Optik - International Journal for Light and Electron Optics 274 (2023) 170506

Contents lists available at ScienceDirect

Optik
journal homepage: www.elsevier.com/locate/ijleo

Bio behavioral, elastic, structural and spectroscopic aspects of

CZPT glasses
N. Rama Krishna Chand a, B.K. Sudhakar a, T. Vennela b, P.V.S. Sairam a,
G. Ravikumar c, *, G. Srinivasa Rao a, *, Ch. Srinivasa Rao a, *
a
Department of Physics, Andhra Loyola College, Vijayawada, AP, India
b
Department of Nano Technology, Pukyong National University, Busan, the Republic of Korea
c
Department of Physics, Sreenidhi Institute of Science and Technology, JNT University, Hyderabad 501301, India

A R T I C L E I N F O A B S T R A C T

Keywords: The Calcium Zinc Phospho Titanate (CZPT) glasses with the composition CaF2–ZnO–P2O5:TiO2
CaF2–ZnO–P2O5glasses are synthesized. The prepared glasses were found to possess a bioactive nature after immersing in
Titanium ions simulated body fluid (SBF) for the various durations at physiological conditions and the pH
IR, Raman, Optical absorption
values/dissociation rates are measured. XRD, SEM, and EDAX studies are carried out for the
ESR
prepared glasses. The influence of coordination states of titanium ions on these glasses was
studied by analyzing the DTA, FTIR, Raman, OA, and ESR spectral studies and the mechanical
properties by analyzing the elastic parameters of prepared glasses. The coexistence of trivalent
and tetravalent titanium ions is established by studying various structural and spectroscopic as­
pects. The FTIR and Raman spectral analysis of present glass samples after deconvolution in­
dicates the presence of both Ti3+ (octahedral) and Ti4+ (tetrahedral and octahedral) ions. The
conversion rate of Ti4+ ions into Ti3+ ions was based on the content of dopant, TiO2 in the glass
matrix.

1. Introduction

The P2O5-based glasses and ceramic glasses have been discovered to be more beneficial in the field of biomaterials and are utilized
to regulate the release of modifier ions needed in the glass network. These glasses are valuable suppliers of phosphate ions for the
growth of host materials to create recombinant proteins due to their high solubility [1]. Phosphate-based glasses, which are amorphous
solid materials with PO4 structural units and are useful in a variety of industries, including optics and the encapsulation of nuclear
waste, and are predominantly useful in different applications of biomedicine due to their non-toxic solubility in living tissue [2,3]. Due
to a rise in network disorderliness, compositional alterations regulate the properties of these glasses. The addition of alkali, alkaline
oxides, and fluorides will be used to control the network alterations inside the phosphate glasses. Due to the increased modifying
activity of alkali, alkaline, and fluorine ions in the glass network, oxyfluorophosphate (OFP) glasses are the finest host materials for
biocompatibility. The Q3 phosphate tetrahedra in P2O5 glasses have three P-O-P bridges, each with three bridging oxygens. The
modifying ions will change the Q3 phosphate tetrahedra into Q2, Q1, and Q0 structural units, releasing enough non-bridging oxygens to
create the network with other cations in the glass. These changes will improve the phosphate glasses regarding chemical, mechanical,
thermal, and bioactive characteristics [4,5]. The OFP glasses are significant because of their low melting point, high refractive index,

* Corresponding authors.
E-mail addresses: gsrinivasarao64@yahoo.com (G.S. Rao), drchsr1971@gmail.com (Ch. Srinivasa Rao).

https://doi.org/10.1016/j.ijleo.2023.170506
Received 4 November 2022; Received in revised form 18 December 2022; Accepted 2 January 2023
Available online 6 January 2023
0030-4026/© 2023 Elsevier GmbH. All rights reserved.
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

high thermal expansivity, high gain density, and greater transparency over a wide range of spectral wavelengths. However, there is a
restriction for these glasses because of their meagre chemical durability, and elevated voltaic and hygroscopic nature.
By accretion of metal oxides such as ZnO to the OFP glasses, these restrictions can be alleviated [6]. The addition of ZnO will
enhance the inter atomic spacing of the OFP glasses, causing the glass network to expand and create additional free space within the
lattice. Due to a larger ionic radius than other cations at the lattice sites, the divalent zinc ions may diffuse into the glass network,
forming single bonds with oxygen atoms liberated by cleavage of P-O-P bonds. ZnO will improve the stiffness of the glass, increase the
number of NBO, and raise the compactness of the glass [7].
By combining ZnO-doped OFP glasses with different metal oxides, such as TiO2, their characteristics are further improved. Tita­
nium ions will take the place of cations at the lattice sites due to their tiny ionic radius. It is discovered that dopant ions of titanium
stabilize the glass matrix by hydrolysing and forming Ti-O-P bonds with the substitution of P-O-P bonds. Based on the composition of
glass, titanium may involve in the glass network either with trivalent (Ti3+) or tetravalent (Ti4+) coordination, which can be distin­
guished by colouring. (Ti3+) ions have a purple-blue, whereas (Ti4+) ions have 6-coordinated, 5-coordinated, or 4-coordinated
oxidation states. Due to their improved qualities, these glasses are significant technologically and have biological uses as well [8,
9]. In this study, we investigate the coordination of titanium ions (Ti3+/Ti4+) about structural characteristics of CZPT bio glasses by
analyzing Raman and FTIR spectra, mechanical durability by using elastic properties and related parameters, thermal stability with
differential thermal analysis (DTA), and spectroscopic studies with optical absorption (OA) and ESR spectra in view of developing
biomaterials useful for orthopedic as well as dental implants.

2. Experimental methods

The correct amounts of reagent grades CaF2, ZnO, P2O5, and TiO2 are used to make the current transparent glasses that are
designated CZPT0 to CZPT6 and have the following composition: 20 CaF2 - 20 ZnO - (60-x) P2O5; x TiO2 where , x = 0, 0.1, 0.2, 0.4, 06,
0.8 and 1.0. In a furnace equipped with a controlled microcontroller, the aforementioned parts of the current CZPT glasses are uni­
formly assorted in an agate mortar and heated to 900 K for a duration of 30 min to create a transparent liquid without any bubbles. The
resulting molten liquid was collected in a mould made of brass and afterward moved to a muffle furnace, which was kept continuously
at 450 K for annealing, roughly 24 h to obtain the bulk glass samples. Following in-lab grinding to the required level, these CZPT
glasses are optically polished to have approximate dimensions ((20 mmx20mmx) 2.0 mm) and a few samples are crushed to a fine
powder to make use of in various characterization methods. By using a plasma analysis approach and an atomic absorption spec­
trophotometer, the trace components of these glasses can be identified and the analyzed and nominal batch compositions of present

Fig. 1. (a): XRD diffraction patterns of TiO2 doped CZPT glasses recorded at room temperature. (b) & (c): SEM micrograph of CZPT4 glass at various
resolutions prior and subsequent to immersion in SBF.

2
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

CZPT glasses are in correlation with in experimental error.

By utilizing Oahu’s digital electronic scale to measure the required weights of components in the air as well as in a buoyant liquid,
O- xylene, it is possible to measure the densities of these glasses using the Archimedes principle. By maintaining a human body
temperature of 37 ◦ C with a hotplate and magnetic stirrer and employing chemicals of the appropriate magnitude following the course
of action described by Kokubo and Takadama, simulated body fluid (SBF) is prepared of the volume of one litre with a pH 7.40 without
any precipitate using Tris buffer reagent and 1.0 M HCl [10]. The vitro bioactive nature of prepared glass samples was tested by
immersing suitable amounts of glass powders approximately 200 mg (with particle size; 200 µm − 250 µm) in the simulated body fluid
of 80 ml for several lengths of time, ranging from 2 days to 10 days, in various plastic tins while keeping them in an incubator where the
temperature is kept at a constant 37 ◦ C subjecting the physiological conditions of human body fluid. These powdered glass samples are
separated with filter paper and later dehydrated for one day at 70 ◦ C and were analysed by SEM and EDS to verify the purpose of
apatite layer formation. The variations in pH of the SBF used to soak the glass powders, as a result of their hydration is measured with a
pH meter. The pH meter was calibrated with standard pH buffer solutions at 9.2, 7.4, and 4.0, for every measurement.
The DTA of these CZPT bio glasses was measured using a differential scanning calorie meter by heating a very small amount of glass
powder at a rate of 10 K per minute in crucibles constructed of aluminium in a nitrogen atmosphere between 310 and 925 K. With
copper Kα radiation at 30 kV, 20 mA, and(1.54A◦ ) in the range of 0◦ to 90◦ , the XRD of these glasses was measured using a Diffrac­
tometer D8. To study the mechanical properties of these glasses, VL and Vs velocities are determined experimentally by measuring the
resonant frequencies of the composite system and that of a single quartz crystal from which young’s moduli and bulk moduli are
determined by using ultrasonic interferometer for solids. By using an FTIR alpha spectrometer, FTIR spectra of CZPT glasses were
performed between 400 and 1500 cm− 1. The Raman spectra of CZPT glasses, was measured in the region of 200–1400 cm− 1 with near-
infrared Raman spectrometer.

