MATERIALS SCIENCE

Part of & A Learner’s Guide

ENGINEERING
AN INTRODUCTORY E-BOOK
Anandh Subramaniam & Kantesh Balani
Materials Science and Engineering (MSE)
Indian Institute of Technology, Kanpur- 208016
Email: anandh@iitk.ac.in, URL: home.iitk.ac.in/~anandh
http://home.iitk.ac.in/~anandh/E-book.htm
What is a bond? Some thoughts.

 Isolated ‘atomic’ species can come together to lower the overall ‘energy’ of the system. This
‘combined’ state, where the atomic species ‘exist together’, is called the bonded state. The
interaction between any of the constituent atomic species can be referred to as a bond.
 The bond may form between a limited set of atomic species to form a ‘molecule’ (e.g. in
H2O, CH4, etc.) or the bond may give rise to an ‘extended solid’ like the Cu crystal or the
silicate glass*.
 Bonding is an ‘easily accessible term’ for the electromagnetic structure of an assemblage of
atoms/molecules/ions. The interaction between atoms/molecules/ions may lead to a
lowering of the energy of the system the bonded state.
 The interaction between the atomic species could be strong or weak. The strong bonding
interactions are: (i) covalent, (ii) ionic & (iii) metallic. The weak interactions include the:
(i) hydrogen & (ii) Van der Walls bonds.
Sometimes, the metallic bond is considered a special case of a combination of the other two types.
 In molecular solids, the bonding responsible for the formation of the molecule (e.g. H2O) is
of covalent nature; however, weak interactions are responsible for the formation of an
extended solid (e.g. the ice crystal**).
 The liquid state can/should also be considered a bonded state as there is some interaction
between the species involved (e.g. Hg, H2O, etc.), which has led to the formation of the
liquid (else we would have a non-interacting gas).
* Glasses are not considered as the ground state of the solid.
** Even in water the hydrogen bonds exist, but the overall system is in a dynamic state (hydrogen bonds are rearranging in time).
 At ‘high enough’ temperatures the bonding forces may be overcome by ‘thermal effects’ and
the atomic species may exist in the form of a gas. On lowering the temperature (or increasing
the pressure), the gas may liquefy. Inert gases can also be liquefied, which implies that there
are weak interactions present even between the atoms of an inert gas like Argon.
 In many solids the bonding may have a mixed character*.
E.g. the bonding in ZnS (Zinc Blende Click here to know more) has both ionic and covalent
character. We have already noted that the bonding in ice has contributions from both
covalent (between O and H) and hydrogen (between the H2O molecules) bonding.
 CCP Fe (stable above 912C at 1 atm) has predominantly metallic character, while BCC Fe
(stable below 912C) has partially covalent character. The partly covalent character is
responsible for the non-close packed structure of BCC Fe.

* In fact the mixed character of bonding may be a rule rather than an exception!
 Funda Checks
What is a molecule?
 The concept of a molecule is most suited for covalently bonded (or with a polar covalent
bond) species like H2O, CH4 & NH3 & C60.
 For crystalline solids (like Cu crystal, NaCl crystal, Diamond crystal) the concept is
‘practically useless’; as the entire solid has to be considered a molecule.
 In molecular crystals like water, we may still want to retain the concept of a H2O molecule
with ‘weak interactions’ with other molecules.
This leads us to a related question: “In a Cu crystal, to which atom is a given atom bonded to?”.
 As pointed out before, the answer is: to all the atoms in the solid! The free electrons mediate the
interaction.

 However, most of the energy contribution usually comes from the first coordination shell of
atoms (nearest neighbours). In many cases only 10-15% arises from the next nearest
neighbours. The contributions from 3rd may fall to few percent and that from higher order
neighbours is often very small.
 This implies that in computations of energy, it is often enough to consider 1st (nearest) and
2nd (next nearest) neighbours with very small errors arising from the process.
In fact in computational methods like MD the errors arising from other sources (e.g. the use
of interatomic potential) is often more than that introduced by using the ‘next nearest
neighbour approximation’.
Nearest Neighbour (NN), Next Nearest Neighbour (NNN), Next to NNN (NNNN)
 Let us consider the example of a simple cubic crystal (e.g. Po).
 The table and diagrams below are self explanatory.
 As mentioned before, the central atom (black) is bonded to not only these atoms (NN, NNN,
NNNN), but the entire crystal (in a metallic bond). As the inter-atomic distance increases the
effect of the bonding ‘fades away’.
NNN

NN

Coordination Direction Distance Number Colour NNNN

NN <001> a 6 Blue
NNN <011> a2 12 Maroon
NNNN <111> a3 8 Green
Effect of Bonding on properties: a broad flavour
 Two important contributing factors to the properties of materials is the nature of bonding
and the atomic structure.
 Both of these are a result of electron interactions and resulting distribution in the material.
 Bonding is an ‘easily accessible term’ for the electromagnetic structure of an assemblage of
atoms/molecules/ions. The interaction between atoms/molecules/ions may lead to a
lowering of the energy of the system the bonded state.

