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Influence of selenium dioxide (SeO2) on properties of bioglass in SiO2-Na2O-

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DOI: 10.1007/s41779-020-00459-z

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Influence of selenium dioxide (SeO2) on
properties of bioglass in SiO2-Na2O-CaO-
P2O5 system

Ram Karan, Priyabrata Manna,

P. K. Maiti & Kaberi Das

Journal of the Australian Ceramic

Society

ISSN 2510-1560
Volume 56
Number 3

J Aust Ceram Soc (2020) 56:1135-1145

DOI 10.1007/s41779-020-00459-z

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 Author's personal copy
Journal of the Australian Ceramic Society (2020) 56:1135–1145
[Link]

RESEARCH

Influence of selenium dioxide (SeO2) on properties of bioglass

in SiO2-Na2O-CaO-P2O5 system
Ram Karan 1 & Priyabrata Manna 1 & P. K. Maiti 1 & Kaberi Das 2

Received: 21 February 2019 / Revised: 9 November 2019 / Accepted: 26 February 2020 / Published online: 16 March 2020
# Australian Ceramic Society 2020

Abstract
The influence of selenium dioxide on bioglass in (45.0-x) SiO2 24.5Na2O 24.5CaO 6.0P2O5 xSeO2 (x = 0.0, 0.5, 1.0, 1.5, and
2.0 wt%) system was investigated by preparing the glass through conventional melting and annealing method. The glass
transition temperature (Tg), crystallization temperature (Tc), and density of prepared glasses were measured by differential
thermal analysis and Archimedes’ principle respectively. The structural and microstructure analyses of glasses were characterized
by Raman spectroscopy, Fourier transformed infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM) with
energy dispersive X-ray analysis (EDX). The formation of hydroxy apatite carbonate (HCA) layer for glasses was investigated
by Raman spectroscopy, FTIR, SEM with EDS, pH measurement, ion concentrations analysis, and (%) weight loss after
immersion in simulated body fluid (SBF) for 10 h to 14 days at 37.5°C. Experimental results showed that SeO2 substitution
for SiO2 in the glass had increased glass density and molar volume whereas network connectivity was decreased. The addition of
selenium oxide reduced the glass transition temperature and also crystallization temperature. The FTIR study of glass confirmed
the P–O bonding after immersion for 14 days in SBF, which was also identified in the Raman spectroscopy. SEM of the 14 days
immersed sample showed the formation of cauliflower like morphology of HA particles on the glass. pH and ion concentrations
analysis also confirmed the formation of HCA layer after 14 days of immersion in SBF.

Keywords Bioglass . Selenium substitution . Molar volume . Network connectivity . Raman spectroscopy

Introduction have been designed to enhance bioactivity of the materials.

A great effort is being put into the understanding of the mech-
Bioactive glasses (BGs) degrade in physiological solutions, anism and factors governing properties.
forming a layer of hydroxy carbonate (HCA) apatite layer Selenium is an essential trace element of a key antioxidant
which is very similar to mineral phase of bones. This helps enzyme [3]. In human and animals, selenium is an essential
to form an intimate bond between glass and living tissue. The element naturally present in the structure of selenoproteins
first BG was developed by Hence in the late 1960s and has and plays an important role in processes such as defense sys-
been clinically used in 1985 [1, 2]. Since then, several new tems, thyroid hormones metabolism, improving immunity,
bioactive glass compositions have been developed varying and preventing cancer [4–6]. It is an important element in
different component of the base (45S5) glass. bone physiology. Its deficiency may retard growth of bones
At present, various types of bioactive glasses are under and increase the risk of bone diseases (i.e., osteoporosis, oste-
research and development and more complex compositions oarthritis) [7]. Selenium, as a constituent of selenoproteins,
plays a significant role in proliferation of osteoblasts and os-
teoclasts. It is considered indispensable below 40 mg/g but
* Ram Karan
ceramic.ramkaran53@[Link] toxic above 4000 mg/g and in some cases it can even cause
death [8–10].
1
Owing to the above mentioned beneficial aspects of sele-
Department of Chemical Technology, University of Calcutta, 92, A.
P. C. Road, Kolkata 700 009, India
nium in human body, bioactive glasses incorporated with se-
2
lenium have gained attention in recent past. Xiang Wang et al.
Department of Ceramic Technology, Government College of
Engineering and Ceramic Technology, 73, Abinash Chandra
reported that selenium incorporated mesoporous bioactive
Banerjee Lane, Kolkata 700 010, India glasses, prepared by sol-gel method, showed excellent
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1136 J Aust Ceram Soc (2020) 56:1135–1145

