Journal of Molecular Structure 1049 (2013) 386–391

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Journal of Molecular Structure

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Absorption spectroscopic studies on gamma irradiated bismuthborosilicate glasses

0022-2860/$ - see front matter � 2013 Elsevier B.V. All rights reserved.http://dx.doi.org/10.1016/j.molstruc.2013.06.056

⇑ Corresponding author. Tel.: +91 0183 2258802/09x3342 (O); fax: +91 01832258820.

E-mail address: ravneet_383@yahoo.com (R. Kaur).

Ravneet Kaur a,⇑, Surinder Singh a, O.P. Pandey b

a Department of Physics, Guru Nanak Dev University, Amritsar 143 005, Indiab School of Physics and Materials Science, Thapar University, Patiala 147 004, India

h i g h l i g h t s

� Gamma ray shielding behaviour of the bismuth based borosilicate glasses has been investigated.� Effect of modifier Bi2O3 has been studied on glass composition.� FT-IR spectroscopy has been employed to study the structural changes in glasses.� Results indicate that the glass structure corresponds to that of radiation hard glasses.

a r t i c l e i n f o

Article history:Received 14 May 2013Received in revised form 23 June 2013Accepted 23 June 2013Available online 1 July 2013

Keywords:c-IrradiationBismuthHeavy metal oxideBorosilicate glassFT-IRNBOs

a b s t r a c t

FT-IR spectroscopic measurements have been employed to investigate the structural changes in quater-nary xBi2O3–15 Na2O–(70 � x) B2O3–15 SiO2 glass system with x = 5, 10, 15, 20 and 25 (mol%). The effectof gamma irradiation in the dose range of 0.1–60 kGy on the infrared absorption spectra of these glassesis also reported. The IR spectra of the prepared samples show characteristic bands related to the sharingof triangular and tetrahedral borate and silicate groups together with Bi–O groups. The effect of the heavymetal oxide Bi2O3 on the glass composition is also studied.

� 2013 Elsevier B.V. All rights reserved.

1. Introduction

Heavy metal oxide (HMO) glasses have been an area of interestfor long due to their unique and characteristic properties such asthermal stability, high refractive index, chemical durability, highinfrared transparency and high density which makes them suitablefor varieties of applications [1]. Particularly, Bi2O3-containingglasses find their use in electronic devices, ceramic materials, ther-mal and mechanical sensors, reflecting windows, optical fibres andradiation-shielding purposes [2]. Bi2O3 exists in a monoclinic form,and exhibits irregular octahedral arrangement of six oxygen atomslocated at interatomic distances from 2.14 to 2.80 Å. Out of these,three are appreciably closer (2.14–2.29 Å) than the other three(2.48 to 2.80 Å) [3]. Due to its low field strength i.e. small chargeto ionic ratio and high polarizability, pure Bi2O3 glass cannot be

obtained as compared with pure B2O3 glass. However, in the pres-ence of very small additions of conventional glass formers such asP2O5, B2O3, and SiO2, it can build a glass network of [BiOn] (n = 3, 6)pyramids [4,5]. With larger additions, glasses over a wide range ofcompositions have been found. Because of its dual properties, as amodifier with [BiO6] octahedral and as glass former with [BiO3]pyramidal units, bismuth ions may influence the physical, struc-tural, optical and electrical properties of oxide glasses [6]. Beinga heavy metal oxide, the addition of Bi2O3 is known to increasethe radiation hardness of the glasses. Such glass systems are ex-pected to sustain or withstand the radiation-induced degradationcaused by high energy radiations such as gamma and X-rays.Therefore, these glasses can be used for radiation shielding pur-poses and applications involving the use of ionizing radiations suchas nuclear reactors, nuclear power stations, spacecrafts, satellitesand military aircraft.

The use of radioactive isotopes in agriculture, industry, science,technology and medical applications has made it essential todevelop a material, which can be used under harsh conditions of

Bi5

Bi4

Bi3

sity

(a.u

.)

