INORGANIC GLASSES 5.

15

around 5Na2O · 23B2O3 · 72SiO2 (mol%) composition with a critical temperature of 765°C.
Compositions within the spinodal dome [5–10 Na2O · 20–35 B2O3 · 55–75 SiO2 (mol%)]
separate at 500 to 600°C into two continuous intertwined matrices, one of which is a 96
percent silica and the other a sodium borate. The latter is dissolved away by using acid (for
instance, 3N H2SO4 at 90°C), which leaves behind the porous silica skeleton. The “thirsty
silica” thus produced may be used as a molecular sieve, or as a time-release encapsulating
container. Upon sintering, one obtains a dense glass sold under the trade name Vycor® by
Corning Inc. Heat-resistant Pyrex® glasses of the borosilicate type have a highly dispersed
separation of tiny sodium borate droplets, with the matrix made silica-rich after separation.
The increase in the matrix silica actually raises the chemical durability; hence, these glasses
are often utilized for chemical laboratory glassware.

5.3.2 Controlled Crystallization of Glass

It may be noted in Fig. 5.2 that the nucleation rate curve has been drawn at temperatures
lower than those for crystal growth rate. This is close to the reality. It is possible for the
two curves to be separated enough such that there is little overlap, and hence little chances
of crystallization during the first cool-down (since, nucleation must precede crystal growth).
The cooled mass, however, does have nuclei grown within the bulk, and a reheat to the
crystal growth regions can readily bring about crystallization. Such material is termed
glass-ceramic. In reality, the mass may be mostly crystalline ceramic particles sur-
rounded by a vitreous layer. The process yields essentially monosized crystals randomly
distributed through the volume with a high number density. These facts, combined with the
absence of porosity, yield a mass that has exceptional strength characteristics. A typical
time-temperature cycle to form a glass-ceramic is shown in Fig. 5.9. Often, the nucleation
step is aided by the presence of small amounts of nucleating agents such as TiO2, P2O5,
ZrO2, and ZrO2.SiO2. Several quite successful commercial products are now available that
utilize this controlled crystallization technique; Corningware® and Visionware® are two
examples. Because of the large increase in viscosity after the “ceramming” step, crystal-
lizable (or devitrifiable) sealing glass is quite useful. The front panel of a television is
usually sealed to the back funnel by a devitrifiable sealing glass, which enables an important
baking step to be carried out after the sealing. Some of the glass-ceramic products are dis-
cussed in Sec. 6.2.7 (Chap. 6).

5.4 ATOMIC ARRANGEMENTS IN GLASS

5.4.1 Structure of Silica Glass

As indicated above, the atomic arrangements in glass are similar to those in a solid except
that there is no long-range order. Some similarity to a crystalline type of order, perhaps out
to about 10 to 20 Å, is actually expected in most multicomponent glasses. Figure 5.10
shows the arrangement of atoms in fused silica glass in a “pancaked” version. The build-
ing block (Fig 5.10a) is an SiO4 tetrahedron comprising a silicon ion bonded to four oxygens.
One negative charge of each of the four oxygens satisfies the four positive charges on
the silicon, which leaves each oxygen to form a corner shared with an adjacent tetrahe-
dron, thus acting as a bridging oxygen (BO). Corner sharing allows three angles, shown
5.16 CHAPTER FIVE

FIGURE 5.9 A typical time-temperature curve for forming a glass-ceramic.

in Fig 5.10b—the bond angle -Si-O-Si-, the azimuthal angle α1, and the twist angle α2—
to assume random values over a large range. Variations in these angles create a random,
three-dimensional, structure lacking long-range periodicity, as shown in Fig 5.10c. Ran-
domness is described in terms of the ring statistic, which is the number of silicon atoms
contacted when a spider takes the shortest path to come back to its origin atom. Much of
the randomness is believed to arise from variations in the three angles shown in Fig. 5.10b.
The tetrahedron does not itself have to be deformed significantly. A typical radial distribu-
tion function for silica glass obtained by using x-ray diffraction is shown in Fig. 5.11. The
peak locations yield the most probable distances between atomic pairs; the number of atom
centers within a coordination shell may be calculated from the area under the peak (defined
with some arbitrary cutoff radial distance limits on the left and right). The first peak, at 1.62 Å,
corresponds to the shortest distance, which is the Si-O distance. The area corre-
sponds to, more or less, four oxygen atoms, confirming a tetrahedral coordination for Si.
 INORGANIC GLASSES 5.17