Table 1 Chemical composition of bioglasses (wt%)

Samples code SiO2 Na2O CaO P2O5 SeO2

Se-0.0 45.0 24.5 24.5 6.0 0.0

Se-0.5 44.5 24.5 24.5 6.0 0.5
Se-1.0 44.0 24.5 24.5 6.0 1.0
Se-1.5 43.5 24.5 24.5 6.0 1.5
Se-2.0 43.0 24.5 24.5 6.0 2.0

hydroxy apatite formation ability when soaked in SBF for

3 days [11]. Trandafir et al. investigated the bioactivity of
SeO2 containing boro-silicate glass with varying Na2O/K2O
replacing SiO2 in 5SeO2.9.5B2O3.52.5SiO2.7.7P2O5.25 CaO
system and observed that selenium does not suppress the ap-
atite layer formation [12].
However, to the best of our knowledge, no systematic and Fig. 1 Differential thermal analysis (DTA) plots of different glasses
comprehensive study on the effect of SeO2 addition on the in-
vitro behavior, structure of Hench (45S5) glass has been re- temperature at a rate of 30°C/h. The compositions and batch
ported till date. The present study reports on the synthesis of code of glasses are given in Table 1.
melt-derived bioglass in (45.0-x) SiO2 24.5 Na2O 24.5 CaO
6.0 P2O5 xSeO2 (x = 0.0, 0.5, 1.0, 1.5, and 2.0 wt%) system,
influence of selenium oxide on the structural properties of Characterization of bioglasses
obtained glass samples, and their in-vitro behavior.
The bioglass samples were characterized by differential
thermal analysis (Shimadzu DT40, Japan), density mea-
surement by Archimedes’ principle, Raman spectroscopy
Experimental procedure (Model: T64000, Make: Horiba), Fourier transform infrared
spectroscopy (FTIR) (Perkin Elmer spectrum two, USA),
Materials and sample preparation and scanning electron microscopy (SEM) with energy dis-
persive X-ray analysis (EDX) (ZEISS EVO R 18 Special
Bioglasses with compositions in system (45.0-x) SiO2 Edition, Germany) as reported by Ram Karan et al. [13].
24.5Na2O 24.5CaO 6.0P2O5 xSeO2 (x = 0.0, 0.5, 1.0, 1.5, Differential thermal analysis was carried out on powdered
and 2.0 wt%) were prepared by the conventional melting- glass samples (− 200 BS sieve) up to 1000°C at 10°C/min
quenching and annealing technique. Appropriate amounts of rate of heating using a powdered alumina as a reference
analytical grade SiO2, Na2CO3, CaCO3, NH4H2PO4, and material.
SeO2 were weighed and thoroughly mixed in an agate pestle Network connectivity (NC) was calculated using equation
and mortar for 45 min. The melting was carried out in an [14]:
electric furnace at 1400°C for 2 h in Pt-Rh crucible. Casting
BO−NBO
was done by pouring the homogeneous melt into a preheated NC ¼ 2 þ
G
cast iron mold of the required dimensions. The prepared glass
samples were annealed in a regulated muffle furnace at 450°C where BO is the total number of bridging oxygen per network-
for 1 h and then the furnace was left to cool to room forming ion, NBO is the total number of non-bridging oxygen

