Material Science (BOE-303/403)

Unit-02

Diffusion in solids

A flow process that governs the movement of atoms and molecules in solids is called
diffusion. The atoms and molecules change their position under influence of the following
factors:

❖ Thermal energy
❖ Stress gradient
❖ Electric and magnetic field gradient
❖ Concentration gradient

Atomic vibration in solids is an inherent phenomenon. Thermal energy derived from these
atomic vibrations is responsible for diffusion of atoms.

Vibration amplitude of atoms increases with increase in temperature. At absolute Zero, the
probability of diffusion is zero.

Some applications of Diffusion:

1- Carburization of gears:
 2- Formation of p-n junction:

Types of Diffusion:

1- Microscopic Diffusion:
It involves movement of individual atoms and molecules in random direction.
2- Macroscopic Diffusion:
In this study, the mass flow process of a large number of atoms and molecules is
considered not in random direction, rather along a predefined direction.

Classification of microscopic diffusion:

a) Self Diffusion- Atoms jumps in pure metal.

b) Inter Diffusion- It is involved with binary metal alloy system such as Cu-Zn, Cu-Ni
etc.
c) Grain Boundary Diffusion- The atoms diffuse along the grain boundaries.
d) Surface Diffusion- The atomic movement takes place along the surface of a system.
e) Volume Diffusion- Movement occurs throughout the volume of Solid.
f) Lattice Diffusion- This is point imperfections induced diffusion in crystals.
g) Pipe Diffusion- This diffusion takes place along a dislocation edge.

Mechanism of Atomic Diffusion:

Following are the mechanism of atomic diffusion.

1- Interstitial Diffusion Mechanism:
Interstitial diffusion involves atoms that migrate from an interstitial position to
neighbouring one that is empty. This mechanism is found for inter-diffusion of
impurities such as hydrogen, carbon, nitrogen and oxygen, which have atoms that
are small enough to fit into interstitial positions.
In most metal alloys, interstitial diffusion occurs much more rapidly than diffusion
by the vacancy mode.
3. Substitutional Mechanism:

Substitutional diffusion proceeds when a substitutional atom jumps from one site to another.
Substitutional diffusion may occur any of the three mode as given below:

a- Direct mechanism
b- Ring mechanism
c- Vacancy mechanism

In direct and ring mechanism of diffusion, the atoms interchange their positions between
themselves. The mechanism may involve two atoms, three, four or more atoms interchange.

Vacancy diffusion occurs if the atoms interchange their positions with surrounding vacant
sites. When these atoms occupy vacant sites, another set of vacant sites is created at the initial
location of these atoms. This is responsible for creep in materials. Both self diffusion and
inter-diffusion occurs by this mechanism. Vacancy diffusion is considered as the most
acceptable mechanism for the substitutional diffusion.
Law’s of Diffusion:

Till now we have discussed microscopic diffusion and their atomistic models. We shall now
describe macroscopic laws of diffusion. Diffusion can occur under the influence of
concentration gradients and thermal energy in all the directions within a material. We shall
consider diffusion (mass flow) under concentration gradient for one dimensional case only.

Fick’s has given two laws of diffusion (Fickean laws or classical linear laws)-

1- Fick’s First Law

2- Fick’s Second Law

Fick’s First Law:

Consider two materials systems in which their atoms move uni-directionally in opposite
direction under the influence of concentration gradient. Concentration is expressed in terms
of mass per unit volume. It may also be expressed as weight per unit volume. Thus
concentration gradient means a change in the mass per unit volume along x-axis in one
dimensional case.

Fick’s first law has come from the analogy as given below:

Description Heat Flow Charge Flow Mass Flow

Flux Heat flux (q) Charge flux or Current Mass flux (j)
(Jm-2s-1) density (j) (Cm-2s-1) (Kg m-2s-1or mole.m-2s-1)
Gradient 𝑑𝑇 𝑑𝑉 𝑑𝐶
𝑑𝑥 𝑑𝑥 𝑑𝑥
(Temperature Gradient) (Electric Potential Gradient) (Concentration Gradient)
Law Fourrier Law Ohm’s Law Fick’s First Law
𝑑𝑇 𝑑𝑉 𝑑𝐶
q = −𝑘 𝑑𝑥 j = −𝜎 𝑑𝑥 j = −𝐷 𝑑𝑥
Material Thermal conductivity (k) Electrical conductivity (σ) Diffusivity or Diffusion
Property Coefficient (k)
Year 1807 1827 1855

Now Fick’s first law may be stated as

𝑑ƞ 𝑑𝐶
= −𝐷𝑥
𝑑𝑡 𝑑𝑥
Where
𝑑ƞ
= number of atoms diffusing per unit time into a cross sectional area A normal to the
𝑑𝑡
direction of diffusion x.
𝑑𝐶
= Concentration gradient
𝑑𝑥

Dx = Diffusion coefficient along x direction or diffusivity

Diffusivity depends on the following factors

1- Temperature
2- Concentration
3- Nature of diffusing species
4- Concentration is a function of time (t)

The negative sign indicates increasing diffusion down the concentration gradient.
1 𝑑ƞ 𝑑𝐶
Jx = − 𝐴 𝑑𝑡 = −𝐷𝑥 𝑑𝑥

𝑑𝐶
Jx = −𝐷𝑥 𝑑𝑥 Fick’s First law

Where

Jx= Diffusion flux (mass per unit cross sectional area per unit time).

