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Effect of annealing temperature onthermoluminescence glow curve for UV andgamma ray induced ZrO2:Ti phosphor

Raunak Kumar Tamrakar a,*, Neha Tiwari b, R.K. Kuraria b, D.P. Bisen c,Vikas Dubey d, Kanchan Upadhyay e

a Department of Applied Physics, Bhilai Institute of Technology (Seth Balkrishan Memorial), Near Bhilai House,

Durg (C.G.) 491001, Indiab Department of Physics, Govt. Autonomous Science College, Jabalpur, Indiac School of Studies in Physics and Astrophysics, Pt. RavishankarShukla University, Raipur (C.G.) 492010, Indiad Department of Applied Physics, Bhilai Institute of Technology (Seth Balkrishan Memorial), Kendri, Raipur,

Pin 492010, Indiae Department of Chemistry, Shri Shanakaracharya Vidhyalaya, Amdi Nagar, Hudco, Bhilai 490006, India

a r t i c l e i n f o

Article history:

Received 26 September 2014

Received in revised form

10 October 2014

Accepted 22 October 2014

Available online 11 November 2014

Keywords:

Thermoluminescence

ZrO2:Ti

Combustion synthesis

CGCD

Effect of annealing

Various heating rate method

* Corresponding author. Tel.: þ91 982785011E-mail addresses: [email protected]

Peer review under responsibility of The Ehttp://dx.doi.org/10.1016/j.jrras.2014.10.0051687-8507/Copyright© 2015, The Egyptian Socopen access article under the CC BY-NC-ND l

a b s t r a c t

The present paper reports the thermoluminescence (TL) properties of combustion syn-

thesized Ti doped ZrO2 nanophosphors the effect of annealing on TL glow curve was also

studied. The structural characterizations were done by X-ray diffraction technique (XRD),

composition by Fourier transformation infrared spectroscopy and surface morphology was

determined by field emission gun scanning electron microscopy (FEGSEM) technique. The

prepared phosphor annealed at 600 �C, 700 �C, 800 �C and 900 �C and its thermolumines-

cence glow curve were recorded. The heating rate effect, the thermal quenching as well as

the annealing temperature of the material were optimized for the TL glow curve of the

sample. The TL glow curves for different UV, gamma doses and for Ti concentration were

studied. The TL glow curve of prepared samples have glow peak at 173 �C. The kinetic

parameters was calculated by Computerized glow curve convolution technique (CGCD)

technique. Fading and reusability studies of the nanophosphor further confirmed the

phosphor's suitability for radiation dosimetry. The main conclusion is that Solution

Combustion Synthesis is one of the appropriate method for synthesis of Ti doped ZrO2

nanophosphors, which is suitable for temperature sensing applications, the post-synthesis

annealing regime being one of the parameters that can affect the intensity and other

parameters.

Copyright © 2015, The Egyptian Society of Radiation Sciences and Applications. Production

and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license

(http://creativecommons.org/licenses/by-nc-nd/4.0/).

3 (mobile)., [email protected] (R.K. Tamrakar).

gyptian Society of Radiation Sciences and Applications.

iety of Radiation Sciences andApplications. Production and hosting by Elsevier B.V. This is anicense (http://creativecommons.org/licenses/by-nc-nd/4.0/).

J o u r n a l o f R a d i a t i o n R e s e a r c h and A p p l i e d S c i e n c e s 8 ( 2 0 1 5 ) 1e1 02

1. Introduction

Thermoluminescence (TL) technique reached at new height in

the field of radiation therapy, space research, geology,

archaeology and other related research areas has attracted

researchers from all over the world. It is an extremely powerful

technique used for estimation of doses of ionizing radiations

as the energy absorbed during irradiation and the following TL

intensity on stimulation is proportional to the radiation doses.

But, one of the main challeng is the limited availability of TL

materials with properties suitable for temperature sensing,

namely a wide range of TL peaks and light insensitivity, among

others (Barth et al., 2003; Bahl et al., 2013; Strehl, 1999).

