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Structure of Silicate Glasses

(by Sujoy Bhattacharyya, Glass Technologist)

Principally any liquid can be cooled to a glassy state provided there is a substantial obstruction to crystallization in the way. Then why all oxide melts cannot form glass ? Zachariasen postulated the following rules for glass formation (i) (ii) (iii) (iv) No oxygen atom may be linked to more than two cations. cation co-ordination number with respect to oxygen is small, 3 or 4. Polyhedra are only shared through corners, not by faces or edges. For 3D networks, at least three corners of the polyhedra must be shared.

Zachariasens postulates are still accepted today, at least for oxide glasses, though there are few exceptions. In TeO2-PbO glass, co-ordination number of tellurium is 6 w.r.t. oxygen. Also in alkali-TiO2 glass Ti4+ is believed to be in octahedral co-ordination and edges of the octahedra are shared, not the corners. We will not discuss these few exceptions here to avoid complication. An oxide can be denoted by MxO y where M is the metal ion (cation) with valency y. Oxygen (anion) valency is -2 in most cases. Metal Depending on the ratio rMy+ : rO2- the metal ion forms several geometric shapes with different co-ordination numbers with oxygen ions in the ionic solid oxide structure. Oxygen ions sit at the apexes of the geometric shapes (polyhedra) and the small cation takes the interstitial position. In actual cases none of the oxides are truly ionic, but always some covalent bonding exists. Notwithstanding, above polyhedra formation take place. Table 1 below presents several possibilities : Co-ordination number 3 4 6 8 12 Geometric shape Planar triangle Tetrahedral Octahedral Body centered cubic Closest packing Limiting ratio, rMy+ : rO20.155 0.225 0.225 0.414 0.414 0.732 0.732 1.000 1.000

Table 1 : Dependence of various co-ordinations on limiting cation : anion radius ratio

Commercial glasses are mixture of several oxides. Property of each oxide from its original metal ion contributes to the final property of the finished glass. Elements from each group of the periodic table play specific role in glass structure formation. Let us take SiO2 system. The rSi4+ : rO2- is 0.42/1.40 = 0.30 which is tetrahedral co-ordination, satisfies rule (ii). Co-ordination number of O2- is 2 w.r.t. Si4+, also satisfies rule (i). So SiO2 forms glass. Consider Al2O3 system. The rAl3+ : rO2- is 0.57/1.40 = 0.407 which is at boarder of 4 and 6 fold coordination. Co-ordination number of O2- is 4 w.r.t. Al3+ which does not satisfy rule (i). So Al2O3 does not form glass. However in aluminosilicate glass co-ordination number of O2- is 2 w.r.t. Al3+ which satisfies rule 3+ 4+ (i). Some Al ions can replace Si ions in tetrahedral site in the glassy network. In general, systems like SiO2, B2O3, GeO2, P2O5 easily form glass on their own. Two oxides As2O3 and Sb 2O3 form glass with difficulty when cooled sufficiently fast. Some other oxides Al2O3, Bi2O3, TiO2, TeO2, SeO2, BeO2, V2O5, MoO3, WO3, PbO, ZrO2 can go into glassy state when melted with one or more other selected oxide. For example in TeO2-PbO system none of the oxides form glass alone, but in combination they do.

Use of Na2O-CaO-SiO2 phase equilibrium diagram is of utmost importance in soda-lime silicate glass. For making glass successfully its very important to avoid any crystallization or devitrification. Glass cools faster than the crystal and the former settles in a higher energy metastable thermodynamic state or vitreous state.

Fig 1: Na 2O-CaO-SiO2 ternary phase diagram

Commercial soda-lime silica glasses fall around the zone with a composition nearly Na2O.3CaO.6SiO2. The liquidus (TL) in this zone is between 750 to 1050 C. It is therefore very crucial to keep the working range (gob delivery or drawing from furnace end to giving final shape, viscosity range 10 3-7 Poise) temperatures well above liquidus temperature. In actual melting liquidus may change due to change in composition like wrong batch, refractory corrosion, stagnation of the melt in a dead zone, foreign body dropping by accident, heavy mineral inclusion from batch, etc. A glass technologist must avoid such situation. It has been observed that liquid-liquid phase separation takes place in glass melt, i.e, more than one vitreous (glassy) phases of different compositions may co-exist in the melt. Electron microscopy and microprobe analysis have shown presence of two vitreous phases in borosilicate and silicophosphate glasses. A homogenous nucleation may take place in the melt. If the size of the nuclei are too small they will dissolve. But the nuclei may grow in favorable conditions as mentioned above and lead to devitrification. The rate of crystal growth, R = ( k/a ) * ( TL T ) where k, a = material constants k = 290, a = 0 in soda lime silica glass T L , T = liquidus and actual working temperature respectively = viscosity at temperature T

