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.



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.

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

p *=2d/z. 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. This approximation closely fits computer simulations of percolation thresholds [8]. N is the total number of atoms in the network.where d is the number of dimensions. z is the average coordination number. but this time the approach is asymptotic. dN basicalls gives r you to total number of bonds. This equation defines the useful value nr. the number of redundant bonds per degree of freedom. and the 1 Nzp−dN 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.

Phillips reasoned that ideally constrained system has enough constraints to prevent motion but not too many as to stress the network rigid. Energy Barrier to Crystallization easily formed. each representing a mechanically stable configuration.). ideal glass-forming ability was discovered to occur in a critical range. as introduced by Phillips [4]. Therefore the optimal glass forms when N co =d . guided by the gradient of the Nd-dimensional hyperspace. where local energy considerations are minimized. they do represent local minima in free energy (Fig 3. the network becomes a crystal. If the network is mostly floppy. This . it takes almost no energy to reconfigure the network. it must reconfigure its topology into Gibbs Free Energy an ordered network. if a glass is to become a crystal. Floppy-Rigid Spectrum point. again.45. and that takes some amount of activation energy. Up until now. which are in accordance with the predictions made by Topological Theory. All these stresses provide enough energy to overcome the Crystal activation barrier and. the Glass redundant bonds serve only to add internal stresses to the system [8]. The two extreme ends Amount of Atomic Order of Fig. They reasoned that. N co . When a network is over-constrained. the number of dimensions. if passes a critical point. not at a single Floppy Critical Rigid Fig 4. Glasses in this region are said to be in a Boolchand Intermediate Phase. This processes is called rigidity percolation [14]. named after its discoverer [10]. Mauro and Gupta [2. and the network can Energy Barrier easily overcome the low energy barrier to form glass. The average number of constraints per atom. This point represents the topological prediction of a network with ideal glass-forming ability. So as N co is varied from one extreme to another. As the Topological Theory was developed further [1. 9]. we obtain ideal glass behavior at m =2. In theory. such as extremely low minimum cooling rates (easily forms glass) and no internal stresses (no extra stress from redundant bonds). we have only considered network at absolute zero. for a system of N atoms and d dimensions.The nature of the floppy and rigid constraints has a profound impact on the behavior of the network. there exists many local minima. For now we will relate this behavior to its glass forming ability. does not only apply to glass-forming ability. Although glasses are not the most favorable thermodynamic state. since thermal energy has not yet entered the discussion. That is to say. Setting d = 3. atoms arrive at these local minima. 4 represent regions where glass is not Fig 3. Glasses in the Boolchand Phase have interesting properties.3] worked to expand topological theory to account for the current temperature of the network.

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

First we assume that only Si4 or Si3 units occur in the network.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.composition). that is a safe assumption [17]. 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]. For relatively low values of x. Each oxygen is then considered a ‘bridging-oxygen’ (BO) linking two Si atoms. As network modifiers are introduced into the system. four coordinated Si (Si4) become three coordinate (Si3). disorder is introduces into the network by a random bond angle between the tetrahedra. count the number of oxygen atoms in the network. N (O )=x ( 1 ) +( 100−x)( 2) The number of Si3 and Si4 groups sum to the total amount of Si. 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. 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. pure vitreous silica. one for each unit of R2O and two for each unit of SiO2. constraint counting is applied and can be fit to experimental parameters with good agreement [11-13]. Next. the structure consists exclusively of bridging-oxygencontaining SiO4 tetrahedra which lack long range order [11-13]. x R2 O∙ ( 100−x ) B 2 O3 . 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. Alkali Borates and Alkali Borosilicates For borates there is a similar compositional formula.

17]. Table 1.95R) 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. The Yun-Bray model [17] and random pair model [15] seem to be conventional choices for a mathematical production of network-forming-species ratios. Rmax = 1 R ≤ Rmax B4 = R (or . three and four coordinated Boron units.95R) B4 = R (or . Ternary Diagram for Na2O-B2O3-SiO2 system. 6. Yun-Bray Prediction of Four Coordinated Boron (N 4) K≤8. Rmax = K/16 + . The Configurational Units of a Borate Glass. The random pair model is used here to demonstrate a theoretical binary borate glass calculation.7). and relies of the knowledge of the possible network forming species of borate systems. There are fewer explanations because the process is similar for SiO 2.As mentioned earlier. these systems of glasses are still under study and debate [12. Table 1 shows the YunBray Prediction [17].25(R – Rmax)/ (1+K) B4 = 1 Na2O R B2O3 SiO2 Fig 6. two B4 tetrahedra (this is the only insta Fig 7. The random pair model uses similar reasoning as before to derive to following concentrations of two. R ≡ Na/B and K ≡ Si/B. Clockwise from K top. 3 N (O )=2 B 4 + B 3=x+ 3(100−x ) 2 B 3+ B 4=2(100−x) Therefore .5 K≥8. which are given in Fig.