3. Results

3.1. Characterization of CZPT glasses

As shown in Fig. 1(a), the nonexistence of sharp peaks in the diffraction patterns noticed in x-ray spectra of TiO2-doped CZPT
glasses indicates their glassy behavior before immersion in SBF. This is also supported by scanning electron microscope images of CZPT
glasses at a resolution of 50 µm as reported in Fig. 1(b) and CZPT4 glass at various resolutions reported in Fig. 2(a) without soaking in
simulated body fluid. The EDS analysis represents the existence of only nominal elements P, O, Zn, Ca, F and Ti in these CZPT4 glass
without any traces of apatite composition as shown in Fig. 2(b). After soaking in SBF for duration of 10 days, the precipitation on the
surface of these glasses slowly increases with the appearance of foam like structure or formation of an apatite cluster occur on these
glass surfaces as represented by Fig. 1(c) at resolution of 50 µm and in particular CZPT4 glass as represented in Fig. 2(d) at various
resolutions. This apatite is a thick layer that covers the glass surface completely as a result of nucleation of crystal growth and is super
saturation of Ca+2, F-, PO3-4 on the glass surface due to soaking in simulated body fluid with an increase in incubation period. The

Fig. 2. (a) & (c): SEM micrographs of CZPT4 glass at various resolutions prior and subsequent to immersion in SBF. (b) & (d): Chemical investigation
of CZPT4 glass before and after immersing in SBF and inset represent the morphology of the glass surface.

3
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

composition of these glasses, which contain phosphorous, calcium, oxygen, zinc, and titanium in varying weights, is clearly explained
by the energy dispersive spectra of CZPT4 glass with and without soaking in simulated bodily fluid, as shown in Fig. 2(b) & 2(d).
Finally, the synthesis of hydroxy apatite after immersing TiO2-doped CZPT glasses for varying lengths of time in simulated bodily fluid
(SBF) supports the bio-behavioral characteristics of these glasses used in this study.

3.2. Physical parameters of CZPT glasses

The properties like Vm, ⍴, Vo, OPD, and other physical parameters are very much useful to know the adjustments occurring within
the glass matrix by the addition of dopant TiO2 to these CZPT glasses and are determined from density, which is displayed in Table 3.
[11,12].
Current CZPT glasses exhibit short-range order, which can be explained by two fundamental properties: density, which decreases
from 2754 kgm− 3 to 2702 kgm− 3 before increasing to 2746 kgm− 3, and molar volume, which increases from 42.507 × 10− 6 m3 mol− 1
to 43.279 × 10− 6 m3 mol− 1 before decreasing to 42.404 × 10− 6 m3 mol− 1 with the content of dopant, TiO2 from 0 to 1.0 mol% as
shown in Fig. 3(a). The trend in density is the same as the trend in oxygen molar volume and molar volume is similar to the oxygen
packing density of current glasses as shown by Fig. 3(b).

3.3. Chemical degradation studies

By conducting dissociation studies on current CZPT glasses with approximate dimensions 20 mmx20mmx 2.0 mm before and after
soaking them in simulated body fluid at human body temperature 309.65 K for various lengths of time - 48, 72, 168, and 240 h
respectively, in an incubation chamber, it is possible to determine the bio durability and biodegradability of TiO2 doped CZPT glasses
by drying them at room temperature for two days [13–15].
The dissociation rate is given by the following expression
ΔW
D= gcm− 2 s− 1
(1)
St

where ΔW is the mean value of loss in weight of present CZPT glass soaked in SBF and is measured for a definite duration of time ‘t′ and
glass surface area is ‘s′ . The above-mentioned parameters are represented in Table 1. It is noticed that weight loss of present CZPT bio
glasses increases exponentially with concentration of dopant TiO2 as well as with duration as represented by Fig. 4(c), whereas an
opposite tendency is found in the dissociation rate of these bio glasses as shown in Fig. 4(a). The bioactive nature of prepared CZPT
glasses known by development of an apatite layer on these glass surfaces and was determined by variations in pH of simulated body
fluid (SBF) used for soaking these glass samples that increase for low incubation period of 3 days and thereafter decrease on further
incubation period of all CZPT glasses except CZPT4 as indicated in Fig. 4(b) and the corresponding pH values are given Table 2.

3.4. Thermal parameters of CZPT glasses

The DTA curves for TiO2 doped CZPT bio glasses as represented by Fig. 5(a) indicate the heat exchanges as a function of

Fig. 3. (a): Deviation in density and molar volume of CZPT glasses with the content of TiO2. 3(b): Deviation in oxygen molar volume and oxygen
packing density of CZPT glasses with the content of TiO2.

4
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

Table 1
Dissolution Rates of CZPT glasses subsequent to immersion in SBF for various durations.
5
Dissolution Rate (X 10− g/cm2S− 1)

Glass 48 h 72 h 168 h 240 h

CZPT0 4.31 3.01 1.68 1.22

CZPT1 3.40 2.38 1.32 0.96
CZPT2 2.37 1.66 0.92 0.67
CZPT3 1.66 1.16 0.647 0.47
CZPT4 0.94 0.66 0.37 0.27
CZPT5 0.46 0.33 0.18 0.13
CZPT6 0.43 0.30 0.17 0.12

Fig. 4. (a): Variation of dissociation rate with content of TiO2 doped CZPT glasses for different incubation periods. (b): Variation in pH of SBF used
for soaking glass samples with time. (c): Variation of Weight loss of glass samples with content of TiO2for different incubation periods.

Table 2
pH values of SBF on immersion of CZPT glasses for various durations of time.
Glass pH values

0h 72 h 168 h 240 h

CZPT0 7.4 7.61 7.51 7.43

CZPT1 7.4 7.52 7.43 7.36
CZPT2 7.4 7.47 7.38 7.31
CZPT3 7.4 7.44 7.34 7.27
CZPT4 7.4 7.57 7.49 7.41
CZPT5 7.4 7.41 7.26 7.20
CZPT6 7.4 7.42 7.29 7.23

temperature regarding phase transitions from which characteristic temperatures of glass, and related thermal stability parameters are
reported in Table 4. The characteristic temperature regarding phase transition of present bio glasses decreases from 694.3 K to 681.4 K
with an enhancement of TiO2below 0.6 mol% and then increases to 691.6 K with further enhancement above 0.6 mol% of TiO2. The
same tendency is noticed for remaining glass characteristic temperatures, as indicated in Fig. 5(b).
Dietzel’s thermal stability parameter, ΔT decreases from 106.5 K to 100.8 K with an enhancement of TiO2 from 0 to 0.6 mol% and
then increases to 103.2 K with further raise of TiO2 up to 1.0 mol%. The same tendency is noticed in other stability parameters with the
content of TiO2, as indicated by Fig. 5(c).

3.5. Elastic parameters of CZPT glasses

The mechanical properties as well as disparity taking place regarding structure in the glass matrix of present CZPT glasses are
studied based on ultrasonic velocities and are measured by an equation.
2d
V= cms− 1
(2)
T

5
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

Table 3
Physical parameters Of TiO2 doped CZPT glasses.
Physical Parameter Error CZPT0 CZPT1 CZPT2 CZPT3 CZPT4 CZPT5 CZPT6

Density, ±0.1 2754.2 2723.1 2702.3 2714.6 2725.1 2736.5 2746.4

ρ (kgm− 3)
Average molecular weight(g) ±0.01 117.06 117.00 116.94 116.82 116.69 116.57 116.44
Molar volume,Vm(10− 6 m3 mol− 1) ±0.01 42.51 42.97 43.28 43.04 42.82 42.60 42.40
Oxygen molar volume, ±0.01 13.28 13.44 13.55 13.50 13.46 13.41 13.38
Vo(10− 6 m3 mol− 1)
Oxygen packing density, ±0.01 75.28 74.40 73.80 74.07 74.31 74.55 74.76
OPD(103 mol m− 3)
Titanium ion concentration ±0.1 0.0 14.0 27.8 55.9 84.4 113.1 142.0
Ni(1026 ions m− 3)
Ionic radius, ri ±0.1 0.0 8.9 7.1 5.6 4.9 4.5 4.1
(Å)
Polaron radius rp ±0.1 0.0 3.6 2.9 2.3 2.0 1.8 1.7
(Å)
Field strength F ±0.001 0.0 0.154 0.244 0.388 0.511 0.621 0.722
(Å− 2)

Fig. 5. (a): Differential Thermal Analysis curves of CZPT glass samples with the content of TiO2. (b): Discrepancy in characteristic temperatures of
CZPT glasses with the content of TiO2. (c): Variation of weighted Stability Criterion (Hg), Dietzel’s Thermal Stability Parameter (ΔT), Hruby’s
Ability Factor (Hr), Saad-Poulin’s Stability Parameter,(S) of CZPT glasses through TiO2 content.

where the width of CZPT glass is ‘d′ and the roundtrip delay time is ‘T′ . The longitudinal velocity, ‘VL’ decreases from 4563 ms− 1 to
4516 ms− 1 with an enhancement of TiO2from 0 to 0.6 mol% and on further raise in concentration up to 1.0 mol%, the velocity in­
creases to 4538 ms− 1where as the shear velocity also follows the same trend with its velocity changes from 2566.7 ms− 1 to 2495 ms− 1
and then increases to 2594.4 ms− 1 in the above-mentioned contents of TiO2. The rigidity regarding cracks in a material as well as the
ability of glass to oppose distress related to temperature is determined by the Elastic modulus of glass [16].