This work is part of an effort to develop new TL materials

with TL peaks in a wide range of temperatures and insensitive

to light, therefore suitable for temperaturemeasurements.We

have been exploring the Solution Combustion Synthesis (SCS)

method (Chick et al., 1990). ZrO2 is one of the widely studied

oxide materials over the last two decades because of its

excellent electrical and optical properties. It is an attractive

material in both fundamental and application-oriented

research. It is well known for low thermal conductivity, high

melting point, and high thermal andmechanical resistance. It

is used as an ideal medium for fabrication of highly lumi-

nescent material due to its high refractive index, low phonon

energy, high chemical and photochemical stability (Chandra,

2010; Tamrakar, Bisen, Upadhyay, & Tiwari, 2014; Tiwari,

Kuraria, & Tamrakar, 2014).

In the present paper, we prepared ZrO2:Ti phosphor by

solution combustion synthesis method and investigated its

thermoluminescence glow curve for the samples annealed at

600 �C, 700 �C, 800 �C and 900 �C. Moreover, previous work has

focused on material properties that are important (Tiwari

et al., 2014), the objective of this work was to investigate the

effect of annealing on the TL properties of Ti doped ZrO2

nanophosphors synthesized by Solution Combustion Method.

The heating rate that affects the thermal quenching as well as

the annealing temperature of thematerial was optimized. The

kinetic parameters were calculated by Computerized glow

curve convolution technique technique. Fading and reus-

ability studies of the nanophosphor further confirmed the

phosphor's suitability for radiation dosimetry.

1.1. Synthesis of ZrO2:Ti nanophosphor

The raw materials, zirconium (IV) oxynitrate hydrate

(ZrO(NO3)3 $ 6H2O: 99.99%, (Sigma Aldrich) and Titanium (IV)

nitrate tetrahydrate (Ti(NO3)4.4H2O Sigma Aldrich) are the

sources of Zr and Ti respectively. Urea was used as fuel.

(Tamrakar, Bisen, & Brahme, 2014a, 2014b).

Scheme 1 e Synthesis o

For the synthesis of ZrO2:Ti (0.2 mol%), required amount of

Urea and aqueous mixture of zirconium (IV) oxynitrate hy-

drate were subsequently added to the titanium nitrate solu-

tion while continuously stirring the mixture to ensure

homogeneous mixing. The mixture was heated on a hot plate

at 60 �C for 1.5 h convert these in to gel form. The Petri dish

containing the homogeneous redox mixture introduced into a

muffle furnacemaintained at 600 ± 10 �C. Initially the solution

boils and undergoes dehydration. Eventually the mixture un-

dergoes decomposition, which results in the liberation of large

amounts of gases (usually CO2, H2O andN2). This was followed

by a spontaneous ignition which resulted in flame type com-

bustion (Chick et al., 1990; Singanahally & Alexander, 2008;

Tamrakar, Bisen, & Brahme, 2014a, 2014b). The whole pro-

cess completed in less than 5 min and a highly porous ZrO2:Ti

nano powder obtained. Finally, samples annealed in a pre-

heatedmuffle furnace from600 �C to 900 �C for fixed periods of

time 2 hour (Tamrakar, Bisen, & Brahme, 2014a, 2014b; Tam-

rakar, Bisen, & Ishwer, 2014, Tamrakar, Bisen, Ishwer and

Bramhe, 2014; Tiwari, Kuraria, & Tamrakar, 2014) (Scheme 1).

1.2. Instrumental details

The final productswere characterized using Panalytical X-pert

PRO MPD X-ray diffractometer (PXRD) with copper k alpha

anode of wavelength 1.5405 A. The diffraction patterns

recorded at room temperature with nickel filter in the 2q range

15e85 at a slow scan rate. The morphological features and

particle size was studied by scanning electron microscopy

(SEM, Hitachi-3000) (Dubey, Tiwari, Tamrakar, Rathore, &

Chitrakat, 2014; Dubey, Tiwari, Pradhan, et al., 2014;

Tamrakar, 2012; Tamrakar, Bisen, Upadhyay & Bramhe,

2014, Tamrakar, Bisen, & Sahu, 2014). Thermally stimulated

luminescence glow curves were recorded at room tempera-

ture The thermoluminescence studies were carried out using

TLD reader I1009 supplied by Nucleonix Sys. Pvt. Ltd. Hyder-

abad. The sample was irradiated by UV radiation 254 nm. The

heating rate used for TL measurement is 6 �C/s. Kinetic

parameter evaluated by Chen's peak shapemethod and graph

plotted by Origin 8.0 programme. For gamma, irradiations a

60Co source was used which produced an exposure rate of

0.69 kGy/h.

