Study of Paramagnetic Species in γ-irradiated Lithium Borate Glasses Doped With Cu2+ Ions Journal of ( 497 )

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Technology in Applied Science
ISSN 2314-8209 e-ISSN 2314-8217

J. Nucl. Tech. Appl. Sci, Vol. 1, No. 4, PP. 497:509 (2013)

Study of Paramagnetic Species in γ-irradiated Lithium Borate

Glasses Doped With Cu2+ Ions
Mansour, A.; Abd-Allah, W.M.; El-Alaily, N.A. and Ezz-Eldin, F.M.

Received 01/08/2013 ABSTRACT

Accepted 23/12/2013 Mixed alkali borate glasses doped with different concentration of CuO
Available on line: 15/3/2014 ranging from (0.1-10) wt% have been prepared by the melt quenching technique.
The prepared samples were studied by means of density, molar volume, infrared
E-mail:[email protected] spectroscopy and electron paramagnetic resonance (EPR) measurements before
and after successive gamma irradiation (50-200 kGy). The results showed that
the density increase while molar volume decrease with the increase of CuO
%. The infrared absorption studies revealed that structure of the glass network
consists of BO3, BO4 and B-O-Cu linkages. Gamma irradiation causes minor
changes in the IR spectral bands which are related to the bond break of the B-O
bond and formation non-bridging oxygen. Gamma irradiation causes irregular
change in the intensities of the EPR spectra for samples doped with 0.1, 0.2 and
10 wt % of CuO, however, no change in the EPR spectra of 2 and 5 wt % of CuO
for all absorbed doses (50-200 kGy). It is expected that the Cu-doped lithium
borate glass 2 and 5 wt % of CuO may be used for radiation shielding.

A
INTRODUCTION
lkali borate glasses are well known due to their high
transparency, low melting point, high thermal stability
and high transition metal ion solubility. Borate glasses
with alkali ions are considered as an important classes
of material in microelectronics, optics and in optical
fibers due to its scientific and technological aspect Rao and Veeraiah
(2004).
KEYWORDS
Copper is being extensively used in several commercial glasses,
Lithium Borate Glass,
CuO, Gamma Irradiation,
such as red glass hematite, aventurine and rubies. Chou containing
IR, EPR. glasses is also important in technological point of view, because of their
semiconducting properties and due to other potential applications Singh
and Ratnam (1998).

1. National Center for Radiation Research and Technology, Atomic Energy Authority, P. O. Box 8029, Nasr City, Cairo11371, Egypt.
( 498 ) J. Nucl. Tech. Appl. Sci., Vol. 1, No. 4 Mansour, A.; et al.

In glasses, copper ions exist in two stable ionic but also to comment on the chemical and structural
states viz., monovalent Cu+ ions, divalent Cu2+ ions environments about the metal ions center.
Prasad et al. (2005) and may also exist as metallic
The first purpose of the present paper is the
copper. The electronic structure of the copper atom
preparation and studies of some characterization
is [Ar] 3d10 4s1; the cuprous ion, having its five d
of properties the lithium borate glass doped with
orbitals, with an absorption band in the visible
different concentrations of CuO wt %. The second
region Kumar and Veeraiah (1997) and Prasad
purpose was to test this system suitable as shielding
et al. (2005) and produce blue and green glasses.
material for gamma irradiation.
The color of the glass depends on the Cu2+content.
Lithium borate glasses (LBG) are of great interest EXPERIMENTAL
because of their good ionic conductance properties.
Preparation of the glasses
Since the addition of Li2O to the borate glass adds
extra oxygen atoms, which are accommodated in Lithium borate glasses prepared from chemical
the network, a transfer of some boron atoms from grade powder. Boric oxide was introduced in the
triangle BO3 to tetrahedral BO4 occurs Cervinka et form of orthoboric acid and lithium oxide was
al. (1992). The introduction of copper oxide (CuO) introduced in the form of its respectively anhydrous
into an oxide glass changes the oxide network. CuO carbonate. Copper was added in the form of pure
has been used as a constituent in several borate and CuO. The compositions of the studied glasses are
vanadate glasses in order to achieve useful physical shown in Table (1). The batches were melted in
properties. Though CuO is not a glass-forming platinum crucibles at 1150ºC ±20 ºC for two hours in
oxide by itself, it can be incorporated in substantial electrically heated furnace and each melt was stirred
quantities into these glasses-forming oxide systems. by rotating the crucible several times every 30 min.
Many investigators have reported that copper (Cu) The homogeneous melts were cast after two hours
may exist in the glass network both as a network of melting into preheated stainless steel molds. Then
former and also as a network modifier-forming the prepared samples were immediately transferred
oxide metals as Cu+ and Cu2+ ions Khattak et al. to an annealing furnace regulated at 450oC±50oC.
(2000). The EPR and optical absorption studies The muffle after one hour was left to cool to room
have made it possible not only to interpret the temperature at rate of 25oC/h.
energy levels involved in the observed transitions,
Table (1) Chemical composition of investigated glass (wt %).

