with the increase in molar volume (Vm) (i.e.

open structure) and increase in oxygen

molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+

ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no

anomalous structural changes with

increasing TeO2 concentration

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

and then decreases with the content

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

increases.
density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the

increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial

distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:
V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V m , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening

of the glass. The largest negative value of

Vm

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,

the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

increases.
density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

case, where the molar

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

ions per

by WO3, the molar volume should

cations per unit found for A2O are replaced by a single cation

in WO3. e increase of molar volume in tungsten-glasses

suggests that the excess of

oxygen, due to the substitution of

additional

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to

structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the

glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density

and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or

any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar

volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

maxima. [1757]

which also

the presence of the density

Calculation of molar volume enables packing density of the glass to be examined

independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

the glass structure

[3112]

the cross-linking between the

Generally,

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

elsewhere for other glass systems [4318]

variation density that occurs with increasing

by

of phosphorus by

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar


molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar
volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion

of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a

function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values

When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease

in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

decreases linearly

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

Generally,

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

this

of phosphorus by

trends for densities and molar

elsewhere for other glass systems [4318]

It is clear that by increasing PbO, the molar volume increases,

variation density that occurs with increasing
glass network interstitially;
by

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.

Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four

fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:
V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of

boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume

relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]

***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

and then decreases with the content

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

[2340]

increases.

stabilize the glass structure

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of

the O/P ratio, figures 10 and 11

respectively. The continuous

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to

the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in

oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.

Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

which also

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

ions per

by WO3, the molar volume should

cations per unit found for A2O are replaced by a single cation

in WO3. e increase of molar volume in tungsten-glasses

oxygen, due to the substitution of
additional

case, where the molar

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

elsewhere for other glass systems [4318]

variation density that occurs with increasing

by

of phosphorus by

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation

[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.

For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:
V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V m , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

Vm

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.
(2004) 729734)
****

Mostafa et al. / Solid State Communications 131

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****

alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]

This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

Generally,

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

this

of phosphorus by

lead causes an expansion of the network. Similar

volumes have already been reported

trends for densities and molar

elsewhere for other glass systems [4318]

It is clear that by increasing PbO, the molar volume increases,

variation density that occurs with increasing
glass network interstitially;
by

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative

understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network

indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+

ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no

anomalous structural changes with

increasing TeO2 concentration

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

and then decreases with the content

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

increases.
density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the

increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial

distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:
V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V m , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening

of the glass. The largest negative value of

Vm

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,

the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

increases.
density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

case, where the molar

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

ions per

by WO3, the molar volume should

cations per unit found for A2O are replaced by a single cation

in WO3. e increase of molar volume in tungsten-glasses

suggests that the excess of

oxygen, due to the substitution of

additional

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to

structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the

glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density

and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or

any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar

volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

maxima. [1757]

which also

the presence of the density

Calculation of molar volume enables packing density of the glass to be examined

independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

the glass structure

[3112]

the cross-linking between the

Generally,

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

elsewhere for other glass systems [4318]

variation density that occurs with increasing

by

of phosphorus by

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar


molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar
volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion

of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a

function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values

When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease

in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

decreases linearly

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

Generally,

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

this

of phosphorus by

trends for densities and molar

elsewhere for other glass systems [4318]

It is clear that by increasing PbO, the molar volume increases,

variation density that occurs with increasing
glass network interstitially;
by

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.

Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four

fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:
V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of

boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume

relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]

***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

and then decreases with the content

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

[2340]

increases.

stabilize the glass structure

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of

the O/P ratio, figures 10 and 11

respectively. The continuous

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to

the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in

oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.

Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

which also

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

ions per

by WO3, the molar volume should

cations per unit found for A2O are replaced by a single cation

in WO3. e increase of molar volume in tungsten-glasses

oxygen, due to the substitution of
additional

case, where the molar

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

elsewhere for other glass systems [4318]

variation density that occurs with increasing

by

of phosphorus by

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation

[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.