2. Results and discussion

2.1. X-ray diffraction results

The crystal structures and the phase purity of the materials

were obtained for each of the synthesized materials both

f ZrO2:Ti phosphor.

Fig. 1 e X-ray diffraction patterns of fresh and annealed ZrO2:Ti (0.2 mol%).

J o u r n a l o f R a d i a t i o n R e s e a r c h a nd A p p l i e d S c i e n c e s 8 ( 2 0 1 5 ) 1e1 0 3

before and after annealing. Fig. 1 shows the PXRD patterns of

fresh and annealed ZrO2:Ti (0.2mol%), nanophosphors (Tiwari

et al., 2014). In addition, it was clearly seen that with the in-

crease of annealing temperature, the diffraction peak of

samples were unchanged i. e. there is no phase change, peak

shifting and line broadening were found with the increasing

annealing temperature. The sample shows cubic structure

and the particle sizewere calculated by Scherer's formula. The

Scherrer formula is given by: D ¼ 0.9 l/b Cos q, Where, D is the

average particle size perpendicular to the reflecting planes, l

is the X-raywavelength, b is the FWHM, and q is the diffraction

angle (Tamrakar, 2012; Tamrakar, Bisen, Upadhyay& Bramhe,

2014, Tamrakar, Bisen, & Sahu, 2014). The average crystallite

sizes were 54 and 73 nm for the annealing temperatures of 600

and 900 �C respectively (Table 1).

2.2. Fourier transformation infrared spectroscope (FTIR)results of ZrO2:Ti (0.2 mol%) nanophosphor

Fig. 2 shows the FTIR spectra of combustion synthesized

ZrO2:Ti (0.2 mol%) phosphor. A strong absorption peak at

Table 1 e Particle size and annealing temperature.

S. No. Annealing temperature Particle size

1. Fresh ZrO2:Ti(.2%) 54

2. 600 �C 60

3. 700 �C 64

4. 800 �C 69

5. 900 �C 73

551.68 cm�1 corresponds to ZreO vibrational modes of ZrO2

phase (Gao et al. 2009). Moreover, the absorption band centred

atz3341.67 cm�1 corresponds to OH stretching vibrations and

peak centred at 1387.11 cm�1 corresponds to bending vibra-

tion of OeH in H2O (Tamrakar, Bisen, Robinson, Sahu, &

Brahme, 2014; Tamrakar, 2013; Tiwari et al., 2014). As

increasing the annealing temperature the OeH Band were

completely vanished.We found nomore significant difference

in FTIR spectra. As similar to PXRD results, FT-IR studies show

no other trace or impurity in the final powder and that it is

pure and crystalline.

2.3. Scanning electron microscope results of ZrO2:Ti(0.2 mol%) nanophosphor

The scanning electron micrographs of freshly prepared sam-

ple and samples annealed at 600 and 900 �C for 2 h are shown

in Fig. 3aec, respectively. ZrO2:Ti (0.2 mol%) nanophosphor

show the crystallites with irregular shape and contain several

voids and pores because of the escaping gases during com-

bustion synthesis. It was observed that the crystallites are non

uniform in shape and size. The non-uniform distribution of

shape and size of phosphor can be correlated with the tem-

perature andmass flow in the combustion flamewhich results

in formation of porous phosphors. This type of porous

network is a typical characteristic of combustion-synthesized

phosphors. (Tamrakar, Bisen, & Brahme, 2014a, 2014b). With

an increase in annealing temperature, the highly porous

structure was seen in the freshly prepared sample (Fig. 3a),

which changes to flaky aggregates with pores in their

Fig. 2 e FTIR spectra of fresh and annealed ZrO2:Ti (0.2 mol%).