Glass number B2O3 Li2O CuO

G1 85 15 0
G2 85 15 0.1
G3 85 15 0.2
G4 85 15 2
G5 85 15 5
G6 85 15 10

Density and molar volume measurement done using a sensitive balance and xylene as an inert
immersion liquid. The density was obtained from the
The density (ρ) of the glass samples was
relation;
determined to an accuracy of 0.001 by the standard
ρ = (a / (a-b)) 0.86
Archimedes principle. These measurements were
Study of Paramagnetic Species in γ-irradiated Lithium Borate Glasses Doped With Cu2+ Ions ( 499 )

Where a is the weight of the glass sample in air, (2000 Ci) with a dose rate 4.26 kGy/h. The samples
b is the weight of the glass sample when immersed were placed in a manner that each glass sample was
in xylene of density 0.865g/cm3. The relationship subjected to the same irradiation dose.
between density and composition of an oxide glass
RESULTS
system can be expressed in terms of an apparent
volume Vm occupied by 1 g atom of oxygen. The Density and molar volume
molar volume, Vm, of all the prepared glasses,
Effect of composition:
defined as the mean molecular weight M of glass
constituents divided by its experimental density as Figure (1) showns the relation between the
given in the following equation: density and molar volume of the glass samples
Vm =M/ρ doped with different concentration of CuO,
resulting values showed gradual increase of density
Infrared absorption spectra measurements
as CuO increases in the glass samples, on the other
The FTIR absorption spectra were registered hand the molar volume decreases with increase
at room temperatures using a JASCO FTIR 6200 of CuO content. Table (2) represents the effect of
spectrometer. The IR absorption spectra were different irradiation doses on the density and molar
measured immediately after preparing the disks volume of glass sample.
of KBr and glass samples. The FTIR spectra were
recorded in the wavenumber range of 400-4000 cm-1.

Electron Paramagnetic Resonance (EPR)

EPR of (LBG) were recorded at room

temperature by using a Bruker EMX spectrometer
(X-band), Bruker, Germany. The microwave power
was set at 5.065 mW, microwave frequency =
9.703 GHz, modulation amplitude = 5.00 Gauss,
modulation frequency = 100 kHz, time constant =
163.84 ms and sweep time = 41.94 s. The magnetic
field was scanned from 2272 to 4272 Gauss.
The peak-to-peak height (A) of EPR signal was
calculated. All EPR measurements were carried out Fig. (1): Composition dependence of glass density (ρ) and
at lab temperature (23 ± 2 oC). The response curves molar volume for lithium borate glasses doped with CuO.
were established in terms of signal height divided
FTIR spectra
by sample weight as a function of irradiation dose
in kGy. Readings were corrected to peak height of Effect of composition on the FT-IR spectra
the reference standard material (DPPH), which was
Figure (2) illustrates the FT-IR spectra of
recorded before and after each EPR measurement
undoped lithium borate glasses consist of three
of the samples in order to correct the change in the
subsequent small bands at 440 ,470,530 cm-1, distinct
spectrometer sensitivity. After measurement, some
prominent band at 870 cm-1, a medium broad band at
samples were sealed with plastic covers and stored
1100 cm-1 followed by two small kinks at about 1470
for EPR signals stability investigation.
and1600 cm-1. Figure (2) also reveals the FTIR of the
Irradiation facility samples containing progressive addition of CuO. It
is evident that the main IR spectral vibrations are
Glasses were subjected to doses of 50, 100, 150
generally persistent but some changes are observed
and 200 kGy using an Indian 60Co gamma-rays cell
which can be summarized as follows: the first band
( 500 ) J. Nucl. Tech. Appl. Sci., Vol. 1, No. 4 Mansour, A.; et al.

Table (2) Density and molar volume values of undoped and doped CuO lithium borate glasses before and after
gamma radiation.
unirradiated 5kGy 100kGy 150kGy 200kGy
Ρ
Vm Ρ Vm Vm Ρ Vm Ρ Vm Ρ
[g/
[cm3/mol] [g/cm3] [cm3/mol] [cm3/mol] [g/cm3] [cm3/mol] [g/cm3] [cm3/mol] [g/cm3]
cm3]
G1 40.86 2.23 37.9758 2.4000 37.8183 2.4100 32.550 2.8000 40.0320 2.2600
G2 39.81 2.29 39.6465 2.3000 39.4749 2.3100 33.4626 2.6538 33.354 2.8175
G3 38.57 2.360 40.1903 2.2700 37.5440 2.4300 36.2032 2.5200 32.5829 2.8000
G4 36.31 2.491 32.9400 2.8000 29.061 2.8223 29.061 2.8223 29.061 2.8223
G5 36.22 2.578 37.3568 2.5000 33.3543 2.81765 33.3543 2.8169 28.464 2.8236
G6 36.21 2.573 37.3602 2.5800 31.3580 2.5600 34.855 2.673 32.617 2.8564