6
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

Table 4
Characteristic temperatures and Thermal stability parameters of CZPT glasses.
Glass sample Glass Characteristic Temperatures Thermal parameters

Tg Tc Tp Tm ΔT S Hr Hg Trg
(K) (K) (K) (K) (K) (K)

CZPT0 694.3 800.8 851.3 1003.1 106.5 7.746 0.5264 0.1534 0.6922
CZPT1 687.8 792.6 840.2 997.3 104.8 7.253 0.5120 0.1524 0.6897
CZPT2 684.9 787.8 835.4 995.2 102.9 7.151 0.4961 0.1502 0.6882
CZPT3 682.4 784.2 831.2 993.5 101.8 7.011 0.4864 0.1492 0.6869
CZPT4 681.4 782.2 828.7 992.6 100.8 6.879 0.4791 0.1479 0.6865
CZPT5 686.6 788.7 837.8 994.2 102.1 7.301 0.4968 0.1487 0.6906
CZPT6 691.6 794.8 846.8 1001.1 103.2 7.759 0.5002 0.1492 0.6908

The deviations in elastic moduli and relevant parameters with the content of TiO2 in present CZPT bio glasses are used to explain
modifications occurring in the glass network that are measured and observed to follow like tendency as that of velocities with the
content of TiO2 as revealed in Table 5 [17–19]. The Young’s modulus and volume modulus of present CZPT glass based on the
Makishima – Mackenzie model are obtained by equations
E = 2Gt Vt (3)

K = 1.2Vt E (4)
The discrepancy in elastic parameters of present CZPT glasses with TiO2 concentration based on calculation from packing factor,
(Vi) and Dissociation energy per unit volume, (Gi) of each component of CZPT glasses obtained from previous literature as well as an
experiment are revealed in Table 5. These parameters other than Poisson’s ratio of present glasses diminish up to CZPT4 glass with
content of TiO2 below 0.6 mol% and thereafter rise in these parameters above 0.6 mol% of TiO2. The disagreement of ultrasonic
velocities of these glasses with the content of TiO2 is represented by Fig. 6(a) and its inset indicate a reverse trend in Poisson’s ratio
compared to other elastic parameters with TiO2 concentration in present CZPT glasses. Fig. 6(b) clearly explains the concurrence in
bulk moduli of present CZPT glasses with deviation in TiO2 concentration based on theory as well as experiment.

Table 5
Calculated and experimental Elastic Parameters of TiO2 doped CZPT glasses.
astic parameter CZPT0 CZPT1 CZPT2 CZPT3 CZPT4 CZPT5 CZPT6

Packing density, 0.600 0.593 0.588 0.586 0.583 0.595 0.597

Vt ( ± 0.002)
Dissociation energy per unit volume, 39.59 39.66 39.74 39.88 40.03 40.17 40.32
Gt ( ± 0.04 kJ mol-1 m-3)
Longitudinal velocity, 4563 4554 4546 4525 4516 4524 4538
VL ( ± 8 ms− 1)
Shear velocity, 2566.7 2552.3 2539.7 2508.3 2495.0 2516.1 2549.4
VS ( ± 4 ms− 1)
Longitudinal modulus, 57.34 56.47 55.84 55.10 54.66 56.00 56.55
L ( ± 2 GPa)
Shear modulus, 18.14 17.74 17.43 16.93 16.68 17.32 17.85
S ( ± 1 GPa)
Poisson’s ratio, 0.2686 0.2710 0.2732 0.2782 0.2803 0.2761 0.2694
σ ( ± 0.002)
Young’s modulus, 46.03 45.09 44.38 43.28 42.72 44.21 45.31
EE( ± 2 GPa)
Young’s modulus, 47.52 47.52 46.76 47.16 47.46 47.70 48.00
E M–M ( ± 2 GPa)
Bulk modulus, 33.15 32.82 32.60 32.53 32.41 32.90 32.75
KE ( ± 2 GPa)
Bulk modulus, 34.22 34.22 33.02 33.46 33.76 33.99 34.28
K M–M ( ± 2 GPa)
Microhardness, 2.80 2.71 2.64 2.50 2.44 2.59 2.74
H ( ± 2 GPa)
Average ultrasonic velocity, 2856 2841 2827 2794 2780 2802 2837
V ( ± 6 ms− 1)
Acoustic impedance, 7.86 7.73 7.64 7.52 7.45 7.67 7.79
Z x 10− 6( ± 0.2 kg m− 2 s− 1)
Debye temperature, 191.96 190.37 189.97 189.30 189.09 189.82 190.87
θD ( ± 1 K)

7
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

Fig. 6. (a): Deviation in longitudinal velocity, Shear velocity of CZPT glasses with content of TiO2. (b): The theoretical (Makishima – Mackenzie)
and experimental comparison of Deviation in bulk modulus of CZPT glasses with content of TiO2.

3.6. FTIR spectra of CZPT glasses

The specific groups of various structural units present in CZPT glasses added with various percentages of TiO2 were revealed by
studying the FTIR absorbance spectra as represented in Fig. 7(a) [20,21]. The assignments of bands observed in present TiO2-doped
CZPT glasses and their corresponding references are given in Table 6.
The following are regions of various wavenumber ranges in FTIR spectra of pure parent CZPT0 glass free from titanium indicating
the existence of diverse structural units in the present glass matrix.

➢ The wavenumber region in the range of 400–600 cm− 1, represents vibrations of different cations involved in a glass matrix.
➢ The region with a wavenumber range, 750–1120 cm− 1 represents vibrations of various phosphate groups of structural units in the
glass matrix.
➢ The region with a wavenumber range, 1120–1400 cm− 1 represents vibrations of diverse phosphate groups of structural units in the
glass matrix.

The discrepancy in peak center and intensity of absorption bands in FTIR spectra of CZPT glasses with concentration of TiO2
represent the structural changes in the glass network. In general, the structure of glass is complicated due to the presence of a large
number of groups in various structural units, especially of present phosphate bio glasses, and is not accounted for by the FTIR spectra of
these CZPT glasses. The peak position as well as a comparative area of a particular band as indicated in Table 7 and are obtained only
by deconvoluting FTIR absorbance spectra using peak fit and are unavoidable to know the behavior of a particular group in the
structural unit (19). Figs. 7(c), 7(d), 7e and 7 f represent indicate deconvoluted FTIR absorption spectra of pure parent titanium free
CZPT0 glass as well as CZPT2,CZPT4 and CZPT6 having TiO2 concentration of 0, 0.2, 0.6 and 1.0 mol% respectively added to pure
parent glass. Changes in the comparative areas of various groups of structural units that present in the phosphate glass network ac­
quired by deconvoluting normalized FTIR absorption spectra of CZPT glasses on changing the content of TiO2 are shown in Fig. 7(b).

3.7. Raman spectra of CZPT glasses

The following are regions of various wavenumber ranges in Raman spectra of pure parent CZPT0 glass free from titanium indicating
the occurrence of a variety of structural units in present glass matrix. The region of wavenumber range 200–800 cm− 1 represents clear
and distinct peaks observed at 264, 342 & 687 cm− 1that are easily assigned without any uncertainty to different structural units
related to metal cations as well as phosphorous oxygen linkages.
The region of wavenumber range 800–1400 cm-1 represents the number of peaks that are not easily illustrious for assignment to
various structural units of the glass matrix. The assignments of Raman peaks observed in present TiO2 doped CZPT glasses and their
corresponding references are given in Table 8. The peak position as well as a comparative area of a particular peak as indicated in
Table 9 are obtained only by deconvoluting Raman spectra using peak fit and is unavoidable to know the behavior of a particular group
in the structural unit. [22].
Fig. 8(a) represent Raman spectra of titanium doped CZPT glasses whereas 8c,8d, 8e and 8 f indicate deconvoluted Raman spectra
of pure parent titanium free CZPT0 glass as well as CZPT2,CZPT4 and CZPT6 having TiO2 concentration of 0, 0.2, 0.6 and 1.0 mol%

8
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

Fig. 7. (a): FTIR absorption spectra with numbers indicating various specified structural units of TiO2 doped CZPT glasses. (b): Discrepancy in
relative areas of various structural units of FTIR bands in TiO2 doped CZPT glasses. (c), (d), (e) and (f) represent deconvoluted FTIR absorption
spectra of CZPT0, CZPT2, CZPT4 and CZPT6 glasses.

respectively added to pure parent glass. The peaks at 264 cm− 1, 342 cm− 1, and 687 cm− 1 are allocated to tetrahedral ZnO4 units,
bending modes of deformation in PO4 units and to the groups (PO3)2- present in Q1 structural units [22–24]. Additional peaks are
observed in the wavenumber range, in region of 897–912 and 618–632 cm− 1 for all the remaining glasses other than CZPT0 and are
assigned to TiO4 and TiO6 structural units respectively. The change in relative areas of various groups of structural units Q0 ,Q1 ,Q2 ,
Q3 and Ti-O bonds present in the phosphate glass network acquired by deconvoluting Raman spectra of CZPT glasses on changing the
content of TiO2 is shown in Fig. 8(b).

