Spectroscopic Investigation of Divalent Metal Oxide Borosilicate Glasses and Its Devitrified Product

International Journal of Innovative Research in Advanced Engineering (IJIRAE) ISSN: 2349-2163
Issue 05, Volume 5 (May 2018) www.ijirae.com
SPECTROSCOPIC INVESTIGATION OF DIVALENT

METAL OXIDE BOROSILICATE GLASSES AND ITS
DEVITRIFIED PRODUCT
Md. Emran Hossain*
Physics Discipline, Khulna University, Khulna-9208, Bangladesh
enranrubd@gmail.com;
Rinku Majumder
Physics Discipline, Khulna University, Khulna-9208, Bangladesh
rinkumajumder02@gmail.com;
Md. Rafiqul Ahsan
Physics Discipline, Khulna University,Khulna-9208, Bangladesh
ranzuphy@yahoo.com;
Manuscript History
Number: IJIRAE/RS/Vol.05/Issue05/MYAE10092
Received: 10, May 2018
Received: 19, May 2018
Final Correction: 23, May 2018
Final Accepted: 27, May 2018
Published: May 2018
Citation: Emran, Rinku & Rafiqul (2018). SPECTROSCOPIC INVESTIGATION OF DIVALENT METAL OXIDE
BOROSILICATE GLASSES AND ITS DEVITRIFIED PRODUCT. IJIRAE::International Journal of Innovative Research in
Advanced Engineering, Volume V, 210-218. doi://10.26562/IJIRAE.2018.MYAE10092
Editor: Dr.A.Arul L.S, Chief Editor, IJIRAE, AM Publications, India
Copyright: ©2018 This is an open access article distributed under the terms of the Creative Commons Attribution
License, Which Permits unrestricted use, distribution, and reproduction in any medium, provided the original author
and source are credited
Abstract ─ The glass system CaO(1-x-z)-SiO2zB2O3 Z= 0, 1, 2, 3, 5, 30, 40 and 50, mol%) are prepared by a
conventional melt quench technique keeping CaO constant. The glass systems are thoroughly investigated by using
X-ray diffraction and FTIR spectroscopy in order to obtain the structural role of Calcium, silica, boron and oxygen in
this glass host. It is found that the melting temperature of the sample increases with increase of SiO2. The IR spectra
of high B2O3 and SiO2 (30-50 mol%) containing glasses show an increased number of distinct peaks in the low
frequency region with several broad Gaussian in the high frequency region. A dramatic variation of three and four-
coordinated boron structure due to Ca─O, B─O, and Si─O arrangements are consistent in all the compositions and
show a nonlinear variation in the intensity with alkali content. The network structure of the studied glasses is
mainly based on BO3 and BO4 placed in different structural groups, the BO3 units being dominant. The measured IR
of different glasses is used to clarify the optical properties of the present glasses correlating them with their
structure and composition.
Keywords ─ Crystallization; Borosilicate glass; Deconvolution curve; FTIR spectra; X-ray diffraction;
I. INTRODUCTION
The Glass composition of CaO(1-x-z)-SiO2zB2O3 system have attracted considerable of their wide range of technical
glass applications as e.g. optical glasses or as container material of nuclear waste. The interesting features of such
glasses are e.g. high chemical durability and thermal-shock resistivity. In addition of alkalis or alkaline-earth oxides
to boron containing glasses, at the beginning boron present as trigonal planar group (BO3) is converted four-fold
coordinated boron (BO4) species, with partial charges on bridging oxygens compensated by the added cations. At
high alkali or alkaline-earth contents, the excess oxygens act as nonbridging oxygens (NBO) and result in a
dypolymerization of the network and the conversion from BO4 to BO3. Temperature and pressure also affect the
boron coordination and hence causes changes e.g. in density, thermal expansion and mechanical properties of the
glass [1-7]. Moreover, a large number of studies have been devoted to the structure of borosilicate glasses.
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For the reason the interest are two peculiarities in the behavior of boron in boron containing glasses [13-18]. The
first peculiarity is that, in contrast to the silicate glasses, the addition of a network modifier to vitreous B2O3 leads
initially to the conversion of BO3-triangles into BO4-tetrahedra, i.e. to the formation of more compact and rigid
regions in the structure borosilicate glasses. The second peculiarity is that the network of borosilicate glasses is not
built up by randomly distributed BO3- and BO4 groups, but by the so called super structural units which consist of
well-defined and rigid arrangements of the basic BO3 and BO4 groups [8, 9-13]. Borosilicate glass contains glass-
