Journal of Non-Crystalline Solids 240 (1998) 144±153

Infrared spectra of sodium phosphate glasses

Y.M. Moustafa *, K. El-Egili
Glass Research Group, Physics Department, Faculty of Science, Mansoura University, Mansoura 35516, Egypt
Received 18 November 1997; received in revised form 23 March 1998

Abstract
Infrared absorption spectra of sodium phosphate glasses, Na2 O ˆ 30±50 mol%, have been studied in the region of
400±2000 cmÿ1 . Spectra were analyzed to determine the relative intensity of the IR bands responsible for the di€erent
phosphate units. Spectral analyses has shown that the substitution of P2 O5 by Na2 O in¯uences the intermediate range
order of the glass matrix. Increasing Na2 O content leads to a gradual degradation of the phosphate ring type structures,
with consequent depolymerization causing compaction of the glass matrix. Analyses of IR spectra illustrates the re-
organization e€ects of Na2 O in the phosphate matrix. Ó 1998 Elsevier Science B.V. All rights reserved.

1. Introduction (DBO). Although the structure of P2 O5 glasses is

Many transition-metal, alkali-, alkaline- and
rare earth oxides form glasses when melted with
P2 O5 . Phosphate glasses are technologically im-
portant materials because they generally have
higher thermal expansion coecients, lower tran-
sition temperature, and higher electric conductiv-
ity than silicate and borate glasses [1]. These
glasses have considerable potential for application
in optical data transmission, solid state batteries,
sensing and laser technologies.
The network of phosphate glasses contains a
polymeric structure that is controlled by the glass
composition in rough agreement with the predic-
tions of Zachariasen [2], Van Wazer [3] and Flory
[4]. This network is dominated by linkages be-
tween PO4 tetrahedra. In the case of vitreous P2 O5 ,
these groups are connected to adjacent units by
three of their four vertices; one place is occupied
by a terminal, double-bonded oxygen atom
*
Corresponding author. Tel.: +20-50 359 363; fax: +20-50 346
781; e-mail: sinfac@mum.mans.eun.eg.
modi®ed with the addition of alkali oxides, the
phosphorous retains fourfold coordination
throughout the full composition range from pure
P2 O5 to the fully alkali oxide saturated ortho-
phosphate MPO4 [5]. Structural units that can be
built from individual phosphorous centres were
described by Van Wazer [6]. As alkali oxide is
added to P2 O5 , the phosphate structural groups
passes from Q3 to Q2 to Q1 to Q0 as the molar ratio
of alkali oxide to P2 O5 , R ˆ M2 O/P2 O5 , passes
from 0 to 1 to 2 to ®nally 3. These modi®cations
are similar to those taking place in a silicate net-
work upon the addition of alkali oxide.
Among the vibrational methods that have been
used to study the glass structure are Raman and
infrared spectroscopy. Although, Raman studies
are more numerous, this may be because absorption
bands are narrower than IR bands and bulk sam-
ples can be examined in Raman while special sample
preparation techniques are required for IR because
of the large absorption coecient, 106 /cm [5].
Several authors have applied infrared spectros-
copy to explain some structural aspects of

0022-3093/98/$ ± see front matter Ó 1998 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 9 8 ) 0 0 7 1 1 - X
 Y.M. Moustafa, K. El-Egili / Journal of Non-Crystalline Solids 240 (1998) 144±153 145

phosphate glasses [7±14]. However, little systematic This linear chain structure results in cleavage of P±
work has been done to identify structural units in O±P linkages and the creation of NBOs in the
such glasses, to determine structural changes over a glass. Calcium ions can serve as ionic cross-links
wide range of composition or to correlate these between the NBOs of two di€erent chains:
changes with the physical properties [7,15±17]. In
most of those studies analyses of IR spectra of
glasses were qualitative based on the assignment
and shift of infrared absorption bands. However,
recently, some authors [18±21] paid attention to the
quantitative analyses of IR spectra of glasses. They
used the deconvolution method for analyzing the
infrared spectra of borate glasses to determine the
concentration of borate structural units. Recently
[20,21] we determined the relative concentration of
the di€erent borate structural units as well as the
fraction of four coordinated boron, N4 . Deconvo-
lution of IR spectra can be considered a useful tool
to extract information about borate glass structure
rather than the traditional analyses of IR spectra. The Q-site model proposed by Lippma et al.
The present work was aimed to illuminate the [26] which previously described the structures of
structure of binary sodium phosphate glasses, with binary silicate glasses has been applied for the ®rst
special attention to the validity of using the band time to phosphate glasses [6]. The possible reor-
deconvolution analyses of IR spectra to follow the ganized structural groups are
structural changes of such glasses.

