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**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.

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

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

each representing a mechanically stable configuration. there exists many local minima. we obtain ideal glass behavior at m =2.45. In theory. Although glasses are not the most favorable thermodynamic state. the network becomes a crystal. Therefore the optimal glass forms when N co =d . Setting d = 3. it takes almost no energy to reconfigure the network. Up until now. Glasses in the Boolchand Phase have interesting properties.3] worked to expand topological theory to account for the current temperature of the network. Energy Barrier to Crystallization easily formed. as introduced by Phillips [4].). atoms arrive at these local minima. if passes a critical point. again. All these stresses provide enough energy to overcome the Crystal activation barrier and. where local energy considerations are minimized. Mauro and Gupta [2. the Glass redundant bonds serve only to add internal stresses to the system [8]. ideal glass-forming ability was discovered to occur in a critical range. So as N co is varied from one extreme to another. not at a single Floppy Critical Rigid Fig 4.The nature of the floppy and rigid constraints has a profound impact on the behavior of the network. and that takes some amount of activation energy. guided by the gradient of the Nd-dimensional hyperspace. does not only apply to glass-forming ability. This processes is called rigidity percolation [14]. the number of dimensions. N co . For now we will relate this behavior to its glass forming ability. for a system of N atoms and d dimensions. This . 9]. 4 represent regions where glass is not Fig 3. When a network is over-constrained. Phillips reasoned that ideally constrained system has enough constraints to prevent motion but not too many as to stress the network rigid. and the network can Energy Barrier easily overcome the low energy barrier to form glass. it must reconfigure its topology into Gibbs Free Energy an ordered network. such as extremely low minimum cooling rates (easily forms glass) and no internal stresses (no extra stress from redundant bonds). if a glass is to become a crystal. named after its discoverer [10]. This point represents the topological prediction of a network with ideal glass-forming ability. they do represent local minima in free energy (Fig 3. since thermal energy has not yet entered the discussion. If the network is mostly floppy. As the Topological Theory was developed further [1. The two extreme ends Amount of Atomic Order of Fig. which are in accordance with the predictions made by Topological Theory. They reasoned that. The average number of constraints per atom. That is to say. Glasses in this region are said to be in a Boolchand Intermediate Phase. we have only considered network at absolute zero. Floppy-Rigid Spectrum point.

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

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

R ≡ Na/B and K ≡ Si/B. The Yun-Bray model [17] and random pair model [15] seem to be conventional choices for a mathematical production of network-forming-species ratios. Table 1 shows the YunBray Prediction [17]. There are fewer explanations because the process is similar for SiO 2. The random pair model uses similar reasoning as before to derive to following concentrations of two. Yun-Bray Prediction of Four Coordinated Boron (N 4) K≤8. which can be found experimentally using NMR analysis and deviates minimally with experimentation for extreme values of K [12] (refer to Fig.17].95R) B4 = R (or . which are given in Fig. and relies of the knowledge of the possible network forming species of borate systems. Rmax = K/16 + . Rmax = 1 R ≤ Rmax B4 = R (or . these systems of glasses are still under study and debate [12.25(R – Rmax)/ (1+K) B4 = 1 Na2O R B2O3 SiO2 Fig 6. three and four coordinated Boron units.As mentioned earlier.7). 3 N (O )=2 B 4 + B 3=x+ 3(100−x ) 2 B 3+ B 4=2(100−x) Therefore . Ternary Diagram for Na2O-B2O3-SiO2 system. 6. two B4 tetrahedra (this is the only insta Fig 7. The Configurational Units of a Borate Glass. The random pair model is used here to demonstrate a theoretical binary borate glass calculation.95R) R ≥ Rmax B4 = Rmax – 0. Clockwise from K top.5 K≥8. Table 1.

this occurs when there are the same number of B 3 units as there are B4 units.5. This is due to random pair model [15] .16].∧x ≤ 1 3 18 x−6 1 1 . there is one B3. This is again due to random pair model theory. Note that it is possible to have concentrations of B4 higher than . but at a certain point (x=. The boron anomaly must be part of our theoretical considerations [3.33). As more network modifiers are added to a borate network. This leads to the follows piecewise equations crossing the x = . ≤∧x ≤ 31−38 x 3 2 . The existence on NBOs must be considered for x ≥.∧x ≤ 5−4 x 3 f ( B )= 10−20 x 1 1 . 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 3 2 f ( B )= 0. which states that NBO can only occur on the three coordinated Boron atoms.33 critical value (the derivations are left as exercises for the reader).∧x ≤ 5−4 x 3 f ( B )= 6−8 x 1 1 . the network runs out of available space to host B4 units. 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. After the x=.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.33 point. which states that the only instance of a B4 units is attached at the corner to only one other B 4 unit. ≤∧x ≤ 31−38 x 3 2 4 4−2 x 1 . or for every B4 unit. { { { 2x 1 . as shown by the Yun-Bray model. the coordination initially increases. due to B3 to B4 modifications.

These methods are verified experimentally by Smedskjaer [11-13].” Proc. three and five constraints.C. Topological Prediction of Mechanical Properties Now that the fractions of each network forming species are known as a function of x. Ellison.. ≤∧x ≤ 31−38 x 3 2 B For concentrations above x = 0. Chem. References 1. so counting the α constraints on the oxygens alone will account for every linear constraint. Sci. respectively. usually around n = 2. having one. Phys. 19780-84 (2009). Mauro.5. 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. B3 and B 4 units. 094503 (2009).. The number of α constraints is not affected by the BO/NBO properties of the oxygen.K. 106. We first employ constrain counting to find the average number of constraints for a given network. A Topological Model incorporating Temperature Dependent Constraints. Fractional network-forming species of other glass systems (ternary or quaternary) follow similar methods. 130.{ 3−2 x 1 . Natl.J. Y.” J. Allan. A. We will start by counting the number of α constraints.S. it would be appropriate to use silica network topological calculations. “Viscosity of Glass Forming Liquids.C. “Composition Dependence of Glass Transition Temperature and Fragility.C Mauro.∧x ≤ 5−4 x 3 f ( O )= 21−28 x 1 1 . J. Angular constraints are counted using B2. Gupta and D. or x and y as in the Yun-Bray model. I.K. . Yue.A. P. 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. P. 2.4. J. Gupta. To do this we recognize that each oxygen is necessarily bonded to two non-oxygen atoms. and would perhaps be the subject of future reports. U. Acad.

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

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