forming constituent’s silica and boron oxide which includes at least five percent boric oxide [14]. The boric oxide
makes the glass resistant to extreme temperature and also improves its resistance to chemical corrosion. Glass
formation in the binary system CaO-SiO2 goes up to about 33.33 mol % CaO; however, in a large part of this area
liquid-liquid phase separation prevents single-phase glasses [15]. In all crystalline silicates the silicon ions are
coordinated by four oxygen ions. The simplest silicate glass is vitreous silica. In vitreous silica all silicon ions are
also coordinated by four oxygen ions [16]. There is a certain distribution in the bond angles, evidenced by X-ray
analysis, which makes the structure of vitreous silica quite uniform at a short range, but there is no order beyond
several units of SiO4 tetrahedral [17]. Various other properties of vitreous silica are also in agreement with the
random network model, for instance infrared absorption, XRD. Here SiO2 and B2O3 are the principle
modifiers/fluxes. The chemical and physical properties of any glass depend on a varying degree on chemical
composition of glass sample. The electronegativity of silicon Si+4 is 1.74 and that of oxygen O2- is 3.50 and Ca2+ is 1.04.
So the bonding affinity of Si-O is much more than Ca-O. However, Ca breaks the Si-O-Si chain but there is not enough
Ca to form most of the bridging and non-bridging oxygen. Thus the absorption band of Si-O-Si is more than Ca-O
bond. The silicate structure promotes the formation of phase separate regions which is highly susceptible to the
corrosion. For the quantitative analysis of IR spectra of glasses the author used the most significant deconvolution
method [18,19]. Deconvolution of IR spectra can be considered as a useful tool to extract information about glass
structure rather than traditional analysis of IR spectra [20]. The present authors have looked at the bonding
mechanisms of CaO–SiO2–P2O5 and CdO–SiO2–P2O5 glasses with the help of IR and NMR techniques [19-21]. These
papers describe a significant structural change of silicon coordination. This has prompted the authors to investigate
CaO–SiO2–B2O3 glasses by spectroscopic technique. In this work we have collected infrared spectra of xCaO(1 -x)-
SiO2 glass with varying amounts of B2O3 and qualitative and quantitative analysis of these spectra were performed
to understand the bonding mechanisms, characteristic frequencies of the vibrational chemical bonds, which are
liable to the structural and spectral changes. XRD pattern of base and heat-treated samples are also used to study
the amorphocity and phases of the glass.
II. EXPERIMENT
For the synthesis of CaO(1-x-z)-SiO2zB2O3 glasses, commercially available reagent grade CaCO3, SiO2 and B2O3 were
chosen as starting composition expressed in mol%. The powder raw material of appropriate amounts, usually 50g
batches, were homogenized by rolling and shaking on a ball milled machine for 6–8 h and then tried to melt in a
crucible in an electric furnace. The melting temperatures of calcium silica binary composition and with10–30 mol%
B2O3 containing glasses are high. An oxyacetylene flame was used to melt some compositions. The glass melt was
then poured onto a milled steel block coated with graphite and was quenched by pressing with another block of the
same material. However, the melting temperature of the glass batches containing more than 30 mol% B2O3 are
lowered and these were melted in an electric furnace in a covered alumina crucible. The composition and melting
temperature along with their nomenclature are shown in Table 1. In order to prepare glass ceramics some quantity
of the base glasses were first pulverized in a mortar and then heat treated at 500 oC for 12 hr in an electric furnace.
However, for comparison some glasses are also heat-treated at different temperature and time. A Carbolite digital
furnace, model CTF12/65, controller eurotherm 91 and porcelain crucible are used for the heat treatment.
TABLE 1- MELTING TEMPERATURE AND OPTICAL QUANTITY OF GLASSES OF VARIOUS COMPOSITIONS
Title of Nominal composition in mol% Melting temperature in oC Optical quantity XRD
the sample CaO SiO2 B2O3
∗
CaBS10 56.67 10 Chocolate, opaque
CaBS20 46.67 20 Milky, clear
CaBS30 36.67 30 White, clear
CaBS40 26.67 40 1250 White, clear
CaBS66.67 33.33 0 66.67 1330 White, clear Amorphous
Ca for calcium, S for SiO2 and B for B2O3