3.8. Optical absorption spectra of CZPT glasses

The cutoff wavelength of an optical absorption spectrum can be used to determine the transitions stimulated by light, the size of the

9
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

Table 6
FTIR and Raman band Assignment of CZPT glasses with references given in brackets (accuracy in measurement of wave numbers is ± 1 cm− 1).
Wavenumber (cm− 1) FTIR and Raman Band Assignment Wavenumber (cm− 1)
Of FTIR bands with Reference Of Raman bands with Reference

460–475 [36] Specific vibrations of Zn–O bonds in ZnO4 units 264 [22]
513–531 [33] Deformation modes of network 342–363 [23]
623–639 [37] OctahedralTiO6 units, 618–632 [39]
765–774 [37] Tetrahedral TiO4 units 897–912 [39]
777–793 [33] Symmetric stretching vibrations of P-O-P linkages of (PO3)2- groups in Q1 units 687–704 [24]
914–931 [33] Asymmetric stretching vibrations of P-O-P linkages of (PO3)2- groups in Q1 units 918–932 [44]
978–991 [33] Symmetric stretching vibrations of P-O- bonds of (PO4)3- groups in Q0 units 958–973 [45]
1086–1098 [33] Asymmetric stretching vibrations of P-O- bonds of (PO4)3- groups in Q0 units 1044–1058 [40]
1129–1145 [36] Symmetric stretching vibrations of O-P-O linkages of (PO2)- groups in Q2 units 1084–1102 [39]
1218–1232 [35] Asymmetric stretching vibrations of O-P-O linkages of (PO2)- groups in Q2 units 1165–1183 [40]
1273–1290 [33] Symmetric vibrations of P = O bonds in Q3 units 1283–1298 [40]
1378–1395 [34] Asymmetric vibrations of P = O bonds in Q3 units ———

Table 7
1
Peak centresand its comparative areas of FTIR spectra of CZPT glasses on deconvolution (accuracy is ± 1 cm− in measurement of wave numbers).
− 1
Glass peak centre (Ϲ) Various Structural units Wavenumbers (cm )
& Rel. area (ᴀ)
ᵥas ᵥs ᵥas (O- ᵥs (O- ᵥas (P- ᵥs (P- ᵥas (P- ᵥs (P- TiO4 TiO6 ᵥ ZnO4
(P = O) (P = O) P-O) P-O) O-) O-) O-P) O-P) units units (O–
–P–O)

CZPT0 Ϲ 1395 1290 1232 1145 1086 978 914 777 — — 513 460
ᴀ 12.0 7.5 21.5 22.9 5.4 4.5 8.0 6.0 — — 7.1 5.1
CZPT1 Ϲ 1391 1286 1229 1141 1089 981 917 781 — 623 518 463
ᴀ 12.5 6.3 21.9 20.1 6.3 4.1 8.9 5.6 — 1.4 7.4 5.5
CZPT2 Ϲ 1387 1281 1226 1138 1092 984 921 785 — 628 523 469
ᴀ 12.9 4.9 22.5 18.4 7.2 3.6 9.7 5.2 — 1.9 7.8 5.9
CZPT3 Ϲ 1382 1278 1221 1134 1095 987 926 789 — 634 528 472
ᴀ 13.1 4.4 22.9 16.5 7.9 3.2 10.4 4.8 — 2.4 8.1 6.3
CZPT4 Ϲ 1378 1273 1218 1129 1098 991 931 793 765 639 531 475
ᴀ 13.5 3.2 23.1 15.2 8.6 2.8 11.4 4.0 0.4 2.7 8.5 6.8
CZPT5 Ϲ 1372 1276 1222 1134 1094 987 927 790 768 636 527 471
ᴀ 12.1 4.1 22.1 15.8 8.1 3.7 10.8 5.1 2.0 1.8 8.1 6.3
CZPT6 Ϲ 1368 1279 1226 1139 1089 984 922 784 774 632 524 468
ᴀ 11.1 4.7 20.4 16.7 7.4 5.1 10.2 6.4 3.5 1.2 7.6 5.7

Table 8
1
Peak centersand its comparative areas of Raman spectra of CZPT glasses on deconvolution (accuracy is ± 1 cm− in measurement of wave numbers).
− 1
Glass Band centre (Ϲ) & Wavenumbers of Various Structural Units (cm )
sample Rel. area (ᴀ)
ᵥs ᵥas (O-P- ᵥs (O-P- ᵥas (P- ᵥs (P- ᵥas (P- ᵥs (P- TiO4 TiO6 ᵥ ZnO4
(P = O) O) O) O-) O-) O-P) O-P) units units (O–
–P–O)

CZPT0 Ϲ 1298 1183 1102 1044 958 918 687 — — 342 264
ᴀ 17.5 31.5 19.8 6.9 5.6 7.1 4.8 — — 2.4 4.4
CZPT1 Ϲ 1294 1179 1097 1047 961 921 691 — 618 347 264
ᴀ 15.9 31.8 18.3 7.7 5.3 7.8 4.4 — 1.1 2.9 4.8
CZPT2 Ϲ 1290 1174 1093 1051 965 924 695 — 623 352 264
ᴀ 14.6 32.2 16.8 8.5 4.8 8.7 3.9 — 1.6 3.4 5.3
CZPT3 Ϲ 1287 1169 1089 1055 968 928 699 897 627 358 264
ᴀ 13.5 32.6 15.3 9.4 4.3 9.7 3.3 0.5 1.9 3.8 5.7
CZPT4 Ϲ 1283 1165 1084 1058 973 932 704 902 632 363 264
ᴀ 12.4 33.1 13.8 10.2 3.8 10.6 2.8 0.7 2.2 4.3 6.1
CZPT5 Ϲ 1289 1169 1088 1053 969 927 698 906 626 357 264
ᴀ 11.9 31.5 14.7 9.3 5.4 9.9 4.1 2.1 1.7 3.8 5.6
CZPT6 Ϲ 1294 1175 1092 1049 964 922 692 912 621 351 264
ᴀ 10.9 30.1 15.4 8.8 6.7 8.9 5.9 3.7 1.1 3.4 5.1

band gap, and related band structure in glasses. This information is typically obtained from the energy absorbed by the lattice or
electrons present in the glass network from photons of incident light. Lattice absorption reveals the nature of atomic vibrations,
whereas electronic transitions between bands brought on by electron absorption reveal information about electron states. When this
occurs, the absorption coefficient quickly increases as electrons transition by absorbing photon energy. The beginning of this rapid
change is referred to as the cutoff wavelength in relation to the energy band gap, whose value in the UV region explains how the energy
levels are organized as well as the types of transitions that light in glasses induces. Even while both types of transitions (direct and

10
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

Table 9
1
optical absorption band assignment of Ti+3 bands in CZPT glasses(accuracy in measurement of wave numbers is ± 1 cm− and related parameters.
Transitions/ Error CZPT0 CZPT1 CZPT2 CZPT3 CZPT4 CZPT5 CZPT6
parameter x (mol%)
2 2
B2 g→A1 g — — 1.4577 1.4471 1.4347 1.4204 1.4326 1.4430
Ti transitions
+3

(Oh) (x 104) cm− 1

2 2
B2 g→B1 g — — 1.8939 1.8726 1.8552 1.8416 1.8587 1.8796
Ti+3 transitions (Oh)(x 104) cm− 1

Optical absorption edge, lo ±0.1 394.5 398 405 412 418 410 404
Nm
Optical band gap, Eo(eV) ±0.01 eV 3.15 2.94 2.79 2.62 2.52 2.78 2.63
Urbach energy, ΔE (eV) ±0.01 eV 1.37 1.12 1.03 0.94 0.87 0.92 0.97
Crystal field splitting energy, Dq ±1 — 1893.94 1872.66 1855.29 1841.62 1858.74 1879.70
cm− 1

Fig. 8. (a): Raman spectra of CZPT glasses with various structural units. 8(b): variation of relative areas of structural units in Raman spectra of CZPT
glasses. 8c, 8d, 8e and 8 f: Raman spectra of CZPT0, CZPT2, CZPT4 and CZPT6 glasses on deconvolution.

11
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

indirect) have a good chance of happening at the optical absorption spectra of many materials, indirect transitions only happen in
amorphous glasses. The absorption coefficient to study optical transitions occurring in glasses is determined by the equation
( )
A
α = 2.303 (5)
t

where’t’ is thickness, and ’A’ is absorbance.

The general equation for direct and indirect optical transitions taking place in glasses is given by

(αhν)n = B(hν − E0 ) (6)

Where n = 2, 1/2 for direct transitions and indirect transitions occurring in glasses respectively. Fig. 9(a) represents OA spectra of
present CZPT glasses with variable TiO2 content in a wavelength range between 370 and 800 nm. The optical absorption spectra of
CZPT0 glass, which is pure parent glass without titanium do not possess any absorption band but other CZPT glasses have two bands,
one between 528 and 543 nm whereas the second band in the range 686 − 704 nm corresponding to transitions 2B2g → 2B1g and
2B2g → 2A1g of Ti+3 ions. It is noticed that, with an enhancement of the content of TiO2up to 0.6 mol%, relative area and intensity of
absorption band increase shifting towards high wavelength and later a reverse trend of decrease in intensity and comparative areas
with a shift in band position towards low wavelength is observed above 1.0 mol% of the content of TiO2. Fig. 9(b) represents the Tauc’s
plot of present glasses from which the cutoff wavelength of CZPT glasses enhances to 418 nm from 394.5 nm whereas the corre­
sponding optical band gap declines to 2.52 eV from 3.15 eV with an enhancement of the content of TiO2 below 0.6 mol% and
thereafter a reverse trend is noticed in cutoff wavelength that reduces to 404 nm whereas related band gap ascends to 2.63eVwith
enhancement of TiO2 content above 0.6 mol%. The measured Urbach’s energy (Δ E) of CZPT glasses was obtained from reciprocal
values of slope taken for a linear region of graphs drawn against lnα versus hν, which reduces to 0.87 eV from 1.37 eV and later rises to
0.97 eV with the change in TiO2 content. Fig. 9(c) represents the band gap variation of CZPT bio glasses with and without soaking in
SBF for various durations that decreases with an enhancement of the content of TiO2up to 0.6 mol% and then enhances above 0.6 mol
%. The cutoff wavelength of these CZPT glasses doped with TiO2 follows a reverse trend with that of the optical band gap as shown in
Fig. 9(d). The wave numbers and band assignments of Ti+3 bands in the optical absorption spectra are tabulated in Table 9. Fig. 10.