R. Kaur et al. / Journal of Molecular Structure 1049 (2013) 386–391 387

nuclear radiation exposure and simultaneously can act as a shield-ing material. For such a material, homogeneity of density and com-position is an important requirement. Glasses are promisingmaterials in this regard. Several glasses have been developed fornuclear engineering applications because they accomplish the dou-ble task of allowing visibility and at the same time can absorb highenergy radiations like gamma-rays and neutrons [7,8]. Borosilicateglasses have been an area of interest for more than two decadesdue to its diversified use in the biological, electrical and pharma-ceutical industries [9]. The use of these glasses has also been madefor the entrapment/immobilisation of high level waste from nucle-ar power plants and armour industries [10–12]. Irradiation effectson the structural, mechanical and optical properties of a goodshielding glass should be small. The effect of irradiation on glassesis dependent on several factors such as on the type and energy ofirradiation, and glass composition [13]. It is well established thatradiation damage in glass causes active defects which can be intro-duced by ionization or atomic displacement mechanisms or via theactivation of the pre-existing defects [14–17]. The knowledge ofthe glass structure before and after irradiation therefore becomesextremely important for the understanding the structural evolu-tion of glasses. In this paper we report the experimental resultsof the gamma irradiation on the glasses of Bi2O3–Na2O–B2O3–SiO2 system. The impact of radiation on the structural changes ob-served by using FTIR spectroscopy on these glasses has been de-scribed. The present work is also focussed to study the effect ofbismuth oxide on the IR spectra of these glasses. We have studiedthe effect of gamma irradiation on BaO–Na2O–B2O3–SiO2 glassesearlier [18] and this work is in continuation of the previous one.

2. Experimental details

The glasses in the system xBi2O3–15 Na2O–(70 � x) B2O3–15SiO2 with x = 5, 10, 15, 20 and 25 (mol%) were prepared by conven-tional melt-quenching method. Analytic reagents Bi2O3 (99.99%),B2O3 (99.99%), SiO2 (99.99%) and Na2CO3 (99.99%) were used asraw materials for 30 g batch. The chemical data for the constituentoxides is shown in Table 1. Melting was carried out in alumina cru-cibles using an electric furnace in the temperature range 1050–1150 �C for one hour. The homogenized melts were then pouredin disc shaped preheated stainless steel moulds for the requireddimensions. The prepared samples were cooled at a rate of25 �C h�1 to room temperature using a muffle furnace. The glassesthus obtained were brown in colour.

All the glass samples were then finely powdered using a cleanagate mortar pestle. Samples were subjected to a series of five radi-ation doses of 0.1 kGy, 1 kGy, 5 kGy, 15 kGy and 60 kGy using 60Cosource of gamma radiation at IUAC, New Delhi. The glass sampleswere irradiated for required time interval to achieve the desiredoverall dose. The dose rate was 7.27 kGy h�1. All the powderedglass samples were wrapped in butter paper and then packed inpolythene sachets before irradiation. The amorphous nature ofthese glass samples was confirmed by X-ray diffraction (XRD)using Bruker Axs diffractometer, Germany (Model D8 Advanced),with Cu Ka radiation of wavelength k = 1.5406 Å. Fourier transforminfrared (FT-IR) spectra of all the powdered samples before and

Table 1Chemical composition of Bi1, Bi2, Bi3, Bi4 and Bi5 samples in mol%.

Composition Bi2O3 Na2O B2O3 SiO2

Bi1 5 15 65 15Bi2 10 15 60 15Bi3 15 15 55 15Bi4 20 15 50 15Bi5 25 15 45 15

after irradiation were recorded at room temperature in the range4000–400 cm�1 using a Thermo Nicolet 380 spectrometer usingthe conventional KBr pellet technique.