Table 2 Density, molar volume, network connectivity, glass transition temperature (°C), and crystallization temperature (°C) of the prepared bioglasses

Samples code Density (gm/cc) Molar volume (cc/mol) Network connectivity Glass transition temperature (°C) Crystallization temperature (°C)

Se-0.0 2.752 22.37 1.90 537 720

Se-0.5 2.754 22.42 1.86 530 710
Se-1.0 2.756 22.46 1.83 520 706
Se-1.5 2.760 22.47 1.80 497 700
Se-2.0 2.765 22.49 1.77 486 690
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Fig. 3 Raman spectra of Se-0 and Se-1.5 glasses after immersion in SBF
solution for 14 days
Fig. 2 Raman spectra of different bioglasses before SBF immersion
resulting solution was buffered at a pH of 7.4 with
per network modifier ion, and G is the total number of glass- tris(hydroxymethyl)aminomethane and 1N hydrochloric acid.
forming units. For a SiO2-Na2O-CaO-P2O5-SeO2 system, The temperature of the solution was maintained at 37.5°C
where P is assumed to enter the glass network (i.e., formation throughout the experiment to simulate with human physiolog-
of P–O–Si bonds), NC was calculated as follows [14]: ical environment. One gram of glass powder (− 200 BS sieve)
½ð2  SiO2 Þ þ ½2  P2 O5 Þ−½ð2  Na2 OÞ þ ð2  CaOÞ þ ð2  SeO2 Þ was immersed in 50 ml of SBF. The SBF solution was taken
NC ¼ 2 þ
½SiO2 þ ½2  P2 O5 Þ out for testing after 10 h, 1 (D1), 3 (D3), 7 (D7), and 14 (D14)
days. The particles were separated from the supernatant liquid
by vacuum filtration using Gooch crucible (G-4), gently
In-vitro studies in simulated body fluid rinsed in double-distilled water, and stored in a vacuum des-
iccator. Structural changes on the surface of the samples treat-
In-vitro study was done on the powder sample after immer- ed in SBF were analyzed using Raman spectroscopy, FTIR,
sion in simulated body fluid (SBF) solution with ion concen- and SEM-EDX techniques. All SEM micrographs were stud-
tration almost equivalent to that of human blood plasma ied on the solid samples of 5mm × 5mm × 1.5 mm. Chemical
which was prepared following the same method as done by dissolution of bioactive glasses was estimated by measuring
Kokubo et al. [15]. Accordingly, reagent grade NaCl, pH change and weight loss of the glass samples after immer-
NaHCO3, KCl, K2HPO43H2O, MgCl26H2O, CaCl2, and sion in SBF solution for different time. The pH was measured
Na2SO4 were dissolved in double-distilled water and the using Orion (Star A214) Thermo Scientific pH meter and

Table 3 Correlation between wave number at which Raman bands emitted and functional groups in bioglasses [18, 19]

Sample/Raman shift (cm−1) Vibration mode

Se-0.0 Se-0.5 Se-1.0 Se-1.5

635 630 632 632 Rocking motion of bridging oxygen in structural units that contain non-bridging oxygen
- 726 - 731 Oxygen-bending motion
872 834 858 827 Symmetric stretching of monomer SiO44− (4NBOs)
945 952 960 957 Symmetric stretching of 2NBO
- 1029 1044 1038 Asymmetric stretching of bridging oxygen in all Q species and
1075 - - - Symmetric stretching of 1NBO
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Table 4 Correlation between wave number at which Raman bands emitted and functional groups in two glasses after immersing in SBF for 14 days
[20–22]