3.9. ESR spectra of CZPT glasses

The Electron Spin Resonance Spectra of CZPT glasses with variable TiO2 content reveal resonance signal for all the glasses except

Fig. 9. a: Optical absorption spectra CZPT glasses doped with TiO2. b:Tauc’s plots of CZPT glasses doped with TiO2. c and d: Cut-off wavelength and
Optical band gap of TiO2 doped CZPT glasses submerged in SBF for various duration of time as indicated in Inset.

12
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

Fig. 10. Illustrates the basic structural units in the glass network of CZPT glass. (Mac- based Chem Draw Ultra version 12.0 was used to plot the
figure). (a) pure tetrahedra of PO4unit. (b) Inclusion of Cations. (c) inclusion of Titanium ions &. (d) inclusion of Zinc ions.

13
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

Fig. 11. ESR spectra of TiO2 doped CZPT glasses at room temperature.

for pure parent CZPT0 glass whose intensity increases with enhancement up to 0.6 mol% of TiO2 and then declines above 0.6 mol% as
indicated in Fig. 11.

4. Discussion

The network of phosphate glasses is altered by adding an appropriate amount of ZnO and CaF2 to the glass matrix and releasing Q2,
Q , and Q0 units, which introduce NBOs into the glass network forming P − O− Metal ions replacing P − O− P connections of the glass
1

matrix [25,26]. Based on the TiO2 concentration, we can anticipate either polymerization or depolymerization of the glass network
when TiO2 is mixed with ZnO-CaF2-P2O5 glasses.
The oxidation states of titanium in the majority of inorganic complex compounds are + 2, + 3, and + 4. Of these, the + 4 state is the
most stable, and the chemistry of the + 2 state is most constrained. However, the + 3 state is also stable in several inorganic glasses.
According to published research, the glassy compounds may contain both titanium’s + 3 and + 4 states as well as various tetrahedral
and octahedral coordination sites. As the concentration of TiO2 increases, the Ti4+/Ti3+ ions may either undergo reduction or
oxidation, which is described by the equation as these ions’ concentrations are composition-dependent.[27].

Ti+4+e-↔ Ti+3

The titanium ions in the generated CZPT glasses may undergo a decline from tetravalent to the trivalent state during the melt
quenching process if the TiO2concentration is less than 0.6 mol%. The trivalent titanium ions solely live in octahedral sites, favouring
modifying activity in the glass network, whereas the tetravalent titanium ions reside in both tetrahedral and octahedral locations with
[TiO6]2- units as corner-sharing. The TiO4 and TiO6 units join the glass network, forming the new P-O-Ti bond as well as other crossing
linkages with different cations. The anions of oxygen and fluorine attempt to disrupt the internal symmetry of the structure, while Zn/
Ca ions occupy interstitial places within the network. In general, glass modifiers such as ZnO and CaF2, involve in the glass network
that may destroy cross connections in the glass matrix [28]. The rate of titanium ion conversion from tetravalent to trivalent reduces at
TiO2 concentrations over 0.6 mol%, while titanium ion occupancy in tetrahedral sites increases at the expense of octahedral sites. As a
glass forming, titanium ions now change non-bridging oxygens into bridging oxygens. The three-dimensional network created by the
connections between the PO4 and TiO4 tetrahedra would increase the structural compactness of the glasses [26]. All forms of Q units of
phosphate tetrahedra are present in all these CZPT glasses, despite any alterations to the structural units of different groups. The
properties of present glasses are influenced by several factors such as alteration in the arrangement of atoms and a readjustment of the
structure of the glass matrix to acquire stability due to different coordination numbers of dopant ions (Ti4+/Ti3+) in the glass network.
[29].
Another crucial factor that provides insight into the CZPT glasses’ structural compactness is their density which follows an opposite
drift at 0.6 mol% up to which the density decreases and thereafter increases with the content of dopant TiO2. This explains a change in
the compression in the glass matrix as indicated by alteration in molar volume as well as other physical parameters of these CZPT
glasses, clearly supporting the different coordination states of titanium ions.
The quantity of active ions generated through dissolution of a glass in SBF, which are useful for repair as well as regeneration of
tissues on implantation inside a human body, were known by measuring weight loss of glasses and pH of SBF used for soaking these
glasses. In general, plain phosphate glasses possess poor chemical durability relative to multi component phosphate glasses due to
action of modifier ions that reduces the dissolution behavior and improves network rigidity of glasses. The degradation of a pure
phosphate glass by the absorption of water forms a gel type layer on glass surface having phosphate ions. The accumulation of dopant

14
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

TiO2to the pure CZPT0 glass reduces the hydration of these glasses by escalating cross-link density with the formation of P-O-Ti bonds.
The brisk augmentation in weight loss of these glass samples soaked for 3 days in SBF with consequent leaching of ions into SBF from
the glass surface and thereafter increase in weight loss is slow on further incubation periods performed. The charge as well as ionic
radius of Ti+4 ions that come into the glass matrix forming P-O-Ti bonds, defy dissolution due to increase in leaching strength of ions.
This reduces the interaction with hydrated layers and lowers the dissociation rate and is the result of including an appropriate amount
of TiO2 to pure CZPT0 glass.
The sharp increase in pH of SBF used to soak these glasses in the beginning for an incubation of three days is may be due to im­
mediate release of Ca+2, Zn+2 ions from the glass that substitute with hydrogen ions present in the simulated body fluid. The decrease
in pH of SBF was noticed with incubation period beyond 3 days as well as with concentration of TiO2 for all CZPT glasses except
CZPT4was due to release of phosphate ions into the soaked body fluid and is ascribed to the formation of phosphoric acid. This is in
agreement with increase in compact glass structure as a result of formation of TiO6 and TiO4 structural units that involve in glass
matrix, forming tough P-O-Ti bonds. The decrease in values of pH as well as degradation is in concurrence with enhancement in density
and glass transition temperature. The CZPT4 glass with 0.6 mol% TiO2 content in pure glass is more bioactive and anticipates greater
hydroxyapatite layer growth, indicating the maximum conversion of Ti4+ ion tetrahedral sites into octahedral sites as well as the
greatest number of Ti4+ ion transfers into Ti3+ ions through reduction in the glass network [30].
Thermal stability of these CZPT glasses can be enlightened by identifying the various temperatures like GTT, CT, PCT, and MT from
thermo grams drawn from the DTA characterization technique. All glassy materials are characterized by a glass transition temperature
which is the equilibrant liquid temperature when the viscosity is around 1013 poise. Above this temperature, the system possesses a
rubbery state and below, it possesses a glassy state. In the prepared CZPT glasses, the value decreases from CZPT0 to CZPT4 glass and
thereafter increases for the remaining glasses on accumulation of TiO2. A similar tendency is noticed in other temperature parameters.
These variations suggest that the titanium ions play a modifying role up to 0.6 mol% TiO2 with more occupancy of octahedral sites and
above 0.6 mol% of TiO2 it plays a glass-forming role indicating the conversion of occupancy from octahedral to tetrahedral sites of Ti4+
ions and oxidation from Ti3+ state to Ti4+ state.
Thermal stability of glassy materials was also studied by certain stability parameters [18]. One of the glass stability parameters is a
more reliable parameter that relates to the change taking place in a super cooled region. The reduced glass transition temperature is
also an indication of the nonexistence of crystalline phases in the glass matrix that supports XRD observations on the CZPT glasses
before immersed in simulated body fluid under physiological conditions [31]. The variations in all these parameters postulate similar
arguments made from the variations in the enhancement in the concentration of TiO2.
One among the various tools to study these CZPT glasses and thereby to assess their mechanical characteristics is the analysis of
different elastic properties concerning the concentration of TiO2. The ultrasonic shear velocity of titled glasses is almost half of the
ultrasonic longitudinal velocity. These longitudinal and shear velocities decrease from CZPT0 to CZPT4 glass and thereafter increase up
to CZPT6 with an augment in the concentration of TiO2.
Young’s moduli of glasses are valuable to considerate the sustainability of these CZPT glasses to mechanical stresses. The con­
ceptual and practical values of the elastic parameters of CZPT glasses are compared by Inaba’s model for phosphate glasses. In the
phosphate tetrahedra the dissociation energy depends on the natural bonding of oxygen atoms with the phosphorous atom and ac­
counts for the Elastic moduli, the non-bridging P = O bond won’t contribute to the Elastic moduli.
The decrease in mechanical parameters of present glasses up to CZPT4 glass with the augment in the content of TiO2 indicates the
possible existence of P– O –Ti bonds causing modifications in the glass matrix. The raise in these parameters with concentration of TiO2
indicates an increase in connectivity in the network [27,32]. The conversion of Q units of phosphate groups in the CZPT glasses is the
following relation

