# The ability to infer the mechanical properties of glass from its structural

**composition is important in the glass industry, where accurate prediction of
**

properties such as viscosity, hardness, and chemical durability have obvious

benefits . So far, the main method for deducing the optimal composition to

maximize certain mechanical properties has been empirical [1]. For example, in

1915, scientists used empirical analysis to discover a very durable, heat and shock

resistant glass known commonly today as Pyrex®[18]. While this method does

arrive at the answer, a theoretical understanding of the connection between a

glass’s composition and its mechanical properties is of more interest in modern

glass science.

One direct approach for explaining a glass behavior based on its structure is

Molecular Dynamics. In short, this process examines the Coulomb interactions

between networks of atoms. Since there are no other types of interactions between

atoms, examining the Coulomb forces is certain to work. However, the computation

forces due to atomic bonding requires a tedious numerical integration with a time

step of 10-15 s [2]. These computational limits preclude the analysis of sufficiently

large networks.

In order to get more useful methods of analysis, some simplification needs to

be made. Topological Constraint Theory [4,6,14] does not calculate or examine any

atomic forces, rather, it examines the mere existence or absence of a bond. This

eliminates the need for a tedious strength

calculation. Constraint Theory makes a

further simplification by discarding any

extraneous forces and only calculating the

main influences on atomic motion, called

constraints. This idea of considering

constraints was first suggested by Maxwell

[5] and was later developed into a

breakthrough theory by Phillips in 1979

[4]. These atomic constraints fall into the

Fig 1. Types of Intermolecular Constraints categories: α Constrains and β Constraints

(Fig 1.) α constraints describe forces

associated with bond stretching, while β constraints describe forces associated with

bond bending.

α

β

**Depending on the number of constraints each atom experiences, the nature
**

of its motion can be deduced. If an atom has two few constraints, it is said to be

floppy, or under-constrained and if has atom has too many, it is said to be rigid

or over-constrained. Extra constraints in a rigid system are called redundant

bonds. There is also a critical number of constraints where the atom is neither overconstrained nor under-constrained. Such an atom is said to be isostatically

constrained [6] (Fig 2.). The number of constraint determines the nature of the

topological connection. Since we want information about the network, not just one

atom, we need to figure out the number constraints of some average particle in the

network. We define the mean coordination number with this in mind.

When an atom has a
coordination number of two. not two. there in one β constraint.m=x N cn ( A )+ y N cn ( B ) +(1− y−x ) N cn (C)
This is a simple weighted average. The Nature of Topological Connections
Next we must discover how many constraints are affecting this average
particle. The initial approximation made by
Maxwell [5] is
r
1
Nzp−dN n ¿
2
¿
dN −¿
f =¿
.
Since rigid bonds add the network rigidity. respectively. it is
useful to express to fraction of floppy modes as a function of the p. here we consider one half constrain per α constraint
because we are only focused on the constraints of one average particle.
Floppy
Two Bonds are Redundant
Isostatically Constrained
Rigid
Fig 2. the probability
that there will exist a bond between two nodes. The number of atomic constraints in the system can be expressed as
N co =
m
+2 m−3
2
First term: Since each bond connects two atoms. each bond adds two α
constraints to the system. and each addition atom
bonded adds two β constraints [4].
Second term: This term counts angular constraints. and floppy modes do not. defined here for a 3 component system
with
N cn
denoting the coordination number (number of neighboring atoms) and x
and y denoting the molar percentage of A and B.

The left-hand simplification shows that f
approaches 0 linearly as p is increased.where d is the number of dimensions. N is the total number of atoms in the network. This approximation closely fits computer simulations of percolation
thresholds [8]. This equation defines the useful
value nr. and the
1
Nzp−dN n ¿ indicated how many of them
2
¿
form constraints.
z is the average coordination number.
. hence the difference between these two values gives you the
number of non-constraining bonds. dN basicalls gives
r
you to total number of bonds. p *=2d/z. the number of redundant bonds per degree of freedom. but this time the approach is
asymptotic. further accuracy can be achieved by using
the series expansion
f =3(1−p)5−2 ( 1− p )6 +O( (1− p )8 )
which also approaches zero as p increases.

