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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.

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

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

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

One the units are identified. Both forms of q(T) are used. 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. q(T) also has the discreet form { q ( T )=θ ( T q−T )= 1. called network-forming species. This knowledge either comes from direct reasoning in simple cases. This function is reminiscent of the classic Fermi energy distribution function. which correlates directly to Shear and Elastic Moduli [2]. We introduce q(T) the network rigidity. the system can flow freely among basins.descent guided by the slope of the surface is termed basin. knowledge of the network behavior much be applied. inter-basin travel is reduced. and t obs is the timescale of the observation. but some models such as the Yun-Bray model for binary and ternany borosilicate glasses have been developed with some success [17]. and there exists only one basin for every stable mechanical configuration. This reasoning was the basis for the temperature considerations of topological theory. Borate classes are complex and their behavior is still under debate[12]. topological theory can be used to predict the viscosity and glass transition temperature of glass networks [1-3]. such alkali/alkali earth silicates[16]. 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. T <T q 0. −∆ F vt obs kT ] q ( T )=[ 1−e ∆F is the activation energy needed for breaking a constraint. A topological analysis begins with the identification of the main configurational units in the network. depending on the needs of the situation. knowing N co also tells you how many bonds are present in the system. At high temperatures. and a function of temperature. After the proper fractions of network-forming species can be mathematically deduces as a function of x (the change in the molar . but the way in which the network navigates this space does depend on temperature. v is the vibrational attempt frequency. The hyperspace is independent of temperature. When the thermal energy in the system is accounted for. but as the system is cooled down. 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 ). Also. or NMR data in more complex systems. Since ) and the vt obs is generally large.

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

6.95R) R ≥ Rmax B4 = Rmax – 0. these systems of glasses are still under study and debate [12.5 K≥8.95R) B4 = R (or . which can be found experimentally using NMR analysis and deviates minimally with experimentation for extreme values of K [12] (refer to Fig. The random pair model is used here to demonstrate a theoretical binary borate glass calculation. There are fewer explanations because the process is similar for SiO 2. Table 1 shows the YunBray Prediction [17]. three and four coordinated Boron units. two B4 tetrahedra (this is the only insta Fig 7. The Configurational Units of a Borate Glass. 3 N (O )=2 B 4 + B 3=x+ 3(100−x ) 2 B 3+ B 4=2(100−x) Therefore . Table 1.17]. Ternary Diagram for Na2O-B2O3-SiO2 system.7). and relies of the knowledge of the possible network forming species of borate systems. Rmax = K/16 + . R ≡ Na/B and K ≡ Si/B. Clockwise from K top. Rmax = 1 R ≤ Rmax B4 = R (or .25(R – Rmax)/ (1+K) B4 = 1 Na2O R B2O3 SiO2 Fig 6.As mentioned earlier. The Yun-Bray model [17] and random pair model [15] seem to be conventional choices for a mathematical production of network-forming-species ratios. which are given in Fig. 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.

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

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

1.P. Chubynsky. and Rader. Zachariasen. 17.J.. Chem. Mater. P.C. Cambridge: Royal Society of Chemistry. Gupta. Gupta. in Rigidity Theory and Applications.. 699-702 (1985) 15. Smedskjaer. Optoelectron Adv.” J. 491-504 (2014) . Mamedov. Phys. Phillips. 115503 (2010). 9.” J.F. J. M. 18. 116. (1986). P. J. 71. 234503 (2009).C. 27. Youngman. Fei. Non-Cryst. Thorpe.J. J.G. M. Yun. A. 53. Soc. W. 16. Soc. P. S.M.M Smedskjaer.C.E. Bull. New York: Kluwer Academic/Plenum. Maxwell. 12. Solids. M. Lett. 105. R. P. 4. B. 54.K.C. Mauro. 3841-51 (1932). Rev. 10. P... Georgiev.V. Y. Vector Percolation and Glass Formation.L. 12930-12946 (2011). Ceram.J. “Introduction to Glass Science and Technology..F. J. Chem. J. Boolchand. 31. 90 (4). “Prediction of Glass Hardness Using Temperature-Dependent Constraint Theory.C. N. 8. Youngman. Smedskjaer. J. 153-81 (1979) 5. “The Atomic Arrangement in Glass. 703-720 (2001).M. Shelby. M. Yue.” J. Thorpe. 2011..H. II. M. J. “Nuclear Magnetic Resonance Studies of the Glasses in the System Na2O-B2O2-SiO2. “Topology of Covalent Non-Crystalline Solids I: Short Range Order in Chalcogenide Alloys.M.” J. 130.. 7. Mater. “Principles of Pyrex® Glass Chemistry: Structure Property Relationships. 2 nd Ed. 27m 294-299 (1864)..” J. Hogue. Y. Y.”Phys.C Mauro. Boolchand. Chem. 1999. 363-380 (1978).H. 2005. “Pressure Raman Effects and Internal Stress in Network Glasses. 174201 (2005)..” Front. D. Proceeding of the International Congress on Glass.” Solid State Commum. Bray. Solids. Phys.. J.” Appl. “Topological Principles of Borosilicate Glass Chemisty. Potuzak.K. D. 11. Smedskjaer.E. J. “Constrain Theory. 115. Mauro. Mauro. 14. 13. “Topological Model for Boroaluminosilicate Glass Hardness. Philos Mag. Generic Rigidity of Network Glasses. 23 (2014). “Composition Dependence of Glass Transition Temperature and Fragility.” Physical Review. Goodman. 6. A Topological Model of Alkali Borate Liquids.M. 34.3.. R.. Non-Cryst. Yue. New Delhi.. 3. C. Phys. C. “Topological Constrain Theory. W. “Discovery of the Intermediate Phase in Chalcogenide Glasses.” Am. Jacobs.C Phillips M. Mauro. A. J. B.

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