Sample/Raman shift (cm−1) Data Vibration mode

Se-0 Se-1.5 400–650 O–P–O bending mode

457 456
497 522
632 627
958 952 ~ 960 P–O symmetric stretching mode
1030 1006–1044 At around 1050 Antisymmetric P–O stretching bands at around 1050
1071 1079 At around 1080 Active vibration mode of ionic carbonate species

weight loss (%) of the prepared glass powder samples was molar volume, network connectivity, glass transition (Tg),
estimated by measuring its weight loss using a digital balance and crystallization temperature (Tc) of bioglasses are given
(Mettler Toledo, Model: CH 8609, Switzerland). The concen- in Table 2. Density was increased from 2.752 to 2.765 g/cc
tration of silicon and calcium ions of the SBF solution after for replacing low-density silica (density of 2.65 g/cc) with
soaking of the glass samples in SBF for 3, 7, and 14 days was high-density selenium oxide (3.95 g/cc). Molar volume of
measured calorimetrically by UV-VIS double beam spectro- the glass also increases from 22.37 cc/mol for Se-0 to
photometer (AU 2701) and EDTA titrimetric method 22.49 cc/mol for Se-2. The increase in density of selenium
respectively. dominates over molar volume increase due to which density
of glass with selenium was increased. The network connectiv-
ity was also decreased with SeO2 content from 1.90 to 1.77.
Results and discussions Reduction in network connectivity and increase in molar vol-
ume are suggesting that SeO2 has induced structural change
Density, glass transition, and crystallization by breaking up glass network and producing non-bridging
temperature of bioglasses oxygen (NBO) substituting bridging oxygen (BO) [16].
Differential thermal analysis (DTA) of the glass containing
Density of the prepared glass was measured by Archimedes’ different amount of selenium was recorded at a heating rate
principle using Xylene as a displacing liquid. The density, of 10°C/min up to 1000°C and is shown in Fig. 1. Both glass

Fig. 4 FTIR transmittance spectra of Se-0 glass for different immersion Fig. 5 FTIR transmittance spectra of Se-1.5 glass for different immersion
time time
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Table 5 Correlation between wave number at which transmittance bands emitted and functional groups in bioglasses Se-0 and Se-1.5 before and after
immersing in SBF [23–27]

Days Wave number cm−1/samples Data Vibration mode

Se-0 Se-1.5

0 471 470 500–400 Si–O–S bending

741 741 800–720 Si–O–Si symmetric
875 875 875 C–O bending
1055 1062 1050–1063 Si–O–Si symmetric/P–O stretching
1417 1417 1530–1400 C–O stretching
1638 1639 1600–1650 H–O–H bending
3663 3463 3000 above H–O–H stretching
14 462 460 500–400 Si–O–S bending
557 543 500–560 P–O bending (crystalline)
591 595 560–600 P–O bending (amorphous)
741 741 800–720 Si–O–Si symmetric
875 875 800–890 C–O bending
1044 1055 1050–1063 P–O stretching
1417 1416 1530–1400 C–O stretching
1642 1640 1600–1650 H–O–H bending
3414 3456 3000 above H–O–H stretching

transition (Tg) and crystallization temperature (Tc) were re- Raman spectroscopy of the glass before and after SBF
duced after substitution of silica by selenium oxide. Reduction treatment
of crystallization temperature (Tc) is generally achieved by
increasing the amount of network modifier oxide relative to The 45S5 bioglass contains ~ 51% modifier oxides mainly
network former oxide. This in turn depolymerizes the network sodium oxide and calcium oxides. All silica tetrahedral has
connectivity by increasing the amount of non-bridging oxy- on average 2 non-bridging oxygen (NBO). Structures of these
gen (NBO) to bridging oxygen (BO) ratio. The behavior of glasses mainly consist of silica tetrahedral chains joined by
glass transition temperature (Tg) thus suggests that the addi- modifier cations. It is commonly known that incorporation
tion of SeO2 results in a weakening of glass network [17]. of modifier ions into glass structure promotes structural
Here we can suggest that selenium acts as a network modifier. changes, detectable by vibrational spectroscopy. Analysis by

Fig. 6 FTIR transmittance spectra of Se-0.5 glass before and after Fig. 7 FTIR transmittance spectra of Se-1.0 glass before and after
immersion in SBF solution for 0 and 14 days immersion in SBF solution for 0 and 14 days
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Fig. 9 Variation of pH with immersion time in SBF solution of glass