2Q1 ↔ Q2 + Q0 (13)
The study of these mechanical parameters indicate an increase in the covalent bond nature that increases the compactness of
remaining glasses beyond CZPT4 with the boost in the content of TiO2.
Poisson’s ratio (s) is an effective parameter used to estimate the order of cross-link density and in CZPT bio glasses its value is
increased from 0.2766 to 0.2803 with the percentage of TiO2 increasing from 0 to 0.6 mol%, and thereafter its value decline to 0.2694
on further raise in the concentration of TiO2 as presented in the inset of Fig. 6(a). The Poisson’s ratio (s) increases up to CZPT4 glasses
and is an indication of an increase of ionic nature in these glasses owing to the introduction of P– O –Ti bonds with a simultaneous
release of NBOs and the decline in Poisson’s ratio (s) in the remaining glasses beyond CZPT4 with the boost in the percentage of TiO2
signifies a decrease in ionic nature due to presence of bridging oxygens involving in the matrix [33–36]. The variation of Poisson’s ratio
suggests a slackly packed phosphate network.
The low values of acoustic impedance up to CZPT4 glasses represent a decline in transmission of ultrasonic waves with TiO2
concentration below 0.6 mol% and the raise in acoustic impedance beyond CZPT4 glasses shows that the ultrasonic wave propagation
and their velocities increase in these glasses [37]. The decrease in Debye temperature with enhancement below 0.6 mol% of TiO2hold
up the decline in the glass rigidity as found in the values of chemical durability as well as surface morphology of CZPT4 glass indicating
the formation of hydroxyapatite layer on immersion in SBF. Since Debye temperature represents the excitation of all vibrational modes
in a solid, its increase with enhancement above 0.6 mol% of TiO2 supports the augment in the rigidity of CZPT glasses [37].
The deconvoluted FTIR absorption spectra of CZPT1, CZPT2, and CZPT3 glasses possess an absorption band around 630 cm-1and
are allotted to octahedral TiO6 structural units whereas the deconvoluted spectra of CZPT4, CZPT5, and CZPT6 glasses contains an
additional band at 770 cm− 1corresponding to tetrahedral TiO4 units along with 630 cm− 1 band corresponding to octahedral TiO6 units

15
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

[38–40]. The changes in structural units with the content of TiO2 reveal that the CZPT glasses contain both tetrahedral and octahedral
units of Ti4+ ions and are evident from the analysis of change in positions of peak and its relative areas with the percentage of TiO2.
The modifications in positions of the peak and its comparative areas of FTIR absorption peaks of ZnO4 units and bending mode units
of O – P – O clearly show the formation/breakage of P – O – Zn/Ti bonds with increasing content of dopant in glass network (modifier
action below the 0.6 mol% of TiO2 and forming action above the 0.6 mol% to TiO2).
The change in the positions of peak and its comparative areas of FTIR bands of TiO6 units around 630 cm− 1 and TiO4 units around
770 cm− 1gives a clear idea of the weakening of the glass matrix due to an augment in quantity of titanium ions involved in the
octahedral sites up to 0.6 mol% of TiO2 and 3-dimensional expansion and strengthening of glass network due to reverse conversion of
octahedral occupancy to tetrahedral occupancy of titanium ions for remaining glasses beyond CZPT4 on augment in concentration of
dopant to pure glass.
The shrink in the relative area with a coincident augment in peak positions of the bands around 780 cm− 1and 980 cm− 1 indicate a
decrease in intensity of units below 0.6 mol% of TiO2 and thereafter a reverse trend is observed in the wavenumber and relative area
that increases the intensity of units indicating the former role of TiO2with enhancement below 0.6 mol% of TiO2.
The rise in wavenumber and decrease in relative areas of bands relate to around 920 cm− 1and around 1090 cm− 1indicate an
amplification in intensity of asymmetrical units indicating the modifier role of TiO2 below 0.6 mol% content of TiO2 whereas an
opposite inclination is noticed in the relative area as well as wave number that decrease the asymmetric units, above 0.6 mol% of TiO2.
The change in positions of the peak and its relative areas of units around 1285 cm− 1 and units around 1385 cm− 1gives clear idea of
the instability of units and the depolymerization of glass network because of modifying the action of titanium ions in present glasses up
to CZPT4 with TiO2 concentration below 0.6 mol% in pure glass and for remaining glasses beyond CZPT4 with TiO2 concentration
above 0.6 mol% in pure glass, there is the extensive alteration in peak positions of the bands of the units indicates the gaining of
stability of units that amplification in compression of glass structure because of former role of dopant titanium ions in the glass matrix
of CZPT glasses.
The decline in units in the glass network for remaining glasses beyond CZPT4 with TiO2 concentration above 0.6 mol% in pure glass
indicates the modifications occurring in positions of the peak and its relative area of bands due to the NBO of (PO2)–groups at around
1225 cm− 1 due to groups around 1130 cm− 1 above the 0.6 mol% of TiO2 the reversal of changes takes place.
The changes in relative areas of the bands observed at around 1090 cm− 1 and 980 cm− 1 for glasses up to CZPT4 with TiO2 con­
centration 0.6 mol% in pure glass, indicate the nature of variation of symmetric and asymmetric absorption bands of
(PO4)3− represents the devitrification of glass network and the reverse trend is observed for the glasses beyond CZPT4 with TiO2
concentration above 0.6 mol% in the pure glass.
The rise of (pyrophosphate) units in glasses beyond CZPT4 is shown by the decrease in the comparative area of peak at about
780 cm− 1 and with a simultaneous increase in the peak area at around 920 cm− 1, with the percentage of TiO2 above 0.6 mol%. Thus an
opposite inclination is seen in signifying the alteration of structural units according to disproportionate Eq. 2Q1 ↔ Q2 + Q0 .The
amplification in symmetric units above 0.6 mol% of TiO2 in these CZPT glasses indicates a rise in the number of non-bridging oxygens
in the glass network that replace less stable P–O–P linkages with chemically durable P–O–Ti linkages as indicated in Fig. 7 f [41] The
growth of P–O–Ti bonds with a simultaneous raise in O–P–O linkages of (PO2)- groups in units according to the disproportion of units
based on Eq. 2Q2 ↔Q1 + Q3 [42]. The decrease in asymmetric units indicates an increase in cross-linkages with raise in TiO2 content
above 0.6 mol% [43]. The amplification in comparative area of band at 765 cm− 1 supports the cleavage of P-O-P bonds and the
formation of P-O-Ti bonds due to TiO4 units.
The Raman spectrum of CZPT0 glass when deconvoluted in the region of 1400–800 cm− 1 yields the successive vibrational bands as
indicated in our previous article.[46] By adding TiO2 to CZPT0 glass in addition to the existing bands, bands at around 620 cm− 1and
900 cm− 1 were noticed in the Raman spectra of CZPT glasses and are related to Ti-O linkages of TiO6 and TiO4 structural units
occupying octahedral and tetrahedral sites in glass matrix respectively. [36]. The Raman spectra of CZPT1, CZPT2, and CZPT3 glasses
on deconvolution give a single band around 620 cm-1and Whereas deconvoluted spectra of CZPT4, CZPT5, and CZPT6 glasses have two
additional bands one around 620 cm− 1 and another at 900 cm− 1.
The respective modifications in Raman spectra of CZPT glasses on deconvolution were noticed with molar percentage of TiO2. The
variations in the structure of CZPT glasses are noticed by the changes in comparative areas and also wave numbers of peaks in the
Raman spectra on the introduction of dopant TiO2 to CZPT0 pure glass that leads to inferences as mentioned below.
The growth of bonds namely P-O-Zn/Ti in the glass matrix due to the modifier role of dopant in present glasses below CZPT4 with
the enhancement of TiO2 up to 0.6 mol% and a former role of dopant in remaining glasses beyond CZPT4 with the enhancement of TiO2
above 0.6 mol% is indicated by the relative area and wavenumber related to bands at 264 cm− 1 and that around 350 cm− 1assigned to
ZnO4 units and O– – P – O bending vibrations.
The decrease of glass rigidity due to depolymerization as a result of the enhancement in octahedral sites of Ti+3 /Ti+4 ions involved
in the network of CZPT glasses is revealed by parameters, comparative area, and wavenumber of a band in the region of 620 cm− 1
assigned to TiO6 structural units with an enhancement of TiO2 below 0.6 mol% whereas above 0.6 mol% of the dopant, a more
compact structured glasses are produced due to hike in tetrahedral sites of Ti+4 with a simultaneous fall in octahedral sites of ions Ti+3
/Ti+4 observed by comparative area as well as wavenumber of bands around 620 cm− 1and 900 cm− 1assigned to TiO6 and TiO4
respectively.
The decrease in the relative area with a simultaneous increase in the wavenumber of the bands around 690 cm− 1 and 965 cm− 1
indicate a decrease in intensity of units below 0.6 mol% of TiO2 and thereafter a reverse trend is observed in the wavenumber and
relative area that increases the intensity of units indicating the former role of TiO2with enhancement above 0.6 mol% of TiO2 in the

