THERMAL STABILITY AND FT-IR STUDY OF B2O3+K2O+CaO GLASSES

R. Ezhil Pavaia* and M. Indhiraa,

a

Department of Physics, Annamalai University,

Faculty of Engineering and Technology, Annamalai University,
Annamalainagar- 608 002, Tamil Nadu, India.
ABSTRACT

The present paper reports on the spectral results pertaining to B2O3-K2OCaO (BKC) glasses. The amorphous nature of the prepared glasses of
composition 60B2O3 - (40-x) K2O x CaO (where x=0, 5, 10, 15and.20 mol
%) has been confirmed from its XRD measurement. Thermal analysis has
been carried out for the precursor chemical mix and its weight loss has
been noticed from the TG profile. Based on the DTA profile, the precursor
chemicals mix transition temperature (Tg) and crystallization temperature
(Tc) have been identified. Glass stability parameters calculated from
characteristic temperatures obtained by differential thermal analysis (DTA)
indicate an increasing tendency towards crystallization with greater modifier
contents, particularly for calcium rich compositions. The transformation of
trigonal BO3 units into tetrahedral BO4 units has evidenced from the
Fourier transform infrared (FTIR) spectrum . The optical absorption spectra
glasses exhibited three absorption bands in the region 790-800, 570-600

and 530-570 nm due to Fe3+ ion transitions. The Photoluminescence

spectra reveals the nature of the luminescence intensity.
Keywords: Borate glasses, density, XRD, FTIR, TG-DTA,UV, Photoluminescence
*Corresponding author: Dr. R. Ezhil Pavai
E-mail address: ezhilpavaibalu@yahoo.com
Mobile No: +91-9486402128

INTRODUCTION
Ternary alkaline borate glasses B2O3-K2O-CaO have been studied
extensively by several researchers [1- 2]. It is known that boric acid forms stable
glasses with alkaline earth oxides MgO, CaO, SrO, BaO and at the same time
alkaline earth oxides improve glass forming ability. These oxides at low
concentrations act as glass network formers (GNF) and at higher concentrations
behave as glass network modifiers (GNM) [3]. Liu et al. [4] suggested that alkaline
earth ions tend to preserve their local structural environment in the glass system
namely, mixed alkaline effect. [5]
Alkaline - earth oxy borate glasses find potential applications in the field of
optics and electronics as electronic polarizer of ions, variety of applications in
phosphors, solar energy converters and in a number of electronic devices, as solid
state batteries. Technological applications like commercial displays and optical
devices [6] are found in many important materials e.g. Fuel ashes, slags, refractory

product glasses and geological applications etc. These glasses are relatively
moisture-resistant; possess high mechanical strength when compared with the pure
borate glasses. These glasses are very advantageous materials for the radiation
dosimetry applications with an outlook that their effective atomic number is very
much related to that of human tissue. [7].
It is of great importance to look into the mixed alkaline effect in glasses as it
changes the properties (such as electrical conductivity,, microhardness, refractive
index, and density) in a non predictive manner [8]. Addition of CaO to borate
network stabilizes the glasses [9]. In this paper, we report physical, and structural
properties of 60B2O3 - (40-x) K2O x CaO (where x=0, 5, 10, 15and.20 mol %)
alkaline glass systems.
EXPERIMENTAL PROCEDURES:

Glass Preparation
The alkaline earth borate glasses 60B 2O3 - (40-x) K2O x CaO were prepared by
conventional melt quenching technique. In the present glass system, the concentration of
MgO was gradually increased from 0 to 20mol% while K 2O concentration was decreased
from 35 to 20mol%.

The Analytical reagent grade powders of boron trioxide (B 2O3),

potassium oxide (K2O) and Calcium oxide oxide (CaO) of appropriate proportion were
grinded in an agate mortar thoroughly for 60 minutes to form a homogeneous mixture and
then melted in a silica crucible for 3 hours in a muffle furnace at 85000 C-900 0C. The bubble
free melt was poured into a brass mould to form samples of dimensions 10mm diameters and

6mm thickness.Glass samples were annealed at 300C for 2 hours to avoid the mechanical
strain developed during the quench process. Then the furnace was switched off and glasses
were allowed to cool gradually to room temperature. The prepared glass samples were
polished and the surfaces were made perfectly plain and smoothened by diamond disc and
diamond powder.

Characterization
The glass samples amorphous nature is confirmed by X-ray diffraction
technique using GE-Inspection technology 3003TT model made in Germany
copper target operating voltage 40 Kv 300 mA current rates. The prepared
glass samples were grinded with Potassium Bromide (KBr) pellet techniques
operated between wave number ranges 400 to 4000 cm-1and the infrared
absorption spectrum is obtained using FTIR Spectrometer. The differential
Thermo gravimetric analysis (TG-DTA) for glass samples was carried out on
a SETARAM Labsys TM TG-DTA16 thermal analyzer between 100K1200 K
temperature range at heating rate of 10 Cmin1. UV-VIS-NIR spectra were
recorded in the wavelength range of (300-2200) nm using a UV-VISNIR
spectrometer Varian Cary 2380. The spectra of the Calcium containing

samples were recorded versus air as reference, corrected for reflectance and
normalised tothe 1 cm thickness of glass specimen. The spectra were
deconvoluted using the software PeakFit. Photoluminescence emission
spectra were recorded at room temperature using a fluorescence
spectrophotometer type (Jasco FP-6500, Japan) equipped with a xenon flash
lamp as the excitation light source. The scan speed is 0.1 s step-1 with a
step length of 0.25 nm and a slit width of 0.2 nm.

RESULTS AND DISCUSSION

X-ray diffraction studies
The XRD pattern of BKC glasses is shown in Fig1a and Fig 1b. The
pattern exhibits

no sharp peaks from which the amorphous nature of the

glass samples is confirmed [10-12] [21-22]. All the prepared glass samples are
glassy nature.