FIGURE 5.10 Silica glass structures: (a) the SiO4 building block––line through the
oxygen implies a bridging end; (b) intermediate range structures in silica glass; (c) A
two-dimensional representation of silica glass structure. (Part b after A. C. Wright,
G. A. N. Connell, and J. W. Allen, J. Non-Cryst. Sol. vol. 42, 1980, p. 69).
5.18 CHAPTER FIVE

FIGURE 5.11 Radial distribution function for silica glass. Curve A is the function measured by x-ray
diffraction. Curve B is the sum of calculated peaks for Si1-O1, O1-O2, Si1-Si2, Si1-O6, O1-O6, and Si1-Si3.
Curve C is the difference.

The second nearest distance is 2.65 Å, corresponding to the tetrahedral O-O edge distance.
Other computed distances are 3.12 Å for Si-Si, 4.15 Å for Si–second O, about 5.0 Å for
O–second O, and about 5.0 Å for Si–second Si. The Si-O-Si bond angles are continuously
distributed randomly between 120 and 180° and have a maximum probability at 144°. Phys-
ical models made with balls and sticks and computer simulations using molecular dynamics
generally support the structure of silica glass as presented in Figs. 5.10c and 5.11. Dis-
agreements tend to be limited to the description of ring statistics.

5.4.2 Structure of Alkali Silicate Glass

The addition of one molecule of sodium oxide (Na2O) to silica glass breaks up a bridge and
creates two nonbridging oxygens (NBO) as follows:

[O]3Si-O-Si[O]3 + Na2O = [O]3Si-O−Na+ + Na+ −O-Si[O]3 (5.1)

Each added sodium ion is attached more or less ionically to one nonbridging oxygen. The
overall electrical neutrality of the structure is thus maintained. (The reader should
note that each BO is counted as a half and each NBO is counted full, and thus mass bal-
ance exists between the two sides of the above equation.) If the oxygen bridges are broken
up, the structure begins to lose connectivity and, as a result, becomes more fluid relative
to the fully connected silica glass at comparable temperatures. The schematics of the atomic
arrangements in alkali silicate glass are shown in Fig. 5.4. The range of relatively easy glass
formation (by ordinary melt cooling techniques) in alkali silicate glasses is shown in
Table 5.3.
 INORGANIC GLASSES 5.19

FIGURE 5.12 Phase equilibria and glass formation region in the soda-lime-silica system. (After K. A.
Shahid and F. P. Glasser, “Phase equilibria in the system Na2O-CaO-SiO2,” Phys. Chem. Glasses, vol. 12,
1971, p. 50.)

5.4.3 Structure of Alkali-Alkaline Earth-Silicate Glass

When an alkaline earth ion containing oxide, such as CaO, is added to silica, the bivalent
alkaline earth ion is attached to two NBOs. The bridge via the Ca++ ion is not as strong as
the direct -O- bridge, but is not as weak as the broken bridge with alkalis. The increased
stability of a soda lime silica glass relative to the sodium silicate glass may be explained
in such qualitative terms. Excellent glasses are formed in the Na2O · 3CaO · 6SiO2 primary
phase field (shown as 1:3:6) around the 15Na2O · 10CaO · 75SiO2 composition in the soda-
lime-silica phase equilibrium diagram (Fig. 5.12). These form the basis of most of the
commercial container, flat, and household lamp (both incandescent and fluorescent) glass
industry. Typical compositions are shown in Table 6.1 in Chap. 6.

5.4.4 Structure of Boric Oxide, Borate, and Borosilicate Glasses

Pure boric oxide is perhaps the best glass former (even better than silica). Crystals of B2O3
are hard to obtain from a melt at the slowest cooling rates. (All of the commercially sold
anhydrous boric oxide is actually boric oxide glass.) The structure is composed of fully con-
nected BO3 triangles with the boron atoms slightly out of the plane formed by the oxygens.
5.20 CHAPTER FIVE

FIGURE 5.13 The boroxol building block in B2O3 glass.

