Materials Chemistry and Physics 115 (2009) 783–788

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Materials Chemistry and Physics

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Neutron irradiation effects on optical and structural properties of silicate glasses

Amanpreet Kaur Sandhu a , Surinder Singh a,∗ , Om Prakash Pandey b
a
Department of Physics, Guru Nanak Dev University, Amritsar 143005, India
b
School of Physics and Materials Science, Thapar University, Patiala 147004, India

a r t i c l e i n f o a b s t r a c t

Article history: The affect of thermal neutron irradiation on the optical and structural properties of the quaternary silicate
Received 27 March 2008 glasses of varying compositions has been studied. Experimental results reveal the formation of colour
Received in revised form 26 October 2008 centers in the visible region of the optical spectra. The optical energy gap and the width of the energy tail
Accepted 19 February 2009
above the mobility gap have been measured before and after irradiation. The optical energy gap has been
found to decrease with increase in neutron fluence. The decrease in the energy gap with the decrease
Keywords:
in silica content of the glass is also observed. The change in glass network structure as revealed by the
Glasses
formation of non-bridging silicon–oxygen (Si–O–NBO) groups has been observed and explained in terms
Irradiation effects
Colour centers
of radiation induced structural defects and composition of the glass.
Optical properties © 2009 Elsevier B.V. All rights reserved.
FTIR

1. Introduction
The radiation induced modification of materials has become a
perspective method for the purposeful changes in material proper-
ties. Radiation creates a variety of defects in the materials, which
then absorb photons at particular wavelengths, resulting in a mod-
ified absorption spectrum of the materials. The difference between
the absorption spectra before and after irradiation is an important
characteristic and is called the induced absorption spectrum (IAS).
Gamma and neutron irradiation affect the structure of the glass
matrix, resulting in changes in the optical, physical and electrical
properties [1–5]. Defect centers induced by ionizing radiation in
glasses are described by microscopic models constructed on the
basis of local information obtained from studies using several spec-
troscopic techniques, such as optical absorption, infrared or Raman
spectroscopy [6]. The most fundamental radiation induced defects
(colour centers) in glasses are the non-bridging oxygen hole cen-
ter (NBOHC: Si O*), the E -center ( Si*), the peroxy radical (POR:
Si O O*) and the trapped electrons (TE), where the notation “ ”
represents three bonds with other oxygens in the glass network and
“*” denotes an unpaired electron [7–9]. In general, NBOHC has an
optical absorption around 620 and 440 nm (440 nm: NBOHC1 and
620 nm: NBOHC2), the E -center has an absorption band at about
215 nm and POR has absorption band near 260 nm in the silicate
glasses [7,9].
∗ Corresponding author. Tel.: +91 183 2257007; fax: +91 183 2258820.
E-mail address: surinder s1951@yahoo.co.in (S. Singh).
The kind and the extent of radiation induced damage in the
materials depend not only on the kind of radiation but also on
the composition of the glass. All observed variations in the prop-
erties (chemical resistance, light transmittance, colour, etc.) are
caused to a different extent by a change in the structure of the
glass. The knowledge of the relation between the glass structure and
the particular radiation defects is of great theoretical and practical
importance.
Neutron interactions with matter occur as collisions, called scat-
tering events, or in capture events. A neutron will collide with a
nucleus of an atom in the material being penetrated, but because
a nucleus is incredibly small (approximately 10,000 times smaller
then the electron cloud surrounding it), the probability of a collision
is low, resulting in the high penetration distances associated with
neutrons. In the case of an elastic scattering event, a neutron col-
lides with a nucleus; it imparts a portion of its energy to the target
nucleus. This energized nucleus, called a recoil nucleus, will move
throughout the material causing excitation and ionization events.
In the case of inelastic scattering events, the neutron is absorbed by
the target nucleus, with a gamma ray and a less energetic neutron
emitted from the target. After a neutron has lost a significant potion
of its kinetic energy through scattering events it may be absorbed
by a target nucleus in a capture event. The result of this event is
that the new atom has its mass number increased by one, and as
such will undergo one of many possible nuclear events. The result
is often the emission of ionizing radiations, which result in the pro-
duction of defects in the material via electron and hole productions.
So, although neutrons are not directly ionizing radiation, they often
produce secondary events that produce various forms of ionizing
radiation.