2. Review of structure and associated IR spectra

Kordes et al. [22,23] were the ®rst to consider

the formation of non-bridging oxygens, NBOs, in
phosphate glasses and they proposed the forma-
tion of di€erent phosphate structural groups dur-
ing the reorganization processes accompanying the
addition of modi®er oxide. They assumed that the
doubly bonded oxygens remain and a one to one
correspondence exists between the number of al-
kali added and the number of NBOs created.
The ®rst addition of alkali or alkaline earth-
oxides such as Na2 O or CaO to P2 O5 glasses re-
sults in conversion of the three-dimensional net-
work, to linear phosphate chains [24,25]:
where Qs are the site models. The phosphate
structural groups pass from Q3 to Q2 to Q1 to Q0
as the ratio M2 O/P2 O5 ˆ R passes from 0 to 1, 2
and ®nally to 3. These di€erent groups participate
in the structure to an extent depending on com-
position. The relative amount of individual units,
at each alkali oxide content, adjust themselves to
satisfy the simultaneous equilibria:
146 Y.M. Moustafa, K. El-Egili / Journal of Non-Crystalline Solids 240 (1998) 144±153
Martin [5] determined experimentally the fraction
of the individual Q-species present as a function of
M2 O fraction according to the Van Wazer equi-
librium model [3,6]. Using 31 P and 23 Na magic
angle spinning nuclear magnetic resonance (MAS
NMR) spectroscopy for sodium phosphate glasses,
Brow et al. [27] concluded that the Q-site distri-
bution depends directly on the (Na+H)/(P) ratio
and not on the (Na)/(P) ratio. This implies that
H2 O must be treated as an additional glass modi-
®er, where all or most of the water is present as
terminal ±OH groups and not as H2 O molecules.
This behaviour is in contrast for silicate glasses
where the composition dependence of Q-site dis-
tribution in sodium phosphate glasses according to
this treatment was found to be in agreement with
that calculated by Van Wazer [6].
Interpretation of the 31 P MAS and 11 B NMR
results [19] suggests the existence of several envi-
ronments to the boron and phosphorus atoms. The
di€erent phosphate units are: the middle (MP), end
(EP), and monomer (MO). The middle unit
(O2=2 POÿ2 ), is usually called the metaphosphate
unit. This unit is connected with two phosphorus
atoms and the end unit (O1=2 PO2ÿ3 ) is connected to
one phosphorus atom. The monomer unit (PO3ÿ 4 ) is
not connected with any phosphorus atoms. These
units are represented by Ducel et al. [28]:
Most research on the vibrational spectroscopy
of phosphate crystals [29] and glasses [30,31] treat
information on their structures obtained in terms
of the oxygen bridges and terminal groups rather
than in terms of polyhedra, or Qn species. Among
various phosphate polyhedra, the isolated (PO2 )3ÿ
orthophosphate anion is the only one inseparable
into dynamically independent groups and there-
fore its vibrations can be treated as a whole. No-
tably, it is the (PO2 )ÿ , (PO3 )2ÿ , and (PO4 )3ÿ
groups, rather than the separate P@O and P±Oÿ
groups, that manifest themselves in the vibrational
spectra of meta-, pyro-, and orthophosphate and
also of phosphate glasses related to the corre-
sponding composition ranges. Based on the above
view, the vibrational spectrum characteristic of
pyrophosphate anion comprises bands related to
the stretching vibrations of (PO3 )2ÿ groups and the
P±O±P bridges, the same phosphorus atoms par-
ticipating in the vibrations of both these frag-
ments. The spectral characteristic of quasi-in®nite
metaphosphate chains comprise bands related to
the stretching vibrations of the (PO2 )ÿ terminal
groups and the P±O±P bridge. Therefore, the
spectral characteristic of any anions intermediate
in chain length comprise bands related to the
stretching vibrations of both the above terminal
groups and the P±O±P bridge, see Ref. [31] and
references therein.
The asymmetric and symmetric stretching vi-
brations characteristic of phosphate lattices are
active in both the IR and Raman spectra. The
Raman spectra are dominated by intense bands
related to the symmetric stretches, whereas the IR
spectra are dominated by intense bands related to
asymmetric stretches. Most studies devoted to the
vibrational spectra of phosphate glasses assume
the assignments of principal bands correspond to
those known for the normal modes in the vibra-
tional spectra of crystalline phosphates. Literature
data on the frequency ranges related to the cor-
responding vibrations of the above structural
groups in various crystalline phosphate and also in
alkali- and alkaline-earth oxide phosphate glasses
are listed in Table 1.
3. Experimental
Binary sodium phosphate glasses in the system
xNa2 O:(100 ) x)P2 O5 , where x ˆ 30, 40, 45 and 50
 Y.M. Moustafa, K. El-Egili / Journal of Non-Crystalline Solids 240 (1998) 144±153 147