at 470 cm-1is progressively increase in intensity and

is replaced at G6 by small peak at 450 cm-1, new
bands appeared at 700 and 1250 cm-1,the band at
870 cm-1 shifted to 925 cm-1, the medium broad band
at 1100 cm-1are shifted to1040 cm-1and increase in
the intensity the band at 1470 cm-1 shift to 1370 cm-1
and increase in the intensity, the weak broad band
at 1600 cm-1 shift to 1660 cm-1 followed by slight
increase in the intensity.

Effect of gamma irradiation on the FT-IR spectra

Figure (3) illustrate the FT-IR spectra of the

studied glasses of lithium borate doped with 2 wt%
Fig. (3): Infrared absorption spectra of G4 before and after
of CuO (G4) before and after irradiations consists of successive gamma irradiation.
sharp peak at 450cm-1, small successive peak at 540,
,670,790 cm-1, disctinct band at 890 cm-1, medium and small peak at 2325cm-1
broad band at 1100 cm-1, small shoulder band at 1230 On subjecting the glass (G4) to different doses
cm-1, two weak broad bands at 1470 and 1660 cm-1 of gamma irradiation, it can be clearly seen from
figure (3), the band at 890 cm-1 and also band 1100
cm-1 decrease in their intensity. The weak broadband
at 1470 cm -1shift to 1400 cm-1. The small kink peak
at 1660 shift to 1600 cm-1 and increase in intensity.
Figure (4) also shows the effect of subjecting the
glass (G4 &G5) to four successive gamma radiation
doses of 50 kGy, 100 kGy, 150 kGy and 200 kGy the
results show some variations, which are summarized
as follows: (a) The intensities of all the IR bands are
observed to slightly decrease in intensity. (b) The
broadness of bands in the region 800–1500cm-1.

EPR

Effect of glass composition on the EPR spectra

Fig. (2): Infrared absorption spectra of lithium borate glass
undoped and doped with varying CuO content. No EPR signal was observed in the spectra of
Study of Paramagnetic Species in γ-irradiated Lithium Borate Glasses Doped With Cu2+ Ions ( 501 )

Gauss. All observed spectra belong to Cu 2+ ions.

The density of spins participated in the

resonance can be calculated using the formula
N = Ipp (ΔH pp)2

This can be used to calculate the density of Cu2+

ions participated in the resonance in lithium borate
glass samples by taking Ipp And ΔHpp as the peak to
peak height and peak to peak width of the resonance
line respectively. Yap was measured from the height
of the first and fourth perpendicular hyperfine
lines. ΔHpp were measured from the maximum
and minimum hyperfine position at the lowest and
the highest fields of the first derivative curve. The
density of spins are thus calculated for various wt%
of Cu2+ ions doped in lithium borate glass samples as
Fig. (4): Infrared absorption spectra of G4& G5 before and
after gamma irradiation (200kGy).

undoped glasses indicating that no paramagnetic

centers were present in the starting materials. When
Cu2+ ions are introduced into the alkali lithium
borate glasses (see Table-1) all the investigated
concentrations exhibit resonance peaks. In all
Fig. (6): Variation of number of spins with wt % of Cu2+ ions
concentrations EPR spectra are quite similar and in lithium borate glass.
consist of pronounced band centered at g = 2349
Gauss with weakly resolved four-component shown in Figure(6).
structure and a relatively shallow quadruplet, Effect of gamma irradiation on the EPR spectra
centered at g=2915 Gauss. All observed spectra
belong to Cu 2+ ions ,four-component structure and Figure.7 presents the EPR spectra of undoped
a relatively shallow quadruplet, centered at g=2915 and doped with 0.2 wt %CuO (G3)lithium borate
glasses after being exposed to 50KGy of gamma-
irradiation at room temperature. In the spectrum
of undoped sample one sharp peak at g = 3455
Gauss can be observed (strong black line). The
EPR spectrum of doped sample is composed of four
peaks at g = 2761 Gauss, 2919 Gauss, 3109 Gauss
and 3349 Gauss which can be attributed to Cu2+ ions
were observed as well as a further fifth peak due to
the base at g = 3455Gauss (weak dashed line). After
gamma irradiation a decrease of the EPR signal
intensity of the base is observed.

