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APL 102

Ionic solids & Glasses

Concepts: Ionic structures, silicate, glass, quartz

Lecture 11
 Recap Solid Solution
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Hume Rothery Rules Ordered/Disordered Solutions
Strengthening
(Substitutional solid solution)
1. Structure factor
2. Size factor
3. Electronegativity factor
4. Valency factor Ordered Solid Random/disordered
Complete solubility systems Solution (Low T) Solid Solution (High T)
Ag-Au, Cu-Ni, Ge-Si
Exceptions! Ionic solids
Ag-Cu Bonds formed b/w oppositely charged ions
Cu-Zn – different crystal structure – unequal sharing of e- Usually (anion) R   R  (cation)
(Zn in Cu had higher solubility
due to its higher valence)
Ligancy: number of anions touching the cations
Hume Rothery rules are
guiding principles
 Ligancy as a Function of Radius Ratio
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Ligancy Range of radius ratio Configuration

2 0.0 ― 0.155 Linear

Lower limit decided by current coordination Upper limit decided by next possible higher coordination
3 0.155 ― 0.225 Triangular

4 0.225 ― 0.414 Tetrahedral

6 0.414 ― 0.732 Octahedral

8 0.732 ― 1.0 Cubic

12 1.0 FCC or HCP

 Effect of radius ratio
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Rc Rc Rc
 0.155  0.155  0.155
Ra Ra Ra

Unstable Critically stable/limiting Stable

Anions not touching the Anions touching

Anions touching central cation
central cation, the central cation
Anions not touching each other
Anions touching each other Anions touching

Rc Rc
 0.155  Ligancy  2  0.155  Ligancy  3
Ra Ra
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Some examples: Pure ionic

character
 Example 1: NaCl (Rock salt)
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RNa 
 0.54
RCl 
0.414  0.54  0.732
 Ligancy 6
Charge neutrality and packing
Octahedral Coordination

Note that in all octahedral positions Na+ ions are sitting

NaCl structure =FCC lattice + 2 atom motif: Cl- 0 0 0

cae2k.com Na+ ½ 0 0
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NaCl structure continued

Effective number of Na ions and Cl ions are

same i.e. 4: charge neutrality is maintained

2 RNa   2 RCl   a
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Example 2 : CsCl Structure
RCs 
 0.91
RCl 
0.732  0.91  1
 Ligancy 8
Cubic coordination of Cl- around Cs+

CsCl structure = SC lattice + 2 atom motif: Cl 000

Cs ½ ½ ½

BCC 2 RCs   2 RCl   3a

seas.upenn.edu
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Some examples:
Mixed nature of bonding
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Example 3: ZnS (Zinc blende or sphalerite) Cubic form

RZn 2
 0.48
RS 2
0.414  0.48  0.732
 Ligancy 6
Octahedral Coordination

However, actual ligancy is 4 (TETRAHEDRAL

COORDINATION)

Explanation: nature of bond is more covalent than ionic

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ZnS structure
FCC packing of anions (S2─), cations (Zn2+) occupy alternate
tetrahedral voids

Note that only half of the available tetrahedral voids are occupied

ZnS structure = FCC lattice + 2 atom motif S2─ 0 0 0

seas.upenn.edu Zn2+ ¼ ¼ ¼
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pixdaus.com
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13
theoasisxpress.com
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Question for thought?
What is common to
1. glass of the window
2. sand of the beach, and
3. quartz of the watch?

pixdaus.com
IIT Delhi Silica (SiO2)
Structure of SiO2
Bond is 50% ionic and 50% covalent

RSi 4
 0.29
RO 2
0.225  0.29  .414
 Tetrahedral coordination of O2─ around Si4+

Silicate tetrahedron
 Structure of Silica
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 Amorphous silica is the bases of most glasses

 Oxygen atoms at the corner of tetrahedron and Si at the centre
of the tetrahedron
 Silicate tetrahedron electrically unbalanced
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4─
2─

4+
2─
2─

2─

O2─ need to be shared between two tetrahedra

IIT Delhi 1. O2─ need to be shared between two tetrahedra.
2. Si need to be as far apart as possible

Face sharing Edge sharing Corner sharing

Silicate tetrahedra share corners

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Hexagonal crystal of
quartz

2D representation of periodically repeating 3D pattern of tetrahedra

in crystalline SiO2. Note that alternate tetrahedra are inverted
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Non crystalline Silica

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arrangement

At some locations Si-Si

distance becoming
shorter

2D representation of 3D random network of silicate tetrahedra in

the fused silica glass
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Question for thought?

What is the difference between Glass and Quartz??

Is there any difference at all?
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Structure of crystalline and non crystalline silica
 If the silicate tetrahedra are arrayed in a regular and ordered manner, a crystalline
structure is formed: Quartz (clocks, watches)

 If the tetrahedra are arrayed in a random manner then amorphous structure is

formed: Glass
 Network Modifiers
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Typically network formers are M3+ or M4+ cations as M1+ or M2+ cations cannot form
a stable random continuous structure and are called as network modifiers.

Network
Modifiers

Addition of Na2O to silica introduces weaker bonds in the network

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Tetrahedral bonds
Network Modification by addition of Soda

Na
+ Na2O =
Na

Modification leads to breaking of primary bonds between silicate tetrahedra

Lime (CaO) is also added for the same purpose

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Easier will be movement

and hence the deformation

2 D representation of 3D random network of silicate tetrahedra in the fused silica glass

 Soda Glass
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Addition of soda lowers the softening temperature of glass by breaking some strong bonds
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Impurity Bond breakage Viscocity

Ref: Hence and West,

Principles of Electronic Ceramics
 Glass Composition (Examples)
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• Pyrex
• 80% SiO2, 14% B2O3, 4% Na2O
• Bottle Glass
• 73% SiO2, 1.5% Al2O3, 5% CaO, 4%MgO, 1.5% Na2O
• Soda Borosilicate chemical ware
• 80.8% SiO2, 2.2% Al2O3, 4% Na2O, 13% B2O3
• Fused Silica
• 99.8% SiO2

Tsoft (Pyrex) < Tsoft (Fused Silica)

 Some Examples
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Vycor: 96% SiO2, 4% B2O3: ST~ 1100 °C

(can withstand high temperatures)

Pyrex: 80% SiO2, 14% B2O3, 4% Na2O ST~ 550 °C

(can withstand normal temperatures)

Window glass: 72% SiO2, 14% Na2O,

9% CaO, 4% MgO, 1% Al2O3: ST~ 120 °C
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Vycor
Pyrex

Window
glass
 Announcement
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 Minor I exam details:

Date: 31-Aug-17
Venue: LH 121 & LH 308
Time: 2:30 to 3:30 pm

 Minor I Syllabus: Topics covered till wednesday (23rd Aug 17) lecture