Table 1
Frequency ranges characteristic of the IR and/or Raman bands related to the stretching vibrations of various phosphate structural
groups [31]
Structural group Frequency ranges of feature locations, cmÿ1
Asymmetric stretches Symmetric stretches
Crystals Glasses Crystals Glasses
P±O±P bridge 850±1060 840±1050 650±800 690±800
(PO4 )3ÿ anion 980±1100 980±1020 920±970 940±950
(PO3 )2ÿ terminal group 1030±1230 1080±1120 940±1090 1020±1050
(PO2 )ÿ terminal group 1140±1320 1080±1330 1000±1170 1020±1200

mol%, were prepared using reagent grade Na2 CO3 , were made in duplicate with maximum error of
and NH4 H2 PO4 as starting materials. NH4 H2 PO4 ‹0.03 g/cm3 .
was ®rst heated in a porcelain crucible at 300°C for
about 30 min in order to evaporate water and
ammonia. Na2 CO3 was then added and the mix- 4. Results
ture was melted in an electric furnace between
900°C and 950°C for 30 min, depending on the Typical infrared spectra of sodium phosphate
composition. After swirling several times and glasses are shown in Fig. 1. The plots have been
complete melting, the melt was quenched on an positioned in such a way to compare the modi®-
iron plate. Samples obtained were homogenous cations accompanying for the replacement of P2 O5
and transparent. by Na2 O. As seen from this ®gure, the frequencies
Infrared spectra were recorded on a Mattson of predominant absorption peaks (based on visual
5000 FTIR spectrometer in the range 400±2000 judgment) are characterized by; a broad peak near
cmÿ1 . The measurements were made on glass 500 cmÿ1 , a weak peak around 600 cmÿ1 , doublets
powder, immediately after glass preparation, dis- in the regions 630±830 cmÿ1 and 850±1060 cmÿ1 , a
persed in KBr pellets (1 wt%). All spectra were peak at 1100 cmÿ1 , weak peak at 1220 cmÿ1 and a
measured at room temperature with 4 cmÿ1 reso- strong broad peak around 1300 cmÿ1 .
lution. The spectra exhibit a weak band in the
region 1600±1660 cmÿ1 , which demonstrates the
presence of small amounts of water absorbed from
air moisture during the preparation of the pellets
for infrared measurements (Table 2).
The density of the glasses were measured at
room temperature using Archimedes method with
Xylene as the immersion liquid. All measurements

Table 2
Composition of studied glasses in mol%, water content and
density
Glass no. Na2 O P2 O5 Water content Density
(%) (gm/cm3 )
g1 30 70 0.63 2.431 ‹ 0.02
g2 40 60 1.95 2.489 ‹ 0.02
g3 45 55 1.09 2.522 ‹ 0.03
Fig. 1. Infrared absorption spectra of the xNa2 O-(100-x)P2 O5
g4 50 50 3.95 2.521 ‹ 0.03
glass system with x ˆ 30, 40, 45 and 50 mol%.
148 Y.M. Moustafa, K. El-Egili / Journal of Non-Crystalline Solids 240 (1998) 144±153