33 point.33. but at a certain point (x=. this occurs when there are the same number of B 3 units as there are B4 units. The existence on NBOs must be considered for x ≥. The boron anomaly must be part of our theoretical considerations [3. as shown by the Yun-Bray model. or for every B4 unit. 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. the network runs out of available space to host B4 units. the coordination initially increases. This implies that for every double B4 unit there are 6 other bonds made with non B 4 units. ≤∧x ≤ 31−38 x 3 2 4 4−2 x 1 .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 ≤ 1 3 18 x−6 1 1 .∧x ≤ 5−4 x 3 f ( B )= 6−8 x 1 1 .∧x ≤ 5−4 x 3 f ( B )= 10−20 x 1 1 . which states that NBO can only occur on the three coordinated Boron atoms. there is one B3.16]. ≤∧x ≤ 31−38 x 3 2 . { { { 2x 1 . 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 = . Note that it is possible to have concentrations of B4 higher than . This is again due to random pair model theory. As more network modifiers are added to a borate network.33).5.33 critical value (the derivations are left as exercises for the reader). This is due to random pair model [15] . ≤∧x ≤ 31−38 x 3 2 3 2 f ( B )= 0. due to B3 to B4 modifications. After the x=.

Phys. Acad. it would be appropriate to use silica network topological calculations. Fractional network-forming species of other glass systems (ternary or quaternary) follow similar methods. Gupta. so counting the α constraints on the oxygens alone will account for every linear constraint.K. 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.C. To do this we recognize that each oxygen is necessarily bonded to two non-oxygen atoms.” J.A. References 1. Gupta and D. P. J. 094503 (2009). 106. Mauro. or x and y as in the Yun-Bray model. “Composition Dependence of Glass Transition Temperature and Fragility.C Mauro. A. Angular constraints are counted using B2. Natl. P. 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.S. three and five constraints. Chem. ≤∧x ≤ 31−38 x 3 2 B For concentrations above x = 0. We will start by counting the number of α constraints. usually around n = 2. J. Sci.{ 3−2 x 1 . 19780-84 (2009). Allan.. We first employ constrain counting to find the average number of constraints for a given network.5. Ellison. 130. These methods are verified experimentally by Smedskjaer [11-13]. B3 and B 4 units. having one. “Viscosity of Glass Forming Liquids. A Topological Model incorporating Temperature Dependent Constraints. .C. 2. The number of α constraints is not affected by the BO/NBO properties of the oxygen.∧x ≤ 5−4 x 3 f ( O )= 21−28 x 1 1 . and would perhaps be the subject of future reports.4. respectively.. I.K. Topological Prediction of Mechanical Properties Now that the fractions of each network forming species are known as a function of x. Yue. Y.J. U.” Proc.

New York: Kluwer Academic/Plenum.M.. “Topological Model for Boroaluminosilicate Glass Hardness. 699-702 (1985) 15.M Smedskjaer. 53.F.H. Chem. Generic Rigidity of Network Glasses. Yun. Mauro. “Nuclear Magnetic Resonance Studies of the Glasses in the System Na2O-B2O2-SiO2. 363-380 (1978). S. 12. Chem. 115503 (2010). 18. 6.C. Yue. Zachariasen.”Phys.L. Vector Percolation and Glass Formation. Smedskjaer. 1999. Potuzak. 2 nd Ed.. 54. Yue.F. “Topology of Covalent Non-Crystalline Solids I: Short Range Order in Chalcogenide Alloys.C Phillips M.. Soc. II.. R. Y.” J. A. 2011. Lett. J. W. Cambridge: Royal Society of Chemistry. 2005. N. Jacobs. 17. Phillips. Non-Cryst. J.M. “Prediction of Glass Hardness Using Temperature-Dependent Constraint Theory. 31. J. M. J.” Front. “Topological Principles of Borosilicate Glass Chemisty. “Principles of Pyrex® Glass Chemistry: Structure Property Relationships..” Solid State Commum.” Appl. Non-Cryst. “Introduction to Glass Science and Technology. Mater. J.J.C. 3.M. P. Youngman.C. Boolchand. Bull. B. 34. 8. Solids. Rev. 9. 7. J. Chubynsky. New Delhi. 115. 14.. Phys. J.C Mauro. P. 13. Shelby. P. J.. Mamedov. Phys. M.K. Thorpe. B. and Rader.” J. Y. 27m 294-299 (1864). Smedskjaer. Smedskjaer. Mauro. R. M. Soc. “Composition Dependence of Glass Transition Temperature and Fragility. Hogue.C. 12930-12946 (2011). 4. Goodman.V. 27. W. Solids. D. 1. 16. “Constrain Theory.H.. P. A Topological Model of Alkali Borate Liquids. D.” J. 174201 (2005).” J. P.. 153-81 (1979) 5. Proceeding of the International Congress on Glass.K. 105. Bray. Phys. 90 (4). Gupta. Georgiev.” Am.J. Fei. Boolchand. 130.J. M. Mater. “Topological Constrain Theory. Youngman. Philos Mag.E.E. Mauro. C. Y. 703-720 (2001). 3841-51 (1932). Optoelectron Adv.” Physical Review. “Discovery of the Intermediate Phase in Chalcogenide Glasses.G. Ceram. A.P. Gupta. 23 (2014). C.C. 11. 71. Chem. in Rigidity Theory and Applications. M.3...M. “The Atomic Arrangement in Glass..” J. Thorpe. 10. (1986). J.. 234503 (2009). 491-504 (2014) . Mauro. “Pressure Raman Effects and Internal Stress in Network Glasses. 116. Maxwell. J.

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