EffectofStepwiseReplacementofNon-OxidetoOxideGroupon …

 

 

International Scholarly Research Network
ISRN Spectroscopy
Volume 2012, Article ID 896492, 5 pages
doi:10.5402/2012/896492

Research Article
Effect of Stepwise Replacement of Non-Oxide to Oxide Group on
Structural Properties of Bi2O3·LiF·B2O3 Glasses

Susheel Arora,1 Virender Kundu,2 D. R. Goyal,1 and A. S. Maan1

1 Department of Physics, Maharshi Dayanand University, Rohtak 124 001, India
2 Department of Electronic Science, Kurukshetra University, Kurukshetra 136 119, India

Correspondence should be addressed to Susheel Arora, susheel arora@yahoo.com

Received 2 August 2012; Accepted 28 August 2012

Academic Editors: V. Di Noto, A. A. Ensafi, and S. Yannopoulos

Copyright © 2012 Susheel Arora et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Bismuth fluoroborate glasses with compositions xBi2O3·(40 − x)LiF·60 B2O3 (x = 0, 5, 10, 15, and 20) are synthesized by melt-
quench method. XRD pattern is obtained for all the samples to confirm their amorphous nature. FTIR spectroscopy is carried out
for the reported samples. It reflects the effect of replacement of a non-oxide group (LiF) with an oxide group (Bi2O3) in the glass
network, due to the presence of the various absorption bands and their shifting with such replacement, assigning a role of network
modifier to Bi2O3. Density and molar volume show an increase in their values with increase in Bi2O3 concentration. Theoretical
optical basicity is calculated for the reported samples, which shows a decreasing trend with the increasing concentration of Bi2O3.

1. Introduction

B2O3 is one of the best glass formers due to the sheet-like
structure of boron-oxygen triangles in borate glasses, with
their ability to connect themselves to form a network [1, 2].
A random arrangement of various atomic and molecular
species is easily formed in borate glasses which is the basic
requirement for glass formation. A number of modifications
in the properties of the borate glasses, with the addition of
alkali halides, have been reported so far [3–9]. The inclusion
of LiF in the borate glass network brings out some structural
changes [3], which in turn become responsible for the change
in various properties. Some new units like BO2F, BO2F2,
BOF3, and BO3F are formed by the replacement of few
oxygen atoms by fluorine ions [4–6]. Also, there may be an
increase in the number of polyhedral groups of boron and
oxygen, which in turn increases the number of nonbridging
oxygen atoms [7–9].

Bi2O3 possesses high third-order nonlinear optical sus-
ceptibility caused by high density and refractive index
[10, 11]. This property makes it to have numerous non-
linearity applications such as optical switching [12, 13],
supercontinuum generation [14], and wavelength conversion
[15]. Luminescent materials have always been studied by
researchers for their wide range of applications. Noto

reported the luminescence spectroscopy of some systems
containing rare earth ions [16, 17]. Also, bismuth ion acts
as an efficient luminescent activator with applications in
lasers as a sensitizer for some rare earth ions [18, 19]. The
purpose of this paper is to report the change in structural
and physical properties of LiF-B2O3 glasses with the stepwise
replacement of LiF by Bi2O3. The addition of Bi2O3 provides
an opportunity for the new molecular units to be formed
with more numbers of NBOs.

2. Experimental Details

Bi2O3 containing fluoroborate glasses with compositions
xBi2O3 · (40 − x)LiF · 60B2O3 (x = 0, 5, 10, 15, and 20) were
synthesized through melt-quench method using Bi2O3, LiF
and H3BO3, reagent grade powders. A uniform mixture of
the various powdered samples was prepared and heated at
1273 K for 30 minutes. The bubble free melt so formed was
pressed between two carbon plates at room temperature. The
glassy samples were thus obtained in the form of thin pallets.
The samples were tested for their amorphous nature
on Rigaku X-ray diffractometer using Cu-Kα radiations.
The samples grinded to powdered form were placed in the
diffractometer and rotated at 1◦/min.

2

ISRN Spectroscopy

FTIR spectroscopy was carried out at room temperature
in the range from 652 to 4000 cm−1. The samples were
exposed to the IR radiations in Perkin-Elmer FTIR spec-
trophotometer. A plot between % transmission and wave
number is obtained to examine various bonds formation in
view of absorption bands obtained in the plot.

Densities (d) of the samples were calculated at room
temperature using Archimedes’ principle with xylene was
taken as an inert immersion liquid.

3. Results and Discussion

3.1. XRD Analysis. The X-ray diffraction pattern for xBi2O3 ·
(40 − x)LiF · 60B2O3 glasses with x = 0, 5, 10, 15 and 20 is
plotted in Figure 1. The patterns contain broad bands but do
not contain any peak, which confirms the amorphous nature
of the samples.