The intensity of the band near 500 cmÿ1 in-

creases and its centre shifts towards lower wave
number with increasing Na2 O content. The weak
band at 600 cmÿ1 for glass containing 30 mol%
Na2 O grows and becomes slightly shifted for
glasses containing higher Na2 O content and a new
well resolved band is observed at about 830 cmÿ1 .
The doublet in the frequency region 850±1060
cmÿ1 becomes broader and shifts towards higher
wave number with increasing Na2 O content. The
intensity of the peak at about 1200 cmÿ1 decreases
with increasing Na2 O content and vanishes for the
glass containing 50 mol% sodium oxide, while the
strong one at about 1300 cmÿ1 becomes stronger
and shifts towards higher wave number. The latter
band becomes broader with increasing Na2 O
content. From Fig. 1, it is dicult to extract new
information about the modi®cations of the glassy
matrix, except that reported in the literature
[15,16] which depend on the type and/or content of
the alkali oxide in the phosphate glasses. There-
fore, we have deconvoluted the IR spectra of the
glasses studied to determine the parameters of the
absorption bands, which may be sensitive to the
intermediate range order changes in the glassy
matrix. Details about the deconvolution tech-
niques and given elsewhere [20].
Infrared spectra seem to consist of relatively
broad absorption bands (Fig. 1). The breadth may
re¯ect the structural disorder of the di€erent
phosphate structural groups. These groups may be
interconnected in several ways increasing the
number of allowed vibrational modes; conse- Fig. 2. (a) The band deconvolution of IR spectra for glass
quently, the absorption peaks become broad. By a containing 45 mol% Na2 O in the spectral region: (a) 400±850
careful inspection of the maxima and shoulders, it cmÿ1 , (b) 850±1400 cmÿ1 , where n n n denotes the experimental
has been found that a deconvolution using the data, . . . denotes the simulated band components and ±±± de-
notes the envelop of the simulated spectrum.
same number of peaks at approximately the same
frequencies yields quite acceptable results. The
Gaussian functional form for all the bands in the reveals a number of absorption bands related to
spectra gives the best ®t with the residuals in ®tting di€erent vibrational modes of the phosphate
always less than 3%. structural groups. The relative intensity of each
Fig. 2 represents an example of the results of component band, In , has been calculated from
peak deconvolution of the IR spectrum of a glass In ˆ Sn =St ; where Sn represents the area of the
containing 45 mol% Na2 O. By using the decon- component band n and St is the area under the
volution analyses of IR spectra the position, am- whole spectrum in the frequency region between
plitude, full width at half maximum (FWHM) and 400 and 1330 cmÿ1 .
the area of each component band were determined The calculated values of In for the studied
for the studied glasses. The deconvolution data glasses are listed in Table 3.
 Y.M. Moustafa, K. El-Egili / Journal of Non-Crystalline Solids 240 (1998) 144±153 149

Table 3
Inherent frequencies and relative intensities of the IR active modes of xNa2 O±(100-x)P2 O5 glasses, x in mol% (the experimental error in
the peak centre (PC) is ‹4 cmÿ1 and ‹3% for the relative intensity (I))
Frequency regions in cmÿ1 x ˆ 30 x ˆ 40 x ˆ 45 x ˆ 50
PC I PC I PC I PC I
458±488 458 16.4 462 17.4 473 33.4 488 17.9
500±543 500 4.7 516 10.9 534 7.4 543 9.1
630±681 681 13.2 680 1.0 630 0.3 666 1.5
715±730 725 4.1 716 6.6 721 3.1 728 13.7
785±830 830 1.2 800 2.7 795 0.8 785 2.3
898±908 908 2.2 905 5.9 900 6 898 11.79
935±960 935 16.2 938 7.1 958 2.2 ± ±
1005±1030 1022 24.8 1028 14.2 1030 10.7 1026 8.34
1100±1130 ± ± 1130 6.0 1109 5.7 1099 11.3
1194±1210 1209 3.1 1216 1.0 1194 1.4 ± ±
1270±1297 1297 4.5 1297 9.6 1283 12.8 1270 17.8
1306±1341 1330 5.2 1341 13.4 1330 15.2 1306 4.0