Fig. 3 e Scanning electron microscope image of ZrO2:Ti (0.2 mol%) (a) freshly prepared; (b) annealed at 600 and (c) annealed

at 900.

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J o u r n a l o f R a d i a t i o n R e s e a r c h a nd A p p l i e d S c i e n c e s 8 ( 2 0 1 5 ) 1e1 0 5

structure at 600 �C (Fig. 3b). Further increase in annealing

temperature to 900 �C results in agglomeration of primary

particles (Fig. 3c), In this case, the particles fuse together,

resulting in larger crystallite sizes, which is consistent with

PXRD results.

Fig. 5 e Heating rate Vs peak temperature plot for different

heating rate for freshly prepared.

2.4. Thermoluminescence studies of ZrO2:Ti (0.2 mol%)

2.4.1. Effect at different heating rates for freshly preparedZrO2:Ti (0.2 mol%)doped phosphorsFrom the TL glow curve with effect of heating rate for opti-

mized concentration (0.2 mol%) of doping ions shows dual TL

glow curve at low and high temperatures (Fig. 4) (Tiwari et al.,

2014). Heating rate varies from 4e8 �C and peak shifts towards

higher temperature side when increase the heating rate it

shows a different pattern and valuable information for trap

depth. The temperature of TL glow curve varies from 164 �C to

193 �C according to the heating rate (Fig. 5). Here from the TL

glow curve of ZrO2:Ti (0.2 mol%) gives the information that TL

glow curve strongly depend upon the heating rate and its

properties varies when heating rate increase. The corre-

sponding kinetic parameters such as activation energy, order

of kinetic and frequency factor calculated by peak shape

method for intense peak of TL glow curve (Table 2). Here from

present table the activation energy as well as frequency factor

is highest for the higher heating rate (8 �C s�1).

2.4.2. Effect of annealing on ZrO2:Ti (0.2 mol%) dopedphosphorsEffect of annealing temperature on TL glow curve from

600e900 �C was studies. It shows the broad single glow curve

(Fig. 6) and the higher temperature peak eliminated due to the

annealing the sample (Fig. 4). The high temperature peak may

be the impurity peak in TL glow curve and it eliminated when

sample is heated. Also the TL intensity of the prepared sample

increase with increase in annealing temperature and no

change in peak temperature was observed. It is observed that

the optimized temperature for heating sample i.e ZrO2:Ti for

optimized concentration of Ti (0.2 mol%) shows intense and

Fig. 4 e TL spectra at different heating rate for freshly

prepared ZrO2:Ti (0.2 mol%) doped Phosphors for fixed

20 min UV exposure time.

broad TL glow curve and the corresponding kinetic parameter

was high for the optimized temperature (Table 3). The linear

response with heating rate versus TL glow curve intensity is

very interesting result on TL glow curve (Fig. 7).

Here the TL glow curve recorded for fixedUV exposure time

20 min as well as fixed heating rate 6 �C for the variation of

600e900 �C annealing temperature. The calculation of kinetic

parameters such as activation energy (E) in eV as well as the

frequency factor in s�1 was determined by peak shape

method. For the variation of 600e900 �C annealing tempera-

ture, the activation energy varies from 0.69 eV to 0.72 eV and

the relative frequency factor found 9.2 � 1008 to 1.5 � 1009 s�1.

All peaks shows the first order of kinetic because the value of

shape factor m ~ 0.42 or less than o.42 (Table 3) shows the first

order kinetics glow curve.

2.4.3. Effect at different heating ratesFor the optimized annealing temperature (900 �C) as well as

the optimized concentration of Ti (0.2 mol%) in ZrO2 host the

Fig. 6 e TL spectra of ZrO2:Ti (0.2 mol%) doped Phosphors

for 20 min fixed UV exposure of time for different

annealing temperature with heating rate 6 �C/s.

Table 2 e Kinetic parameters at different heating rates for freshly prepared ZrO2:Ti (0.2 mol%) doped Phosphors fixed20 min UV exposure time.