∗ 1100 < < 2000 .
___________________________________________________________________________________________________
To obtain IR absorption spectra of a glass sample, KBr pellet technique is employed. The glass samples were ground
in a clean mortar to a fine powder and weighed quantity ( 0.004 g) of the powder was intimately mixed with
desiccated highly purified (99.99%) KBr powder ( 0.01 g). The mixture was then pressed with a pressure of 5 tons
per square inch to yield a transparent pellet of approximate thickness 0.01 mm suitable for mounting in the
spectrophotometer. All infrared spectra of the glasses were collected on a Shimadzu IR470 spectrophotometer over
the range of wavenumber 4000–400 cm-1. The X-ray diffraction measurements of the stored sample were carried
out using X-ray diffractometer system; model JDX-8P, Jeol, Japan. The phases in the devitrified samples were
identified by comparing the experimental interplaner spacing and intensity of the diffraction pattern with standard
JCPDS files.
III. RESULTS
The infrared absorption spectra of low (10-30 mol%) and high (40-66.67 mol%) B2O3 containing ternary CaO-SiO2-
B2O3 glasses along with binary CaO-SiO2 is shown in Fig. 1. The Spectrum of CaBS10 of two main bands in the low-
and high frequency region. The low frequency bands 1200-500 cm-1 are more distinct than high frequency band
3700-1200 cm-1 and consists of number of small peaks and shoulder on both sides of the central maxima at 1100
cm-1 . There are some sharp peaks in the high frequency region.
Absorbance (arbitrary unit)
CaBS66.67
CaBS60
CaBS50
CaBS40
CaBS30
CaBS20
CaBS10
400 900 1400 1900 number2400

Wave (cm-1) 2900 3400 3900
Fig. 1. Base line corrected infrared spectra of CaO(1-x-z)-SiO2zB2O3 glasses.

The peak height of the low frequency band is relatively greater than the high frequency band. Addition of small
amount (10-30 mol%) of B2O3 alters this situation. The sharpness of the spectra is increased with the increase of
B2O3 and the absorption in the high frequency region is higher than the low frequency band. All the frequency bands
are convolution of Gaussian conspicuous by small peaks and shoulders on both sides of them. The strong shoulders
observed in the CaBS10 at 1100 cm-1 is disappeared in CaBS20 and new weak shoulders arise around 1000 cm-1.
Also, position of the two main bands remains the same. In CaBS20 the low- and high frequency band shifts to higher
wave number slightly and the weak shoulder arises in CaBS10 at 917 cm-1 becomes stronger and turned into peak in
CaBS40 glass. The low frequency bands of CaBS40 became resolved into two overlapped Gaussians with band
maxima at 687 and 1100 cm-1. Though the low frequency bands of CaBS20 and CaBS40 differ in shape the high
frequency bands are very similar but differ in absorption intensity. In the high B2O3 (50–66.67 mol%) containing
glasses the variation of absorption spectra is remarkably different from the low amounts of B2O3 containing glasses.
The strong peak observed in the CaBS40 glass at 676 cm-1 and in CaBS50 is 786 cm-1 . Also, the high frequency band
consists of broad overlapped Gaussians with absorption maxima at 1100 and 1400 cm-1. The band developed in the
frequency region 600–1400 cm-1 in CaBS50, CaBS60 and CaBS66.67 and the shoulder at 820 cm1 becomes stronger.
As a whole the low frequency band resolved into two overlapped Gaussians with maxima at 650 and 825 cm-1. Also,
the new bands developed in CaBS60 at 1030 and 1200 cm-1 become stronger in CaBS66.67. The absorption patterns
in the high frequency region are very similar to CaBS50 glass with differing intensities.
TABLE 2:DECONVOLUTION BAND POSITION AND ASSIGNED CHEMICAL BONDS OF CaO(1-x-z)-SiO2zB2O3 GLASSES.
Samples Low frequency Region High frequency region
Band position in cm-1 Chemical bonds Band position in cm-1 Chemical bonds
CaBS10 525 Si-O-Si 1251 Si-O-H
627 Si-O-Ca 1355 B-O-
660 Si-O-Ca 1439 B-O3
680 Si-O-Ca 1640 H 2O
925 B-O-B
___________________________________________________________________________________________________