For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:
V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V m , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

Vm

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.
(2004) 729734)
****

Mostafa et al. / Solid State Communications 131

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****

alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]

This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

Generally,

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

this

of phosphorus by

lead causes an expansion of the network. Similar

volumes have already been reported

trends for densities and molar

elsewhere for other glass systems [4318]

It is clear that by increasing PbO, the molar volume increases,

variation density that occurs with increasing
glass network interstitially;
by

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative

understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network

indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+

ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no

anomalous structural changes with

increasing TeO2 concentration

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

and then decreases with the content

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

increases.
density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the

increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial

distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening

of the glass. The largest negative value of

Vm

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,

the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

increases.
density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

case, where the molar

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

ions per

by WO3, the molar volume should

cations per unit found for A2O are replaced by a single cation

in WO3. e increase of molar volume in tungsten-glasses

suggests that the excess of

oxygen, due to the substitution of

additional

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to

structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the

glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density

and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or

any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar

volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

maxima. [1757]

which also

the presence of the density

Calculation of molar volume enables packing density of the glass to be examined

independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

the glass structure

[3112]

the cross-linking between the

Generally,

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

elsewhere for other glass systems [4318]

variation density that occurs with increasing

by

of phosphorus by

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar


molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar
volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion

of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a

function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values

When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease

in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

decreases linearly

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

Generally,

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

this

of phosphorus by

trends for densities and molar

elsewhere for other glass systems [4318]

It is clear that by increasing PbO, the molar volume increases,

variation density that occurs with increasing
glass network interstitially;
by

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.

Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four

fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:
V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of

boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume

relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]

***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

and then decreases with the content

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

[2340]

increases.

stabilize the glass structure

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of

the O/P ratio, figures 10 and 11

respectively. The continuous

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to

the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in

oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.

Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

which also

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

ions per

by WO3, the molar volume should

cations per unit found for A2O are replaced by a single cation

in WO3. e increase of molar volume in tungsten-glasses

oxygen, due to the substitution of
additional

case, where the molar

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

elsewhere for other glass systems [4318]

variation density that occurs with increasing

by

of phosphorus by

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation

[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.

For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:
V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V m , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

Vm

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.
(2004) 729734)
****

Mostafa et al. / Solid State Communications 131

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****

alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]

This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

Generally,

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

this

of phosphorus by

lead causes an expansion of the network. Similar

volumes have already been reported

trends for densities and molar

elsewhere for other glass systems [4318]

It is clear that by increasing PbO, the molar volume increases,

variation density that occurs with increasing
glass network interstitially;
by

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative

understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network

indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+

ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no

anomalous structural changes with

increasing TeO2 concentration

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

and then decreases with the content

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

increases.
density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the

increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial

distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:
V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V m , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening

of the glass. The largest negative value of

Vm

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,

the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

increases.
density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

case, where the molar

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

ions per

by WO3, the molar volume should

cations per unit found for A2O are replaced by a single cation

in WO3. e increase of molar volume in tungsten-glasses

suggests that the excess of

oxygen, due to the substitution of

additional

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to

structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the

glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density

and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or

any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar

volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

maxima. [1757]

which also

the presence of the density

Calculation of molar volume enables packing density of the glass to be examined

independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

the glass structure

[3112]

the cross-linking between the

Generally,

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

elsewhere for other glass systems [4318]

variation density that occurs with increasing

by

of phosphorus by

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar


molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar
volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion

of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a

function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values

When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease

in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

decreases linearly

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

Generally,

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

this

of phosphorus by

trends for densities and molar

elsewhere for other glass systems [4318]

It is clear that by increasing PbO, the molar volume increases,

variation density that occurs with increasing
glass network interstitially;
by

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.

Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four

fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:
V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of

boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume

relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]

***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

and then decreases with the content

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

[2340]

increases.

stabilize the glass structure

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of

the O/P ratio, figures 10 and 11

respectively. The continuous

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to

the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in

oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

Vm

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.

Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

which also

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

ions per

by WO3, the molar volume should

cations per unit found for A2O are replaced by a single cation

in WO3. e increase of molar volume in tungsten-glasses

oxygen, due to the substitution of
additional

case, where the molar

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

elsewhere for other glass systems [4318]

variation density that occurs with increasing

by

of phosphorus by

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation

[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.

For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:
V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V m , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

Vm

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.
(2004) 729734)
****

Mostafa et al. / Solid State Communications 131

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+
ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****

alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no
increasing TeO2 concentration

anomalous structural changes with

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]

This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

and then decreases with the content

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

increases.

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

Generally,

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

this

of phosphorus by

lead causes an expansion of the network. Similar

volumes have already been reported

trends for densities and molar

elsewhere for other glass systems [4318]

It is clear that by increasing PbO, the molar volume increases,

variation density that occurs with increasing
glass network interstitially;
by

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative

understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the
increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network

indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial
distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

E
molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:

V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V Em , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of

V Em

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.
Since the molar volume represents the spatial distribution of the structural units and ions in a
glass network, therefore it deals directly with the spatial structure of the glass. So, it is better
to discuss the observed changes in a glass structure in terms of its molar volume. The
calculated molar volume values (Table 4) show approximately a stable value for each glass
system, and this reflects an approximate structural stability for the obtained glassy phase.
This can be taken as an evidence for the supposition that there is no any crystalline phase or
any precipitated phase appeared anywhere. (A.G.