Hardness Electrical
Bond Melting point Examples
(Ductility) Conductivity
Diamond,
Covalent High Hard (poor) Usually Low
Graphite, Ge, Si
Ionic High Hard (poor) Low NaCl, ZnS, CsCl

Metallic Varies Varies High Fe, Cu, Ag

Van der Waals Low Soft (poor) Low Ne, Ar, Kr

Hydrogen Low Soft (poor) Usually Low Ice

Physical/atomic structure
Properties of Materials
Atomic level factors Electromagnetic structure Bonding
 Two types of crystals can be identified (based on bonding): the Molecular and Non-
molecular crystals. We shall deal only with non-molecular crystals in this chapter.

CRYSTALS

Molecular Non-molecular
• Molecule held together by primary covalent bonds
• Intermolecular bonding is Van der Waals, Hydrogen bonding (or
other weak interactions)
COVALENT

Click here to know more about Real crystals have IONIC

ice → a molecular crystal bonding characteristics
lying somewhere in this
triangle METALLIC

 The three types of bonding (Covalent, Ionic, Metallic) represent three extreme forms (like
the corners of a triangle)  actual bonding in many crystals could have a mixed character.
 Additionally, within a single compound more than one type of bonding may be present (e.g.
salts of complex anions). More about this later.
 As we are talking about crystals, ‘metallic’ crystals are considered above. But, we can have
liquids which are metallic (e.g. Hg at room temperature) and also amorphous metallic
materials (e.g. Zr41.2Ti13.8Cu12.5Ni10Be22.5 is a composition of a ‘bulk’ metallic glass).
 The position within the periodic table is a good indicator of the type of bond that the
element forms. Electronegativity is an important deciding factor in this regard, along with
ionization energy.
 Ionically bonded structures tend to have high symmetry, with high coordination number
(which maximizes the electrostatic attractive forces). Alkali and alkaline earth elements
usually form ionic structures in combination with small electronegative anions (e.g. O2,
F).
 Covalent bonds are characterized by a high degree of directionality, which often leads to
low coordination number.
Covalent bonding is promoted by:
 small sized atoms with high valency, which are highly polarizing in the cationic state
(B3+, Si4+, P5+, S6+)
 large atoms, which are highly polarizable in the anionic state (I, S2).
 In the context of Molecular Crystals ‘weak’ interactions (like Van der Waals forces) were
mentioned. These forces are not only important to consider in the crystalline state of
molecules but also in other contexts, especially liquids
► Where they control the association of molecules.
 This association of molecules determines the physical properties like:
► Melting point, boiling point, solubility, etc.
► Molecular organization into larger structures: membranes, etc.
► Molecular recognition: substrate/enzyme docking, etc
 The metallic bond is very different from the ionic and covalent bonds.
 Hence, an alternate way of looking at the bonding picture is as in the figure below.
 This implies that metals are good conductors (no band gap), while non-metals have a band
gap and are insulators at 0K.

Bonds  In metallic crystals the bonding electron density is

~uniform throughout the crystal.
 In Covalent crystals the electron density is high
Metallic Non Metallic between the nuclei.
Ion cores in a  In ionic bonding the electron density is higher around
Equal sharing of electrons one of the nuclei.
‘sea’ of electrons
Covalent bond
Unequal sharing of electrons
Ionic bond

Cu Non-directional Directional -Sn

 Binding Energies of Bonds

Bond Type Energy (eV) Energy (kJ/mole) Energy (kJ/mole)

Ionic ~5-15 (strong) ~500-1500 NaCl: 640

Covalent ~1-10 (strong) ~100-1000 Diamond: ~710

Metallic ~0.5-8.5 (strong) ~50-850 Fe: 406

Hydrogen ~0.05-1.5 ~5-155 H2O: 51

Van der Waals ~0.01-0.5 ~1-50 Ar:7.7

kBT ~ 0.026 eV at T = 300 K

Mixed bonding
 Many materials have a mixed bonding characteristics, between covalent and ionic bonding.
Examples are as below.

 Oxides: % ionic bonding ~ 70%

 Nitrides: % ionic bonding ~ 40%
 Carbides: % ionic bonding ~ 15~20%
Metallic-Covalent Mixed Bonding: The Transition Metals are an example where dsp bonding orbitals lead to high melting points.

 In Li2SO4, ionic bonding exists between Li+ and SO42 ions, while the bonding character is
covalent within the SO42 ions (the S-O bond).
 In TiO the bonding character is between ionic and metallic.
 CdI2 is an interesting bonding character: that between ionic-covalent-van der Waals.
 Molecular crystals typically have covalently bonded molecules forming
a crystal with WEAK INTERACTIONS acting between the molecules
Electron cloud distribution in various kinds of bonding

Van der Waals interactions

Click here to know more about Weak Interactions

Schematics
Funda Check In a Cu crystal to which atoms is the atom at (0,½,½) bonded to?

 The nearest neighbours to the atom at (0,½,½) are given by the co-ordination polyhedron
(shape of cuboctahedron, coordination number 12) as in the figure below. These atoms are
at a distance of a2/2 from the atom.
 However, these are not the only atoms to which the atom at (0,½,½) is bonded to. In fact it
is bonded to all the atoms in the solid, as Cu has metallic bonding, wherein each atom
donates one electron to the entire solid (‘electron cloud). This situation is very different
from the covalent bond.
 The atomic interactions gets weaker as one goes from the nearest neighbour to the next
nearest neighbour atoms, to atoms still farther away.