552 Si-O-Si 1645 H 2O
810 O-B-O 3310 B-O-H
853 B-O-Ca 3476 B-O-H
957 B-O-B 3565 B-O-H
706 Si-O-Ca 1550 B-O3
894 O-B-O 1639 H 2O
965 B-O-Ca 3305 B-O-H
967 B-O-B 3505 B-O-H
CaBS40 700 Si-O-Ca 1484 BO3
850 B-O-Ca 1642 H 2O
830 O-B-O 3300 B-O-H
908 B-O-B 3492 B-O-H
956 B-O
CaBS50 515 O-B-O 1262 B-O-
620 Si-O-B 1595 H 2O
740 Si-O-Ca 3296 B-O-H
871 B-O-Ca 3467 B-O-H
916 B-O
CaBS60 604 Si-O-Si 1314 B-O-
653 Si-O-B 1482 BO3
904 B-O-B 3313 B-O-H
965 B-O-Ca 3427 B-O-H
990 B-O 3566 B-O-H
CaBS66.67 555 O-B-O 1460 B-O-
684 Si-O-B 1490 BO3
820 O-B-O 3220 B-O-H
888 B-O-B 3480 B-O-H
995 B-O
1 .0
O r i g i n P r o 8 E v a l u a t io n O r i g i n P r o 8 E v a l u a t io n
0 .8 O r i g i n P r o 8 E v a l u a t io n O r i g i n P r o 8 E v a l u a t io n
Absorbance (arbitrary unit)
0 .6
0 .4
0 .2
0 .0
500 1 000 1500 2000 2500 3000 350 0 400 0
-1
W a v e n u m b e r (cm )
Fig. 2. A typical deconvolution spectra.