they do
represent local minima in free energy (Fig 3. Energy Barrier to Crystallization easily formed. the
Glass
redundant bonds serve only to add internal
stresses to the system [8]. Mauro and Gupta
[2. 9]. the number of dimensions. This
. The two extreme ends
Amount of Atomic Order of Fig.
N co .). This processes is called
rigidity percolation [14]. and that takes some
amount of activation energy. As the Topological Theory was developed further [1. Although glasses are not the most favorable thermodynamic state. Glasses in this region are said to be in a Boolchand Intermediate Phase. atoms arrive at these
local minima. there
exists many local minima.
named after its discoverer [10]. guided by the gradient of the Nd-dimensional hyperspace. we obtain ideal
glass behavior at m =2. If the network is
mostly floppy. which are in
accordance with the predictions made by Topological Theory. Glasses in the Boolchand Phase have interesting
properties.
ideal glass-forming ability was discovered to occur in a critical range. it takes almost no energy to
reconfigure the network.
Phillips reasoned that ideally constrained system has enough constraints to prevent
motion but not too many as to stress the network rigid. if passes a critical point. each
representing a mechanically stable configuration. So as
N co
is varied from one
extreme to another. as introduced by Phillips [4]. we have only considered network at absolute
zero. For now we will relate this behavior to its glass forming
ability. not at a single
Floppy
Critical
Rigid
Fig 4. Setting d = 3. such as extremely low minimum cooling rates (easily forms glass) and
no internal stresses (no extra stress from redundant bonds).45.3] worked to expand topological theory to account for the current temperature of
the network. Therefore the optimal glass
forms when N co =d . They reasoned that. In theory. That is to say. for a system of N atoms and d dimensions. When a network is over-constrained.The nature of the floppy and rigid constraints has a profound impact on the
behavior of the network. Floppy-Rigid Spectrum
point. All these stresses
provide enough energy to overcome the
Crystal
activation barrier and. and the network can
Energy Barrier
easily overcome the low energy barrier to form
glass. This point represents the topological
prediction of a network with ideal glass-forming ability. the network
becomes a crystal. it must reconfigure its topology into
Gibbs Free Energy
an ordered network. if a glass is to become
a crystal. does not only apply to
glass-forming ability. Up until now. 4 represent regions where glass is not
Fig 3. where local energy considerations are minimized.
The average number of constraints per atom. since thermal energy has not yet entered the discussion. again.

or NMR data in more complex systems. but the way in which the network navigates this space does depend
on temperature. k is
Boltzmann’s constant. Also. v is the vibrational attempt frequency. which correlates directly to Shear and Elastic Moduli [2]. T >T q
where Tq is the temperature of rigidity percolation. A topological analysis begins with the identification of the
main configurational units in the network. called network-forming species. Borate classes are
complex and their behavior is still under debate[12]. One
the units are identified. Since
) and the
vt obs
is generally
large. This
reasoning was the basis for the temperature considerations of topological theory. the system can flow freely among basins. The hyperspace is independent
of temperature. After the proper fractions of network-forming species can
be mathematically deduces as a function of x (the change in the molar
. At high temperatures. T <T q
0.
When the thermal energy in the system is accounted for.
−∆ F vt obs
kT
]
q ( T )=[ 1−e
∆F
is the activation energy needed for breaking a constraint. and a function of temperature. such alkali/alkali
earth silicates[16]. knowing
N co
also tells you how many bonds are present in
the system. and
t obs
is the
timescale of the observation. This function is reminiscent of the classic Fermi
energy distribution function. but some models such as the
Yun-Bray model for binary and ternany borosilicate glasses have been developed
with some success [17]. where q is rigid at T =0 (
network becomes floppy as it gets hotter (
lim q ( T )=0
T→∞
lim q ( T )=1
T→0
). Both forms of q(T) are used.
but as the system is cooled down. inter-basin travel is reduced. knowledge of the network behavior much be applied.
We introduce q(T) the network rigidity.descent guided by the slope of the surface is termed basin. topological theory
can be used to predict the viscosity and glass transition temperature of glass
networks [1-3]. and there exists only
one basin for every stable mechanical configuration.
As Applied to Specific Networks
Now we shall apply the principles of Topological Constrain Theory to several
specific glass networks.
depending on the needs of the situation. q(T) also has the discreet form
{
q ( T )=θ ( T q−T )= 1. and the point at
which there is no inter-basin travel is dubbed the glass transition temperature. This
knowledge either comes from direct reasoning in simple cases.

composition). constraint counting is applied and can be fit to experimental
parameters with good agreement [11-13].
Alkali Borates and Alkali Borosilicates
For borates there is a similar compositional formula.
N (O )=x ( 1 ) +( 100−x)( 2)
The number of Si3 and Si4 groups sum to the total amount of Si. four
coordinated Si (Si4) become three coordinate (Si3). count the number of oxygen atoms in the network. disorder is introduces into the network by a random bond angle
between the tetrahedra. Each oxygen is then
considered a ‘bridging-oxygen’ (BO) linking two Si atoms. one for
each unit of R2O and two for each unit of SiO2.5 Si
With NBO counting as a full oxygen and a BO counting as half an oxygen atom
because it will ultimately be counted twice. First we assume that only
Si4 or Si3 units occur in the network.
Alkali Silicates
We begin with an analysis of binary alkali silicate glasses of the composition
x R2 O∙ ( 100−x ) Si O2
For x = 0. the structure consists exclusively of bridging-oxygencontaining SiO4 tetrahedra which lack long range order [11-13]. Next. Rearranging the above equation leads
to
3
Si =2 x
Si 4 =100−3 x
This implies that each addition of an R 2O group creates two Si3 groups and takes
away three Si4 groups. that is a safe
assumption [17]. As network modifiers are introduced into the system.
x R2 O∙ ( 100−x ) B 2 O3
. pure vitreous silica. Note: Silica tetrahedral
occur in pairs. To molar amount of oxygen is
used to deduce to ratio of Si4/Si3 in the following way[16].
Si 4 + Si 3=100−x
We can also deduce the number of oxygen atoms from the connectivity of each Si
unit
4
3
N (O )=2 Si +2. For relatively low values of x.

