STRUCTURE OF SOLIDS

CHAPTER 1
CONTENTS
• INTRODUCTION TO METALS,NON-METALS AND ALLOYS
• CRYSTAL STRUCTURE
• SOLID SOLUTIONS AND ITS TYPES
• SOLUBILITY LIMIT
• COMPONENTS
• DIFFUSION IN SOLIDS
Introduction to Metals, Non-metals and
Alloys
• Engineering material can be defined as:
“Engineering material is a subject which deals with the
manufacturing, properties and uses of material used in applied
engineering.”
• The range of engineering material varies from light weight to
heavy materials. For example, Alloys for air-craft,
Semi-conductor chips for pcs, Photovoltaic for energy storage,
Semi-conductor, Semi-conductor scanners etc.
 Classification of engineering materials
• Metallic materials:
• Ferrous metals
• Irons, steels, carbon steels, stainless steels etc.
• Non ferrous materials
• Aluminium, copper, zinc, tungsten, titanium etc.
• Non metallic materials:
• Composites, polymers, ceramics etc.
• Special materials:
• Glass, semiconductors, superconductive materials, refractory materials etc.
• Alloys :
• Ferrous ;
• Stainless Steel, Nickel steel, Tungsten steel, Vanadium steel, Molybdenum steel, Manganese steel etc.
• Non ferrous;
• German silver, Dialuminium, Brass, Bronze etc.
Properties of materials
(Depends upon the structure of the material)
• Mechanical properties:
• Youngs modulus, tensile strength, compressive strength, shear strength,
hardness, toughness etc.

• Physical properties:
• Magnetic properties, optical properties, conductance etc.

• Chemical properties:
• Corrosion, catalysis, oxidation, reduction etc.
 Metals v/s Non metals
• Good conductors of electricity • Poor conductors of electricity
• Good conductors of heat • Poor conductors of heat
• High density • Low density
• Malleable and ductile • Brittle
• Shining appearance • Dull appearance
• High melting point • Low melting point
Atomic structure
• In year 1899, J.J. Thomson proposed atomic model which is the basis
of current atomic structure and is treated as the building blocks of all
the materials.
• These days we are capable of observing an individual atom.
• Atoms are stable and can exist a billion of years without any change.
• They combine together to make solids and can interact with different
atoms to make compounds.
Atomic models
• First atomic model was proposed by J. J. Thomson, in year 1899 was
studied and the shortcomings of this model were corrected by other
atomic models which are shown below in chronological order:
• Thomson model
• Rutherford model
• Bohr’s model
• Sommerfield-Wilson model
• Vector model or modern atomic model
Key points
• Atomic number = no. of electrons = no. of protons
• Atomic weight (amu) = protons + neutrons
• Mass of electron = 9.1093837 × 10-31 kilograms
• Plank’s constant h, = 6.62607015 × 10-34 m2 kg / s (Js)
• Velocity of light = 3×108 m/s.
• Charge on electron = 1.60217662 × 10-19 J
• Avogadro number Na = 6.02214076 × 1023
Crystal structure
• The properties of engineering materials depends upon the type of
bonding between atoms, and arrangement of atoms (structure) in the
unit cell of a lattice in the crystal.
• Solid materials either crystalline or non crystalline (amorphous) like
wood, glass etc.
• Generally metals are polycrystalline yet single crystals are also exist in
nature and can be developed in the laboratory.
• Single crystal examples are quartz used for generation of ultrasonic
waves and single crystal of silicon used in semiconductors.
Types of bonds
• Atoms are bonded with each other
in solids by different mechanisms
• IONIC BOND
• When solid has more than one type
of atoms, then one atom donates
its valence electrons to different
atoms, filling the outer energy shell
of second atom.
• The donor acquires positive charge
and become cation and the atom
getting electron acquire negative
charge thus called anion.
• NaCl, MgO, AlO
Covalent bond
• In covalent bonded solids
sharing of electrons among two
or more atoms takes place.
• Sharing of electrons by
overlapping of orbitals make
strong bonding e.g. DIAMOND
• Poor electrical and thermal
conductivity and poor ductility.
• Silicon, diamond, silicon carbide
Vander-waals bond
• Secondary bonding which joins
molecules or group of atoms
with weak electrostatic force.
• Heating water to its boiling point
breaks vander walls bonds
between water molecules and
change water to steam
Metallic bond
• Metals are aggregate of atoms
arranged in crystal structure
• Properties of metal depend upon
the nature of constituent atoms
and how these are bonded.
• Characteristics of both ionic and
covalent bonding
• Possibility of long range/chain of
periodicity of arrangement of
atoms
• Mercury, copper, nickel, iron etc.
Atomic
structure of a
crystal
 Space lattice and crystal lattice
• Space lattice is defined as an infinite array of points in three-dimensional
space, in which each point is identically located with respect to the other
points. A study of space lattice clarifies the crystal structure of the
existing materials.