16
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

CZPT glasses.
The bands around 925 cm− 1and 1050 cm− 1 assigned to and respectively are noticed to fall in their comparative areas and raise in
wavenumber representing a hike in the strength of and units indicating the modifier role of dopant TiO2 below 0.6 mol% content of
TiO2 whereas a converse trend is noticed in the relative area and also wave number that decreases the asymmetric units and above
0.6 mol% of TiO2.
The peak around 1090 cm− 1allocated is observed to decline in its comparative area and an opposite inclination is noticed in the
band around 1170 cm− 1 fixed due to non-bridging oxygens present in (PO2) - groups. The reduction in units of the glass matrix is
supported by a red shift in the above-mentioned bands.
The peak fixed to at 1290 cm− 1 declines in the comparative area and is red shifted represents undoubtedly the decline of units as
well as the unsteadiness due to depolymerization of the glass network and modifier action of TiO2 below 0.6 mol% whereas an opposite
trend is noticed in this band above 0.6 mol% of TiO2 indicating that titanium enters into glass network occupying tetrahedral sites as
TiO4 structural units.
The augment in comparative areas of bands assigned to ZnO4, bending modes of a network, and asymmetrical units at the expense
of symmetrical units obtained by deconvoluting normalized Raman spectra of present CZPT glasses indicates the intensification of
structural units and with concomitant shrink of structural units and, that results in depolymerization and weakening of glass matrix,
with enhancement below 0.6 mol% of TiO2 in present CZPT glasses whereas a reverse trend is noticed in comparative areas as well as
the conversion of structural units with enhancement above 0.6 mol% of TiO2 as examined in the Raman spectra of present CZPT glasses
on deconvolution. The rise of the comparative area of the peak around1050cm− 1 represents a hike in pyrophosphate units (Q1 ) in glass
network and is obvious by raise in the potency of P – O – P linkages followed by a reverse inclination in the peak around 690 cm− 1 is
identified. The asymmetric bands of vibration regarding pyrophosphate units (Q1 ), orthophosphate units (Q0 ), and metaphosphate
units (Q2 ) of the phosphate network identified around 925,1050, and 1170 cm− 1concomitant reduction in relative areas of symmetric
bands of vibration of units mentioned above at 690, 965, 1090 and 1290 cm− 1as indicated by Fig. 8(b). The manifestation of
1290 cm− 1bands in present TiO2 doped CZPT glasses denotes the occurrence of units despite an abnormal reduction of units taking
place with enhancement in the percentage of TiO2up to 0.6 mol% and thereafter above 0.6 mol% of TiO2 a reverse tendency is
identified. The Infrared, as well as Raman spectra of these CZPT glasses, are unable to explain separate Ti+3 and Ti+4 ions in common
and octahedral TiO6 and tetrahedral TiO4 structural units exactly in these glasses. Hence, the study of the OA spectrum of present CZPT
glasses is done to learn about structural adjustments explaining the coordination atmosphere of various titanium ions and their
structural units present in a glass matrix.
The titanium atom (Z = 22) possesses an electronic configuration of 1 s2 2 s2 2p6 3 s2 3p6 3d2 4 s2or ([Ar] 3d24 s2). In the prepared
CZPT glasses, we may expect the titanium ions to exist either in Ti3+ stable trivalent state ([Ar] 3d1) or Ti4+ stable tetravalent state
([Ar] 3d0) by the following oxidation reactions, which is evident from both FTIR and Raman studies.

Ti ↔Ti3+ + 3e–

Ti ↔Ti4+ + 4e–

Ti3+ ↔Ti4+ + e–

In the present glass system, various cations in the lattice positions and interstitial positions create very strong octahedral or
tetrahedral ligand fields, these fields may split the 2D(ground) state of Ti3+ (3d1) ions degenerates into two substates 2E and 2 T2. The
tetragonally distorted field surrounding the Ti3+ ions will split the 2 T2sub-state into three distinct energy states. The tetragonally
distorted octahedral field surrounding Ti3+ ions will split the 2E sub-energy state into A1B1states. Tanabe-Sugano diagrams indicate
that bands detected around 535 nm and 690 nm in OA spectra of TiO2-doped CZPT glasses are related to the transitions of Ti+3 ions.
The study of optical absorption spectra of TiO2 doped CZPT glasses reveals that titanium ions exist both inTi3+as well as Ti4+ states.
The peak positions of both the transitions are displacing towards the higher wavelength side with a regular raise in peak area with an
increase of the percentage of TiO2 up to 0.6 mol% and a reverse trend is observed with a further increase of the percentage of TiO2.
These facts suggest that there is a gradual transfer of Ti4+ ions into Ti3+ ions in the octahedral sites and also there is a conversion of
tetrahedral occupancy of Ti4+ ions into octahedral occupancy, up to the 0.6 mol% of TiO2 suggesting the modifying role of titanium
ions in the CZPT glasses and above the 0.6 mol% of TiO2 the reverse trend suggests the forming role of titanium ions in the glasses.
The resonance signal observed in ESR spectra of present TiO2 doped CZPT glasses at g = 1.94 is due to tetragonally compressed
octahedral sites of Ti+3 ion. The spectrum of each CZPT glass is a triplet and is ascribed due to the hyperfine interaction of a single
unpaired electron of 3d1 with two equivalent nuclear spins I= 1/2. The negative shift in g is attributable to a negligible splitting of a
trigonal field of orbital triplet due to the principal octahedral field. The relatively high-intensity pattern is observed in the case of
CZPT4 glass among all these studied.
Glasses suggest a higher rate of reduction of Ti+4 ions into Ti+3 ions.

5. Conclusions

➢ The patterns of X-ray diffraction obtained for TiO2 doped CZPT glasses indicate the glassy/amorphous behavior of present glasses
before immersion in SBF and the probable elements present in glasses are explained by EDS before and after soaking in SBF.
➢ The bioactivity of these glasses symbolized by hydroxy apatite layer as clearly shown by the SEM images and is highest for CZPT4
glass with 0.6 mol% of TiO2 after incubation in SBF and is evidenced by the values of pH and dissociation rates suggesting the

17
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

maximum conversion of tetrahedral sites of Ti4+ ions into the octahedral sites of Ti3+ ions through reduction process that leads to
structural compactness above 0.6 mol% of TiO2.
➢ The change in physical, thermal, elastic parameters as well as characteristic temperatures enlightens the variations occurring in
glass matrix forming either TiO6 units in octahedral sites by Ti+3/Ti+4 ions as a modifier with P-O-Ti bonds due to depolymerization
of glass network transforming a fraction of structural units Q3 and Q2 into Q1 units and Q0 units consequently with TiO2 content
below 0.6 mol% or TiO4 units in tetrahedral sites by Ti+4 ions as a former by increasing connectivity and network dimensionality in
the glass matrix signifying the switch of structural units Q1 into Q2 and Q0 structural units according to disproportionation
expression given by 2Q1 ↔Q2 + Q0 with content of TiO2 above 0.6 mol%.
➢ The increase in non-bridging oxygens due to the decline in cross-linkages in glass network represents a reduction in the number of
covalent bonds and may be results in enhance Ti+3 ions in the glass matrix, which is confirmed by a concurrent increase in Poisson’s
ratio, oxygen packing density as well as the shrink in acoustic impedance implies a weakening of ultrasonic wave propagation and
is supported by a simultaneous decrease in Debye temperature decreasing the rigidity of glass network with enhancement below
0.6 mol% of TiO2 and thereafter an opposite behavior is noticed in all the above-said properties that result in an increase in
compactness due to increase in covalent bond nature observed that increases network connectivity due to increase in tetrahedral
sites of Ti+4 with a simultaneous decrease in octahedral sites of Ti+3 above 0.6 mol% of TiO2 as supported by physical parameters
density and molar volume.
➢ The augment in comparative areas of bands assigned to ZnO4, bending modes of a network, Q1as , Q2as , and Q0as units at the expense of
Q0s , Q1s , Q2s andQ3s units obtained by deconvoluting FTIR absorbance spectra as well as normalized Raman spectra of present CZPT
glasses indicates the intensification of structural units Q1 and Q0 with the concomitant shrink of structural units Q2 and Q3 , with
enhancement below 0.6 mol% of TiO2 and is the result of enhance in octahedral sites more precisely by Ti+3/Ti+4 ions involving
TiO2 in glass network with TiO6 structural units forming new linkages as a modifier due to depolymerization whereas a reverse
trend is noticed in comparative areas as well as the conversion of structural units with enhancement above 0.6 mol% of TiO2 and
may be due to an increase in tetrahedral sites of Ti+4 forming TiO4 structural units by the former role of TiO2 increasing
compactness of glass matrix.
➢ The OA spectra of present CZPT glasses indicate two bands of absorbance especially related to transitions2B2g → 2B1g
and2B2g → 2A1g of Ti+3 ions, with a rise in the comparative area as well as wavenumber revealing that titanium ions are involved in
glass matrix as a modifier forming TiO6 structural units by occupying octahedral sites subjected to tetragonal compression in the
glass matrix with enhancement below 0.6 mol% TiO2 and a reverse trend is observed both in wavenumber as well as relative areas
of these bands above 0.6 mol% of TiO2 represent that titanium ions have tetrahedral co-ordination due to former action of TiO2
forming structural units TiO4 by Ti+4 ions in the glass network and is confirmed by resonance signal of Electron Spin Resonance
Spectra of these glasses.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

Data availability

No data was used for the research described in the article.

Acknowledgements

The authors would like to thank DST- India for providing Andhra Loyola College with FIST grant SR/FST/College-2017/48.