these systems of glasses are still under study and
debate [12. Rmax = 1
R ≤ Rmax
B4 = R (or .
Table 1.
The random pair model uses similar reasoning as before to derive to following
concentrations of two.95R)
B4 = R (or .7).5
K≥8. Table 1 shows the YunBray Prediction [17]. Yun-Bray Prediction of Four Coordinated Boron (N 4)
K≤8. R ≡ Na/B and K ≡ Si/B.25(R – Rmax)/
(1+K)
B4 = 1
Na2O
R
B2O3
SiO2
Fig 6. and relies of the knowledge of the possible network
forming species of borate systems. Rmax = K/16 + .17]. The random pair model is used here to demonstrate a theoretical binary
borate glass calculation. Clockwise from
K top. The Yun-Bray model [17] and random pair model [15] seem to be
conventional choices for a mathematical production of network-forming-species
ratios. There are fewer
explanations because the process is similar for SiO 2. three and four coordinated Boron units. The Configurational Units of a Borate Glass.As mentioned earlier.
3
N (O )=2 B 4 + B 3=x+ 3(100−x )
2
B 3+ B 4=2(100−x)
Therefore
. two B4 tetrahedra (this is the only insta
Fig 7. which are given in Fig.95R)
R ≥ Rmax
B4 = Rmax – 0. which can be found experimentally using NMR analysis and
deviates minimally with experimentation for extreme values of K [12] (refer to
Fig. Ternary Diagram for Na2O-B2O3-SiO2 system. 6.

Note that it is possible to have
concentrations of B4 higher than . The boron
anomaly must be part of our theoretical considerations [3.33 point. the further addition of network modifying cations transform B 3 species
into B2 which is a three-coordinated boron atom with two BOs and one NBO.16].∧x ≤
1
3
18 x−6 1
1
. The existence on NBOs must be considered for
x ≥.33 critical
value (the derivations are left as exercises for the reader). This is
again due to random pair model theory. As more network
modifiers are added to a borate network. or for every B4 unit. the coordination initially increases. which states that NBO can only occur on
the three coordinated Boron atoms. which states that
the only instance of a B4 units is attached at the corner to only one other B 4 unit. This leads to the follows piecewise equations crossing the x = .33).∧x ≤
5−4 x
3
f ( B )=
6−8 x 1
1
.33.N ( B 4 )=2 x
N ( B 3) =200−2 x
And it follows that the number of bridging oxygens must be
N ( OB ) =300−2 x
And so the total is given by
N ( OB + B4 + B3 ) =5−4 x
Calculating the fractions of each network-forming species follows. ≤∧x ≤
31−38 x 3
2
. ≤∧x ≤
31−38 x 3
2
3
2
f ( B )=
0. there is one B3. the network runs out of
available space to host B4 units. After the
x=. this occurs when there are the same number of B 3
units as there are B4 units.5. due to
B3 to B4 modifications. This is due to random pair model [15] . ≤∧x ≤
31−38 x 3
2
4
4−2 x
1
.
This implies that for every double B4 unit there are 6 other bonds made with non B 4
units.
{
{
{
2x
1
. as shown by the Yun-Bray model. but at a certain point (x=.∧x ≤
5−4
x
3
f ( B )=
10−20 x 1
1
.

or x and y as in the Yun-Bray model. U. Gupta.
References
1. Fractional network-forming species of other glass systems
(ternary or quaternary) follow similar methods.C. 106. Sci. having one.K.
Angular constraints are counted using B2.J. P. Allan. so counting the α
constraints on the oxygens alone will account for every linear constraint.C Mauro. Phys. A. P. We will
start by counting the number of α constraints. Mauro. it would be appropriate to use silica network
topological calculations. I.K.
. 130.” Proc.” J. The
number of α constraints is not affected by the BO/NBO properties of the oxygen. These methods are verified
experimentally by Smedskjaer [11-13]. and would perhaps be the subject of
future reports. We first employ constrain
counting to find the average number of constraints for a given network. J.. Hence the average number of constraints is
n ( x )=2 (3−2 x )+ f ( B2 )+3 f ( B 3 ) +5 f ( B4 )
Now linearization of some arbitrary property A can be used to predict the
compositional dependence property A. Gupta and D. Yue. usually around n = 2.
2.
Topological Prediction of Mechanical Properties
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function of x.5. respectively. Natl.4.{
3−2 x
1
. J.S. 19780-84
(2009). Chem. Ellison. To do this we recognize that each
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31−38 x 3
2
B
For concentrations above x = 0. “Composition Dependence of Glass Transition
Temperature and Fragility.∧x ≤
5−4 x
3
f ( O )=
21−28 x 1
1
. Acad.
Linearization of A:
A ( x) =
Where
dA
(n ( x )−n crit )
dn
dA
dn
is determined empirically and
ncrit
is chosen to be in the Boolchand
intermediate phase. B3 and B 4 units. three and
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Glass Forming Liquids. A Topological Model incorporating
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