5. Discussion when Na2 O is increased. By inspection of the

IR analyses reveals that the low frequency en-
velope around 450±530 cmÿ1 consists of more than
one absorption peak. The envelope in the range
450±530 cmÿ1 is resolved into two component
bands at 458 and 500 cmÿ1 . A shift towards
higher frequencies of both component bands was
observed on increasing Na2 O content (Table 3). It
was reported [14,32] that the band at about 466±
475 cmÿ1 is assigned as the bending vibration of
O±P±O units, d(PO2 ) modes of (POÿ 2 )n chain
groups, and the band at 500 cmÿ1 is described as
a fundamental frequency of (PO3ÿ 4 ) [33] or as
harmonics of P@O bending vibration [32]. The
band at about 537 cmÿ1 was assigned to O@P±O
bending vibration [34] and the bands in the region
400±600 cmÿ1 may be attributed to the bending
vibrations of bridging phosphorous such as O±P±
O and/or O@P±O. The amount of bridging phos-
phorous, as indicated by the relative area shows a
maximum value for the glass containing 45 mol%
Na2 O. The considerable change in the amount of
these bridges may re¯ect the modi®cation in the
glass structure due to the depolymerization of the
phosphate matrix with increasing Na2 O content
from 30 to 50 mol%.
It is interesting to observe that the relative area
of the IR feature at 680 cmÿ1 has predominant
value for the glass containing 30 mol% Na2 O and
drastically vanishes and shifts to lower frequencies
values of the relative area of this band (Table 3) it
can be assigned to the bending vibration of P@O
units [35] and not to symmetric vibration of POÿ 2
groups, ts (O±P±Oÿ ) having an ionic character, as
reported by Bridge et al. [7] and Grith [36]. This
attribution is based on the assumption that in-
creasing Na2 O content leads to a breakdown of
some terminal bonds (P@O) in the glass network.
Such alteration in the structure decreases the bond
strength, consequently the peak centre is shifted
towards lower wave number as observed.
The frequency region 700±830 cmÿ1 was re-
solved to two component bands at 725 and 830
cmÿ1 . The band at 830 cmÿ1 has small relative
area, and dramatically shifts towards lower fre-
quency (830 ® 785 cmÿ1 ). A similar shift was also
observed for the band at 725 cmÿ1 . The relative
area of the latter is relatively high and composition
independent. These two components may be at-
tributed to the symmetric stretching vibration of
P±O±P rings [37±40]. The variation of the fre-
quency of P±O±P bonds with increasing Na2 O
content is in consistent with breakage of cyclic
P±O±P bonds in the glass when the sodium oxide
act as network modi®er.
The IR absorption in the region 850±1200 cmÿ1
was found to be sensitive for the di€erent meta-
phosphate groups in the form of chain-, ring-,
terminal groups [18,19]. The spectral analyses of
this region shows the existence of ®ve bands: 908,
150 Y.M. Moustafa, K. El-Egili / Journal of Non-Crystalline Solids 240 (1998) 144±153
Fig. 3. The band deconvolution of IR spectra for glass con-
taining 30 mol% Na2 O for the spectral region 850±1250 cmÿ1 ,
where n n n denotes the experimental data, . . . denotes the
simulated band components and ±±± denotes the envelop of the
simulated spectrum.
935, 1022, 1130 and 1209 cmÿ1 , Fig. 3 (as an
example). The absorption band at 908 cmÿ1 is
attributed to asymmetric stretching vibration of P±
O±P groups linked with linear metaphosphate
chain [36,39,41], while that at 935 cmÿ1 is assigned
to asymmetric stretching of P±O±P groups linked
with large metaphosphate rings [19,42]. The strong
feature at 1022±1030 cmÿ1 is attributed to asym-
metric stretching of P±O±P groups, tas (P±O±P)
modes, linked with small metaphosphate rings as
cyclotriphosphate [P3 O3ÿ 9 ] or smaller rings [19].
The band at 1130 cmÿ1 is assigned to asymmetric
stretching of POÿ ÿ
2 group, tas (PO2 ) modes [37,40].
The considerable shift in the position of this band
toward lower wave number (1098 cmÿ1 ) and the
increase in its relative area with increasing Na2 O
content may be considered as an indication for the
formation of the terminal phosphate groups,
PO2ÿ3 . The absorption band at 1200 cm
ÿ1
has not
been observed before. This band may be consid-
ered as due to harmonics of the terminal groups.
The analyses of the IR spectra of the studied
glasses reveals that the total content of P±O±P
bridges with ring structures (935±1022 cmÿ1 ) de-
creases when increasing the Na2 O content (Fig. 4).
Fig. 4. E€ect of Na2 O on the relative intensities of bands re-
lated to metaphosphate chains (900 cmÿ1 ), metaphosphate
rings (935±1000 cmÿ1 ) and PO2ÿ
3 terminal groups (1130±1200
cmÿ1 ). Intensities were normalized with respect to the inte-
grated absorption of the deconvoluted bands in the wave
number region 850±1200 cmÿ1 . Lines are least squares ®ttings.
The decrease of the relative area of component
bands produced by such ring structures is a good
indication for the formation of terminal PO2ÿ 3
groups (1130±1200 cmÿ1 ) and P±O±P with chain
structure (900 cmÿ1 ). The occurrence of a contin-
uous breakdown of the ring type structures into
short arrangements such as small metachains and
terminal phosphate groups upon network depoly-
merization may also account for this behaviour.
This development decreases the average length of
phosphate chain structures.
The broad IR features at 1270±1290 cmÿ1 is
attributed to the stretching of the doubly bonded
oxygen vibration, tas (P@O) modes [43], while that
at 1330 cmÿ1 is related to the harmonics of the
above modes [7]. Osaka et al. [44] have shown that
the PO4 units have two bridging oxygen bonds
along with two non-bridging bonds such as P@O
and P±Oÿ , which are in resonance with each other.
Therefore, the IR spectra, as in the present study,
are split into two bands with a higher energy and
strong double bond character (1200±1340 cmÿ1 )
and a lower energy band with frequency at 1100±
1130 cmÿ1 . This means that the P@O double bond
 Y.M. Moustafa, K. El-Egili / Journal of Non-Crystalline Solids 240 (1998) 144±153 151