According to current beliefs, a significant fraction of the triangles make up a boroxol unit
shown in Fig. 5.13. Variation in the three bridging oxygen bond angles at the ends provides
most of the randomness. The amount of these units decreases with increases in tempera-
ture. Addition of an alkali ion, M+, to boric oxide brings about two possibilities, as shown
in Fig. 5.14:

1. Each sodium ion converts one bridging oxygen to one nonbridging oxygen (NBO) and
attaches itself to the NBO as in silicate glasses.
2. One triangularly coordinated boron (B3) is converted to a tetrahedrally coordinated
boron (B4). Since boron is a trivalent ion, the presence of four oxygens leaves the BO4
group with one net negative charge, which is satisfied by the univalent alkali ion bonded
loosely to the group. Conversion of B3 to B4 yields a greater level of network connec-
tivity (without the creation of any NBO), resulting in increasing glass transition
temperature and decreasing thermal expansion coefficient.
It has been suggested that the addition of alkali to boric oxide proceeds through option 2
initially up to about 33 mol% added alkali oxide, corresponding to about 50 percent B4
conversion. Continuing additions of alkali subsequently create NBO through option 1.
Thus, it is also agreed that the appearance of extrema in physical properties such as
 INORGANIC GLASSES 5.21

FIGURE 5.14 Structural changes in B2O3 on alkali addition: (a) formation of nonbridging oxygen;
(b) conversion of triangularly coordinated boron to tetrahedrally coordinated boron.

the thermal expansion coefficient at 13 to 17 mol% alkalis in alkali borate glasses (see
Sec. 5.11.4), otherwise known as the boric oxide anomaly, has little to do with the stop-
ping of the B3 to B4 conversion, earlier thought to occur in the anomalous region. The range
of glass formation in an alkali borate system is shown in Table 5.3.
In alkali borosilicate glasses, the alkali is believed to prefer its association with
boron; thus, no NBOs are present in the structure for mol Na2O/B2O3 < 0.5. Thereafter,
the alkalis are distributed between borons and silicons, depending on the composition and
temperature.

5.4.5 Structure of Alkali Aluminosilicate Glasses

In alkali aluminosilicate system, it is believed that the Al3+ ion initially goes into the net-
work as a former creating AlO4 tetrahedra. Like the boron ion, the trivalency then forces
the alkali ion M+ to be loosely connected to the AlO4 group. Such is the case for mol
Al2O3/M2O < 1. On further addition, the Al3+ ion enters the network as a network modifier
with an octahedral coordination of oxygens. There are other suggestions based upon steric
considerations, and supported by molecular dynamic simulations in recent years, that argue
against the need for an octahedral coordination of Al at Al2O3/M2O > 1. An oxygen atom
may be shared between three tetrahedra of SiO4 and AlO4, forming a tricluster arrangement.
Possibilities also exist that all the three tetrahedra could be either AlO4 or SiO4, leading to
a phase-separated structure.

5.4.6 Structure of Phosphate Glasses

In phosphate glasses, the network is composed of PO4 tetrahedra. Since P is a pentava-

lent ion, only three of the four oxygens are corner-shared with adjacent tetrahedra. The
fourth oxygen is attached to the P with a double bond to satisfy charge neutrality and acts
5.22 CHAPTER FIVE

FIGURE 5.15 Structures in P2O5 glasses: (a) PO4 tetrahedron; (b) P4O10 molecule.

as a terminator. Pure P2O5 glass may contain isolated P4O10 molecules (Fig. 5.15) with van
der Waals forces between the molecules. With additions of network modifiers, such as Na2O
and CaO, the molecules begin to break up to form linear chains and sheet-like structures.
Glass structures are, therefore, not as rigid and stable as those of the silicates, and may
readily crystallize or be attacked by chemical media. The range of glass formation in some
phosphate systems is shown in Table 5.3.

5.4.7 Structure of Lead and Zinc Silicate Glasses

Although classified by Sun as an NWM, PbO can go into the network as both a former and
a modifier. Pure PbO does not make a glass; however, glasses with as high as 90 wt% PbO
can be made. It is possible that two SiO4 tetrahedra are joined via a Pb atom. Another sug-
gestion has been the formation of twisted PbO4 pyramids with a Pb atom sitting at the apex.
Similar considerations hold for ZnO, though not as strongly.

5.5 COMPOSITION-STRUCTURE-PROPERTY
RELATIONSHIPS

5.5.1 Presentation of Glass Formulas

As stated above, the entire body of a glass is a single unit cell. Hence, the chemical for-
mula for glass need not be simple. The various component oxides that constitute traditional
oxide glasses may be written as mol%, mol fraction, weight % (abbreviated wt%), and