3. Results and discussion

The XRD spectra of the unirradiated glass samples Bi1-5 isshown in Fig.1. The broad humps appearing in the spectra of allthe glass samples indicate the amorphous nature of these samples.The IR absorption spectra of the bismuth borosilicate glasses i.e.Bi1 (5 mol%), Bi2 (10 mol%), Bi3 (15 mol%), Bi4 (20 mol%) and Bi5(25 mol%) before irradiation is shown in the Fig. 2. The FTIR spectraof the glasses is studied in the range 4000–400 cm�1 and the activevibrational IR bands assigned to [BOn, n = 3 and/or 4], [BiOn, n = 3and 6] and [SiO4] structural units, are located in the mid infraredregion, i.e. in the spectral range 1600–400 cm�1. It is observed thatall the bismuth containing glasses show the prominent absorptionbands in the following three regions.

(1) 600–800 cm�1

(2) 800–1200 cm�1

(3) 1200–1600 cm�1

Borosilicate glass is a composite glass which consists of struc-tural units like trigonally coordinated boron (BO3), tetrahedrallycoordinated boron (BO4) and silicon (SiO4) structural units [19].Bi2O3 containing glasses have four fundamental vibrations in theIR spectral regions at 830 cm�1, 620 cm�1, 450 and 350 cm�1.The results of IR spectra in the present investigation are inter-preted using the method given by Tarte [20,21] and Condrate[22,23] where the experimental datas are compared with the re-sults obtained for the crystalline samples. To study the effect ofgamma rays and effect of bismuth oxide on the glass system, theabsorption spectra of each composition before and after irradiationis discussed separately below.

3.1. Bi1 glass

3.1.1. Before irradiationThe IR absorption spectrum of the unirradiated Bi1 glass con-

taining 5 mol% Bi2O3 is illustrated in Fig 2. The unirradiated glassreveals three clear and distinct regions containing several absorp-tion bands extending from the beginning of the measurements at400 cm�1 up to 4000 cm�1. Bi2O3 in binary bismuth borate glassescan share in the structure in three different ways; it creates a fourcoordinated state by giving part of its oxygen to the boron,

10 20 30 40 50 60

Bi2

Bi1

Inte

n

2 Theta

Fig. 1. XRD spectra of Bi1-5 glass samples before irradiation.

500 750 1000 1250 1500 1750 2000 2250 2500

541502

4481466

9281380

12201050

684

Bi5

Bi4

Bi3

Bi2

Bi1

Abso

rban

ce (a

.u.)

Wavenumber (cm-1)

Fig. 2. IR spectra of Bi1-5 glass samples before irradiation.

500 750 1000 1250 1500 1750 2000 2250 2500

448

13821232

1020

828

680

60 kGy

15 kGy

5 kGy1 kGy

0.1 kGy

Abso

rban

ce (a

.u.)

Wavenumber (cm-1)

Fig. 3. IR spectra of Bi1 glass after irradiation at doses 0.1 kGy, 1 kGy, 5 kGy, 15 kGyand 60 kGy.

388 R. Kaur et al. / Journal of Molecular Structure 1049 (2013) 386–391

secondly, it participates in the glass structure by forming BiO3

groups belonging to the pyramidal point group C3v and thirdly, itintroduces some NBO’s in the glass network [24].

In the Bi1 glass system, the weak absorption bands are observedin the region 440–411 cm�1 which can be ascribed to the silicatebending rock mode. The bands observed at 448 cm�1 accompaniedby a shoulder at 502 cm�1 and a small peak at 541 cm�1 can beconsidered to be superposed with the borate deformation modes,such as the in-plane bending of boron–oxygen triangles and nor-mal vibration of Bi–O bond in the deformed BiO6 octahedral units[25,26]. A sharp and distinct band at 684 cm�1 along with a shoul-der at 740 cm�1 is due to bending vibrations of Si–O–B bridges[27]. Another very small band at around 828 cm�1 can be relatedto the symmetrical stretching vibration of the Bi–O bonds in the[BiO3] groups [28]. The bands observed in region 850–1200 cm�1