is more strongly localized in the central position
phosphate groups. This suggestion is con®rmed by
the larger relative intensity of the 1200±1340 en-
velop compared with that in the frequency region
1100±1130 cmÿ1 .
The frequency of P@O bridges is a€ected by the
water content (which is probably taken up during
the preparation of the plates for the IR measure-
ments). The relative intensity of the absorption
band responsible to the P±O±H bridges (1645
cmÿ1 ) was found to be less than 5% for all glasses
and increased slightly with increasing Na2 O
(Fig. 5). The shift to lower wave number of P@O
absorption band with increasing Na2 O content is
possibly due to the polarization e€ect of the
modifying cation (Na‡ ) and the P±O±H bonding.
Fig. 5. The dependency the relative intensities of bands related
to P@O (1270±1290 cmÿ1 ) and P±O±H (1600±1660 cmÿ1 ) bonds
on Na2 O content. Lines are drawn as guides for eye.
This suggestion is con®rmed by the appearance of
the pyrophosphate band at 1100±1130 cmÿ1 . Since
the formation of pyrophosphate groups in alkali
phosphate glasses begins to take place only when
the ratio of the modi®er to phosphorus oxide is
greater than unity. This implies that the absorbed
water modi®es the phosphate matrix together with
the Na2 O, consequently, the ratio ((Na2 O + H2 O)/
P2 O5 ) is greater than unity and the appearance of
the band related to pyrophosphate groups is ex-
pected. The change in the vibrational frequency of
pyrophosphate groups with increasing Na2 O con-
tent causes a decrease in the P±Oÿ vibration fre-
quency from 1130 to 1100 cmÿ1 . Table 4 includes
the general band assignments for IR bands (400±
1400 cmÿ1 ) for the studied glasses. These assign-
ments correspond only to the main contributions
of the observed bands.
The modi®cation in the metaphosphate struc-
ture, resulting from increasing Na2 O content in
glasses, can be interpreted in terms of the change
in charge density at the anionic site [19]. On in-
creasing the Na2 O content, some of the ring
structures (low condensed phosphate anions) open
and form smaller structures such as short chains
and terminal structures (high condensed phos-
phate anions). Thus, the charge density at the ring
structure sites may decrease while that at chain
structures and terminal sites may increase with
increasing Na2 O content. It is expected that in-
teraction between Na‡ ions and ring structure
metaphosphate site becomes weaker while that
between sodium ions and chain or terminal meta-
phosphate sites becomes stronger. This is con-
®rmed by observed shift to lower frequencies for
the bands responsible for P±O±P with ring struc-
tures (830 cmÿ1 ) and the shift in position of the