0254-0584/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2009.02.032
784 A.K. Sandhu et al. / Materials Chemistry and Physics 115 (2009) 783–788

Table 1
Chemical composition of quaternary silicate glasses studied.

Sample code SiO2 Na2 O MgO Al2 O3 (mol%)

Comp-I 75 15 5 5
Comp-II 70 20 5 5
Comp-III 65 25 5 5
Comp-IV 60 30 5 5

The purpose of our work is the identification and characteriza-

tion of the kind and the extent of the damage induced by thermal
neutrons irradiation on artificially prepared silicate glasses on the
basis of optical absorption (UV–vis) and infrared absorption mea-
surements (FTIR) performed before and after irradiation. Also the
work is extended to investigate the effect of the variation of glass
composition on their optical and vibrational properties.

2. Experimental procedure

2.1. Sample preparation

Table 1 gives the chemical composition of the quaternary silicate glasses studied.
The glasses were prepared from analytical grade pure chemicals (in order to avoid
the incorporation of impurities which could lead to wrong conclusion due to addi-
tional signals) in amount sufficient to produce 75 g glass. These raw materials were
quartz granules, anhydrous sodium carbonate, magnesium oxide and aluminum
oxide. Appropriate amount of dried ingredients were ball milled in acetone medium
for 2 h. After drying acetone, the batch was heated in alumina crucibles at 900 ◦ C for
1 h in high temperature resistance heating furnace. The temperature was then raised
to 1560 ◦ C, held at this temperature for half an hour and afterwards the melt was
casted into preheated graphite mould of dimensions 12 × 12 × 45 mm3 and annealed
in a muffle furnace at 300 ◦ C for 1 h. The annealed specimen was cut into the samples
of 2 mm thickness by using Buehler Isomet low speed saw diamond cutter. Grinding
was performed with SiC abrasives and aluminum oxide and polishing was done with
cerium oxide in order to obtain maximum flatness.
2.2. Neutron irradiation
All the samples were packed in aluminum capsules and were sent to BARC
(Bhabha Atomic Research Center, Trombay, Mumbai) for thermal neutron irradia-
tion in CIRUS Reactor at IC-1 position with varying neutron fluence of 1014 , 1015 ,
1016 and 1017 n cm−2 . The dose rate was 1 × 1011 n cm−2 s−1 .
2.3. XRD measurements
X-ray diffraction studies were carried out on glasses of four different composi-
tions by using Brooker AXS diffractometer (Cu K␣ ). The pattern was recorded at a
scanning rate of 2 min−1 and angular range (2) of 10–60◦ . The XRD pattern before
and after irradiation for glass samples of Comp-IV was also recorded.
Fig. 2. X-ray diffraction analysis of glass Comp-IV before and after irradiation: (a)
blank; (b) 1014 n cm−2 ; (c) 1015 n cm−2 ; (d) 1016 n cm−2 ; (e) 1017 n cm−2 .
wavelength range 200–600 nm using air as a reference. Infrared transmission spectra
were recorded using the same weight of glass powder dispersed in KBr pelletes. For
it a 2.0 mg from each sample was mixed with 100 mg of KBr in an agate mortar and
pressed into pellets. The data was recorded by Shimadzu FTIR-8400S spectropho-
tometer from 400–4000 cm−1 at room temperature.
3. Results and discussion
3.1. X-ray diffraction analysis
X-ray diffraction investigations of the unirradiated glasses of
Comp-I, II, III and IV reveal no diffraction peaks or lines, indicating
no crystalline phases. The results as shown in Fig. 1 indicate that
the studied glasses are completely amorphous. Fig. 2 shows the XRD
pattern for glass Comp-IV after irradiation with thermal neutrons at
different fluences. There is no peak formation in the studied angle
range further indicating the glass to remain in amorphous state
even after irradiation.
3.2. Colouration of glass

2.4. Optical measurements

Radiation can induce numerous changes in the physical prop-
Optical transmittance measurements were performed on glass samples before erties of glass; one of the most obvious effects is the visible
and after irradiation using UV–vis spectrophotometer (Shimadzu UV-160A) in the colouration, which is caused by the colour centers (defects).