are located at 928 cm�1, 984 cm�1, 1010 cm�1 along with a peakat 1051 cm�1. These bands indicate the B–O bond stretching ofthe tetrahedra BO4 units that are connected by the bismuth cat-ions. In other words, the symmetrical stretching vibrations of theBi–O bond in the BiO3 polyhedral and the vibrations of the variousarrangements are containing BO4 units [26,29]. The existence of[BO4] units indicates that the addition of Bi2O3 into the glassreplacing B2O3 causes a progressive conversion of [BO3] units to[BO4] units [30]. The bands observed around 1000 cm�1 are dueto the combined stretching vibrations of Si–O–Si and B–O–B net-work of tetrahedral structural units. The region between 1200and 1500 cm�1 shows prominent absorption bands at 1273 cm�1,1345 cm�1, 1413 cm�1and 1466 cm�1. The band at around1345 cm�1 is assigned to the stretching vibrations of B–O [BO3]units from meta and ortho borate groups [31,32]. The absorptionbands at 1273 cm�1 are specific to the B–O stretching vibrationsof BO3 triangular units with non-bridging oxygen (NBO) atoms.The peak at around 1479–1429 cm�1 is assigned to anti-symmetri-cal stretching vibrations with three NBOs of the B–O–B groups [33].

3.1.2. After irradiationThe Bi1 glass shows significant changes in the infrared spectra

in terms of band intensity and position at five successive gammairradiation dose of 0.1, 1, 5, 15, 60 kGy as shown in Fig. 3. It canbe seen that in the far infrared region the bands due to BiO6 mergeto form a hump. This shows that radiation has caused the breakageof Bi–O bonds thereby reducing the BiO6 structural units. The bandcentred at 684 cm�1 shows a remarkable decrease in intensitywhich is assigned to the B–O–B linkages. The broad band in the re-gion 850–1200 cm�1 centred 1020 cm�1 shows a decrease in inten-sity indicating a decrease in the formation of structural BO4 groups.

The individual bands in the region 1200–1500 cm�1 combine toappear in the form of a shoulder at 1232 cm�1 and weak peak at1382 cm�1. This band is slightly broader than that observed inthe base glass. This broadening can be related to the formation ofBO3 groups along with NBOs. The changes are more pronouncedin case of 1 kGy sample and thereafter.

3.2. Bi2 glass

3.2.1. Before irradiationThe IR absorption spectra of Bi2 glass is illustrated in Fig 2. With

the increase in bismuth content from 5 mol% to 10 mol% visiblechanges appear in the spectra of the glass. A prominent peak at540 cm�1 along with a kink 448 cm�1 which appeared in the Bi1glass shifts towards lower wavelength at 446 cm�1 with the in-crease in the bismuth content indicating the formation of BiO6

units in the glasses. The shift in the band from 684 cm�1 (Bi1) to709 cm�1 (Bi2), can be assumed due to the influence of the electro-static field associated with the strongly polarizing Bi2+ ions. Withthe increase in the Bi2O3 content in the glass, there is an increaseof the electron cloud density around oxygen of [BO3] units. Thiscauses an increase in the roll torque of B–O–B bond and shiftingof the bending vibration B–O–B bond towards higher wave number[26]. The small bands at 928 cm�1, 984 cm�1, 1010 cm�1 alongwith a peak at 1051 cm�1 merge to form a broad band with smallabsorption peaks at 980 cm�1 and 1041 cm�1. This infrared spec-tral region is typical for the stretching vibration of [BO4] units[34]. The addition of Bi2O3 into the glass causes a transformationof trigonal [BO3] units into tetrahedral [BO4] units. This region isalso characteristic of silicate glasses. Thus slight broadness of thisregion can be due to increase of BO4 and SiO4 groups. Also this re-gion corresponds to vibration of the modifier cations. This meansthat bismuth atom gets incorporated in the glass network throughB–O–Bi bonding. The bands in the region 1200–1600 cm�1 appearin the form of a shoulder 1225 cm�1 and low intensity bands at1366 cm�1 and 1456 cm�1. The shoulder around 1225 cm�1 foundin this glass system is assigned to the B–O stretching vibrations of[BO3] units with non-bridging oxygen atoms.