Fig. 8 FTIR transmittance spectra of Se-2.0 glass before and after attributed to vibration of structural units built up by silica
immersion in SBF solution for 0 and 14 days
tetrahedron with different number of NBOs. Bands at 827 to
872 cm−1 are ascribed for monomer SiO44− (4NBOs). Bands
Raman spectroscopy allows noticing the relative intensities at 945–959 cm−1 may be due to silica tetrahedron with 2
and the position of Raman line changes with the glass com- NBOs and peaks at 1038 to 1075 cm−1 are assigned to vibra-
position. The Raman spectroscopy of the glass without and tion involving silica tetrahedron with 1 NBO [19].
with different selenium oxide content is shown in Fig. 2. By analyzing the spectra of the samples after immersion in
Functional group analyses of Raman spectra of glasses Se-0, SBF solution, some changes are noted. Figure 3 is the Raman
Se-0.5, Se-1.0, Se-1.5, and Se-2.0 are shown in Table 3. Peak spectra of Se-0 and Se-1.5 glasses after immersion in SBF
at around 635 cm−1 is due to the bond rocking vibration of Si– solution for 14 days. Functional group analyses of Raman
O–Si [18]. Main important features of Raman Spectra of sili- spectra of two glasses Se-0 and Se-1.5 after immersion in
cate glasses are bonds associated with asymmetric and sym- SBF solution for 14 days are shown in Table 4. The sharp
metric stretching vibration of SiO2 network in 850–1200 cm−1 peak at ~ 960 cm−1 is due to the P–O symmetric stretching
region. This region is of main interest as it gives the informa- mode which indicates the formation of crystalline hydroxy
tion of glass network connectivity which is very much related apatite. Other important bands, observed in 400–650 cm−1
to the bioactivity. Main Raman bands of these silicates are region, are assigned to O–P–O bending mode. In SBF solution

Table 6 Correlation between wave number at which transmittance bands emitted and functional groups in bioglasses Se-0.5, Se-1.0, and Se-2.0 before
and after immersing in SBF [23–27]

Samples/days Vibration mode

Se-0.5 Se-1.0 Se-2.0

D0 D14 D0 D14 D0 D14

491 471 491 472 461 473 500–400 Si–O–S bending

- - - - - 565 500–560 P–O bending (crystalline)
- 587 - 596 - 594 560–600 P–O bending (amorphous)
715 741 728 744 714 727 800–710 Si–O–Si symmetric
855 860 864 855 814 863 800–890 C–O bending
1028 1051 1031 1052 1032 1051 1020–1080 Si–O–Si symmetric/P–O stretching
1407–1465 1461 1441 1436 1410 1497 1530–1400 C–O stretching
1649 1665 1648 1651 1667 1669 1600–1700 H–O–H bending
3406 3447 3348 3431 3405 3438 3000 above H–O–H stretching
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The spectra show transmittance bands at 712–741 cm−1 are