Table 4
IR band assignments in the 300±1400 cmÿ1 range for studied phosphate glasses
Range frequency cmÿ1 Band assignment
458±680 Bending vibrations of bridging phosphorus, d(O±P±O) and/or d(P@O)
715±830 Symmetric stretch of P±O±P bridges, ms (P±O±P)
880±1022 Asymmetric stretch of (P±O±P) bridges in metaphosphate con®gurations (Q2), mas (POÿ
2)
1100 Asymmetric stretch of (P±O±P) bridges in pyrophosphate groups (Q1), mas (PO2ÿ
3 )
1200 Symmetric stretch of (P@O) bonds, ms (P@O)
1260±1340 Asymmetric stretch of (P@O) bonds, mas (P@O)
152 Y.M. Moustafa, K. El-Egili / Journal of Non-Crystalline Solids 240 (1998) 144±153
bands corresponding to chain and terminal meta-
phosphate (Fig. 6).
The compactness in the glass matrix upon ad-
dition Na2 O (Fig. 7) is due to the increase of the
cross-link density of sodium ions either by dis-
rupting the bonds connecting neighbouring PO4
groups and/or by the conversion of metaphosphate
rings into chain and terminal ones. In this respect,
Fig. 6. The composition dependence of the centre of the IR
absorption bands for the studied glasses. Lines are drown as
guides for eye.
Fig. 7. The composition dependence of the molar volume of the
studied glasses. Line is least squares ®tting.
sodium ions provide ionic cross-linking between
the non-bridging oxygens of di€erent chains and/
or groups. This cross-linking increases the bond
strength of this ionic cross-link, consequently the
glass strength is expected to be improved. This
expectation is con®rmed with the observed de-
crease in the molar volume when Na2 O content is
increased (Fig. 7).
6. Conclusion
Spectral analyses shows that increasing Na2 O
content leads to a breakdown of the ring type
structures. Reorganization of intermediate range
order structures decreases the average phosphate
chain length due to the formation of monomer
phosphate units and terminal groups. The pre-
dominant factor a€ecting the frequency shift of the
absorption band corresponding to P@O bonds
was the polarization due to the modi®cation of
Na2 O and H2 O. Increasing Na2 O content de-
creases molar volume.
Acknowledgements
The authors thank Professor H. Doweidar,
Physics Department, Faculty of Science, Man-
soura University, for the discussion with him and
for his valuable comments on this manuscript.
Professor M. El-Shehawy, Chemistry Department,
Faculty of Science, Mansoura University, is
gratefully acknowledged for his available help
throughout this work.
References
[1] H.A.A. Sidek, I.T. Collier, R.N. Hampton, G.A. Saunders,
B. Bridge, Philos. Mag. B 59 (2) (1989) 221.
[2] W.H. Zachariasen, J. Am. Chem. Soc. 54 (1932) 3841.
[3] J.R. Van Wazer, J. Am. Chem. Soc. 72 (1950) 644.
[4] P.I. Flory, Principles of Polymer Chemistry, Cornell
University, Ithaca, NY, 1953.
[5] S.W. Martin, Eur. J. Solid State Inorg. Chem. 1 (1991) 163;
and references therein.
[6] J.R. Van Wazer, The Phosphorous and its Compounds,
vols. 1 and 2, Interscience, New York, 1951.
 Y.M. Moustafa, K. El-Egili / Journal of Non-Crystalline Solids 240 (1998) 144±153
[7] B. Bridge, N.D. Patel, J. Non-Cryst. Solids 91 (1987) 27.
[8] B.V. Chowdari, R. Gopalakrishnam, J. Non-Cryst. Solids
105 (1988) 269.