3.2.2. After irradiationFig. 4 depicts the IR spectra of the Bi2 glass after a gamma dose

of 0.1 kGy, 1 kGy, 5 kGy, 15 kGy and 60 kGy. The spectra of Bi2glass do not show any significant change in position of bands afterirradiation at a dose of 0.1 kGy and 1 kGy as shown in Fig. 4. At adose of 5 kGy there is a sudden decrease in intensity of bands inthe region 900–1200 cm�1. This signifies that the BO4 tetrahedra

500 750 1000 1250 1500 1750 2000 2250 2500

145712251051

928540

709446

60 kGy15 kGy

5 kGy

1 kGy

0.1 kGy

Abso

rban

ce (a

.u.)

Wavenumber (cm-1)

Fig. 4. IR spectra of Bi2 glass after irradiation at doses 0.1 kGy, 1 kGy, 5 kGy, 15 kGyand 60 kGy.

500 750 1000 1250 1500 1750 2000 2250 2500

5041380

12201015706

604440

60 kGy

15 kGy

5 kGy

1 kGy

0.1 kGy

Abso

rban

ce (a

.u.)

Wavenumber (cm-1)

Fig. 5. IR spectra of Bi3 glass after irradiation at doses 0.1 kGy, 1 kGy, 5 kGy, 15 kGyand 60 kGy.

R. Kaur et al. / Journal of Molecular Structure 1049 (2013) 386–391 389

are decreasing in the glass. The position of the band at around980 cm�1 remains same which is assigned to the combinedstretching vibrations of Si–O–Si and B–O–B network. This showsthat the glass structure consists of borate and silicate groups evenat 5 kGy dose. A small peak appears at 580 cm�1 which can be as-cribed to either the Bi–O bonds vibrations in BiO6 units or the Bi–O-

stretching vibration in the BiO6 units [35]. The absorption band at1457 cm�1 becomes intense with irradiation which indicates thatsuper structural units with NBOs are increasing. At 60 kGy the re-gion 1200–1500 cm�1 shows splitting of bands which is due to theweakening of network grouping vibrations as a result of energytransferred by gamma rays. It is assumed that gamma rays causedisruption of already random network in glasses and as a resultthe arrangement of groups becomes unsymmetrical leading tothe possible weakness of network grouping vibrations.

3.3. Bi3 glass

3.3.1. Before irradiationThe addition of 15 mol% Bi2O3 causes a splitting of 540 cm�1

band and three peaks could be identified at 435 cm�1, 484 cm�1

and 521 cm�1 in the FT-IR spectra of Bi3 glass as shown in Fig. 2.The splitting of the far-IR bands indicates the possible changes inthe Bi–O distance and/or band strength [25]. The appearance ofprominent peaks in this region 430–520 cm�1 and their shifting to-wards lower wavenumber with increasing bismuth content hasbeen attributed to the variation in the local symmetry of highlydistorted BiO6 polyhedra by Dimitriev and Mihallova [36] andthe same has been reported in IR spectra of other bismuth basedglasses. The region 600–850 cm�1 acquires a sharp band at706 cm�1 and can be assumed to be due to symmetric stretchingvibrations of Bi–O bonds in BiO3 pyramidal units superposed withthe O3B–O–BO3-bending vibrations [32,37]. The presence of thisband suggests that at least some superstructural units of this glasssystem are retained in the structure [38]. Also a small band centredat 604 cm�1 appears in this region which is related to the presenceof NBOs in the glass.

The bands in the region of 800–1200 cm�1 becomes more in-tense, showing a clear peak at 1015 cm�1. This indicates that withthe increase in the bismuth oxide content, the number of BO4 unitsfrom tri, tetra and pentaborate groups along with SiO4 tetrahedra isincreasing, leading to a stable glass. The shift in this band towardslower wavelength side can also be explained by accepting theassumption that with the increase in the bismuth content, newbridging bond of Bi–O–B is formed due to strongly polarizing Bi3+

ions. Since the stretching force constant of Bi–O bonding is

significantly lower than that of the B–O, the stretching frequencyof Bi–O–B might tend to be lower causing a blue shift in absorptionband [26]. The intensity of the band in the region 1200–1400 cm�1

decreases visibly and the peak width decreases indicating a fall inthe formation of BO3 groups with increasing modifier content.

