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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.

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

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

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

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

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

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

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

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

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

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