Heating rate T1

(�C)Tm

(�C)T2

(�C)t d u m ¼ d/u Activation energy

E in eVFrequency factor

S in s�1

4 129 164 189 35 25 60 0.417 0.69 1.1 � 1009

5 130 169 189 39 20 59 0.339 0.621 2.2 � 1008

6 129 173 189 44 16 60 0.267 0.549 1.4 � 1007

7 129 180 190 51 10 61 0.164 0.475 1.4 � 1006

8 161 193 220 32 27 59 0.458 0.87 3.4 � 1010

Fig. 7 e Intensity vs annealing temperature of ZrO2:Ti

(0.2 mol%) doped Phosphors for 20 min fixed UV exposure

of time for different annealing temperature with heating

rate 6 �C/s.

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recorded TL glow curve with different heating rate (4, 5, 6, 7

and 8 �C s�1) shows good TL glow curve (Fig. 8). The peak in-

tensity remains constant for every hating rate but the peak

position shifted towards the higher temperature size. The

increase of heating rate in TL glow curve peak temperature

versus heating rate plot shows linear response (Fig. 9). From

these TL glow curve it is very clear that high temperature peak

is more stable as compared to lower temperature peak. The

high stability and less fading in TL glow curve shows the

application of dosimeter in TL glow curve. The reproducibility

of sample was also determined by the higher temperature

peak. Here the peak centred at 164, 172, 180 and 194 �C with

variable heating rate. Here the heating rate 8 �C s�1 is suitable

for TL dosimetric application due to its high stability. This TL

glow curve recorded for 20 min UV exposure and fixed con-

centration of Ti in host lattice ZrO2. It is very interesting that

the UV exposure form the shallow traps which is responsible

Table 3 e Kinetic parameters of ZrO2:Ti (0.2 mol%) doped Phosannealing temperature with heating rate 6 �C/s.

Annealing temperature(�C)

T1

(�C)Tm

(�C)T2

(�C)t d

Fresh 138 173 198 35 25

600 137 173 199 36 26

700 138 173 197 35 24

800 137 173 199 36 26

900 138 173 198 35 25

for TL glow curve and TL glow peak is lower when shallower

traps was formed. But in the case of ZrO2:Ti phosphor the

formation of both traps surface trap (shallower trap) and deep

trapping phenomenon both occurs and the high temperature

peak indicate that the formation of deep trap in prepared

sample (Dubey, Kaur, Agrawal, Suryanarayana, & Murthy,

2014; Dubey, Kaur, & Agrawal, 2013a, 2013b; Dubey et al.

2010; Dubey, Kaur, Agrawal, 2014a, 2014b; Dubey, Kaur,

Agrawal, Suryanarayana, & Murthy, 2014; Kaur, Parganiha,

Dubey, Singh, & Chandrakar, 2014; Tamrakar, Dubey, et al.,

2013). The kinetic parameter for the TL glow peaks were

calculated by peak shape method the activation energy is

highest for the higher heating rate of TL glow curve (Table 4).

2.4.4. Effect at gamma exposure on ZrO2:Ti (0.2 mol%) dopedphosphorsWhen we compare the TL glow curve induced by UV exposure

with gamma exposure 0.5, 0.75 and 1 kGy gamma exposure

well resolved peak found at higher temperature 205 �C (Fig. 10)

higher than the UV induced sample (173 �C). It is concluded

that the gamma induced sample ismore stable and less fading

was found so the suitability of prepared sample for gamma

dosimetry (Tamrakar, Bisen, & Brahme, 2014a, 2014b;

Tamrakar, Bisen, Sahu, & Brahme, 2014a, 2014b).

The sample shows linear response with gamma dose

(Fig. 11) it presents the sample is suitable for dosimetric

application for gamma induced. The ZrO2:Ti (0.2 mol%) for

optimized annealing temperature 900 �C has the good TL peak

centred at 205 �C and the formation of deep trapping

confirmed from higher temperature peak.

According to experimental the results here described, the

presence of transition metal ions (Ti) changes the TL glow

curve structure either enhancing or quenching the TL effi-

ciency. These changes are a consequence of the crystalline

field perturbation due to the different characteristics of the

dopant ions which supposedly replaces the zirconium sites.