FT-IR Spectroscopy:
FT-IR spectral study was carried out to identify the local structure
and functional groups. The FT-IR spectrum of the BKC glass is shown in the

Fig 2. The structural information in potassium borate glasses was

extensively studied by Singh et al. [53]. This study of these glass systems
gives the information not only about structure, but also about the
coordination number of the compound with respect to oxygen, network
formers, and change in oxygen bonds of the framework which also is
induced by the cations modifiers [132, 133]. IR studies of potassium borate
glasses in the wavenumber range of 4502000cm1 are shown in the
Figure 8. Due to small mass as other network forming elements, the main
vibrational modes associated with the glass network appear well above 500
cm1 (in the mid-infrared region), and these networking modes are well
separated from the metal ion site vibrational modes which are active in the
far infrared region [9496]. Boron has an ability to change its coordination
number with oxygen between three and four providing a range of anionic
environment that can coordinate the modifying metal ions. The main IRabsorption peaks in B2O3 containing glasses lie at different wavenumbers of
710, 1260, and 1420cm1. The absorption peak near 1420cm1 occurred
due to the ring stretching of the boroxol groups, and the 1260cm1 vibration
is due to the BOB bond constituting the linkage of boroxol groups to
neighbouring groups [134]. The absorption bands near 680 and 1350

cm1 can be attributed to bending vibrations of BO 3 triangles and stretching

vibrations of BO3 units with nonbridging oxygens (NBOs), respectively [135
138]. The band near 1066cm1 was observed due to BO bond stretching
vibrations from triborate, tetraborate, and pentaborate groups. This
indicates that there is a formation of four-coordinated boron units with the
addition of heavy metal oxide. The broad absorption peaks at around 1210
cm1 can be attributed to asymmetric stretching vibrations of BO bond in
metaborates, pyroborates, and orthoborates. With the addition of calcium
Oxide potassium borate glasses give significant change in their IR spectra
In the infrared range, the vibrational modes of the borate network
have three regions. The absorption bands around 1200-1400 cm -1 arises
due to the linkage of boron atom with three oxygen atoms [1]. The bands in
the range 800 cm-1 -1200 cm-1 are due to stretching vibrations of tetrahedral
oxygen coordinated boron present in tri, tetra and Penta-borate groups [17,
18]. The absorption peaks present between 400 cm -1 -800 cm-1 are due to
the band bending vibrations of the B-O-B linkage. Since CaO act as network
modifier, with the substitution of CaO with K 2O in B2O3 glass system, the
intensity of vibrations band due to the BO3 groups has been observed to
increase at the expense of BO 4 Structural Units. The band at 1342 cm -1 is

assigned to B-O bonds stretching vibrations of BO 3 units in Meta borates

and from various borate groups [28-31] and the band at 1240 cm 1 is due to
the BOB bond constituting the linkage of boroxol groups to neighboring
groups [25-27]. The band around 1002 cm-1 can be referred to stretching
vibrations of BO4 tetrahedral from Tri, tetra and Penta-borate groups, The
band at 719 cm-1 indicates the B-O-B bending vibrations. [23-25]. The band
at 455 cm-1 in the glass system is assigned to the specific vibrations of Ca-O
and B-O-B bending vibrations. In general, the absorption band at 806 cm -1
is attributed to the boroxol ring in the borate glass network. In the present
study, the peak at 806 cm-1 could not be found, which indicates the absence
of boroxol ring in the glass network due transformation of BO 3 triangles into
BO4 tetrahedrals.

THERMO GRAVIMETRIC DIFFERENTIAL THERMAL ANALYSIS

The TG analysis indicates the weight loss and DTA produces the thermal stability
of the glasses. The TGA curves shows only a small weight loss less than 6% and increases
for the complete range of investigation. The DTA curve of the BKC glass from the figure
shows differential thermal analysis, curve for BKC1, BKC2, BKC3 and BKC4 glasses, a
small endothermic hump corresponding to the glass transition temperature (T g,) from 170 0 C
to 190 0 C , followed by an exothermic peak corresponding to the crystallization temperature
(Tc) ranging between 504 0 C to 620 C and the second endothermic peak corresponding to
the melting temperature (Tm) from 850 0 C to 900 C .The T g, Tc and Tm of BKC glass
increases with the addition of CaO into the binary BK glass[16]. The values of T g, Tc and Tm
are shown in the table 2. These results indicate that increase in CaO concentration increases
the rigidity of the glass network.

Optical measurements.
The optical measurements were made using a UV-VIS spectrometer
(Shimadzu, Japan), with a dual light source capable of outputting ultraviolet
as well as visible light. Working in the wavelength range 200 900 nm, the
percentage transmission spectra was calculated using air as the reference
and optical cut off was obtained by finding the intercept of the steepest

slope of the rapid transmission dropoff with the baseline preceding it.
Optical band gap has been calculated by model proposed by Mott and Davis
[21]. According to this model, the absorption coefficient varies with the
angular frequency in the following manner:
, (1) []20)(EB=
where is a constant. In order to calculate the mobility gap, a graph was
plotted between and for each sample, and from the linear extrapolation to
zero ordinate, the value of was calculated. B )(0E21)]([ 0E
18 J. Singh, S. P. Singh, D. Singh, G. S. Mudahar, K. S. Thind
Infrared absorption spectra of powdered glass samples were recorded using
KBr technique in the range 4004000 cm1 at room temperature. A
recording spectrometer of Perkin Elmer1600 type was used. Corrections for
the dark current noise and background were done for the spectra using a
two point baseline correction. The spectra were normalized by making
absorption of any spectrum varying from 0 to 1 with arbitrary units.