The EPR spectra at different absorbed doses

(50-200 kGy) were also recorded for undoped and
Fig. (5): EPR spectra at different concentration of Cu2+ doped (LBG) to study the irradiation dependence
before irradiation.
( 502 ) J. Nucl. Tech. Appl. Sci., Vol. 1, No. 4 Mansour, A.; et al.

of the intensity of the resonance line. Figure (8)

shows the dependence of EPR signal intensity on the
absorbed dose for a derivative spectrum. It should be
noted that the intensity of EPR spectra of G1,G2,G3
and G6 have irregular trend after successive gamma
ray EPR, but both G4 and G5 demonstrate stability
to gamma rays (no change in their EPR signal
intensity), however it is pointed out retardation to
gamma rays. Figure (9) reveals the EPR spectra of
CuO-doped lithium borate glasses before and after
4000

Undoped at 50 kGy
3000 Doped at 50 kGy
First derivative of Absorption

2000 a

1000

-1000

-2000
Fig. (8): EPR spectra of different concentration of Cu2+ ions
doped in LBG at different absorbed doses.
-3000

-4000
2500 3000 3500 4000
c. CuO-doped glass with 0.2 wt % (G3)
Magnetic Field (Gauss)

Fig. (7): EPR spectra of undoped and doped with CuO The un-irradiatedG3reveals (Figure9c) strong
0.2wt% (G3) LBG after gamma irradiation (50 kGy). EPR spectra consisting of pronounced band centered
at 3341 Gauss with weakly resolved four-component
successive gamma irradiation. The experimental
results can be summarized as follows. structure and a relatively shallow quadruplet at
about 2768, 2919, 3146 and 3339 Gauss as well as
a. Undoped glass or blank (G1) a further fifth small peak is resolved at about 3455
EPR signal was observed in the spectra of Gauss which may be due to G1. With the first gamma
G1 before irradiation. The irradiated G1 reveal (Fig. radiation dose, the EPR peaks decrease in intensity.
9a) a strong EPR spectra consisting of two peaks at On further gamma irradiation, the overall intensities
about 2956 and 3449 Gauss. On gamma irradiation, of the EPR peaks increase, followed by decrease to
the EPR peaks grow in intensity and the rate is reach a saturation figure (8). It is important to note
higher in the second peak than the first one and then that the further fifth small peak grow with successive
this approaches almost saturation with highest dose gamma irradiation.
figure (8).
d. CuO-doped glass with 2 wt % (G4)
b. CuO-doped glass with 0.1 wt % (G2)
The unirradiated G4 reveals figure (9d) very
The un-irradiated G2 reveals (Figure 9b) a strong EPR spectra consisting of pronounced band
weak EPR spectrum consisting of pronounced centered at 3349 Gauss with weakly resolved
band centered at 3341Gauss with weakly resolved three-component structure and a relatively shallow
four-component structure and a relatively shallow quadruplet at about 2776, 2924 and 3154 Gauss.
quadruplet at about 2771, 2923, 3119 and 3394 On radiation, the EPR spectra very slightly increase
Gauss. On gamma irradiation, the EPR signal grows (this increase may be due to EPR fluctuation) in
in intensity as in G1 figure (8). intensity. EPR results show that the rate of induced
paramagnetic centers is very low (no significant
change in EPR spectra and their intensities) for all
Study of Paramagnetic Species in γ-irradiated Lithium Borate Glasses Doped With Cu2+ Ions ( 503 )

a- Blank b- 0.1 wt %
2000
2000

EPR Signal Intensity (a. u.)

EPR Signal Intensity (a. u.)

0
0

-2000 unirradiated -2000 unirradiated

50 kGy 50 kGy
100 kGy 100 kGy
150 kGy 150 kGy
200 kGy 200 kGy
-4000 -4000

3360 3380 3400 3420 3440 3460 3480 3500 3520

3350 3400 3450 3500
Magnetic Field (Gauss)
Magnetic Field (Gauss)

500 c- 0.2 wt %
d- 2 wt %
0
0
EPR Signal Intensity (a. u.)

EPR Signal Intensity (a. u.)

-500
-5000
-1000

unirradiated unirradiated
-1500
-10000 50 kGy
50 kGy
100 kGy
100 kGy
150 kGy
-2000 150 kGy
200 kGy
200 kGy
-15000
-2500
2600 2800 3000 3200 3400 3600
2600 2800 3000 3200 3400 3600
Magnetic Field (Gauss)
Magnetic Field (Gauss)

10000

e- 5 wt % 10000
f- 10 wt %

5000
EPR Signal Intensity (a. u.)

EPR Signal Intensity (a. u.)