Mostafa et al. / Solid State Communications 131

(2004) 729734)
****

with the increase in molar volume (Vm) (i.e. open structure) and increase in oxygen
molar volume (VO) due to the addition of Al2O3 as a glass former at the expense of Na2O
(see Table 2), caused the decrease in N4 value and consequently the decrease in all elastic
moduli values
When the volume change occurs without change in the nature of the bonding or change in the
coordination polyhedra, (Ke)(Vm) plots generally are linear, as shown in Fig. 9.
The observed increase in bulk modulus in spite of the decrease in volume shows that in
addition to volume, the type of bonding is also important in determining the composition
dependence of bulk modulus in these glasses. Therefore, the increase in bulk modulus with
ZnO content in the aluminium sodium diborate glass network led one to conclude that Zn2+

ions try to form ring structures in the form of regular ZnO4 tetrahedral coordination as a
network former [16], and compensate for the decrease in the average coordination number of
boron atoms (the decrease in N4 values). Such an increasing bulk modulusvolume
relationship was observed in some other types of glasses [ M.S. Gaafar et al. / Journal of Alloys and Compounds
475 (2009) 535542 ]

***
This decrease is associated with a decrease in the number of non-bridging oxygens and with a
contracting effect of the network due to the formation of Fig. [GeO6] structural units which
are slightly larger in size than the [GeO4] species. For the sample with x10 mol% MoO3,
the formation of [GeO6] octahedral structural units in the network results in better packing
and hence the increase of density. [492]
****

decrease in the density; this is indicative of decreasing structural compactness of the

material. In general, the structural compactness, the modification of the geometrical
configuration of the glassy network, the change in the coordination of the glass forming ions
and the fluctuations in the dimensions of the interstitial holes are the factors that influence the
density of the glass ceramic material [493]
***
The replacement of an intermediate/modifier CdO with Na2O which is a modifier only,
develops more nonbridging oxygen than bridging oxygen in the glass network.17,18 The
development of nonbridging oxygen may inflate the glass system and thus increases its molar
volume. The increase in molar volume may cause decrease in oxygen packing density and
mass density [582]
****
alkali metal oxide cleaves the structure and disturbs the bonding between glass forming
cations and oxygen anions. This increases the number of nonbridging oxygens and thus
develops a more open structure. Consequently, the expansion of the structure increases the
molar volume which causes a decrease in the oxygen packing density and hence a decrease
in the density of the glass sample. The decrease in oxygen packing density along with the
decrease of mass density and increase of molar volume of these glasses make them less
resistive mechanically. This may

have caused an increase in the coefficient of linear

expansion and decrease in the transition temperature and the softening temperature [585]
****
The observed nearly linear compositional dependences of the density and molar volume on
TeO2 content (see Table 1) indicates that there are no

anomalous structural changes with

increasing TeO2 concentration

in the glasses. The observed decrease in the molar volume

can be attributed to an increase of the atom packing density in the glass network [976]
***
From

the structural point of view, the molar volume, V M=r;

weight of the glass and r the mass

density, has frequently been used [6,7]. Molar volume is

more sensitive to structural differences between glasses than

normalises for atomic weights of
the

where M is the molecular

to density because it

different glass constituents. This normalisation leads to

non-linearity observed in the variation of the molar volume [1090]

The systematic decrease in molar

glass network,

volume indicates that the silver ions do not expand the

instead filling the free volume within the glass structure,

contributes to the increase in glass density

[1377]

The observed decrease in the molar volume (Fig. 7) with

indicates a decrease in the free space in
strengthens the

which also

increasing alumina content

the glass. This is consistent with reports that Al31

glass network by cross-linking phosphate chains.16,38,39 The competition

between weight and volume effects may be responsible for

the presence of the density

maxima. [1757]
Calculation of molar volume enables packing density of the glass to be examined
independent of effects of ion mass.The increase in molar volume suggests the increased free
space within the glass structure [1944]
This behavior

is generally observed when increasing the content of amodifier

metaphosphate glasses. The change in density of such systems

the formed structural units when
decreases linearly

oxide in

is related to the density of

introducing the modifier oxide. The molar volume VM

with increasing the content, confirming that the copper does

reticule the network. [2323]