• Crystal lattice: A regular arrangement of the constituent particles, i.e.,

atoms, ions or molecules of a crystal, in three-dimensional space. When
the constituent particles are represented by dot (.), the periodic and
systematic arrangement of these dots in three dimensions is called
crystal lattice.
Unit cell
• Unit cell: The smallest
three-dimensional portion of a
complete space lattice which
when repeated over and again in
different directions produces the
complete space lattice. If we
repeat unit cell in all dimensions,
we obtain a structure of the
crystal. The properties of unit
cell are measured by length of
edges and the angles between
the edges.
Fourteen bravais lattices
Common crystal structures
• Non-directional nature of metallic bond results in highly symmetrical
close packed structures.
• Each metal atoms tend to surround itself as many neighbours as
possible to minimize the potential energy. Common crystal structures
in metals are:
• Body centred cubic BCC
• Face centred cubic FCC
• Hexagonal close packed HCP
BCC and FCC crystal structures
HCP Structure

A primitive cell may be defined as a geometrical shape which is

repeated in three dimensions generates a space lattice
Atomic packing factor and Co-ordination
number
•
Atomic
packing
factors of
SCC,BCC and
FCC
Atomic
packing
factors of
HCP
ALLOYS
• An alloy is a mixture of two or more metals or a mixture of a metal
and a non-metal.
• There are two types of alloys:
• 1. Substitutional alloys
• 2. Interstitial alloys
• In a substitutional alloy, some of a metal's atoms are substituted by another
element's atoms of a similar size. In an interstitial alloy, the smaller atoms of
another element fill in the "gaps" in a metal's structure.
Difference between metals and alloys
• Alloys are harder than component metals
• Alloys are more resistant to corrosion than pure metals
• Alloys have a lower melting point than component metals
• Alloys are more ductile than component metals
• Alloys are more durable than component metals
• Alloys are less conductive than component metals
• These properties make alloys more useful than pure metals. For example,
steel (iron + carbon) is a common alloy used in building materials. This
makes sense since it can hold more weight, is less likely to corrode, and can
be more easily shaped than iron.
Some common alloys with their compositions and applications
Name of Alloy Composition Example of use

Amalgam Mercury (45-55%), remaining (45-55%): silver, tin, Dental filings

copper, and zinc
Brass Copper (65-90%), zinc (10-35%) Door knobs and locks
Bronze Copper (78-95%), tin (5-22%), remaining %: manganese, Statues
phosphorus, aluminum, or silicon

Cast iron Iron (96-98%), carbon (2-4%), remaining %: silicon Cookware, casings bodies etc.

Gunmetal Copper (80-90%), tin (3-10%), zinc (2-3%), remaining %: Guns

phosphorus
Pewter Tin (80-99%), remaining %: copper, lead, antimony Decorative items

Stainless steel Iron (>50%), chromium (10-30%), remaining %: carbon, Jewellery, medical equipment etc.
nickel, manganese, molybdenum, and other metals.