3.2. FTIR Analysis. Figure 2 corresponds to the Fourier
transform infrared spectra of the compositions xBi2O3 −
(40 − x) − 60B2O3, with x = 0, 5, 10, 15, and 20. The spec-
tra were recorded in the range, 652–4000 cm−1. However,
absorption bands obtained in the range of 1700–4000 cm−1
correspond to those due to water groups, the said range is not
shown in the figure.

In the composition with x = 0, there appears an absorp-
tion band around 685 cm−1. This absorption is attributed to
the bending of B–O–B linkage in the borate network [20].
However for the compositions with x = 5, 10, 15, and 20,
in general, this absorption becomes very weak which reveals
that the structural changes are taking place due to the
addition of Bi2O3. For all the samples, there appears an
absorption band with small but increasing intensity, around
779 cm−1. This absorption is due to the formation of B–F
bonds [21]. This indicates that due to addition of Bi2O3,
structure of the glass is greatly affected as fluorine gets
encouraged to take interstitial positions in the glass network.
In the composition with x = 0, the absorption band
around 910 cm−1 is attributed to the B–O bond stretching
in BO4 units of diborate groups [22]. In the compositions
except x = 0, there appears another band originating at
901 cm−1. Intensity of this band increases with increase in
Bi2O3 concentration. It may be due to the Bi–O and Bi–O–Bi
bonds in BiO6 octahedra [20, 21, 23–25].

For the samples with x = 5, 10, 15 and 20, inclusion of
Bi2O3 in the host composition facilitates the presence of
more oxygen atoms in the glass network. The availability
of these oxygen atoms encourages the formation of more
pentaborate and diborate species [26, 27] in the glass net-
work. Presence of these species is attested by the increasing
intensity band in x = 5, 10, 15, and 20 at 1100 cm−1, which
is almost absent in x = 0.

In the literature [22, 26, 28], the absorption range 1160–
1600 cm−1 is assigned to the B–O bond stretching vibrations
in BO3 units. Here one can observe two sub-bands in all
the compositions. For x = 0, the sub-bands are centered at
1220 cm−1 and 1365 cm−1. The former band corresponds to
the stretching vibrations of B–O bonds in BO3 units from

meta and ortho-borate groups [21, 22, 25–28] and the later
is due to the B–O asymmetric stretching vibrations in BO3
− units [22, 25, 26]. For the compositions other than
and BO3
x = 0, these sub-bands appear at 1210 cm−1 and 1370 cm−1
respectively, with an enhanced intensity. The enhancement
in the intensity of the band centered at 1210 cm−1 may be
due to the formation of more BO3 units in meta and ortho
borate groups with the addition of oxygen containing Bi2O3
molecule in the glass network. The increasing intensity of
the band centered at 1370 cm−1 is due to the presence of
BiO− units in the samples other than that with x = 0 [23].
In addition to these two high-intensity bands, there exists a
shoulder absorption at 1295 cm−1 for the samples with Bi2O3
concentration. This shoulder absorption is assigned to the
BO2F units [29] and also may be due to Bi–O–Bi vibrations
of BiO6 octahedral units [23]. Furthermore the absorption
band centered at 1440 cm−1 and 1530 cm−1 in all the samples
except x = 0, is due to BO− stretching vibrations of BO3 units
from varied types of borate groups [30].

All these results are summarized in Table 1.

3.3. Density and Molar Volume. Using Archimedes principle,
density (D) of all the samples was calculated, and its values
are ploted against Bi2O3 mol% in Figure 3. It is observed
that density of the samples increases with increasing concen-
tration of Bi2O3. This shows that the atomic and molecular
species get more closely packed with the addition of Bi2O3.
The increase of the density of the glasses with the addition
of Bi2O3 is probably attributable to a change in cross-link
density and coordination numbers of Bi3+ ions [30]. It is
supported by another fact that Bi2O3 has larger molar mass
as compared to LiF, so the replacement of LiF by Bi2O3 makes
the density to increase.

The molar volume (VM) of each glass sample was

calculated using the formula [31]

VM =

(cid:2) xi Mi
d ,

(1)

where xi is the molar fraction and Mi is the molecular weight
of the ith component. It also increases with the increase in
Bi2O3 content.