Fig. 1. X-ray diffraction analysis of unirradiated glasses: (a) Comp-I; (b) Comp-II; (c) Comp-III; (d) Comp-IV.
 A.K. Sandhu et al. / Materials Chemistry and Physics 115 (2009) 783–788
Fig. 3. Absorption spectra of neutron irradiated glass of Comp-I. Inset: Urbach plots
of the same glass samples.
The melted unirradiated glasses are colourless, with no char-
acteristic absorption bands to be observed in both the ultraviolet
and visible regions. On subjecting the glasses to low neutron flu-
ence, their colour becomes yellowish brown, which changes to dark
brown at higher neutron fluences.
Ionizing radiation in form of gamma rays is also usually present
during irradiations with thermal neutrons in the thermal column
of nuclear reactors. However, its dose is so small that hardly any
observable changes are observed. As reported in one of our previ-
ous works on the gamma irradiated silicate glasses, the observable
changes are observed only at a gamma dose of 1 kGy or above, a
dose much larger as compared to the gamma dose in the thermal
column of nuclear reactors [10].
Figs. 3 and 4 show respectively the absorption spectra of base
glass of Comp-I and Comp-II before and after neutron irradiation.
Two characteristic absorption bands with maxima at about 360 nm
and 430 nm are observed. Increasing neutron irradiation fluence
has no effect on the band peak positions, which are relatively con-
stant, whereas the change in the band heights suggests that only
the population of the defects is getting effected by the irradiation
dose.
The ionizing radiation produces electron–hole pairs, which
individually become trapped at various defect sites in the glass
Fig. 4. Absorption spectra of neutron irradiated glass of Comp-II. Inset: Urbach plots
of the same glass samples.
785
structure. Accordingly, new optical absorption bands may develop.
In general, these absorption bands are associated with either oxy-
gen deficiency or oxygen excess in the glass network [7,8]. In the
neutron irradiated glasses, hole trapped colour centers with char-
acteristic absorption band around 430 nm are formed, leading to the
development of brown colour. Thus, the absorption band at 430 nm
is identified as absorption of NBOHC1, and the band at 360 nm is
attributed to the trapped electrons [11,12]. The NBOHC1 ( Si O*)
is a hole trapped in the 2p orbital of one non-bridging oxygen, and
it is the principal trapped hole in irradiated glasses correlating the
visible absorptions.
3.3. Optical mobility gap and the width of the energy tail
3.3.1. Theory
The problem of interaction of optical radiation with matter is
usually considered in the frame of excitation of different electronic
states in a condensed matter in accordance with energy zone dia-
gram. Effect of structural disorder on the electronic structure of
amorphous solids is clearly recognized at the band edges [13,14] and
is shown in Fig. 5. There is the formation of localized states within
band tails in the case of amorphous materials. These effects on elec-
tronic structure are reflected in the absorption edge of amorphous
solids by two separate regions. The absorption coefficient ˛(h) as a
function of the photon energy, in one of the regions called “Urbach
region”, at a particular temperature, obeys an empirical relation
[15] given by
˛(h) = ˛0 exp(h/EU ) (1)
where h is the photon energy, ˛0 is a constant and EU is an energy
which is interpreted as the width of the localized states in the nor-
mally forbidden band gap, also known as the Urbach energy. This
region is attributed to the optical electronic transition between a
localized band tail and an extended band. The absorption coeffi-
cient ˛(h) for the second region, called “Tauc region”, attributed to
a transition between the extended valence band and the conduction
band is given by the Tauc equation [16]
 2

