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(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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
ions per
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
Vm
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)
****
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
ions per
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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
(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]
****
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
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
niobium and/or
ions per
[3112]
Generally,
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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]
****
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
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
decreases linearly
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
niobium and/or
ions per
[3112]
the density and the molar volume show opposite behaviors, but in
this
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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
***
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
density of
increases.
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
ions per
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
ions per
cations per unit found for A2O are replaced by a single cation
niobium and/or
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
Vm
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)
****
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]
****
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
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
niobium and/or
ions per
[3112]
the density and the molar volume show opposite behaviors, but in
this
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
ions per
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
Vm
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)
****
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
ions per
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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
(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]
****
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
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
niobium and/or
ions per
[3112]
Generally,
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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]
****
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
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
decreases linearly
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
niobium and/or
ions per
[3112]
the density and the molar volume show opposite behaviors, but in
this
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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
***
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
density of
increases.
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
ions per
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
ions per
cations per unit found for A2O are replaced by a single cation
niobium and/or
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
Vm
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)
****
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]
****
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
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
niobium and/or
ions per
[3112]
the density and the molar volume show opposite behaviors, but in
this
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
ions per
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
Vm
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)
****
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
ions per
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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
(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]
****
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
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
niobium and/or
ions per
[3112]
Generally,
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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]
****
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
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
decreases linearly
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
niobium and/or
ions per
[3112]
the density and the molar volume show opposite behaviors, but in
this
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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
***
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
density of
increases.
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
ions per
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
ions per
cations per unit found for A2O are replaced by a single cation
niobium and/or
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
Vm
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)
****
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]
****
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
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
niobium and/or
ions per
[3112]
the density and the molar volume show opposite behaviors, but in
this
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
ions per
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
Vm
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)
****
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
ions per
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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
(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]
****
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
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
niobium and/or
ions per
[3112]
Generally,
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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]
****
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
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
decreases linearly
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
niobium and/or
ions per
[3112]
the density and the molar volume show opposite behaviors, but in
this
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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
***
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
density of
increases.
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
ions per
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
Vm
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
ions per
cations per unit found for A2O are replaced by a single cation
niobium and/or
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
Vm
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)
****
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]
****
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
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
niobium and/or
ions per
[3112]
the density and the molar volume show opposite behaviors, but in
this
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
of the glass. The largest negative value of
V Em
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)
****
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]
****
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
can be attributed to an increase of the atom packing density in the glass network [976]
***
From
[1377]
which also
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
oxide in
increases.
density of
[2340]
cations per unit found for A2O are replaced by a single cation
Generally,
[3112]
the density and the molar volume show opposite behaviors, but in
of phosphorus by
ionic bonds between Pb ions and singly bonded oxygen atoms. Therefore,
this
by
niobium and/or
ions per
if
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
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
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
its positive values suggest dominance of dispersion forces [76,77] between them. In the
present study, the negative
V Em
interactions between the mixing components of the glass leading to structural strengthening
Vm
indicates the closed packing of the atoms of the components of this glass.