3.3.2. After irradiationFig. 5 shows the spectra of Bi3 glass after irradiation at doses

0.1 kGy, 1 kGy, 5 kGy, 15 kGy and 60 kGy. There is overall decreasein the intensity of the bands after the glass is subjected to gammairradiation. However no major change is observed in terms of posi-tions of bands at a dose of 15 kGy. This shows that no new struc-tural groups are formed in the glass after irradiation. In otherwords, it can be concluded that this glass system is radiation hardup to a dose of 5 kGy i.e it is resistant to the damage caused by highenergy gamma radiations at this dose. An increase in the intensityat around 650–700 cm�1 is observed in samples at an irradiationdose of 15 kGy, which is assigned to the bending of B–O–B linkagesin the borate networks. This region confirms the presence of NBOsin the glass structure. The band around 450–600 cm�1 vibrations inBiO6 units is retained in almost all the samples. The componentpeaks in the band between 1200 and 1500 cm�1 also shifts towardslower wave numbers at 1220 and 1380 cm�1 and the increasedintensity of these bands represents the increase of BO3 group withnon-bridging oxygens (NBOs). The decrease in intensity of theband centred at around 1020 cm�1 can be due to decrease in num-ber of BO4 and SiO4 groups. A new band at around 2300 cm�1 isattributed to the stretching of O–H bond inside the glassy network.The O–H groups form at non-bridging oxygen sites [39].

3.4. Bi4 glass

3.4.1. Before irradiationThe infrared spectrum of Bi4 glass sample before irradiation is

shown in Fig. 2. It can be observed that there is an increase inthe intensity of the bands in the region 420–550 cm�1 indicatingthat SiO4 and BiO6 units have further increased. The centre of theband at around 700 cm�1 shifts slightly towards 712 cm�1 while,the centre of the band at about 1020 cm�1 shift to lower wavenumbers at 1006 cm�1 and shows an increase in intensity. Thesebands are associated with the vibrations of Bi–O bonds, where itis known that the behaviour of Bi in the glass matrix has discontin-uous character [40]. It is accepted that introduction of Bi2O3 trans-forms some of the BO3 triangles to BO4 tetrahedra and theappearance of the bands at 1020 cm�1 is probably due to the

500 750 1000 1250 1500 1750 2000 2250 2500

13601280

470 1000720

60 kGy

15 kGy

5 kGy

1 kGy0.1 kGy

Abso

rban

ce (a

.u.)

Wavenumber (cm-1)

Fig. 7. IR spectra of Bi5 glass after irradiation at doses 0.1 kGy, 1 kGy, 5 kGy, 15 kGyand 60 kGy.

390 R. Kaur et al. / Journal of Molecular Structure 1049 (2013) 386–391

vibrations of BO4 tetrahedra present as tetraborate and diborategroups [34]. As the Bi2O3 content is increased to 20 mol% bothbands at 1245 and 1375 cm�1 decrease in intensity and also the re-gion becomes narrower. This also shows that the non bridging oxy-gens along with BO3 groups are decreasing in the glass. This makesthe glass more stable and rigid making it suitable for the radiationshielding purposes.

3.4.2. After irradiationFig. 6 shows the absorption spectra of the Bi4 glass system at a

successive gamma doses in the range from 0.1 kGy to 60 kGy. It canbe seen that the bands at 700 and 1020 cm�1 show a further de-crease in intensity but the band in the range 1200–1500 cm�1 isfound to be increase in intensity, clearly indicating an increase inthe stretching vibrations of BO3 groups. The band in this range takea new shape centred at around 1490 cm�1 and can be assigned toanti-symmetrical stretching vibrations with three NBOs of theB–O–B groups [33]. This composition can be regarded as radiationhard upto a dose of 15 kGy similar to Bi3. Even changes are notmuch pronounced at a dose of 60 kGy.