(h − Eopt )
˛(h) = const (2)
h
where h is the photon energy and Eopt is the optical energy gap. EU
and Eopt are useful parameters for describing the structural disorder.
3.3.2. Optical properties
Measurements of the transmittance in the UV and visible spec-
tral range can be used to calculate the radiation induced absorption,
the optical energy gap and the width of the energy tail above the
Fig. 5. Energy diagram of electron states in glass.
786 A.K. Sandhu et al. / Materials Chemistry and Physics 115 (2009) 783–788
Fig. 6. Absorption spectra of unirradiated glasses of Comp-I; Comp-II; Comp-III and
Comp-IV.
Fig. 7. Optical energy gap, Eopt , as a function of log (neutron fluence) for glass samples
of different compositions.
gap. Changes in these parameters are indicative of the change in the
structure of the glass [17].
It is clear from Figs. 3 and 4 that the glass samples of Comp-
I and Comp-II shows strong absorption in the UV region. Also the
absorption edge is shifting towards the longer wavelength side with
increasing fluence of neutrons. Fig. 6 shows the absorption spectra
of unirradiated glass samples of Comp-I–IV. The spectra reveal a
slight shift of the beginning of the absorption edge towards the
longer wavelength with increasing content of Na2 O from Comp-
I–IV. According to Stevals [18], the absorption edge in oxide glasses
corresponds to the transition of an electron belonging to an oxygen
ion to an excited state. The more weakly these electrons are bound,
the more easily absorption occurs.
The values of Urbach energy (EU ), which is the inverse of the
slope of the Urbach plots (insets of Figs. 3 and 4), for the blank and
neutron irradiated samples of different fluences and different com-
positions are given in Table 2. Fig. 7 shows the variation in optical
energy gap (Eopt ), which is the extrapolation of the linear region of
Table 2
The variation of Urbach energy with increasing neutron fluence in glasses of Comp-I, Comp-II, Comp-III and Comp-IV.
Glass sample → neutron fluence↓ (n cm−2 ) Urbach energy EU (eV)
Comp-I
Blank 0.262
1014 0.267
1015 0.323
1016 0.483
1017 0.473
the plots of (˛h)1/2 against h to (˛h)1/2 = 0, versus log of neutron
fluence for thermal neutron irradiated glass samples of different
compositions. It clearly shows the decrease in the optical energy gap
with increasing neutron fluence. Similar results have been obtained
in the microscopic glass slide irradiated with thermal neutrons in
one of our previous works [19]. The decrease of the energy gap val-
ues after irradiations can be related to the change in the structure of
the glass matrix. It has been reported by several authors [18,20,21],
that in oxide glasses the shift of the optical energy gap to lower
energies can be related to the formation of non-bridging oxygen
(NBO), which binds excited electrons less tightly than the bridg-
ing oxygen. The high dose or high dose rate of neutron irradiation
breaks up the normal silicon–oxygen bonds in the glass network
and displaces oxygen out of its normal position, resulting in NBOs,
i.e., high dose irradiation causes radiolysis. As seen from Fig. 6, the
absorption edge is shifting slightly towards the longer wavelength
side on going from Comp-I–IV and the band gap energy decreases
(Fig. 7). Increasing the percentage of Na2 O from Comp-I–IV breaks
up Si–O–Si chains in the glass network, with the production of two
non-bridging oxygens per Na2 O molecule and Na ion going into the
interstitial. The negative charges on the NBOs have larger magni-
tude than that on the bridging oxygens. Increasing the ionicity of
oxygen, by converting them from bridging to non-bridging oxygen
ions, raises the top of the valance band resulting in the reduction of
the optical energy gap (Eopt ). Hence, ultraviolet absorption occurs
at lower photon energies, as the oxygen atom becomes NBO [22].
The width of the energy tail is a measure of the disorder or vari-
ety of environment affecting the cations. The Urbach rule (1) for
absorption coefficient is an attempt to explain the observed expo-
nential tail in term of internal electric fields generated within a
solid. This internal electric field leads to the exponential broaden-
ing of the energy states. The measured values of the width of energy
tail, EU , for the thermal neutron irradiated glass samples with vary-
ing fluence are listed in Table 2. The value of the Urbach energy
increases with increasing neutron fluence, which may be related
