O4 with additions of europium ions, b)
Giving the reason for the decrease of materialś sensitivity by sintering
the powders like in the case of LiF doped with Mg, Cu, Na, and Si as
activators. The phenomena associated with sintering like neck forma­
tion, diffusion, pore shrinking, and grain growth, to some extent, should
give account to the materials’ luminescent properties. Since they also
affect the microstructure, the glow curve structure and luminescent ef­
ficiency depend not only on the sintering temperature but also on other
sintering process parameters such as holding time, heating/cooling rate,
11
Chemical Engineering Journal 443 (2022) 136522
and atmosphere. c) Conduct experimental design-based investigations to
determine the quantitative effect of doping and double-doping and the
processing parameters, including the dopant concentration, tempera­
ture, time, atmosphere (amongst others), and the possible interactions
between parameters on the TL intensity and other related luminescent
properties. Of much usefulness will be determining the quantitative ef­
fect of the interaction resulting from double doping. The methodology
should include determining the optimal conditions to maximize a given
response variable or property and the associated experimental error
value, followed by confirmation tests that compare the projected value
of the response variable with that obtained in experimental verification
tests.
The current literature shows that it is necessary to continue exploring
the development of composite materials with superior properties more
suitable for radiation dosimetry, such as a greater sensitivity over a wide
range of linear response doses, between 1 µGy and 1 kGy. So far, such a
feature has not been found in any solid-state TL dosimeter. In many
cases, a combination of different dosimetric techniques is the only way
to obtain the desired information. The TLD-100 commercial dosimeter
has linearity in the dosing interval between 0.001 and 10 Gy, so it is
intended that synthetic composites present a better linear response, and
they can serve as a replacement for the commercially offered dosimeters.
Synthetic dosimeters have the advantage of controlled stoichiometry,
with a precise chemical composition, microstructure, and high repro­
ducibility. Previous studies carried out by the research group at
CINVESTAV-Saltillo have made it possible to suggest the potential for
applying synthetic topaz in the area of dosimetry. Therefore, it is
considered pertinent to continue with the investigation of the thermo­
luminescent properties of topaz composites, representing a window of
opportunity for its use.
Future work may focus on the development of composites with
natural and/or synthetic phases, as well as the need to understand the
role that defects play in the behavior of synthetic topaz-corundum do­
simeters, including the effect of dopants in composites, thereby
achieving a better understanding of luminescence mechanisms. Ther­
moluminescence can be used to analyze such defects by studying a
comparative graphical and quantitative analysis of the improvement of
thermoluminescent properties when forming the composites. It is worth
mentioning that the authors of this work are currently developing syn­
thetic topaz and studying the thermoluminescent properties of sintered
synthetic topaz-corundum composites.
Finally, and as evidenced by the scarcity of reports in the current
literature, more contemporary contributions would be geared toward
developing multifunctional dosimetric materials, namely, materials that
perform more than one function by virtue of their natural or engineered
properties.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
S. A. Sinclair gratefully acknowledges Conacyt (National Council of
Science and Technology in Mexico) for granting a doctoral scholarship.
The authors are thankful to Cinvestav for providing facilities for
research on advanced composite materials.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2022.136522.
S.A. Sinclair and M.I. Pech-Canul Chemical Engineering Journal 443 (2022) 136522

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