The density of these glasses first increases
of TiO2 while

corresponding molar volume first decreases and then

The density of these glasses should decrease

weight P2O5 by

and then decreases with the content

due to replacement of high molecular

low molecular weight TiO 2. But it is found that the

these glasses increases with addition of TiO 2

decreases, indicating

increases.
density of

and correspondingly molar volume

that the titanium polyhedra form some new

interconnections within the structural network and thus

stabilize the glass structure

[2340]

thus the addition of WO3 can

the

promote a relatively open structure causing an increase in

molar volume. is behaviour was observed in the present

volume of the glass systems increases

suggesting that
n

with the growth of the WO3 concentration,

the molecular volume is inuenced by the number of O 2

unit of volume. Apparently, while substituting A2O

decrease because two

cations per unit found for A2O are replaced by a single cation

oxygen, due to the substitution of

suggests that the excess of

Li2O or Na2O by WO3, induces the formation of

nonbridging oxygen and/or the formation of voluminous

tungsten structural units such as WO6/NbO6

density and the calculated molar

(tabulated in Table 1) which clearly indicates network

expansion on account of participating magnesium ions in

the network connectivity.

the glassy matrix and increase

Such asymmetric bridging oxygen formation leads to a

length shortening of the phosphate chains and strengthen

shorter phosphate chains in

Generally,

the glass structure

the cross-linking between the

[3112]

the density and the molar volume show opposite behaviors, but in

study, different resultswere obtained. In this glass, the substitution

lead causes an expansion of the network. Similar
volumes have already been reported

of phosphorus by

elsewhere for other glass systems [4318]

variation density that occurs with increasing

glass network interstitially;

which is similar to the

PbO content. The Pb ions may enter the

hence, some network P\O\P bonds are broken and replaced

ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,

one assumed that the only effect of adding Pb cations was to

P\O\P bonds, then an increase in the
expected for the entire

this

trends for densities and molar

It is clear that by increasing PbO, the molar volume increases,

by

niobium and/or

octahedron in the glass network. [2472]

This explanation is in line with the results of the

volume of the glasses

ions per

by WO3, the molar volume should

in WO3. e increase of molar volume in tungsten-glasses

additional

case, where the molar

if

break down the network

molar volume with PbO content would be

vitreous range of the studied glass system. [4318]

This simplified structural model is consistent with the results of the oxygen molar volume,
Vom, and the PDof the studied glasses as a function of
respectively. The continuous

the O/P ratio, figures 10 and 11

decrease in Vom and the slight increase of PD confirm the

gradual reduction in the concentration of bridging POP bonds with an increasing O/P ratio
[522]
Volumetric studies
Volumetric properties of the glasses are vital for understanding the microscopic
structural transformations in the glass matrix [69]. Molar volume is more sensitive to
structural differences between glasses than to density because it normalises for atomic
weights of

different glass constituents. These parameters of the glassy material are

influenced by the structural compactness, the modification of the geometrical configuration

of the glassy network, the changes in the coordination of the glass forming ions and the
fluctuations in the dimensions of the interstitial hole. Even though the density of the sample
depends on the densities of its individual constituents [70], in the case of glasses many other
factors like their preparation, thermal history of the sample, creation of non-bridging
oxygens, field strength of the modifier etc. also influence the final density of the sample [70]
to a greater extent. From the measured densities () at room temperature and effective molar

molecular weights ( M ), the physical parameters like molar volume (Vm), oxygen molar

volume (VO), oxygen packing density (OPD), cobalt ion concentration (N i), interionic
distance (ri), polaron radius (rp) and field strength (F) are computed using the relations
mentioned in the literature [71,72] and are presented in Table 2. The quantitative
understanding of these parameters is essential for exploring the basic structural modifications
that take place in ZnO-CaF2-P2O5 glasses with the variation of NiO content.
Fig. 2 shows the variation of density, oxygen packing density, molar volume and
oxygen molar volume of ZnO-CaF2-P2O5 glasses on NiO content. It is observed that the
density decreases initially from 2754 (pure glass) to 2739 kgm -3 with the addition of 0.2 mol
% of NiO into the glass and then increases nonlinearly with the increase of NiO content and
reaches the maximum value of 2831 kgm -3 for 1.0 mol% of NiO doped glass. Also, it is
noticed that oxygen packing density showed the same trend while molar volume and oxygen
molar volume followed an opposite trend. The nonlinear compositional dependence of these
parameters on NiO content indicates that there are structural changes in the glasses with the

