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N cn
Isostatically Constrained
Rigid
N co =
m
+2 m3
2
First term: Since each bond connects two atoms, each bond adds two
constraints to the system, here we consider one half constrain per constraint
because we are only focused on the constraints of one average particle, not two.
Second term: This term counts angular constraints. When an atom has a
coordination number of two, there in one constraint, and each addition atom
bonded adds two constraints [4].
Since rigid bonds add the network rigidity, and floppy modes do not, it is
useful to express to fraction of floppy modes as a function of the p, the probability
that there will exist a bond between two nodes. The initial approximation made by
Maxwell [5] is
r
1
NzpdN n
2
dN
f =
where d is the number of dimensions, N is the total number of atoms in the network,
z is the average coordination number, p *=2d/z. This equation defines the useful
value nr, the number of redundant bonds per degree of freedom. dN basicalls gives
r
you to total number of bonds, and the
1
NzpdN n indicated how many of them
2
form constraints, hence the difference between these two values gives you the
number of non-constraining bonds. The left-hand simplification shows that f
approaches 0 linearly as p is increased, further accuracy can be achieved by using
the series expansion
f =3(1p)52 ( 1 p )6 +O( (1 p )8 )
which also approaches zero as p increases, but this time the approach is
asymptotic. This approximation closely fits computer simulations of percolation
thresholds [8].
The nature of the floppy and rigid constraints has a profound impact on the
behavior of the network. For now we will relate this behavior to its glass forming
ability. Although glasses are not the most favorable thermodynamic state, they do
represent local minima in free energy (Fig 3.). That is to say, if a glass is to become
a crystal, it must reconfigure its topology into
Gibbs Free Energy
an ordered network, and that takes some
amount of activation energy. If the network is
mostly floppy, it takes almost no energy to
reconfigure the network, and the network can
Energy Barrier
easily overcome the low energy barrier to form
glass. When a network is over-constrained, the
Glass
redundant bonds serve only to add internal
stresses to the system [8]. All these stresses
provide enough energy to overcome the
Crystal
activation barrier and, again, the network
becomes a crystal. This processes is called
rigidity percolation [14]. The two extreme ends
Amount of Atomic Order of Fig. 4 represent regions where glass is not
Fig 3. Energy Barrier to Crystallization easily formed. So as
N co
extreme to another, if passes a critical point. This point represents the topological
prediction of a network with ideal glass-forming ability, as introduced by Phillips [4].
Phillips reasoned that ideally constrained system has enough constraints to prevent
motion but not too many as to stress the network rigid. Therefore the optimal glass
forms when N co =d , the number of dimensions. Setting d = 3, we obtain ideal
glass behavior at m =2.45. As the Topological Theory was developed further [1, 9],
ideal glass-forming ability was discovered to occur in a critical range, not at a single
Floppy
Critical
Rigid
descent guided by the slope of the surface is termed basin, and there exists only
one basin for every stable mechanical configuration. The hyperspace is independent
of temperature, but the way in which the network navigates this space does depend
on temperature. At high temperatures, the system can flow freely among basins,
but as the system is cooled down, inter-basin travel is reduced, and the point at
which there is no inter-basin travel is dubbed the glass transition temperature. This
reasoning was the basis for the temperature considerations of topological theory.
We introduce q(T) the network rigidity, and a function of temperature.
F vt obs
kT
]
q ( T )=[ 1e
F
t obs
is the
lim q ( T )=0
lim q ( T )=1
T0
). Since
) and the
vt obs
is generally
q ( T )= ( T qT )= 1, T <T q
0, T >T q
where Tq is the temperature of rigidity percolation. Both forms of q(T) are used,
depending on the needs of the situation.
When the thermal energy in the system is accounted for, topological theory
can be used to predict the viscosity and glass transition temperature of glass
networks [1-3]. Also, knowing
N co
the system, which correlates directly to Shear and Elastic Moduli [2].
