This action might not be possible to undo. Are you sure you want to continue?

# 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.

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.

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

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

the Glass redundant bonds serve only to add internal stresses to the system [8]. This processes is called rigidity percolation [14]. Up until now. That is to say. When a network is over-constrained. N co . each representing a mechanically stable configuration. As the Topological Theory was developed further [1. If the network is mostly floppy. 4 represent regions where glass is not Fig 3.3] worked to expand topological theory to account for the current temperature of the network. not at a single Floppy Critical Rigid Fig 4. again. Glasses in the Boolchand Phase have interesting properties. there exists many local minima. The average number of constraints per atom. For now we will relate this behavior to its glass forming ability. Glasses in this region are said to be in a Boolchand Intermediate Phase. and the network can Energy Barrier easily overcome the low energy barrier to form glass. which are in accordance with the predictions made by Topological Theory. Therefore the optimal glass forms when N co =d . guided by the gradient of the Nd-dimensional hyperspace. Mauro and Gupta [2. it takes almost no energy to reconfigure the network. Phillips reasoned that ideally constrained system has enough constraints to prevent motion but not too many as to stress the network rigid. if a glass is to become a crystal. So as N co is varied from one extreme to another. The two extreme ends Amount of Atomic Order of Fig. such as extremely low minimum cooling rates (easily forms glass) and no internal stresses (no extra stress from redundant bonds). they do represent local minima in free energy (Fig 3. In theory. Floppy-Rigid Spectrum point. does not only apply to glass-forming ability. ideal glass-forming ability was discovered to occur in a critical range. Although glasses are not the most favorable thermodynamic state. the network becomes a crystal.The nature of the floppy and rigid constraints has a profound impact on the behavior of the network. atoms arrive at these local minima. it must reconfigure its topology into Gibbs Free Energy an ordered network. named after its discoverer [10].). 9]. the number of dimensions. They reasoned that. Energy Barrier to Crystallization easily formed. where local energy considerations are minimized. since thermal energy has not yet entered the discussion. if passes a critical point. Setting d = 3. for a system of N atoms and d dimensions. 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.45. we have only considered network at absolute zero. and that takes some amount of activation energy. This . as introduced by Phillips [4]. we obtain ideal glass behavior at m =2.

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

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

Rmax = K/16 + . 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].25(R – Rmax)/ (1+K) B4 = 1 Na2O R B2O3 SiO2 Fig 6.95R) B4 = R (or . Yun-Bray Prediction of Four Coordinated Boron (N 4) K≤8. two B4 tetrahedra (this is the only insta Fig 7.As mentioned earlier. which can be found experimentally using NMR analysis and deviates minimally with experimentation for extreme values of K [12] (refer to Fig. 6. which are given in Fig. The random pair model is used here to demonstrate a theoretical binary borate glass calculation.5 K≥8. The Configurational Units of a Borate Glass.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. Clockwise from K top. There are fewer explanations because the process is similar for SiO 2. Rmax = 1 R ≤ Rmax B4 = R (or .95R) R ≥ Rmax B4 = Rmax – 0. R ≡ Na/B and K ≡ Si/B. Table 1. three and four coordinated Boron units. and relies of the knowledge of the possible network forming species of borate systems.17]. these systems of glasses are still under study and debate [12. The random pair model uses similar reasoning as before to derive to following concentrations of two.

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

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

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