References

[1] T.H. Toshihiro, N. Mitsuo, Phosphate glasses and glass-ceramics for biomedical applications, Phosphorus Res. Bull. 26 (2012) 8–15.
[2] J.C. Knowles, Phosphate based glasses for biomedical applications, J. Mater. Chem. 13 (2003) 2395–2403.
[3] M. Tiskaya, S. Shahid, D. Gillam, R. Hill, The use of bioactive glass (BAG) in dental composites: a critical review, Dent. Mater. 37 (2) (2021) 296–310 (Feb).
[4] Y. Wang, C. Zhu, A. Parsons, C. Rudd, I. Ahmed, N. Sharmin, Effects of ZnO addition on properties of P45Mg24Ca16Na(15− x)Znx glasses, Biomed. Glass 5
(2019) 53–66.
[5] R.K. Brow, Review: the structure of simple phosphate glasses, J. Non Cryst. Solids 263&264 (2000) 1–28.
[6] H.A.S. Al-Shamiri, A.S. Eid, Optical and ultrasonic properties of chromium oxide in sodium zinc phosphate glass, Photonics Optoelectron. 1 (2012) 1–8.
[7] Y.B. Saddeek, Elastic properties of Gd3+-doped telluro vanadate glasses using Pulse-echo technique, Mater. Chem. Phys. 91 (2005) 146–153.
[8] D. Toloman, R. Suciu, C. Leostean, A. Regos, I. Ardelean, The influence of TiO2 concentration in some calcium-phosphate glasses, Phys. B 438 (2014) 84–87.
[9] Imran M. Asif, Richard M. Shelton, Paul R. Cooper, Owen Addison, Richard A. Martin, In vitro bioactivity of titanium-doped bio glass, J. Mater. Sci. Mater. Med.
25 (2014) 1865–1873.
[10] T. Kokubo, H. Takadama, How useful is SBF in predicting in vivo bone bioactivity? Biomaterials 27 (2006) 2907–2915.
[11] A. Mandlule, F. Döhler, L. van Wüllen, T. Kasuga, D.S. Brauer, Changes in structure and thermal properties with phosphate content of ternary calcium sodium
phosphate glasses, J. Non Cryst. Solids 392&393 (2014) 31–38.
[12] R.R. Reddy, Y. Nazeer Ahammed, P. Abdul Azeem, K. Rama Gopal, T.V.R. Rao, S. Buddhudu, N. Sooraj Hussain, Absorption and emission spectral studies of Sm3
+
and Dy3+ doped alkali fluoroborate glasses, J. Quant. Spectrosc. Radiant. Transf. 77 (2003) 149–163.

18
N. Rama Krishna Chand et al. Optik 274 (2023) 170506

[13] D.S. Brauer, N. Karpukhina, M.D. O’Donnell, R.V. Law, R.G. Hill, Fluoride containing bioactive glasses: effect of glass design and structure on degradation, pH
and apatite formation in simulated body fluid, Acta Biomater. 6 (2010) 3275–3282.
[14] L. Hupa, S. Fagerlund, J. Massera, L. Bjorkvik, Dissolution behavior of the bioactive glass S53P4 when sodium is replaced by potassium, and calcium with
magnesium and strontium, J. Non Cryst. Solids 432 (2016) 41–46.
[15] N. Sharmin, M.S. Hassan, T. Islam, C. Pang, F. Gu, A.J. Parsons, I. Ahmed, Effect of dissolution rate and subsequent ion release on cytocompatibility properties of
borophosphate glasses, Biomed. Glass 5 (2019) 85–97.
[16] S. Inaba, S. Fujino, K. Morinaga, Young’s Modulus and compositional parameters of oxide glasses, J. Am. Ceram. Soc. 82 (350) (1999) 1–7.
[17] A. Makishima, J.D. Mackenzie, Calculation of bulk modulus, shear modulus and Poisson’s ratio of glass, J. Non Cryst. Solids 17 (1975) 147–157.
[18] N. Rama Krishna Chand, B.K. Sudhakar, G. Ravikumar, G. Srinivasa Rao, Ch Srinivasa Rao, Influence of manganese ions on elastic and spectroscopic properties
of ZnO doped novel calcium fluorophosphate bio active glasses, Phys. Scr. 96 (2021), 125020.
[19] S.Y. Marzouk, M.S. Gaafar, Ultrasonic study on some borosilicate glasses doped with different transition metal oxides, Solid State Commun. 144 (2007)
478–483.
[20] Y.B. Saddeek, E. R.Shaaban, El Sayed Moustafa, H.M. Moustafa, Spectroscopic properties, electronic polarizability, and optical basicity of Bi2O3–Li2O–B2O3
glasses, Phys. B 403 (2008) 2399–2407.
[21] Y.M. Moustafa, A.K. Hassan, G. E1-Damrawi, N.G. Yevtushenko, Structural properties of V2O5, Li2O, B2O3 glasses doped with copper oxide, J. Non Cryst. Solids
194 (1996) 34–40.
[22] B.K. Sudhakar, G. Srinivasa Rao, Vibrational spectral analysis of structural modifications of Cr2O3 containing oxyfluoroborate glasses, J. Non Cryst. Solids 356
(2010) 2211–2217.
[23] Y.M. Lai, X.F. Liang, B. Dai, Raman and FTIR spectra of iron phosphate glasses containing cerium, J. Mol. Struct. 992 (2011) 84–88.
[24] S. SreehariSastry, B. Rupa Venkateswara Rao, Structural and optical properties of vanadium doped akaline earth lead zinc phosphate glasses, Indian J. Pure
Appl. Phys. 52 (2014) 491–498.
[25] U. Hoppe, A structural model for phosphate glasses, J. Non Cryst. Solids 195 (1996) 138–147.
[26] R.K. Brow, ‘Review: the structure of simple phosphate glasses, J. Non Cryst. Solids 263&264 (2000) 1–28.
[27] A. Shaim, M. Et-tabirou, L. Montagne, G. Palavit, Role of bismuth and titanium in Na2O-Bi2O3 -TiO2 -P2O5 glasses and a model of structural units, Mater. Res.
Bull. 37 (2002) 2459–2466.
[28] Srinvasa Ch, T. Rao, Y. Srikumar, V. Gandhi, Ravikumar, N. Veeraiah, Dielectric and spectroscopic investigations of lithium aluminium zirconium silicate glasses
mixed with TiO2, Philos. Mag. 91 (6) (2011) 958–980.
[29] G. Murali Krishna, N. veeraiah, N. Venkataramaiah, R. Venkatesan, Induced crystallization and physical properties of Li2O-CaF2-P2O5: TiO2 glass system,
J. Alloy. Compd. 450 (2008) 477–485.
[30] A. suneel kumar, T. Narendrudu, S. Suresh, M.V. sambasiva Rao, G. Chinna Ram, D. Krishna Rao, Role of titanium ions on the physical and structural properties
of calcium zinc bismuth phosphate glass ceramics, J. Non Cryst. Solids 434 (2016) 62–70.
[31] X. Li, H. Yang, X. Song, Yue Wu, Glass forming region, structure and properties of zinc iron phosphate glasses, J. Non Cryst. Solids 379 (2013) 208–213.
[32] C.E. Smith, R.K. Brow, L. Montagne, B. Revel, The structure and properties of zinc aluminophosphate glasses, J. Non Cryst. Solids 386 (2014) 105–114.
[33] V. Rajendran, A. NisharaBegum, M.A. Azooz, F.H. El Batal, Microstructural dependence on relevant physical-mechanical properties on SiO2-Na2O-CaO-P2O5
biological glasses, Biomaterials 23 (2002) 4263–4275.
[34] B. Bridge, N.D. Patel, D.N. Waters, On the elastic constants and structure of the pure inorganic oxide glasses, Phys. Stat. Sol. (a) 77 (1983) 655–668.
[35] V. Rajendran, H.A. El-Batal, Behaviour of acoustical parameters of mixed alkali silicate glasses, Indian J. Pure Appl. Phys. 33 (1995) 29–33.
[36] J.M. Farley, G.A. Saunders, Elastic properties of semiconducting phosphate glasses, Phys. Stat. Sol. (a) 28 (1975) 199–203.
[37] D.A. Magdas, O. Cozar, V. Chis, I. Ardelean, N. Vedeanu, The structural dual role of Fe2O3 in some lead-phosphate glasses, Vib. Spectrosc. 48 (2008) 251–254.
[38] D. Toloman, A.R. Biris, D. Maniu, I. Bratu, L.M. Giurgiu, A.S. Biris, I. Ardelean, Phosphate glassy network depolymerization induced by CaO doping, Part. Sci.
Technol. 28 (2010) 226–235.
[39] A.V. Ravi kumar, Ch Srinivasa Rao, T. Srikumar, Y. Gandhi, V. Ravi kumar, N. Veeraiah, Dielectric dispersion and spectroscopic investigations on Na2SO4-B2O3-
P2O5 glasses mixed with low concentrations of TiO2, J. Alloy. Compd. 515 (2012) 134–145.
[40] P. Venkateswara Rao, M. Srinivasa reddy, V. Ravi kumar, Y. Gandhi, N. Veeraiah, Dielectric dispersion in PbO-Bi2O3-B2O3 glasses mixed with TiO2, Turk. J.
Phys. 32 (2008) 341–356.
[41] S.F. Khor, Z.A. Talib, W.M. Daud, H.A.A. Sidek, Degradation study on ternary zinc magnesium phosphate glasses, J. Mater. Sci. 46 (2011) 7895–7900.
[42] H. Li, X. Liang, C. Wang, H. Yu, Z. Li. YangS, Structural aspects of calcium iron phosphate glass containing neodymium oxide, J. Mol. Struct. 1067 (2014)
154–159.
[43] O. Cozar, D.A. Magdas, L. Nasdala, I. Ardelean, G. Damian, Raman spectroscopic study of some lead phosphate glasses with tungsten ions, J. Non Cryst. Solids
352 (2006) 28–29.
[44] A. Santic, C.W. Kim, D.E. Day, Structural properties of Cr2O3–Fe2O3–P2O5 glasses, Part I, J. Non Cryst. Solids 353 (2007) 1070–1077.
[45] G.L. Saout, P. Simon, Y. Vaills, Raman and infrared study of PbO)x(P2O5)(1− x) glasses, J. Raman Spectrosc. 33 (2002) 740–774.
[46] N. Ramakrishna chand, B.K. sudhakar, G. Ravi kumar, V. Gayathri, P. Devika, T. Vennela, G. Srinivasa Rao, Ch Srinivasa Rao, Influence of multi valent states of
vanadium ions in ZnO doped novel calcium fluoro phosphate bio glasses, J. Mech. Behav. Biomed. Mater. 131 (2022), 105230.

19