The traps and the glow curve structure are also dependent

phors for 20 min fixed UV exposure of time for different

u m ¼ d/u Activation energyE in eV

Frequency factorS in s�1

60 0.417 0.72 1.6 � 1009

62 0.419 0.699 9.2 � 1008

59 0.407 0.718 1.5 � 1009

62 0.419 0.699 9.2 � 1008

60 0.417 0.72 1.6 � 1009

Fig. 8 e TL spectra of ZrO2:Ti (0.2 mol%) doped phosphors

for 20 min fixed UV exposure annealed at 900 �C for

different heating rate.

Fig. 9 e Heating rate vs peak temperature of ZrO2:Ti

(0.2 mol%) doped Phosphors for 20 min fixed UV exposure

annealed at 900 �C for different heating rate.

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upon the morphology of the surface area which in turn de-

pends on the nanocrystallite size. The nanocrystallite size

depends also on the dopant ion. Furthermore, the obtained

experimental results show that the presence of dopant ions

also modifies the TL recombination efficiency which was

found to be different for each irradiation type (UV and gamma

dose) and the specific exposed material. It is important to

notice that using the right dopant concentration (Ti 0.2 mol%),

Table 4 e Kinetic parameters of ZrO2:Ti (0.2 mol%) doped PhosDifferent heating rate.

Heating rates T1(�C)

Tm(�C)

T2(�C)

t d u m ¼ d/

4 128 161 187 33 26 59 0.441

5 130 164 189 34 25 59 0.424

6 129 173 189 44 16 60 0.267

7 129 180 190 51 10 61 0.164

8 161 193 220 32 27 59 0.458

it is possible to maximize the TL efficiency and improve

sensitivity and dose linearity for a specific irradiation type

(Dubey et al., 2014b; Tamrakar & Bisen, 2013; Tamrakar,

Upadhyay, & Bisen, 2014).

Thermoluminescence (TL) phosphors generally exhibit

glow curves with one or more peaks when the charge carriers

are released. The glow curve is characteristic of the different

trap levels that lie in the band gap of the material. The traps

are characterized by certain physical parameters that include

trap depth (E) and frequency factor(s). For many TL applica-

tions, a clear knowledge of these physical parameters is

essential. In the study of relatively deep trapping effect-states

in various solid state materials as well as TL dating, a detailed

analysis of TL glow curves is indispensable.

Chen's method (Chen & Kirsh 1981) was used to determine

the kinetic energy parameters of the glow peak of the TL

materials. This method is mainly based on the temperature

Tm, T1 and T2, where Tm is the peak temperature, while T1 and

T2 are temperatures at half the intensity on the ascending and

descending parts of the glow peak respectively. To determine

the kinetic parameter the following shape parameters are to

be determined: the total half intensity width u ¼ T2 � T1. The

high temperature half width d ¼ T2 � Tm and the low tem-

perature half width t ¼ Tm � T1 the peak shape method is

mainly used to calculate the order of kinetics. Order of kinetic

can be evaluated from the symmetry factor (mg) of the glow

peak. mg is calculated using Eq. (1) from the known peak shape

parameters d andu.

mg ¼d

u¼ T2 � Tm

T2 � T1(1)

Order of kinetics depends on the glow peak shape. The

value of mg for the first order and second order kinetics is 0.42

and 0.52 respectively. Chen has provided a plot which gives of

geometric factor (mg). Another parameter proposed by Balarin

gives the kinetic order as a function of the parameter.

g ¼ d

t¼ T2 � Tm

Tm � T1(2)

For the first order kinetics, the Balarin parameter (g) ranges

from 0.7 to 0.8 for the second order kinetics (g) varies from 1.05

to 1.20. Generally in the first order, the process of retrapping is

negligible and the trap should be situated very close to the

luminescent centre. The characteristics of the second order

peak are wider and it is more symmetric than the first order

peak. For a fixed heating rate, in first order kinetics both peak

temperature and shape are independent of the initial trapped

electron concentration but in the second order, the peak

phors for 20 min fixed UV exposure annealed at 900 �C for

u Activation energy E in eV Frequency factor S in s�1

0.727 3.4 � 1009

0.713 1.9 � 1009

0.549 1.4 � 1007

0.475 1.4 � 1006

0.87 3.3 � 1010

Fig. 10 e TL glow curve of ZrO2:Ti (0.2 mol%) doped

phosphor annealed.