In figure two concentration profiles are shown under steady state situation. Straight line
profile indicates that diffusion is independent of concentration. Profile will be non-linear
when Dx = f(C)
𝑑𝐶
So 𝐷𝑥 𝑑𝑥 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

The plot does not show time as a variable because in steady state, the profile and
diffusivity are not functions of time.

Jx (x,t) = Diffusion flux can change with position and time (unsteady state)

Jx (x) = Diffusion flux do not change with time (Steady state)

Fick’s Second Law:

This law deals with the practical situations of diffusion in materials. It considers the non
steady state flow.

Jx = f(x, t)

Let us consider an elemental slab of thickness ∆𝑥 along the diffusion direction x.

This thickness is enclosed between planes x & 𝑥 + ∆𝑥 which are perpendicular to direction x.
As diffusion proceeds the concentration changes with time and diffusing atoms accumulate
into or move out from the region under consideration. The number of atoms crossing over the
area A at plane x are not the same as number of atoms crossing over the same area at plane

𝑥 + ∆𝑥.

Mass entering ∆𝑉 at x in time interval ∆𝑡

𝑚𝑥 = 𝑗𝑥 . A. ∆𝑡

Mass leaving ∆𝑉 at 𝑥 + ∆𝑥 in time interval ∆𝑡

𝑚𝑥+∆𝑥 = 𝑗𝑥+∆𝑥 . A. ∆𝑡

Mass accumulating in ∆𝑉 in time interval ∆𝑡

∆𝑚 = (𝑗𝑥 - 𝑗𝑥+∆𝑥 ) A. ∆𝑡

∆𝑚 = - ∆𝑗A. ∆𝑡

Change in concentration in ∆𝑉 in time interval ∆𝑡

 ∆𝑚
∆𝐶 =
∆𝑉
− ∆𝑗A. ∆𝑡
∆𝐶 =
∆𝑉
− ∆𝑗A. ∆𝑡
∆𝐶 =
𝐴. ∆𝑥
− ∆𝑗. ∆𝑡
∆𝐶 =
∆𝑥
∆𝐶 − ∆𝑗.
=
∆𝑡 ∆𝑥
∆𝐶 − ∆𝑗.
𝑙𝑖𝑚∆𝑡→0 = 𝑙𝑖𝑚∆𝑥→0
∆𝑡 ∆𝑥
𝜕𝐶 𝜕𝑗
= − … … … … … … (1)
𝜕𝑡 𝜕𝑥
Equation (1) is the first form of Fick’s Second law.

𝜕𝐶
𝜕𝐶 𝜕(−𝐷 )
=− 𝜕𝑥
𝜕𝑡 𝜕𝑥
𝜕𝐶 𝜕 2𝐶
= 𝐷 2 … … … … … … . (2)
𝜕𝑡 𝜕𝑥
Equation (2) is the second form of Fick’s Second Law.

Limitations of Fick’s laws:

1- The diffusing media are taken as semi infinite which is not the real situation.
2- Except interface of two media, the other ends of materials are assumed infinite. This
is not possible to meet in actual condition.
3- It does not predict well the diffusion in three dimensional cases.
4- It does not take into account the effects of boundary contours and the surface texture
of the material. The boundary profile may be flat, curved, smooth or rough and
influence the diffusion rate.

Iron-Carbon Equilibrium Phase Diagram:

If carbon % is more than 6.67%, material become too much brittle to use commercially. So it
is not important.

𝛿-ferrite: it is an interstitial solid solution of C in 𝛿 iron (BCC) at high temperature.

𝛾 (Austenite): it is an interstitial solid solution of carbon having FCC crystal structure.

α-ferrite: It is an interstitial solid solution of carbon in BCC iron at low temperature.

Fe3C (Cementite): It is an inter-metallic compound of Fe & C orthorhombic crystal structure.

Invariant Reactions:

1) Peritectic Reaction:

2) Eutectic Reaction:

3) Eutectoid Reaction:
Eutectoid, Hypo-eutectoid & Hyper-eutectoid steels are important due to point of view of
micro-structure control and availability at low temperature.

Micro Structure of Eutectoid Steel:

Microsturcture of Steel & Iron:

Carbon is found in different forms in iron & steel, therefore various microsturctures are found
in them. These are as given below.