When a resultant spectrum consists of more than one band, either the peak or the shoulder positions do not appear
at the center of gravity of the individual band, rather they often move towards the center of gravity of all the bands
present in the spectrum. Therefore, the deconvolution of the experimental spectrum provides with the exact
position of the absorption band. The band position and widths obtained from the deconvolution are thus considered
to be true representation of the spectra. The deconvoluted band positions and their assigned chemical bonds are
summarized in Table 2. A typical deconvoluted spectrum is shown in Fig. 2.
IV. DISCUSSIONS
4.1. CaO-SiO2 glass
The infrared spectrum of binary glass mainly consists of the effect of bridging and nonbridging oxygens. The band
observed at 525 cm-1 is assigned to Si–O–Si bending vibrations as observed by Kholi et al. [22] in the rare earth
aluminosilicate glasses containing 10–20 mol% samaria within the 451–480 cm-1range.
___________________________________________________________________________________________________
The intensity of the band is very weak, as it is associated with bridging oxygen in Si–O–Si of SiO4 tetrahedra. The
relative intensities of the deconvoluted band at 627, 660 and 680 cm-1 are strong in this glass, can be attributed to
Si–O–Ca asymmetric bending mode that exists in the glass. This agrees with the expected increase in nonbridging
concentration as the silica network is depolymerized by calcium. The three shoulders within this close range are due
to the asymmetry in the Si–O–Ca bond distribution as a range of environments can also exist in the glassy materials.
The bands with maxima at 604 cm-1can be assigned to Si–O–Si bending vibrations as observed by Higby et al. [23].
The observed absorption bands in the high frequency envelop can be accounted for by a different role of H2O
molecule in the structure. In particular, the atmospheric moisture is easily absorbed by the sample or by the pellet,
causing the appearance of IR band belonging to H2O molecule although the sample under investigation does not
contain H2O as unit in the network. Ryskin [24] observed water related as much as four bands in the 3000–1200 cm-
1 range denoted by 2600–2950 (A), 2200–2460 (B), 1500–1950 (C) and 1200–1400 (D) for the hydrates of
phosphate and silicate crystals. Based on the above observations the bands at 1251, 1350 and 1370 cm-1 can be
ascribed to bending and stretching mode of the Si–O–H group forming the hydrogen bonding. Ryskin defined
another band 1590–1700 cm-1 within that range for the bending mode of the H2O molecule. The band at 1705 cm-1 is
closer to the upper limit of this band. So the band at 1645 cm-1 can be assigned to bending mode of the H2O molecule.
The single broad band relatively free of sharp features in the high frequency region indicates that a wide
distribution of types of nonbridging oxygen ions exists for this glass.
4.2. Low Borate glasses (10-30 mol% B2O3)
In the ternary glass system, the ratio of CaO/SiO2 was initially 1.7 and B2O3 was substituted systematically in the
system. The IR spectra reveal that the relative intensities of the absorption bands in the low- and high frequency
region of CaBS10– CaBS20 are almost similar. The IR spectrum of CaBS40 is characterized by a double in the low
frequency region. By a careful inspection of the maxima and shoulders 5 and 6 Gaussians are fitted to CaBS10–
CaBS20 and CaBS40 spectra, respectively. The relative intensities of the high frequency band of CaBS10– CaBS40
glasses are much higher than CaBS10 and the sharpness of bands increased significantly. The similar patterns of
high frequency spectrum are deconvoluted to 4 Gaussians to estimate the band position and relative amounts of
various bonding mechanism. The well known SiO2 peaks at 1080, 604 and 510 cm-1 are generally due to Si–O–Si
band stretching, O–Si–O band bending and Si–O–Si band rocking vibrational modes, respectively, [25]. The presence
of interstitial oxygen is characterized by bands at 515 cm-1 known to be due to vibrational modes of a non-linear
molecular unit of Si–O–Si vibrations [26, 27]. Based on these observations the weak bands at 510, 525 and 560 cm-1
in CaBS10– CaBS40 glasses can be assigned to Si–O–Si bending vibrations. Incorporation of high CaO into the
tetrahedral network causes the introduction of Ca++ ions into the silica network and breaks some of the silicon
oxygen bonds with the production of groups of the type Si–O–Ca–O–Si. In this situation the calcium oxygen and
silicon oxygen networks could interwine to form a stable glass. So the bands at 627, 660, 700 and 706 cm-1 of these
glasses can be ascribed to Si–O–Ca asymmetric bending vibration. The absorption bands at 810, 830 and 894 cm-1
are very closer to the O–B–O bending vibrations [28]. The broad Gaussian bands at 1595, 1640 and 1645 cm-1 are
for bending mode of H2O molecule as observed by Ryskin [24]. Also, by analogs of Ryskin’s band 1500– 1950 cm-1
(C) the bands observed at 1640 and 1645 cm-1 in CaBS10 and CaBS20 glasses can be assigned to stretching mode of
B–O–H groups forming the hydrogen bonding. For various glasses three water related bands in the 3220–3296,
3300–3313 and 3313–3566 cm-1 ranges were found [29, 30]. This group forms the strongest hydrogen bonding with
the nonbridging oxygen.
4.3. High Borate glasses (40–66.67 mol% B2O3)
In the high B2O3 containing glasses the systematic change in the absorption spectra and development of new peak in
the low frequency region (Fig. 1) gives more information about the structural change. The change of absorption
spectra in the low frequency region is systematic and more informative. The high frequency band observed in the
high B2O3 glasses becomes broader than that in binary calcium silica glasses. The developments of new bands in the
region 1260–1100 cm-1 in 40 and 50 mol% B2O3 containing glasses justify the structural change.
Depending on the spectral shape 5 Gaussians are fitted to the low- and high frequency region, respectively (Table 2).
Usually, Si–O–Si bond rocking was observed in silicate glasses within 512–650 cm-1 range. However, Padmaja and
Raluca [32, 33] have assigned the bands in the region 450–550 cm-1 to the possible modes of B–O–B linkage. The
ascribed harmonics of bending B–O–B and O-B─O vibrations for weak shoulder at 530 cm-1 in the B2O3 glass.
However, they attributed these bands at 500 cm-1 to the harmonics of B–O–B bending. So the weak band observed at
430 cm-1 in CaBS40, CaBS66.67 glasses are due to harmonics of bending B–O–B and O─B─O vibrations. The
arrangement of silicon has an absorption centered on 660 cm-1 was observed by Locker et al. [34]. While the bands
at 917, 970 and 1037 cm-1 can be due to B─O normal mode. There is no band observed in the mid frequency region
at 1600 and 3000 cm-1 in all glasses. In the high frequency region the bands at 3220, 3305, 3480 and 3566 cm-1 are
due to B─O─H stretching mode. Its shift may be attributed to the increase in the bond order of B─O bond [32, 33].
The strong overlapped Gaussians having maxima within 1251–1645 and 3220–3566 cm-1 can be assigned to
components of the stretching modes of the P–O–H group.
___________________________________________________________________________________________________
4.4. Effect of B2O3 on CaO.SiO2 glass