3.4. Theoretical Optical Basicity. Optical basicity is an impor-
tant parameter related to the optical properties of the
glasses. Electronic polarizability and optical basicity have an
intrinsic relationship. Optical basicity is expressed in terms
of the electron density carried by anions. Theoretical optical
basicity for the present series of samples is calculated using
following formula [32]:

Λth =

(cid:2) (Zi ri)
(cid:4) .
(cid:3)
Z(cid:3)
i /γi

(2)

is the ratio of number of cations “i” to total
Here ri
number of oxide ions, γi
is basicity modulating factor,
Zi is the oxidation number of cations “i” and Z(cid:3)
is the
i
oxidation number of corresponding anions. The basicity

ISRN Spectroscopy

3

10

20

30

50

60

70

40
2θ (deg)

Figure 1: XRD plots for samples with x = 0, 5, 10, 15, and 20 in the
compositions xBi2O3 · (40 − x)LiF · 60 B2O3..

)
.
u
.
a
(

y
t
i
s
n
e
t
n
I

)
.
u
.
a
(

n
o
i
s
s
i

m
s
n
a
r
T
%

x = 20

x = 15

x = 10

x = 5

Table 1: FTIR absorption assignments of the samples with x = 0, 5,
10, 15, and 20 in the compositions xBi2O3 · (40 − x)LiF · 60B2O3.

Wavenumber
(cm−1)

Assignment

Bending of B–O–B linkage in borate network

B–F bonds

Bi–O and Bi–O–Bi bands in BiO6 octahedra

B–O bond stretching in BO4 units

x = 0

1100

Pentaborate and diborate species

1210, 1220

Stretching vibrations of B–O bonds in BO3 units
from meta and orthoborate groups

BO2F units and Bi–O–Bi vibrations of BiO6
octahedral units

B–O asymmetric stretching vibrations in BO3 and
BO3

− units

1440, 1530

BiO units
B-O− stretching vibrations of BO3 units from
varied types of borate groups

685

779

901

910

1295

1365

1370

)
3

m
/
g
k

3
0
1
×
(

y
t
i
s
n
e
D

4.5

3.5

4

3

2

2.5

x = 20

x = 15

x = 10

x = 5

x = 0

34

32

30

28

26

24

22

20

)
3

m

3
−
0
1
×
(

e
m
u
o
v

r
a
l
o
M

l

5

10
Bi2O3 (mol%)

15

20

0

D
VM

1650 1500 1350 1200 1050 700 750

Wavenumber (cm−1)

Figure 2: FTIR plots for samples with x = 0, 5, 10, 15, and 20 in
the compositions xBi2O3 · (40 − x)LiF · 60 B2O3.

Figure 3: Density and Molar Volume of the samples with x =
0, 5, 10, 15, and 20 in the compositions xBi2O3 · (40 − x)LiF ·
60B2O3.

moderating parameter “γi” can be calculated from the
following equation:

γi = 1.36(xi − 0.26),

(3)

where “xi” is Pauling’s, electronegativity of the cation. Values
of Λth are plotted in Figure 4. It is observed that theoretical
optical basicity decreases with increase in Bi2O3 content.

4. Conclusions

Study of the series of amorphous materials with composi-
tions xBi2O3 · (40 − x)LiF · 60B2O3, x = 0, 5, 10, 15 and 20
reflects following conclusions

(1) XRD analysis, suggests that the samples are amor-
phous in nature as the XRD spectra of all the samples
contain no sharp peak.

(2) In FTIR analysis it can be concluded that Bi2O3 plays
an important role in modifying the glass network.

4

y
t
i
c
i
s
a
b

l
a
c
i
t
p
o

l
a
c
i
t
e
r
o
e
h
T

0.53

0.52

0.51

0.5

0.49

0.48

0.47

0.46

0.45

0

5

15

20

10
Bi2O3 (mol%)

Figure 4: Theoretical Optical Basicity of the samples with x =
0, 5, 10, 15, and 20 in the compositions xBi2O3 · (40 − x)LiF ·
60B2O3.

The presence of the absorption bands at 901, 1295,
and 1370 cm−1 attests these modifications which are
due to Bi2O3 content and are absent in the sample
with x = 0. Further, an important conclusion is
that with the addition of Bi2O3 in place of some
concentration of LiF, there is an almost elimination
of an absorption band (685 cm−1) and shifting of
some absorption band centers (1210 to 1220 cm−1
and 1365 to 1370 cm−1) from x = 0 to x = 5, which
approves the role of Bi2O3 as a network modifier in
the present glass system.

(3) Density and molar volume increase with increase in
Bi2O3 content due to replacement of a larger molar
mass group (Bi2O3) with a smaller molar mass group
(LiF).

(4) Theoretical optical basicity decreases with increase in

Bi2O3 content on the cost of LiF content.

Acknowledgment

The financial support provided to one of the authors (S.
Arora) by CSIR, New Delhi (India), is gratefully acknowl-
edged.

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