increasing NiO concentration. As evident from x-ray diffraction patterns and infrared spectra,
these glass samples are still in an amorphous state indicating that there is no detectable
change to crystallization. Hence, the variation in these parameters can be attributed only to
the differences in linkages between different structural species [73] due to the formation of
more non-bridging oxygens than bridging oxygens in the glass network and the modification
of less stable P-O-P bonds.
Volumetric studies
The initial decrease in the density and oxygen packing density (Fig. 2) of the glasses,
an indicative of decreasing structural compactness of the material with the addition of 0.2
mol% of NiO is unpredicted as NiO has a higher density than P 2O5. This anomaly of the
glasses indicating the loose packing of the atoms in the glass structure is due to the expansion
of phosphate Q3 network to accommodate Ni2+ ions in the interstices of PO4 network
indicating the formation of PONi2+ bonds which may be due to the disproportionation
[65,74] of different phosphate groups present in the glass matrix. Also, this initial decrease in
the density can be attributed to the formation of more NiO 6 octahedral units than NiO4
tetrahedral units in the ZCP:Ni 0.2 network. On the other hand, NiO cleaves the structure and
disturbs the bonding between glass forming cations and anions. This decreases the number of
non-bridging oxygens and thus develops a more open structure. Consequently, the expansion
of the structure increases the molar volume which causes a decrease in the oxygen packing
density and hence a decrease in the density of the glass sample.
The observed increase in the density from 2754 kg m-3 (pure glass) to 2802 kg m-3 (0.6
mol% of CoO) and oxygen packing density from 75.28 (pure) to 76.43 x 10 3 mol m-3 (0.6 mol
% of CoO) along with the decrease in the molar volume (V m) and oxygen molar volume (Vo)
up to 0.6 mol% of CoO suggest that cobalt ions are filling the interstices of the glass network
indicating the formation of PONi linkages. Also, cobalt ions in glass network exist in both
four (Co2+) and six (Co2+, Co3+) fold coordinations, whereas P5+ ion in glass network is in four
fold coordination [61]. Therefore, average coordination number of the cation in the glass
network increases with increasing CoO content up to 0.6 mol%, which improves glass
compactness [61]. Hence, an increase in the density and oxygen packing density can be
expected up to 0.6 mol% of CoO. The increase in the density up to 0.6 mol% of CoO may
also be attributed to the formation of CoO4 tetrahedral structural units and the conversion of
CoO6 octahedral structural units to CoO 4 tetrahedral structural units through the formation of
some more CoOP bonds which probably results in better packing causing strengthening of
the glass network. Also, the decrease in molar volume, which represents the spatial

distribution of the ions in the glass structure up to 0.6 mol% of CoO is an indication of the
increased compactness of the glass due to the increased cross-linking density. This increase in
oxygen packing density along with the increase of mass density and decrease of molar
volume of these glasses make them more resistive mechanically.
The replacement of P2O5 with CoO develops more non-bridging oxygens than
bridging oxygens in the glass network due to the replacement of less stable P-O-P bonds by
chemically durable P-O-Co bonds. The observed increase in the density with the increase of
CoO up to 0.6 mol% may be due to increase in non-bridging oxygens in the glass network
indicating the increasing crosslinking of various units leading to a decrease in its molar
volume [73]. The decrease in molar volume may cause an increase in oxygen packing density
and mass density. This is due to the fact that the divalent cobalt ions form higher number of
NBOs than the trivalent cobalt ions.
For better understanding of the structural variations in the glass, a qualitative and
quantitative analysis is carried out by theoretical estimation of mass density and excess molar
volume of these glasses. Theoretical values of the density are estimated using the relation th
= ixi where i and xi are the density and mol% of the glass components respectively. The
estimated and the measured values of density of these glasses are depicted in Fig. 3a as a
function of CoO concentration. The difference in values of density may be due to the
variation in atomic arrangement between the structure of glass and component molecules.
E
Excess volume ( V m ) is a quantity derived from the molar volume of the sample (V m) and

molar volumes of the individual components (Vi) of the glass. V m is calculated using [70]:
V Em=V m x i V i
i

(3)

Fig. 3b represents the variation of the excess molar volume of CoO doped ZCP glasses. It is
an established fact in the case of liquid mixtures that the negative values of excess molar
volume

V m , suggest specific interactions [75,76] between the mixing components while

its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative

V Em

values (Fig. 3b, Table 2) indicate the presence of specific

interactions between the mixing components of the glass leading to structural strengthening

of the glass. The largest negative value of

Vm

for 0.6 mol% of CoO doped ZCP glass

indicates the closed packing of the atoms of the components of this glass.