Sterling silver Silver (92.5%), copper (7.5%) Medical tools

Types of alloy structures
• Solid solutions
• Substitutional solid solution
• Ordered Substitutional solid solution
• Random Substitutional solid solution
• Interstitial solid solution
• Compounds
• Intermediate phases
• Mechanical mixtures
Structure of solid solutions (interstitial and
substitutional)
Grain structure of metals and alloys
• The individual crystal structures
group together to form grains.
These grains combine to form the
grain structure, which can be
viewed through a microscope. The
image shown is the grain structure
for stainless steel.
• The grains themselves are formed
when the molten material
solidifies.
• The grain structure is adapted for
the application of the metal alloy.
Grain structure contd.
• The size and orientation of the grains are dependent on:
• Composition (alloy)
• Chemical influences (ex. corrosion)
• Physical influences (ex. heat)
• Mechanical influences (due to the forming process, ex. forging)
• Looking at the grain structure (also called the microstructure)
the properties of the material such as strength, hardness, and
ductility can be predicted.
Diffusion in solids
• Diffusion can simply be thought of as the rearrangement of the atoms
inside the crystal (lattice) structure of the metal. Diffusion is
controlled by the rate at which these atoms change position and
increases exponentially when temperature is applied.
• Diffusion is material transport by atomic motion.
• Inhomogeneous materials can become homogeneous by diffusion.
• For an active diffusion to occur, the temperature should be high
enough to overcome energy barriers to atomic motion.
• Self-diffusion is diffusion in one-component material, when all atoms
that exchange positions are of the same type.
Diffusion mechanisms
• Vacancy diffusion (Fig. 1) is the
predominant diffusion mechanism
in metals due to the low energy
required to move atoms into
atomic vacancies that form during
heating. The vacancy diffusion
process occurs when an atom on a
normal lattice site jumps into an
adjacent unoccupied (vacant) site.
It turns out that only adjacent
atoms move into a vacancy. The
rate depends on concentration of
vacancies in the lattice.
Chemical diffusion
• Chemical diffusion (aka
inter-diffusion or impurity
diffusion; Fig. 2) is the exchange
of atoms when two metals or
alloys are placed in contact and
migration across the contact
boundary occurs by atom
exchange. Diffusion of atoms is
typically from high concentration
to low concentration.
Interstitial diffusion
• Interstitial diffusion (Fig. 3) occurs if a
solute atom is sufficiently small and
moves to a position between larger
solvent atoms in an energy-favorable
configuration. Atoms move from an
interstitial position to another
interstitial site nearby. Migrating
atoms are typically small in size (e.g.,
N, C, H and O). Interstitial diffusion
occurs much more rapidly than
diffusion by the vacancy mode since
interstitial atoms are smaller and more
mobile. This movement (or jump)
involves a considerable distortion of
the lattice.
Self diffusion

• Self-diffusion (Fig. 4) occurs when the atoms of a metal exchange

positions within that metal.
Grain boundary diffusion
• Besides diffusion within the
crystal, grain boundary (figure 5)
diffusion may occur. As the grain
boundaries regions are
saturated with crystal lattice
imperfections, energy barrier
(activation energy) here is
relatively low, therefore the
diffusion rate along these
regions is much higher, than the
volume diffusion rate.
Laws of diffusion
• First Fick’s law is used for diffusion in steady state (concentration
gradient of the diffusing element does not change in time).
• First Fick’s law states:
• J = - D ( ∂C/∂x )
• Where
• J – diffusion flux (quantity of material that crosses a plane of unit area
perpendicular to the diffusion direction for time unit), mol/ (length2 *time);
• D – diffusion coefficient or diffusivity of the material, length2/time ;
• ∂C/∂x – concentration gradient in the diffusion direction, mol/(length3
*length).
Second Fick's law
• Second Fick’s law is used for transient (not steady state) diffusion process.
• Second Fick’s law states:
• ∂C/∂t=D(∂2C/∂x2)
• Where
• ∂C/∂x – concentration gradient in the diffusion direction, mol/(length3 *length);
• D – diffusion coefficient or diffusivity of the material, length2/time ;
• C – concentration of the diffusing material, mol/length3
• The diffusion coefficient is not a constant. It is a function of crystal structure, temperature and material concentration.
• The temperature function is expressed by the following equation:
• D = D0e-Q/RT
• Where
• D - the diffusion coefficient, length2/time;
• D0 - the maximum diffusion coefficient, length2/time;
• Q -activation energy for diffusion, energy/mol;
• T - absolute temperature, Kelvin;
• R - gas constant, energy/(temperature*mol).