The effect of B2O3is obvious for certain bonding mechanisms where BO3 plays a significant role. The variation of
band position and band intensity upon the addition of B2O3 (10–66.67 mol%) to the calcium silica binary glass is
shown in Figs. 3 and 4. A major change is observed in the variation of Si–O–Si, Si–O–Ca, O–B–O and B–O–B bonds at
low B2O3 concentration. The band position and relative area of Si–O–Si and Si–O–Ca shifts to minimum at 10 mol%
B2O3 containing glass and then increases up to 40 mol% B2O3 containing glasses. These two bands were not
observed in the high B2O3 glasses. The absence of these bands represent the change of glass structure due to the
depolymerization of silicate matrix.
1000
Band position in wavenumber (cm-
900 B-O-Ca
800
Si-O-Ca
1)
700
600
Si-O-Si
500
1 2 3 4 5 6 7
B2O3 concentration in mol%
1100
Band position in wavenumber (cm-1)
1000 B-O-B B-O
900
O-B-O
800
700 Si-O-B
600
500
10 20 30 40 50 60 70
4000
Band position in wavenumber
B-O-H B-O-H
3500
B-O-H
3000
(cm-1 )
2500
2000
H2O
BO3
1500 B-O-
Si-O-H
1000
10 20 30 40 50 60 70
Fig. 3. Variation of band position of the various bonds with B2O3 concentration
___________________________________________________________________________________________________
40
35 B-O-Ca
Relative area in %
30
25
20
Si-O-Ca
15
10
5
1 2 3 4 5 6 7
B2O3 concentration mol%
40
Si-O-B
30
Relative area in %
B-O-B
20
10
0 O-B-O
10 20 30 40 50 60 70
B2O3 concentration mol%
50
H2 O
40
Relative area in %
B-O-H
30
B-O-H
20
10
B-O B-O-
0
10 20 30 40 50 60 70
Fig. 4. Variation of relative area in % of the various bonds with B2O3 concentration.
Again the band position and relative area of B–O–Ca shift slightly toward more positive. These could result in
shifting of band position towards higher frequencies as observed in these glasses. The almost constant band
position apart from BO3 for higher amounts of B2O3 glasses represents a stable local environment which was formed
in CaBS50. The variation in the band position of the vibrational bonds of major network forming bonds B–O–B and
O–B–O shows a noticeable change at all levels of B2O3. The relative intensities of B–O–B and O–B–O decrease up to
CaBS20 and then increase. Also, in case of B–O–B bond it decreases up to 40 mol% B2O3 (Fig. 4). This change may be
explained by the fact that one of the borate species. The band position for Si–O–B and B─O bonds almost remains
unchanged but there relative intensity increases with the increase of B2O3.
___________________________________________________________________________________________________
This variation in relative intensity of Si–O–B bond can be explained as B+ occupies SiO4+ lattice by breaking
tetrahedral network it remains as Si–O–B structures, and the formation of these bands suggests the bending
vibration of SiO6 octahedra rather than silicon tetrahedra. The increase in intensity of B─O bond indicates the weak
cationic effect in the glass matrix. Ionic character of borate group can be explained by the formation of B–O group.
Usually this stretching vibration of B–O group occurs between 956 and 1460 cm-1, and the intensity of this band is
very weak. In the present work, the band appearing at 956 cm-1 is attributed to B–O stretching vibrations, which is
basically present in B2O3. The band position of B–O group is nearly unaffected with the increase of B2O3. The slight
increase in band position (Fig. 3) can be attributed to shortening of the B–O bond for the increase in the network
packing. This also suggests that the borate species was formed around 50 mol% B2O3 remain unchanged at 60 and
66.67 mol% and the breakdown of covalent vitreous network into small ionic groups B-O- expected. This band is not
observed in the CaBS10–CaBS30 glasses and the band intensity is very low in the high B2O3 containing glasses. We
conclude that new species either silicate or borate or both may form at this level of B2O3. The variation in intensity