1. Ferrite
2. Cementite
3. Pearlite
4. Ludeburite
5. Martensite
6. Troostite
7. Sorbite
8. Austenite
9. Bainite
10. Allotropic forms

Ferrite:

It is soft and ductile. It cannot be hardened by rapid cooling. Low carbon steel and wrought
iron consist of ferrite. It is in the form of flakes.

Cementite:

It is carbide of iron (Fe3C), and is extremely hard. Presence of carbon in iron and steel
increases the hardness but decreases the ductility. The carbon is in the form of knots in
cementite.

Pearlite:

Pearlite is a mixture of ferrite and cementite, and is found in low and medium carbon steels.
An increment in hardness is achieved by increasing the proportion of pearlite. The coarse
crystals of pearlite are formed during slow rate of cooling in between 723°𝐶 to 625°𝐶.

Ludeburite:

Its microstructure is of layered formation and is found in cast iron. It posseses lubricating
property that imparts good machinibility to cast iron. It is brittle, cannot be forghed or rolled,
but can be easily casted.

Austenite:

The solid solution of iron carbide (Fe3C) in γ iron is known as austenite. Complete structural
changes occur in steel when it is heated above higher critical temperature. The non-magnetic
austenite absorbs excess ferrite & cementite.

Bainite:

It is a mixture of ferrite and cementite having finer crystal than pearlite. Its formation start
below 625°C
Martensite:

It is the hardest constitutent of steel, and has needle like structure. It is a solid solution of iron
carbide in ex-iron. It is produced when steel heated above 723°C is rapidly cooled by sudden
quenching. Martensite is least ductile & negligible tough.

Troostite:

It is obtained by sudden quenching of heated steel, or by cooling the steel rapidly. Its
structure is slightly granular. Toorstite may be of Primary or secondary types. Primary
troostite is formed directtly from austenite. Secondry troostite results from tempering of
martensite. Troostite is intermediate in hardness between martensite and sorbite.

Sorbite:

When the reheating temperature is increased, decomposition of steel begins that causes
change of troostite into sorbite. The formatin of sorbite does not take place spontaneously,
rather it occurs gradually. Although sorbite is less ductile than pearlite but its tensile strength
and yield point is higher. Depending upon the chemical composition, size of job and degree
of hardening, the sorbite begins to form at about 400°C and ends at about 680°C.
Allotropic forms of steel:

Some substances exist in more than one crystalline form. These forms are stable, have same
composition but different crystal structures. This change in crystal structure occurs at
different temperatures or pressures or both. This behaviour is known as polymorphism or
allotropy.

Example- 𝛼 iron (BCC), 𝛾 iron (FCC) & 𝛿 iron (BCC). Iron is non-magnetic above 768°C
temperature.

Transformation in steel and critical cooling curve or

(Isothermal transformation diagram) or T-T-T diagram:

The transformation in steel can be conveniently understood by time temperature

transformation (T-T-T) curve as shown in figure. Due to its shape from start to the end of
transformation it is also called C-curve. The nose indicates the least time taken for certain
transformation. Line AB passing through the nose indicates fall in temperature in OB time.
This line is known as critical cooling curve and its rate is termed as critical cooling rate. Its
value is 300°C/s.
Effect of rate of cooling:

The rate of cooling slow or fast, decides the transformation processes. These processes may
be summarized as follows-

1- Annealing is a heat treatment process in which cooling is done in furnace and rate of
cooling is very slow, as slow as 10°C/s or less.
2- Normalizing is a heat treatment process in which cooling is done in presence of
ambient air and rate of cooling is 50°C/s or less.
3- Quenching a heat treatment process in sudden cooling is done and rate of cooling is
350°C/s or more.
4- The formation of martensite starts at Ms and finishes at Mf.
5- Martensitic structure distort to Body Centered Tetragonal (BCT) due to interstitial
carbon atoms.

𝒄
>𝟏
𝒂

Tempered Martensite:

Martensite is very hard & so brittle that it cannot be used for most applications. The ductility
and toughness of martensite may be enhanced & internal stresses relieved by a heat treatment
process known as tempering.

Tempering is heating a martenistic steel to a temperature below the eutectoid for a specified
time period. This tempering allows, by diffusion processes formation of tempered martensite.

Martensite (BCT single phase) → Tempered Martensite (𝛂 + 𝐅𝐞𝟑 C)

Temperature is 250°c to 650°c.

Micro-Structure in increasing order of hardness:

Effect of alloying elements on steel:

W- imparts red hardness

V- induces fine grain distribution

Cr- improves resistance to corrosion & oxidation

Mo- increases hardenbility

Mn- imparts wear resistance

Ti- increases abrasion resistance

Ni- improves tensile strength & toughness

P- enhances machinability