-5000
-10000

unirradiated unirradiated
-10000
50 kGy 50 kGy
100 kGy 100 kGy
150 kGy 150 kGy
-20000 -15000
200 kGy 200 kGy

-20000
2600 2800 3000 3200 3400 3600 2600 2800 3000 3200 3400 3600

Magnetic Field (Gauss) Magnetic Field (Gauss)

Fig. (9): EPR spectra of Cu2+ ions doped in lithium borate glass sample at different doses.
( 504 ) J. Nucl. Tech. Appl. Sci., Vol. 1, No. 4 Mansour, A.; et al.

absorbed doses figure (8). Then, G4 demonstrates still retain without change to different times. This is
retardation to gamma rays indication that both G4 and G5 are very stable at this
irradiation dose with storage time.
e. CuO-doped glass with 5 wt % (G5)
DISCUSSION
The un-irradiated G5 reveals figure (9e) very
strong EPR spectra consisting of pronounced band Density and molar volume
centered at 3328 Gauss with weakly resolved
Effect of composition
three-component structure and a relatively shallow
quadruplet at about 2773, 2908 and 3109 Gauss. The density is a very sensitive tool that can
On radiation, the EPR spectra did not increase in easily detect any structural changes in the glass
intensity. EPR results show that the rate of induced network. The density is affected by the structural
paramagnetic centers is fixed (no change in EPR softening/compactness, change in geometrical
spectra and their intensities) for all absorbed doses configuration, coordination number, cross-link
figure (8).Then G5 demonstrates no effect on their density and dimension of interstitial spaces of the
EPR spectra due to their exposure to the given dose glass. The obtained density values showed gradual
of gamma rays increase as CuO gradually increased. This could be
explained that most of the Cu enters as a modifier in
f. CuO-doped glass with 10 wt % (G6)
the glass lattice, the covalency of the Cu2+–O bonds
The un-irradiated G6 reveals figure (9f) strong increase when the B–O bonds become weaker, also
EPR spectra consisting of three peaks at about 2774, the non-bridging oxygen decreases in the glass
2921, and 3086 Gauss and followed by a prominent network with increasing the CuO, which consolidates
broad peak centered at 3271Gauss. With progressive their structure and increases their density Kashif et
gamma radiation, the EPR measurements reveal the al. (2008). The Vm values creases with the increase
same spectra with clear decreasing in their intensities of CuO, this result may be due to the fact that Chou
and at the last dose the EPR signal growing rapidly plays the role of the network modifier and introduces
to equal the intensity of un-irradiated sample figure the excess structural free volume
(8).
Effect of radiation on density and molar volume
Stability of lithium borate glasses
Irradiation of samples produces only slight
To investigate the stability of LBG, the prepared changes in the density, this may be due to the stability
samples (G4& G5) were irradiated at 50 kGy by using in the number of NBOs. A probable explanation may
60
Co gamma-ray, the intensities of EPR spectra at be that radiation compaction includes displacements,
room temperature was plotted against time as shown electronic defects and breaks in the B–O bonds,
in Figure (10), the spectral shape is very similar and besides the coexistence of Cu+ and Cu2+ in glass
network that plays double roles of depression and
capturing NBOs induced by gamma radiation Zhang
et al. (2013), they found that the nuclear irradiation
is believed to cause noticeable structural changes
such as:

1. Some bond angles become smaller, i.e., a

compact state are produced.

2. Increase or decrease in density depending on

composition or state of aggregation.
Fig. (10): Peak-to-peak height of gamma irradiation G4 and
G5 as a function of post-irradiation for 115 days.
Study of Paramagnetic Species in γ-irradiated Lithium Borate Glasses Doped With Cu2+ Ions ( 505 )

3. Induced damage that is responsible for induced of borate groups containing BO3 and BO4 units
color centers. Ghoneim et al. (2011). The bands in the region
1200 and 1500 cm-1 are due to the presence Of BO3
FTIR
structural units in the glass. The component bands in
Effect of composition on the IR spectra this region appear at 1470 cm-1 is attributed to anti-
symmetrical stretching vibrations with three NBOs
Infrared spectroscopy is one of the most useful
of B–O in BO3 units groups Kaur et al. (2013), the
experimental techniques available for the structural
band at 1660 cm−1 are attributed to H–O–H bending
analysis of glasses. It is a powerful tool for the
vibrations, which indicate that the compound
structural studies of glasses modified by metal
contains water, Rao et al. (2004). By the addition of
oxides, as this technique leads to the understanding
different concentrations of CuO a new bands appear
of structural aspects related to both the local units
such as the band at 700cm-1 is attributed to oxygen
constituting the glass network and the anionic sites
bridges between one tetrahedral and one trigonal
hosting the modifying metal cations. Further, it is
boron atom Kashif et al. (2008), also another new
accepted that the main vibrational modes associated
band appears at 1250cm-1, which is attributed to the
with structural chain in the glass network appears
stretching bond of BO3. The intensity of this band
above the wavenumber 400 cm-1 in mid infrared range.
increase with the increase of the addition of Cu ion
These network modes are clearly distinguishable
until it reaches 5%. At the highest concentration of
from the metal ion site vibrational modes active
Cu ions (10%) this band is almost vanished, this
in the far infrared region. The absorption bands in
can be related to the forming of new B―O―Cu
the region 420-470 cm-1are assigned to specific
bridging bonds due to the aforementioned induced
vibrations of Li-O bonds El-Batal et al. (2012). The
electrostatic field causing a weakening of the borate
absorption bands in the region extending from 800
network.
cm-1 to 1200 cm-1 are observed at 870 cm-1 and 1100
cm-1. The band at 870 cm-1 is due to the stretching A summary of the previous interpretation is
vibration of B-O bonds in the BO4 units from tri-tetra presented in the table (3) which depicts the observed
and penta-borate groups Stefan et al. (2012), the IR absorption bands their assignments.
band at 1100 cm-1is due to overlapping contributions
Table (3) Assignment of IR bands obtained from the base and CuO–doped lithium borate glasses.