assigned to symmetric stretching vibration of Si–O bond.
Band at 450–475 cm−1 is associated with Si–O–Si bending
and at 1030–1050 cm−1 is for Si–O–Si asymmetric stretching
in silica tetrahedron units. Deep transmittance band at 1428–
1442 cm−1 is due to symmetrically co-ordinated pure carbon-
ate ions absorbed on the surface of the glass because of
exposure to atmospheric CO2 before immersion in SBF
[23]. During immersion in SBF, surface carbonate was dis-
solved as indicated through reducing intensity of carbonate
at ~ 1442 cm−1 even after 10 h of immersion [24, 25]. After
14 days soaking, significant changes are noticed at around
500 to 600 cm−1, 860–875 cm−1, and 1000–1150 cm−1. Twin
peaks at 500–560 and 560–600 cm−1 are due to the P–O
bending (crystalline) and P–O bending (amorphous) vibra-
tion respectively [23]. The HCA layer is characterized by P–
Fig. 10 Silicon ion concentration of SBF solution after immersion of
glass samples for 3, 7, and 14 days
O bending vibration peaks at 557 cm−1 and 591 cm−1 and P–
O asymmetric stretching vibration bands between 1000 and
treated samples, the antisymmetric P–O stretching bands at 1150 cm−1. The bands due to bending vibration of P–O
around 1050 cm−1 are masked by active vibration mode of bonds are mostly used to discriminate between HCA and
ionic carbonate species at around 1080 cm−1 in Raman spectra bioactive material as P–O stretching band is superimposed
[20–22]. on Si–O stretching band (1030–1050 cm−1) corresponding to
glasses while band corresponds to Si–O bending between
400 and 500 cm−1 at lower frequencies compared with P–O
Fourier transformed infrared transmittance spectra bending in HCA. Characteristic twin peaks shown in Fig. 4
at 543 cm−1 and 595 cm−1 are indicating characteristic HCA
Fourier transformed infrared (FTIR) transmittance spectra of formation in glass soaking for 14 days. Transmittance band
glass Se-0 and Se-1.5 before and after immersion in simulat- at ~ 875 cm −1 corresponds to C–O (stretch) and at ~
ed body fluid (SBF) solution for 0, 10 h, 1, 3, 7, and 14 days 1425 cm−1 is due to symmetrically co-ordinated pure ionic
are displayed in Figs. 4 and 5 respectively. Functional group carbonate ions and a minor peak at around 1640 cm−1 and
analyses of FTIR spectra of glass Se-0 and Se-1.5 before and 3456 cm−1 is due to the presence of (hydroxyl) O–H groups
after immersion in SBF solution for 0 and 14 days are shown on the glass surface. These bands are in conforming to the
in Table 5. Prior to soaking in SBF solution, transmittance formation of hydroxy carbonate apatite layer (HCA) after
peaks of both the glasses are more or less similar in nature. immersion for 14 days [26, 27]. FTIR spectra of glasses

Fig. 11 Calcium ion concentration of SBF solution after immersion of Fig. 12 Weight loss (%) of glass samples soaked in SBF solution at
glass samples for 3, 7, and 14 days 37.5°C as a function of time (days)
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Fig. 13 Secondary electron image (magnification, × 10,000) of the glass sample Se-0 before and after immersion in SBF for a (D0), b 10 h, c D3, and d
D7 and EDS spectra of e D0 and f 10 h