As Applied to Specific Networks
Now we shall apply the principles of Topological Constrain Theory to several
specific glass networks. A topological analysis begins with the identification of the
main configurational units in the network, called network-forming species. One
the units are identified, knowledge of the network behavior much be applied. This
knowledge either comes from direct reasoning in simple cases, such alkali/alkali
earth silicates[16], or NMR data in more complex systems. Borate classes are
complex and their behavior is still under debate[12], but some models such as the
Yun-Bray model for binary and ternany borosilicate glasses have been developed
with some success [17]. After the proper fractions of network-forming species can
be mathematically deduces as a function of x (the change in the molar
x R2 O ( 100x ) Si O2
For x = 0, pure vitreous silica, the structure consists exclusively of bridging-oxygencontaining SiO4 tetrahedra which lack long range order [11-13]. Each oxygen is then
considered a bridging-oxygen (BO) linking two Si atoms. Note: Silica tetrahedral
occur in pairs, disorder is introduces into the network by a random bond angle
between the tetrahedra. As network modifiers are introduced into the system, four
coordinated Si (Si4) become three coordinate (Si3). To molar amount of oxygen is
used to deduce to ratio of Si4/Si3 in the following way[16]. First we assume that only
Si4 or Si3 units occur in the network. For relatively low values of x, that is a safe
assumption [17]. Next, count the number of oxygen atoms in the network, one for
each unit of R2O and two for each unit of SiO2.
N (O )=x ( 1 ) +( 100x)( 2)
The number of Si3 and Si4 groups sum to the total amount of Si,
Si 4 + Si 3=100x
We can also deduce the number of oxygen atoms from the connectivity of each Si
unit
4
N (O )=2 Si +2.5 Si
With NBO counting as a full oxygen and a BO counting as half an oxygen atom
because it will ultimately be counted twice. Rearranging the above equation leads
to
3
Si =2 x
Si 4 =1003 x
This implies that each addition of an R 2O group creates two Si3 groups and takes
away three Si4 groups.
Alkali Borates and Alkali Borosilicates
For borates there is a similar compositional formula.
x R2 O ( 100x ) B 2 O3
As mentioned earlier, these systems of glasses are still under study and
debate [12,17]. The Yun-Bray model [17] and random pair model [15] seem to be
conventional choices for a mathematical production of network-forming-species
ratios. The random pair model is used here to demonstrate a theoretical binary
borate glass calculation, and relies of the knowledge of the possible network
forming species of borate systems, which are given in Fig. 6. Table 1 shows the YunBray Prediction [17], which can be found experimentally using NMR analysis and
deviates minimally with experimentation for extreme values of K [12] (refer to
Fig.7).
K8, Rmax = 1
R Rmax
B4 = R (or .95R)
B4 = R (or .95R)
R Rmax
B4 = 1
Na2O
R
B2O3
SiO2
3
N (O )=2 B 4 + B 3=x+ 3(100x )
2
B 3+ B 4=2(100x)
Therefore
N ( B 4 )=2 x
N ( B 3) =2002 x
And it follows that the number of bridging oxygens must be
N ( OB ) =3002 x
And so the total is given by
N ( OB + B4 + B3 ) =54 x
Calculating the fractions of each network-forming species follows. The boron
anomaly must be part of our theoretical considerations [3,16]. As more network
modifiers are added to a borate network, the coordination initially increases, due to
B3 to B4 modifications, but at a certain point (x=.33), the network runs out of
available space to host B4 units, this occurs when there are the same number of B 3
units as there are B4 units. This is due to random pair model [15] , which states that
the only instance of a B4 units is attached at the corner to only one other B 4 unit.
This implies that for every double B4 unit there are 6 other bonds made with non B 4
units, or for every B4 unit, there is one B3. Note that it is possible to have
concentrations of B4 higher than .5, as shown by the Yun-Bray model. After the
x=.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. This is
again due to random pair model theory, which states that NBO can only occur on
the three coordinated Boron atoms. The existence on NBOs must be considered for
x .33. This leads to the follows piecewise equations crossing the x = .33 critical
value (the derivations are left as exercises for the reader).
{
{
{
2x
1
,x
54 x
3
f ( B )=
68 x 1
1
, x
3138 x 3
2
4
42 x
1
,x
54
x
3
f ( B )=
1020 x 1
1
, x
3138 x 3
2
3
f ( B )=
0,x
1
3
18 x6 1
1
, x
3138 x 3
2
32 x
1
,x
54 x
3
f ( O )=
2128 x 1
1
, x
3138 x 3
2
B
A ( x) =
Where
dA
(n ( x )n crit )
dn
dA
dn
ncrit