The influence of heavy mineral oxide in the melt is also equally important for commercial soda lime silica glass because they are often present as impurity in the sand, felspar and other natural raw materials. There are heavy minerals like chromites, corundum, sillimanite, kyanite, andalusite, zircon, ilmenite, rutile, etc. commonly found in natural minerals. Normally refractory minerals with specific gravity more than 2.9 3.0 are considered as heavy minerals ; their grain size should be below 63 m for a trouble free melting. Oxides play three clearly distinct roles in the network (i) Network formers (ii) Network modifiers and stabilizers (iii) Intermediates Crystalline silica (quartz) form infinite 3D network of (SiO4) 4- tetrahedral ring structure in a highly periodic arrangement. Pure SiO2 glass also form similar structure, but in random arrangement. Fig 2(a) and 2(b) 4+ 2below show the difference. The small filled circle is Si , and large circle is O ion :

Fig 2(a): 2D view of Crystalline silica (quartz)


Fig 2(b) : 2D view of puree silica glass


Further note that all O ions are shared in pure SiO2 glass through the corners of (SiO4) tetrahedra (denoted as Q). Such oxygen ions are called bridging oxygen (BO) as they form so in between two adjacent tetrahedra. This kind of structure is very rigid as the Si O bond has very high dissociation energy. Normally a large of rings ( > 6) form the network. Therefore it requires very high temperature to melt pure SiO2 glass more than 1720 C. When a network modifier (alkali/alkaline earth oxide) is added to the pure SiO2 network, it breaks the BOs and convert them to non bridging oxygen (NBO). Refer Fig 3(a) and 3(b) below :

Fig 3(a) : Effect of alkali oxide addition into (SiO 4)4-

Fig 3(b) : Effect of alkaline earth oxide addition into (SiO4)4-

Number of NBO/Q depends on the R2O/RO : SiO2 ratio. In xR 2O.(1 x)SiO2 binary system, at x = 0.33 2 virtually only Q3 exists; which transforms almost completely to Q at x = 0.5. In the intermediate compositional range both Q3 and Q2 exist. Refer Fig 4 below, Qi represents tetrahedron with i-number of bridging oxygen atoms.

Fig 4 : Effect of alkali oxide addition into (SiO4)4- glass network, change of Qi configurations

The most common intermediate is Al2O 3 in commercial glass. As modifier Al takes three Q3 units to link with 3 no. of NBO atoms. But Al3+ also forms glassy network by replacing Si4+ ions. When it does so one negative charge in the Q-unit has to be balanced by a univalent (alkali metal) cation, or two negative charges in the 2 no. Q-units have to be balanced by a divalent (alkaline earth metal) cation. Such a structure is highly cross linked. Raman spectra showed discrete bands of SiO3, Si(OAl), =Si(OAl)2, Si(OAl)3 and Si(OAl)4 tetrahedral (Q) groups. The proportion of bonding electrons in the SiO bridging bonds of SiOSi and SiOAl is unaffected because Al3+ balances its charge with modifying metal cations. Aluminosilicate glasses found special commercial application in E-fiber (low alkali, contains 7 8% B2O3 by wt), A-fiber (high alkali, contains 0.5% B2O3 by wt), S-fiber (borate and flux free, very high strength, chemical resistant). They have excellent scratch resistant property and higher viscosity at elevated temperature due to presence of Al3+ in Q-units and very high degree of polymerization. That way they are superior than many borosilicate glasses. Low alkali aluminosilicate glasses also have special application like combustion tube, outer enclosure of halogen and sodium vapor lamp, substrate material, cell phone panels and display glass, etc. because of their high chemical durability. They offer very good thermal shock resistance due to lower co-efficient of expansion and have high modulus of elasticity. Therefore these glasses are also used in boiler pressure gage casing, high temperature thermometers, thermally and electrically loadable film resistors.