Se-0.5 Se-1.0 and Se-2.0 before and after immersion in SBF the bioglass. The increase in silicon ion concentration is due to
solution for 0 and 14 days are displayed in Figs. 6, 7, and 8 the dissolution of silica network at high pH in the early period
respectively. Functional group analyses of FTIR spectra of of soaking. The pH of SBF increased significantly from an
glasses Se-0.5 Se-1.0 and Se-2.0 before and after immersion initial value of pH 7.4 to 9.1, 9.2, 9.22, 9.25, and 9.01 for
in SBF solution for 0 and 14 days are shown in Table 6. Se-0, Se-0.5, Se-1.0, Se-1.5, and Se-2.0 respectively after
Characteristic crystalline P–O bonding at 500–560 cm−1 is 14 days immersion in SBF solution. The high value of pH
absent in 0.5 and 1.0% SeO2 containing glass samples after demonstrates the dissolution of cations from the glass surface.
immersion in SBF solution for 14 days. The results suggest that substitution of SiO2 by SeO2 is bene-
ficial in releasing of ions from the glass. This could be due to
Chemical dissolution test of BGs (changes in pH, ion the disrupted of network connectivity of the glass which is
concentration, and % weight loss) shown in Table 2. High pH of the Se-1.5 leads to high disso-
lution rate of the glass in SBF. The high pH therefore favors an
The glasses were immersed in SBF solution for different im- early development of hydroxy carbonate apatite (HCA) layer
mersion time. Figure 9 presents the change in pH of the SBF on the glass surface as evident from SEM image. pH of the
solution as function of immersion time. All the glasses indicate SBF solution with selenium was observed high with 1.5 wt%
an increase in concentration of calcium and silicon ions as well whereas 0.5 and 1.0 wt% are very much similar to that of
as pH with increase in time. For this measurement, the sample standard. As we observe in NC and molar volume, low net-
with constant mass of glass to volume of the SBF ratio was work connectivity means high value of NBO which is related
maintained. All the samples, the pH varies with composition to molar volume also. The increase of pH was associated with
for given time of immersion. The slope of the line joining the first stage of reactions of surface dealkalization. Later, the
0 days and 3 days is much steeper with respect to the other network dissolution stage tended to dominate [29]. Decrease of
period of immersion time. The high value of pH is due to quick Ca ion of SBF with increasing soaking time (after 3 days) is
release of sodium and calcium ions from the glass in exchange due to the formation of amorphous calcium phosphate and
of H3O+/H+ ions in SBF solution. The rate of alkali ion subsequently formation of crystalline apatite on the surface
leaching from glass is extremely rapid and proportional to t1/2 of glass by consuming calcium ions and phosphate ions.
[28]. Due to release of sodium ion as well as Ca2+ ions, the pH Formation of hydroxyapatite (HA) from constituent ions is
of the solution increased leading to breakage of the Si–O–Si given by 10 Ca2+ + 6(PO4)3− + 2OH− ➔ Ca10(PO4)6(OH)2
bonds and formation of silanol Si–OH and Si (OH)4 groups on [30].
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Figures 10 and 11 show the Si4+ and Ca2+ ion concentra- weight loss was decreased after 7 days due to formation of
tion in SBF before and after different immersion time for glass HCA layer on the glass surface inhibiting the leaching out of
powder. For all the samples, concentration of Si4+ released Ca2+ and Na+ ions from glass [34]. Percent weight loss of the
into solution increases rapidly during 3 days of soaking and different glass is 5.78, 5.89, 5.95, 5.96, and 5.62 for Se-0, Se-
then the concentration was decreased. The same trend was 0.5, Se-1.0, Se-1.5, and Se-2.0 respectively after 14 days im-
also observed in the case of calcium ion concentration. The mersion in SBF solution. The weight loss is very much related
release of the silicon ions indicates the first step of dissolution to the degradability of glass structure in SBF solution. This is
of silica network Si–O–Si bond at high pH due to the ex- also supported by the pH value.
change reaction between H3O+/H+ ion in SBF and sodium
and calcium ions in glass. Silicon ion release is reduced at
Surface morphology by SEM-EDS before and after SBF
the later stage of the immersion due to the formation of calci-
immersion
um phosphate layer on the silica-rich layer [23, 31, 32]. This
process is dependent on the silica content of the glass and the
HCA formation of the glass samples was estimated by mi-
pH of the SBF solution. For glass which have relatively low
crostructural analysis of the glass samples. Microstructure
silica content, Si–OH and Si(OH)4 form rapidly in SBF. Silica
of the glass samples (Se-0 and Se-1.5) before and after SBF
layer forms on the surface of the bioglass due to condensation
immersion is shown in Figs. 13 and 14 respectively. It was
and repolymerization of Si–OH groups following the reaction
observed that morphology/texture of the sample surface
[33]:
was changed from surface like glassy nature to a surface
Si–OH þ HO–Si−−−−−−−−−➔Si–O–Si þ H2 O: covered by cotton ball like aggregates, characteristics of
hydroxy carbonate apatite (HCA) after immersion in SBF
for several hours to several days [35]. After soaking into
Weight loss (%) as function of immersion time in SBF is the SBF solution, the glass surface was remarkably
displayed in Fig. 12. After 1 day, rate of weight loss is much changed for the chemical reaction between the bioglass
higher with respect to the rest of the SBF immersion time. The and the SBF solution. Secondary electron image of the
high rate of weight loss is due to the leaching out of the Na+ glass samples after immersion of Se-0 sample for 10 h
and Ca2+ ions from the glass structure with the exchanging demonstrates that few aggregates of granules are scattered
H3O+ or H+ ion of the SBF solution. At high pH, Si–O–Si (Fig. 13). The EDS analysis of the glass surface also con-
network was disrupted to form Si–OH or Si(OH)4. The rate of firms that silicon and sodium ion concentration is quite