Position (cm-1) Assignment

1660 H–O–H bending vibrations
1600 Symmetric stretching vibrations of BO3 units
1350 - 1550 B- O stretching vibration of BO3unit in meta, pyro and ortho borate groups
1200 - 1350 B- O stretching vibration of BO3unit in boroxol rings
1100 Vibrations of BO4 tetrahedra
870 Tti-,penta-,and diborate groups
700 oxygen bridges between one tetrahedral and one trigonal boron atom
440- 460 Vibration of lithium cations

50,100,150 and 200 kGy as shown in figure (3). The

Effect of gamma irradiation on the IR spectra
IR spectra reveal characteristic changes compared to
Gamma irradiation causes a minor decrease of the unirradiated samples. It can be clearly seen from
the intensities of the main IR bands. The effect of Figures (3&4) after high doses, there is an overall
subjecting glass samples doped with 2wt% CuO (G4) decrease in the intensity of bands accompanied by
and exposed to gamma ray irradiation with dose the broadness of bands in the region 800–1500 cm-1.
( 506 ) J. Nucl. Tech. Appl. Sci., Vol. 1, No. 4 Mansour, A.; et al.

This signifies that the changes in glass structure are oxygen hole center (BOHC) are holes trapped on the
taking place by the conversion of BO4 units into BO3 bridging oxygen in triangle unit and boron electron
units with the creation of super structural units with centers (BEC) is an electron trapped on over-
NBOs after irradiation Kamitsos et al. (1993) and coordinated oxygen (the O3+ defect) as well as the
shifting to lower wavenumber which relates to the peroxy radicals. From figure (6), it is clear that as the
increase in the number of non-bridging oxygens with concentration of Cu2+ ion is increased, the number of
gamma radiations Kaur et al. (2013). spins participating is increased.

Effect of glass composition on the EPR spectra Effect of gamma irradiation on the EPR spectra

The EPR spectra of the lithium borate glasses The EPR spectra of G1 and G3 irradiated to
doped with Cu are presented in a dose of 50 kGy (at room temperature) were
represented in Figure (7). It’s seen that the tow
figure (5). In all lithium borate glasses EPR
signals have the same position at 3447 G (point a).
spectra are quite similar and consist of pronounced
The concentration of defects induced in G1 only is
band centered at g= 3349 Gauss with weakly-
very high, but these defects decreases when G1 doped
resolved four-component structure and a relatively
with Cu as in G2. It should be noted that this decrease
shallow intensity centered at 2915 Gauss. Four
may be due to the combination between the G1 free
weakly-resolved components related to hyperfine
radicals (defects) and Cu2+ ions in G2. On the other
structure, caused by the 63Cu and 65Cu isotopes
hand, the transition metals ions can compete with the
nuclei (natural abundance- 69.1 % of 63Cu and 30.9
intrinsic defects already present in the glass to trap
% of 65Cu, nuclear spin I=3/2 for both isotopes).
the electrons and holes produced by irradiation. The
The observed Cu2+ EPR spectra in the glasses with
capturing process depends strongly on the nature
Li2B2O3 compositions can be described by the spin
of the transition metal ion and its concentration
Hamiltonian axial symmetry in the form
as well as on the type of host glass. The effect of
Ĥ= g// β Bz Ŝz + g┴ β (Bx Ŝx + By Ŝy) + A// Ŝz transition metal ions can be understood by assuming
Iz + A┴ (Ŝz Iz+ Ŝy Iy) (1) that these ions are available as potential traps for the
radiolytic electrons and holes Friebele et al. (1991)
where z has been taken as the symmetry axis
and Ehrt et al. (2000). It is speculated that many
of individual Cu2+ complex. The symbols in Eq. (1)
transition metal ions compete successfully with the
have their usual meaning and the nuclear quadrupole
intrinsic traps for the radiolytic charges Williams et
and nuclear Zeeman interaction terms are ignored
al. (1986) and Friebele et al. (1991). Figures (8 and
Sreekanth et.al. (2006). The following parameters,
9a) indicate that the irradiated G1 at different doses
g// = 2.07599 ± 0.0038, g┴ = 2.09875 ± 0.00427,
reveals induced strong EPR signal at g = 3451Gauss.
A// = 299.65 ± 23.58, A┴ = 315.89 ± 31.58 Gauss
On successive gamma irradiation the EPR signal
was calculated. The peak-to-peak line width of
progressively slightly decrease after that increase
hyperfine components at room temperature is 86.32
(this may be due to the formation and recovery rates
Gauss. The line width of parallel and perpendicular
of paramagnetic centers). Also Figure. (9b, 9C) and
hyperfine lines increase, this broadening may be
(9f) show EPR spectra of G2, G3 and G6 respectively.
attributed to the microenvironment fluctuation
It can be seen that there is variation in EPR signal
around Cu2+ in which is intrinsic to the glassy state.
intensity, i.e. these sample are not retarded gamma
The structure distribution in glass causes fluctuation
rays (not suitable for radiation shielding). As one can
in ligand field, it is reflected in the distribution of
see, the intensity of EPR signals of G4 and G5 did not
the spin-Hamiltonian parameters. Later electron
growth at increasing irradiation dose as in Figures
paramagnetic resonance studies in alkali borate
(8, 9d and 9e). By comparing the intensity of EPR
glasses have indicated that all variants of boron
spectra after irradiation to different doses; it is found
Study of Paramagnetic Species in γ-irradiated Lithium Borate Glasses Doped With Cu2+ Ions ( 507 )