3.5. Bi5 glass

3.5.1. Before irradiationThe intensity of the bands near 720 and 1280–1365 cm�1 fur-

ther decreases. The presence of BiO6 units in all the compositionsaround 420–550 cm�1 shows the modifying action of the bismuthoxide. There is a sharp increase in the intensity of the band in theregion 800–1200 cm�1 showing a prominent peak around1000 cm�1 as shown in Fig 2. It indicates that at this concentrationbismuth ions have entered the glass matrix as network former andalso suggests that more stable sp3 tetrahedral BO4 groups areincreasing at the expense of BO3 groups. Thus, it is clear that at25 mol% bismuth ions have entered into the glass network viaBi–O–B bonding. Also the peak area and peak intensity shows thatBi5 glass has more number of BO4 units as compared to other com-positions. The high number of tetrahedral BO4 units increases theinterconnectivity of the glass atoms and tend to lead to harderglasses. The addition of Bi2O3 in the glass system resulted in a de-crease in the bending vibrations of B–O linkages and stretchingvibrations of the B–O of trigonal BO3 units.

3.5.2. After irradiationEffect of gamma irradiation on the FT-IR spectra Bi5 glass sys-

tem can be observed from the Fig. 7. Up to a dose of 15 kGy, nochange is observed in the spectra of these glasses. The positions

500 750 1000 1250 1500 1750 2000 2250 2500

472428

13751245

1006712

60 kGy

15 kGy

5 kGy

1 kGy

0.1 kGy

Abso

rban

ce (a

.u.)

Wavenumber (cm-1)

Fig. 6. IR spectra of Bi4 glass after irradiation at doses 0.1 kGy, 1 kGy, 5 kGy, 15 kGyand 60 kGy.

of different bands do not change their position even at radiationdose of 60 kGy, which suggest that main building units remainthe same. Thus the Bi5 glass can be considered as radiation hardglass and can tolerate doses higher than 60 kGy.

4. Conclusion

Studies of the composition dependence of IR absorption spectrashow that these glasses are built up of the [SiO4], [BO3], [BO4],[BiO3] and [BiO6] structural units. The addition of Bi2O3 contentcauses a progressive conversion of [BO3] to [BO4] units leading toincrease of the strength of the glass structure and interconnectionof the structural units. The results indicate that the present glasssystem is a good shielding glass and with increasing the Bi2O3 con-tent in the glass its radiation hardness increases.

Acknowledgement

The authors are thankful to IUAC, New Delhi for providing thefinancial assistance and necessary experimental facilities for thecompletion of this work.

References

[1] V. Dimitrov, T. Komatsu, J. Non-Cryst. Solids 249 (1999) 160.[2] L. Baia, R. Stefen, W. Kiefer, J. Popp, S.J. Simon, J. Non-Cryst. Solids 303 (2002)

379.[3] E.S. Moustafa, Y.B. Saddeek, E.R. Shaaban, J. Phys. Chem. Solids 69 (2008) 2281–

2287.[4] A. Wells, Structural Inorganic Chemistry, fourth ed., Clarendon Press, Oxford,

1975.[5] W. Vogel, Chemistry of Glass, American Ceramic Society, Westerville, OH,

1985.[6] N. Ahlawat, S. Sanghi, A. Agarwal, N. Kishore, S. Rani, J. Non-Cryst. Solids 354

(2008) 3767.[7] J.F. Krocher, R.E. Browman (Eds.), Effects of Radiation on Materials and

Components, Reinhold, New York, 1984.[8] D. Saritha, Y. Markandeya, M. Salagram, M. Vithal, M.A.K. Singh, G.

Bhikshamaiah, J. Non-Cryst. Solids 354 (2008). 5573–557.[9] M. Hasanuzzamana, M. Sajjia, A. Rafferty, A.G. Olabia, Thermochim. Acta 555

(2013) 81–88.[10] M.J. Plodinec, Glass Technol. 41 (2000) 186–192.[11] J.D. Vienna, Int. J. Appl. Glass Sci. 1 (2010) 309–321.[12] M. Arab, C. Cailleteau, F. Angeli, F. Devreux, L. Girard, O. Spalla, J. NonCryst.