to the increase in the amorphousity of the glass structure. This
increase in EU can be attributed to an increase of the disorder related
part Ed of Urbach energy; the other phonon part (Eph ) being con-
stant at a particular temperature. Similar results have been reported
with gamma irradiated microscopic glass slides [23].
3.4. FTIR spectral analysis
Fig. 8 shows the effect of neutron irradiation on Fourier trans-
form infrared (FTIR) spectra of glass samples of Comp-IV. The
spectra show three characteristic fundamental IR bands of silica
glass at about 600, 750 and 1034 cm−1 attributed respectively to
O Si O bending modes, Si O Si symmetric stretching of bridging
oxygen and Si O Si anti-symmetric stretching of bridging oxygen
within the tetrahedral [24–26]. The transmission intensity of all
the three bands decreases with increasing neutron fluence while
the band at 1034 cm−1 also becomes broader without any change
in the band peak position. The decrease in the band intensity and
its broadening is due to the Si O Si bond scission with thermal
neutron irradiation.
Comp-II Comp-III Comp-IV
± 0.002 0.252 ± 0.001 0.238 ± 0.002 0.229 ± 0.001
± 0.001 0.275 ± 0.002 0.263 ± 0.001 0.249 ± 0.001
± 0.001 0.299 ± 0.002 0.283 ± 0.002 0.313 ± 0.002
± 0.001 0.409 ± 0.001 0.350 ± 0.003 0.396 ± 0.001
± 0.001 0.451 ± 0.001 0.356 ± 0.001 0.431 ± 0.001
 A.K. Sandhu et al. / Materials Chemistry and Physics 115 (2009) 783–788
Fig. 8. FTIR spectra of glass of Comp-IV before and after irradiation.
Fig. 9 shows the effect of variation of glass composition on
the infrared spectra of the glass for a particular dose of neu-
trons (1017 n cm−2 ). The FTIR spectra show peaks at 460 cm−1
corresponding to the Si O Si bending mode and at 750 cm−1 cor-
responding to Si O Si symmetric stretching of bridging oxygen
within the tetrahedral. For Si O Si bond, the angle in the silica
glass is distributed between 120◦ and 180◦ and it is relatively unsta-
ble at smaller values. The shift of the peak position is an indicator
of a change of the average bond angle. The transmission intensity
of Si O Si bond has been observed to decrease from glass samples
of Comp-I–IV, which is due to the scission of this bond as the con-
centration of network modifiers increases (from 15 mol% Na2 O in
Comp-I to 30 mol% Na2 O in Comp-IV). Also the peak at 750 cm−1
is getting broadened which is also an indication of the scission of
Si O Si chain in the glass network. Moreover, from Comp-I–IV, two
new bands at 840 cm−1 and 900 cm−1 emerge in the infrared spec-
tra. The band at 900 cm−1 is associated to the Si–O stretching with
one non-bridging oxygen (Si O NBO) per SiO4 tetrahedron (Q3
group) and the band centered at 840 cm−1 is assigned to the Si–O
stretching with two non-bridging oxygen (Si–O–2NBO) per SiO4
Fig. 9. FTIR spectra of glasses of different compositions.
787
tetrahedron (Q2 group) [27]. These bands are not at all observed
for glass samples of Comp-I and II, the reason being the increasing
concentration of Na2 O breaks the network structure of glass former
thus producing NBOs with the gradual incorporation of the ions in
the glass structure.
4. Conclusions
We have performed optical and FTIR measurements of a series of
silicate glasses exposed to different fluences of thermal neutrons.
Radiation induced colouration in the visible region indicates the
formation of hole type colour centers. The decrease in the opti-
cal energy gap with decrease in the mole percentage of SiO2 has
been discussed on the basis of formation of non-bridging oxy-
gen. Using FTIR analysis, different bands associated with bridging
oxygen bonds and NBO have been identified, and their intensity
variation with dose have been discussed. Formation of two new
bands (Q3 and Q2 groups) with varying composition have been
attributed to a decrease in the local symmetry as a consequence
of the incorporation of alkali ions into the glass former network
structure.
Acknowledgements
Financial support provided to one of the authors (AKS) by
Inter-University Accelerator Center (IUAC), New Delhi is grate-
fully acknowledged. Authors are thankful to BARC for providing
neutron irradiation facility and Dr. R. Thangaraj, Professor, Depart-
ment of Applied Physics, Guru Nanak Dev University, Amritsar for
his valuable suggestions for spectral analysis. Mr. T.M. Singh is
acknowledged for the help provided during the grinding and pol-
ishing of the glass samples.
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