[9] N. Machida, Y. Shinkuma, T. Minami, J. Ceram. Soc. Jpn.
97 (1989) 1104.
[10] X. Pan, H. Zhao, Y. Bao, Solid State Ionic 28±30 (1988)
1470.
[11] N. Machida, Y. Shinkuma, T. Minami, Solid State Ionic 45
(1991) 123.
[12] N. Machida, Y. Shinkuma, T. Minami, T. Shigematsu, N.
Nakanishi, J. Electrochem. Soc. 139 (1992) 1380.
[13] N. Machida, S. Tsuchida, T. Minami, T. Shigematsu, N.
Nakanishi, J. Ceram. Soc. Jpn. 100 (1992) 104.
[14] P. Znasik, M. Jamnick, J. Non-Cryst. Solids 146 (1992) 74.
[15] M. Jamnick, P. Znasik, D. Tunega, M.D. Ingram, J. Non-
Cryst. Solids 185 (1995) 151.
[16] N. Machida, M. Chusho, T. Minami, J. Non-Cryst. Solids
101 (1988) 70.
[17] D.E.C. Corbridge, M.S. Pearson, C. Walling, Topics in
Grith, Interscience, New York, 1966, p. 254, 275.
[18] E.I. Kamitsos, A.P. Patsis, M.A. Karakassides, G.D.
Chryssikos, J. Non-Cryst. Solids 126 (1990) 52.
[19] E.I. Kamitsos, J.A. Kapoutsis, G.D. Chryssikos, J.M.
Hutchinson, A.J. Pappin, M.D. Ingram, J.A. Du€y, Phys.
Chem. Glasses 36 (3) (1995) 141.
[20] Y.M. Moustafa, H. Doweidar, G. El-Damrawi, Phys.
Chem. Glasses 35 (1994) 104.
[21] Y.M. Moustafa, A.K. Hassan, G. El-Damrawi, N.G.
Yevtushenko, J. Non-Cryst. Solids 194 (1996) 34; Y.M.
Moustafa, I.A. Gohar, A.A. Megahed, E. Mansour, Phys.
Chem. Glasses 38 (2) (1997) 92.
[22] E. Kordes, Z. Anorg. Allgem. Chem. 241 (1939) 1.
[23] E. Kordes, W. Vogel, R. Feterowsky, Z. Electrochem. 57
(4) (1953) 282.
[24] B.C. Bunker, G.W. Arnold, J.A. Wilder, J. Non-Cryst.
Solids 64 (1984) 291.
153
[25] Y.B. Peng, D.E. Day, Glass Technol. 5 (1991) 166.
[26] E. Lippma, M. Magi, A. Samoson, G. Englehardt, A.R.
Grimmer, J. Am. Chem. Soc. 102 (1980) 4889.
[27] R.K. Brow, R.J. Kirkpatrick, G.L. Turner, J. Non-Cryst.
Solids 116 (1990) 39.
[28] J.F. Ducel, J.J. Videau, K.J. Suh, J. Senegas, J. Alloys
Comp. 188 (1992) 157; Phys. Chem. Glasses 35 (1994) 10.
[29] G.T. Stranford, R.A. Condrate Sr., B.C. Cornilsen, J. Mol.
Struct. 73 (1981) 231.
[30] B.N. Nelson, G.J. Eharhos, J. Chem. Phys. 71 (1979) 2379.
[31] A.M. E®mov, J. Non-Cryst. Solids 209 (1997) 209; and
references theirein.
[32] A. Abdel-Kader, A.A. Higazy, M.M. Elkholy, J. Mater.
Sci.: Mater. Electron. 2 (1991) 157.
[33] K. Nakamoto, Infra-Red Spectra of Inorganic and Coor-
dination Compounds, Wiley, New York, 1963.
[34] P.P. Tasi, M. Greenblatt, J. Non-Cryst. Solids 103 (1988)
101.
[35] U. Selvaraj, K.J. Rao, J. Non-Cryst. Solids 72 (1985) 315.
[36] W.P.G. Grith, J. Chem. Soc. A (1967) 905.
[37] M.C.R. Shastry, K. Rao, J. Spectrochim. Acta A 46 (1990)
1581.
[38] J.P. Malugani, R. Mercier, Solid State Ionics 13 (1984) 293.
[39] G.J. Exarhos, in: G.E. Walrafen, A.G. Revez (Eds.),
Structure and Bonding in Non-Crystalline Solids, Plenum,
New York, 1986, p. 203.
[40] M. Scagliotti, M. Villa, G. Chiodelli, J. Non-Cryst. Solids
93 (1987) 350.
[41] A. Rulmont, R. Cahay, M. Liegeois-Duychaerts, P. Tarte,
Eur. J. Solid State Inorg. Chem. 28 (1991) 207.
[42] D.E.C. Corbridge, E.J. Lowe, J. Chem. Soc. 57 (1954)
4555.
[43] B.V.R. Chowdari, K.I. Tan, W.T. Chia, R. Gopalakrish-
nam, J. Non-Cryst. Solids 119 (1990) 95.
[44] A. Osaka, K. Takahashi, M. Ikeda, J. Mater. Sci. Lett. 3
(1984) 36.