that there is a very little change may be due to the oxygens. At 2% and 5 wt% of CuO, that Cu ion
fluctuation of EPR spectroscopy. Also the spectral may be enter the glass network through B―O―Cu
shape is very similar and still retains without change bonding, making glass more resistant to the effect of
to different doses, i e.G4and G5retarded gamma rays. gamma radiation.
Computer simulation of the spectrum of Cu2+ center
* EPR spectra of Cu-doped lithium borate
Padlyak et al. (2009) gave the principle g-values
glasses have been measured before and after gamma
g1= 2.0014, g2=2.0147 Sreekanth et al. (2006).
irradiation. No EPR spectra of the undoped host
EPR spectra similar to those values were obtained
glass before irradiation while Cu-doped glasses
for gamma irradiated lithium borate glass doped
show specific EPR spectra.
with CuO. The observed induced EPR signals could
be ascribed in accordance with the assumption of * The induced EPR spectra reveal the evolution
MÖncke and Ehrt (2001), who postulated that the of radiation induced paramagnetic centers from the
formed extrinsic defects are due to photochemical host glasses together with the sharing of the Cu2+
(photo-oxidation or photo-reduction) of the transition ions through photo-chemical reactions. Gamma
metal ions by the effect of gamma radiation. The radiation causes a decrease in the intensities of the
effect of transition metal ions on the formed induced EPR spectra companied with losing its sharpness.
color or paramagnetic centers can be outline as
* The rate of paramagnetic centers formation is
follows: before irradiation, the Cu-doped glass
unchanged at 2 and 5 wt%.
reveals strong EPR spectra consisting of four peaks
and a broad peak. Finally, it is of great importance REFERENCES
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• Cervinka, L.; Rocca, F.; Fornasini, P. and Dalba,
time dependence of EPR signal of doped LBG. As
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shown in Figure (10), G4 and G5irradiated to 50 kGy of the composition (Ag2O·2B2O3)1-x(AgI)x and
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Solids. J., 240:263.
CONCLUSION
• ElBatal, H.; Abdelghany, A. and Ali, I.S. (2012):
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*The density increase while molar volume
• Friebele, E.J.; Uhlmann, D. and Kreidle, J (1991):
decreases with the increases of CuO %due to
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coexistence of Cu+ and Cu2+ in glass network that
Society. J., 2o5.
plays double roles of depressing and capturing NBOs
induced by effect of gamma radiation. • Ghoneim, N.A.; El-Batal, H.A.; Abdelghany, A.M.
and Ali, I.S. (2011): Shielding behavior of V2O5
*Infrared absorption spectra of the glasses doped lead borate glasses towards gamma irradiation.
indicate the presence of both triangular and Alloys and Compounds. J., 509: 6913.
tetrahedral borate units besides the sharing of Cu–O
• Kamitsos, E.I.; Patsis, A.P. and Chryssikos, G.D.
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(1993): Infrared reflectance investigation of alkali
lithium (Li+) cations vibrations. Gamma irradiation
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to the triangular BO3 one along with non-bridging • Kamitsos, E.I.; Karakassides, M.A. and
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Chryssikos, G.D. (1987): Vibration spectra of investigations of BaO–Ga2O3–P2O5 glasses doped by