Fig. 14 Secondary electron image (magnification, × 10,000) of the glass sample Se-1.5 before and after immersion in SBF for a D0, b 10 h, c D3, and d
D7 and EDS spectra of e D0 and f 10 h
 Author's personal copy
1144 J Aust Ceram Soc (2020) 56:1135–1145

high. If we look at the secondary electron image of Se-1.5 Conclusion

glass surface, the sample surface is nearly fully covered by
fibers and granules of hydroxy apatite carbonate (Fig. 14). 45S5 bioglass with substitution of SiO2 by SeO2 up to 2 wt%
EDS analysis also confirms the low concentration of sili- has been prepared at 1400°C for 2 h by conventional melting
con and sodium ions on the surface. The morphology of the quenching followed by annealing process. Density and molar
calcium phosphate precipitate is granular in Se-0 but fi- volume were increased with higher amount of selenium diox-
brous in Se-1.5 sample. The microstructure provides the ide but network connectivity (NC) was decreased. The glass
visual evidence of formation of a HCA layer on the surface transition temperature (Tg) and crystallization temperature
of glass sample which was also confirmed by FTIR/Raman (Tc) were also decreased with substitution SeO2 in 45S5
spectra analysis. HA layer growth rate is much higher in bioglass. Raman and FTIR spectra confirmed the formation
Se-1.5 samples with respect to the Se-0 samples. D3 and of P–O bonds and hydroxy apatite (HCA) after immersion in
D7 day samples do not show significant differences in their SBF solution for 14 days. Secondary electron image shows
morphology except the size of the balls. But after 14 days, the formation of cauliflower like three-dimensional growth
three-dimensional overgrowth just like cauliflower of HCA after immersion in SBF. Best in-vitro results were observed
agglomeration is noticed [36–39]. The rounded agglomer- with 1.5 wt% SeO2 containing glass. The size of the HA
ation is much more elevated. The size of the HCA agglom- agglomeration of this glass is much higher than that of the
eration of Se-1.5 samples is much higher than that of Se-0 without selenium-containing samples.
samples (Fig. 15). Moreover, the agglomeration size of the
hydroxyl apatite is increased as function of selenium con- Acknowledgments The authors thankfully acknowledge the Department
of Ceramic Technology, Government College of Engineering and
tent from 0 to 1.5 wt%.
Ceramic Technology, Kolkata, India, for providing necessary facilities
Best HCA formation was observed with 1.5 wt% SeO2 for the present research work.
containing glass which was confirmed by observing the max-
imum pH of SBF solution for 14 days, higher ion concentra- Funding information This study was financially supported by the
tion (Si4+ and Ca2+) after 3 days immersing in SBF. The size University Grants Commission (UGC) of Minor Research Project (File
No. [Link]-269/15-16 (ERO) DT19.01.2017). One of the authors (Ram
of the HCA agglomeration of glass is much bigger with in Se-
Karan) would like to thank University Grants Commission (UGC) New
1.5 glass with respect to other selenium containing glasses Delhi, India, for financial support of Research Fellowship (UGC-RGNF,
after 14 days immersing in SBF. F1-17.1/2014-15/RGNF-2014-15-SC-RAJ-61456).

Fig. 15 SEM micrograph (magnification, ×5000) of glass samples after immersion in SBF for 14 days. a Se-0. b Se-0.5. c Se-1.0. d Se-1.5
 Author's personal copy
J Aust Ceram Soc (2020) 56:1135–1145 1145

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