Solids 354 (2008) 155–161.[13] N. Dogan, A.B. Tagrul, in: Annual Meeting on Nuclear Technology’99,

Tatungsbericht Proceedings, 1999, p. 681.[14] U. Natura, D. Ehrt, Glastech. Ber. Glass Sci. Technol. 72 (9) (1999) 295.[15] S.Y. Marzouk, F.H. ElBatal, Nucl. Instr. Meth. B 248 (2006) 90.[16] S.Y. Marzouk, F.H. ElBatal, A.M. Salem, S.M. Abo-Naf, Opt. Mater. 29 (2007)

1456.

R. Kaur et al. / Journal of Molecular Structure 1049 (2013) 386–391 391

[17] F.H. ElBatal, S.Y. Marzouk, M.A. Azooz, Phys. Chem. Glasses: Eur. J. Glass Sci.Technol. B 47 (5) (2006) 588.

[18] R. Kaur, S. Singh, O.P. Pandey, Physica B 407 (2012) 4765–4769.[19] S.K. Sharma, J.F. Mammone, M.F. Nicol, Nature 292 (1981) 140.[20] P. Tarte, Spectrochim. Acta 18 (1962) 467.[21] P. Tarte, in: I.A. Prins (Ed.), Non Cryst. Solids. Phys., Elsevier, Amsterdam, 1964.[22] R.A. Condrate, in: L.D. Pye, H.I. Stevens, W.C. Lacourse (Eds.), Introduction to

Glass Science, Plenum Press, New York, 1972.[23] R.A. Condrate, J. Non-Cryst. Solids 84 (1986) 26.[24] F.H. ElBatal, M.A. Marzouk, A.M. Abdelghany, J. Mater. Sci 46 (2011) 5140–

5152.[25] F.H. ElBatal, S.Y. Marzouk, N. Nada, S.M. Desouky, Physica B 391 (2007) 88–97.[26] G. Chryssikos, L. Liu, C. Varsamis, E. Kamitsos, J. Non-Cryst. Solids 235 (1998)

761.[27] K. El-Egili, Physica B 325 (2003) 340.[28] H.A. Saudi, A.G. Mostafa, N. Sheta, S.U. ElKameesy, H.A. Sallam, Physica B 406

(2011) 4001–4006.[29] D.E.C. Corbridge, E.J. Low, J. Chem. Soc. Part I (1954) 493.

[30] I. Pal, A. Agarwal, S. Sanghi, Indian J. Pure Appl. Phys. 50 (2012)237–244.

[31] S.G. Motka, S.P. Yawale, S.S. Yawale, Bull. Mater. Sci. 25 (2002) 75.[32] E.I. Kamitsos, A.P. Patsis, M.A. Karakassides, G.D. Chryssikos, J. Non-Cryst.

Solids 126 (1990) 52.[33] Y.B. Saddeek, E.R. Shaaban, El.S. Moustafa, H.M. Moustafa, Physica B 403 (2008)

2399–2407.[34] G. El-Damrawi, K. El-Egili, Physica B 299 (2001) 180.[35] S.M. Abo-Naf, R.L. Elwan, M.A. Marzouk, J. Mater. Sci: Mater. Electron, doi:

10.1007/s10854-011-0541.[36] Y. Dimitriev, V. Mihallova, in: A. Dufan, F. Navarro (Eds.), Proc. Int. Cong. on

Glass, vol. 3, Madrid, 1992, p. 293.[37] A.K. Hassan, L. Borjesson, L.M. Torell, J. Non-Cryst. Solids 172–174 (1994) 154.[38] V. Dimitrov, Y. Dimitriev, A. Montenero, J. Non-Cryst. Solids 180 (1994) 51.[39] (a) H. Dunken, R.H. Doremus, J. Non-Cryst. Solids 92 (1987) 61;

(b) R.D. Husung, R.H. Doremus, J. Mater. Res. 25 (1996) 2209.[40] I. Pal, A. Agarwal, S. Sanghi, M.P. Aggarwal, Opt. Mater. 34 (2012)

1171–1180.