Fig. 11 e Gamma dose vs intensity ZrO2:Ti (0.2 mol%)

doped.

Fig. 12 e CGCD curve of experimental TL glow peak of

ZrO2:Ti (0.2%) for fixed 1 kGy with heating rate 6 �C/s.

Table 6 e Trapping parameters of a typical glow curve forZrO2:Ti(.2%) for fixed 1 kGy with heating rate 6 �C/s.

Peaks T1 (K) Tm (K) T2 (K) mg b E (eV) S (s�1)

Peak 1 448 477 505 0.49 1.9 1.05 7.62 � 1011

Peak 2 469 511 551 0.48 1.7 0.801 7.7 � 1008

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temperature and shape are strongly dependent on initial

trapped charge concentration.

The activation energy (E) can be calculated by the general

expressions formulated by Chen and is given by

E ¼ Ca

kT2m

a� ba2kTm (3)

Where k is Boltzmann constant. Tm is peak temperature. The

constant Ca and bawere also calculated by the Chen's equation(Chen, 1969). The activation energy and the frequency factor

were seen in Table 5. The activation energy is found in be-

tween 0.48 and 0.53 eV and the frequency factor is range of

1.5 � 1009 to 1.7 � 1011 for UV irradiated phosphor.

Table 5 e Kinetic parameters of ZrO2:Ti (0.2 mol%) doped Phos

Dose in kGy T1 Tm T2 t d u m ¼ d/

.5 167 205 241 38 36 74 0.486

.75 174 205 238 31 33 64 0.516

1 174 205 240 31 35 66 0.53

2.4.5. CGCD curve fitting techniques for ZrO2 Ti(0.2%)phosphorThe comparison between theoretical and experimental TL

glow curve was presented by computerized glow curve deco-

volution (CGCD) technique (Fig. 12). The curve is fitted by

origin 8 programme and the experimental glow peak shows

good TL glow peak centred at 476 K. Other two peaks are

prominent for the study of area under the glow curve and the

corresponding kinetic parameters are calculated by peak

shape method (Table 6). The peaks shows second order of

kinetic for the CGCD peaks as well as the activation energy is

very high for that (Puchalska & Bilski, 2006).

The kinetic parameters were calculated by (Computerized

glow curve convolution technique) CGCD technique, activa-

tion energy was found in between 1.05 and 0.801, and the

frequency factors are found in the range of 7.7 � 1008 to

7.62 � 1011 s�1 (Tamrakar, Kowar, Uplop, & Robinson, 2014;

Tamrakar, Upadhyay, & Bisen, 2014; Tamrakar, Upadhyay, &

Bisen, 2014).

2.4.6. ConclusionThe samples were prepared by combustion a synthesis tech-

nique and annealed at 600 �Ce900 �C. There is no any phase

change found due to annealing of the prepared ZrO2:Ti (0.2%)

phosphor. Sample shows cubic structure and the particle size

phor annealed at 900 �C for Different gamma dose.

u Activation energy E in eV Frequency factor S in s�1

0.774 1.5 � 1009

0.959 1.7 � 1011

0.962 1.9 � 1011

J o u r n a l o f R a d i a t i o n R e s e a r c h a nd A p p l i e d S c i e n c e s 8 ( 2 0 1 5 ) 1e1 0 9

calculated by Scherer's formula ringing form 54 and 73 nm.

The good connectivity with grains and the semi-sphere line

structure was found by SEM. Phosphor was irradiated by UV

254 nm source and optimized the heating rate. Sample shows

well resolved and higher intensity peak at 173 �C for 6 �C/s.The kinetic parameters were calculated by (Computerized

glow curve convolution technique) CGCD technique, activa-

tion energy is found in between 1.05 eV to 0.801 eV, and the

frequency factors are found in the range of 7.7 � 1008 to

7.62 � 1011 s�1.

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