(Fig. 4) certainly suggests that the structure of the glass changes in such a way that borate tetrahedra dominates the
network. The frequency and intensity of B-O bridge is affected by the water content (which is probably taken up
during the preparation of the pellet for the IR measurement) and the ratio of CaO/SiO2 + B2O3. The shifting of band
position and intensity toward more positive with increasing B2O3 is possibly due to the polarization effect of the
modifying cation Ca++. The variation of band position and relative intensity of B–O–H bond with B2O3 indicates that
the glass with high B2O3 contains more water than those with smaller amounts. The splitting of B–O–H stretching
mode is due to a multi site effect.
4.5. XRD of heat treated sample
The CaO–SiO2–B2O3 glasses are heat treated at 500 0C/12 h. Also, for comparison of some samples like CaBS60 and
CaBS66.67 are heat treated at different temperatures and different time. The low B2O3 containing sample, i.e.
CaBS10–CaBS40, show the crystallinity and contains different phases. The diffraction pattern of CaBS10 and CaBS20
are similar and Ca2SiO4 phase is detected in it. In CaBS40 glass in addition to Ca3Si2O7 phase, γ-Ca2P2O7 is present in
the sample. Also, high B2O3 containing samples CaBS60 and CaBS66.67 although they are heat-treated at different
temperature and different time, did not show any crystallinity except amorphous haloes.
V. CONCLUSIONS
The glass system xCaO(1-x-z)-SiO2zB2O3 were prepared by conventional method were the concentration of B2O3
with 0, 1, 2, 3, 5, 30, 40, 50, 60, 66.67mol%. Introducing of B2O3 (10mol% to 66.67 mol%) in CaO-SiO2 system
keeping the amount of CaO constant, the band position are greatly changed.
The B2O3 content is responsible for the variation of the structure the glasses. Incorporation of small and large
amounts of B2O3 in the material suggests that B2O3 occupies the network former position and forms the linkage Si–
O–B. The Si–O–B bond may lead to the bending vibration of SiO6 octahedra rather than silicon tetrahedra. A general
trend of shifting of the band position toward high frequency also caused by the local field of the Si–O–Ca bonding
due to B2O3. The formation of B–O–H band express the hygroscopic nature of the glass. The information is helpful in
drawing conclusion about the chemical durability of borosilicate glasses.
ACKNOWLEDGMENTS
The authors would like to thanks Chairman, Department of Physics, Rajshahi University, Rajshahi, Bangladesh for
sample preparation. The authors thank Mr. Md. Saiful Islam, senior scientific officer, Central science laboratory,
Rajshahi University for recording IR spectra. The authors also thank the Chairman, Department of Physics, Rajshahi
University of Engineering and Technology, Rajshahi for recording X-ray diffraction pattern.
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Spectroscopic Investigation of Divalent Metal Oxide Borosilicate Glasses and Its Devitrified Product

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Spectroscopic Investigation of Divalent Metal Oxide Borosilicate Glasses and Its Devitrified Product

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International Journal of Innovative Research in Advanced Engineering (IJIRAE) ISSN: 2349-2163

Issue 05, Volume 5 (May 2018) www.ijirae.com

SPECTROSCOPIC INVESTIGATION OF DIVALENT

Ca for calcium, S for SiO2 and B for B2O3

400 900 1400 1900 number2400

Fig. 1. Base line corrected infrared spectra of CaO(1-x-z)-SiO2zB2O3 glasses.

CaBS20 510 Si-O-Si 1350 Si-O-H

Fig. 2. A typical deconvolution spectra.

4.4. Effect of B2O3 on CaO.SiO2 glass

1000 B-O-B B-O

B2O3 concentration mol%

B2O3 concentration mol%

9. J. Biscoe, B.E.Warren, J. Am. Ceram. Soc. 21 (1938) 287, http://dx.doi.org/10.1111/j. 1151

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