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• Rao, R.B. and Veeraiah, N. (2004): Study on some
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(2008): Effect of copper addition on density and
• Shkrob, I.; Tadjikov, B. and Trifunac, A. (2000):
magnetic susceptibility of lithium borate glasses.
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and Cu2+ Centers in Lithium and Potassium–Lithium
• Zhang, Z.; Baccaro, S.; Cemmi, A.; Shen, W. and
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 ‫‪Study of Paramagnetic Species in γ-irradiated Lithium Borate Glasses Doped With Cu2+ Ions‬‬
‫مجــــلة‬ ‫) ‪( 509‬‬

‫التقنيــات النــوويــة‬
‫فى العلوم التطبيقية‬
‫جملد ‪ ، 1‬عدد ‪ ، 4‬ص ‪)2013( ، 509 : 497‬‬

‫دراسة املراكز البارامغناطيسية الناجتة عن تشعيع زجاج بورات الليثيوم املطعم‬

‫يصدرها‬
‫بأيونات النحاس‬
‫اجلمعية امل�شرية للعلوم الإ�شعاعية وتطبيقاتها‬
‫‪2‬‬
‫عبده حممد ابراهيم منصور ‪ -1‬وسام حممدعبداللة مجعة ‪ -2‬جنية عبد احلميد العاليلى ‪ - 2‬فتحى حممود عزالدين‬

‫مت حتضير عينات من زجاج بورات الليثيوم املطعم بأيونات النحاس بتركيزات ‪ 5 - 2 - 0.2- 0.1‬و ‪% 10‬‬
‫اإللكترونياحلمراء والرنني‬
‫واألشعة حتت‬
‫املوقع‬ ‫عن طريق الصهر و التبريد‪ .‬والعينات احملضرة مت قياسها من حيث الكثافة‬
‫‪www.esrsa.com‬‬
‫اإللكترونى الدورانى‪ .‬اوضحت القياسات تأثر الكثافة واحلجم املوالرى‪ .‬حيث وجد زيادة الكثافة بزيادة اضافة‬
‫هاما فى حتسني‬ ‫تلعب دورا‬
‫اإللكتروني‬ ‫اكسيد النحاس وبالتالى نقص احلجم املوالرى وتفسير هذا أن أيونات النحاس البريد‬
‫‪[email protected]‬‬
‫خواص الشبكة البلورية و بعض أيونات النحاس تكون ضمن تكوين الشبكة عندما تزداد نسبة النحاس‬
‫فى الزجاج احملضر‪ .‬كمااتضح حدوث زيادة تدريجية فى الكثافه بزياده اجلرعه االشعاعيه حيث يزداد معدل‬
‫اجتذاب الفجوات املوجبه لاللكترونات وبالتالي يحدث انضغاط في اجلزيئات‪ .‬وقد اظهرت األ شعة حتت‬
‫امتصاص جديدة‬ ‫احلمراء تواجد سلسلة البورات وتكون متميزة بقمم امتصاص اخلاصة بها‪ .‬ثم ظهور قمم‬
‫مجـــــــــلد ‪1‬‬
‫قمم االمتصاص‬ ‫)‪(2013‬‬‫انخفضت‬‫عند التركيزات ‪ 0.2 – 0.1‬و ‪ % 10‬بعد تعرضها لالشعاع و عند التركيزات ‪ 2‬و ‪ % 5‬عدد ‪1‬‬
‫واختفت بعض القمم وخاصة عند اجلرعات العالية وأظهرت نتائج الرنني اإللكترونى الدورانى أن معدل‬
‫تكوين املراكز البارامغناطيسية يكون سريع فى بداية التشعيع ثم يقل بزيادة اجلرعة اإلشعاعية عند‬
‫التركيزات ‪ 0.2 – 0.1‬و ‪ % 10‬وعدد هذه املراكز البارامغناطيسية يظل ثابتا بزيادة اجلرعة اإلشعاعية عند‬
‫التركيزات ‪ 2‬و ‪ % 5‬وهذا يعنى أن زجاج بورات الليثيوم املطعم بأيونات النحاس بتركيزات ‪ 2‬و ‪ % 5‬ال‬
‫تتأثر بأشعة جاما و بالتالى ميكن إستخدمها كدروع مقاومة لإلشعاع‪.‬‬

‫‪1‬قسم الوقاية االشعاعية ‪ -‬املركز القومي لبحوث وتكنولوجيا اإلشعاع‪ ،‬ص‪.‬ب‪ 29 .‬مدينة نصر‪ ،‬القاهرة‪ ،‬مصر‪.‬‬ ‫‪.1‬‬
‫‪2‬قسم الكيمياء االشعاعية ‪ -‬املركز القومي لبحوث وتكنولوجيا اإلشعاع‪ ،‬ص‪.‬ب‪ 29 .‬مدينة نصر‪ ،‬القاهرة‪ ،‬مصر‪.‬‬ ‫‪.2‬‬