Elements of Physical Metallurgy

19Y304

Faculty
Dr. Manu S Mohan
Assistant Professor
Metallurgical Engineering Department
PSG College of Technology, Coimbatore
Chapter-3
 1.Diffusion- Definition and Mechanisms

(1)Mechanisms of Diffusion

Based on the site occupied by the atom in the lattice, the diffusion mechanisms operating are vacancy mechanism and
interstitially.

(1.1)Vacancy Mechanism
Substitutional atoms diffuse by vacancy mechanism. Substitutional atom oscillates at the lattice site.
The mean energy possessed by each atom is 3 kT (k is the Boltzmann Constant, which has a value of 1.381*10 -23 JK-1).
Substitutional atom jumps to an adjacent vacant site (vacancy), if the atom vibrates at a particular violent oscillation.

The probability that an atom can jump into a vacancy depends on the probability that it can acquire sufficient vibrational
energy.
The rate at which substitutional atom can jump into vacant site depends upon the concentration of vacancies.
 1.Diffusion- Mechanisms

Fig.1. (a) Atomic packing in (111) plane in FCC having a vacant site. For the atom to jump to the vacant site in the direction
indicated by arrow, the atoms indicated by 1 and 2 must move apart (b) Atoms 1 and 2 and other atoms that move apart
when the atom jumps into vacant site are indicated in unit cell.

(1.2)Interstitially
An atom occupies an interstitial site when its size (diameter) is appreciably lower than the diameter of the solvent atom.
An interstitial atom can jump into adjacent intersitial site if it acquires sufficient energy to overcome the strain energy barrier
for migration.
Usually the concentration of interstitial atoms is low that an interstitial atom is always surrounded by adjacent vacant sites.

Interstitial sites in FCC- mid way along cube edge and center of the unit cell.
Interstitial sites in BCC- mid way along cube edge and center of the face.
 1.Diffusion- Mechanisms

Fig.2. A {100} plane in an FCC lattice showing the path of an interstitial atom diffusing by the interstitial mechanism.
2.Interstitial Diffusion-Fick’s First Law

Fig.3. (a)Atomic arrangement in the lattice :Interstitial atoms

and Solvent atom (b) Concentration of interstitial atoms
across the lattice sites shown in (a)
2.Interstitial Diffusion-Fick’s First Law (Derivation)
2.Interstitial Diffusion-Fick’s First Law
 2.Interstitial Diffusion-Fick’s First Law

Remarks-Fick’s First Law

1. In non cubic lattices the probability of jump in different directions is not equal and D varies with direction.
2. Though D is not found to have dependence on concentration in eq(11), experiments show that D is a function of
composition.
e.g. Diffusion coefficient of C in FCC Fe-0.15C wt.% at 1000 °C = 2.5*10 -11 m2s-1
Diffusion coefficient of C in FCC Fe-1.4C wt.% at 1000 °C = 7.7*10-11 m2s-1
With increase in C concentration, there is more strain in the lattice. Hence, the C atoms can diffuse more easily when
the C concentration is higher.
2.Interstitial Diffusion-Effect of Temperature on intrinsic Diffusion Coefficient

Fig.4. (a)Interstitial atom in equilibrium

position, and (b) at the position of
maximum distortion; (c) Variation in Free
Energy as a function of position of the
interstitial
2.Interstitial Diffusion-Effect of Temperature on intrinsic Diffusion Coefficient
2.Interstitial Diffusion-Effect of Temperature on intrinsic Diffusion Coefficient
 2.Interstitial Diffusion-Steady State Diffusion

If the concentration at every point does not change with time during diffusion then it can be said that there exists a steady
state.

2.Interstitial Diffusion-Non-Steady State Diffusion

 2. Interstitial Diffusion-Derivation of Fick’s Second Law

Fig. 5. (a)The concentration

profile,(b) the flux and (c) the area
element .
2. Interstitial Diffusion-Derivation of Fick’s Second Law

2. Interstitial Diffusion-Solution to Fick’s Second Law

 2. Interstitial Diffusion-Solution to Fick’s Second Law (Homogenization)

The concentration of interstitial is shown schematically below

Center of interdendritic
region Center of
Dendrite arm

Fig.6. Variation of Concentration with Distance

and time
 2. Interstitial Diffusion-Solution to Fick’s Second Law (Homogenization)

t β0
0 β0
β0 /e
β0 /e2
 2. Interstitial Diffusion-Solution to Fick’s Second Law (Carburization)

In Carburization process, the diffusion of C atoms towards the steel surface at a high temperature results in the increase of
surface hardness.
Commercial carburizing may be accomplished by pack carburizing, gas caburizing and liquid carburizing.

When a low C steel (0.2 wt. %C) at 927 °C is exposed to CO gas, the following reaction takes place.
Fe+2CO →Fe(C)+CO2 where Fe(C) represents C dissolved in Austenite.

The rate of diffusion of C from surface to core is dependent on the concentration gradient and Diffusion coefficient.

Fig. 7. Carbon-Concentration in a carburized steel with 0.08 in a steel

 2. Interstitial Diffusion-Solution to Fick’s Second Law (Carburization)

Fig. 8. Carbon-Concentration as function of distance and time

2. Interstitial Diffusion-Solution to Fick’s Second Law (Carburization)

Fig. 9. Erf(Z) vs Z
 2. Interstitial Diffusion-Solution to Fick’s Second Law (Carburization)

Numerical-2
 3. Substitutional Diffusion

We know that an atom can only jump if there is a vacant site adjacent to lattice site and it vibrates at particular frequency .
Simplest case of substitutional diffusion is self diffusion of atoms in a pure metal.

3. Self Diffusion
Self diffusion means the diffusion of atoms in a pure metal.

Since vacancies are required for the exchange of atoms, the jump frequency (Γ) is dependent on the concentration of
vacancies in the crystal.

3. Self Diffusion-Estimation of Self Diffusion Coefficient

Self Diffusion Coefficient (DA) at a temperature can be determined experimentally. Radioactive isotope atoms (A*) of known
quantity (M) are deposited onto the ends of two bars of A, which are then joined as shown in Fig.10. After annealing
treatment at the appropriate temperature and time the concentration of radioactive element (C) is determined across the
bars. The concentration at each position is determined by measuring the radioactivity at each location after annealing
treatment.
3. Substitutional Diffusion-Self Diffusion

Fig.10. (a) Initial diffusion couple with planar source of

radioactive gold Au*. (b) Distribution of Au* after
diffusion for 100 h at 920°C. (After A.G. Guy,
Introduction to Materials Science, McGraw-Hill, New
York, 1971.)
3. Substitutional Diffusion-Self diffusion
3. Substitutional Diffusion-Self diffusion
3. Substitutional Diffusion-Diffusion in Binary alloys and Darken’s Equations

When pure A block and pure B block are welded together and annealed at
annealed at a high temperature the following composition profile is obtained
(Fig.11a).

Fig. 11. Interdiffusion and vacancy flow. (a) Composition

profile after interdiffusion of A and B. (b) The corresponding
fluxes of atoms and vacancies as a function of position x. (c)
The rate at which the vacancy concentration would increase
or decrease if vacancies were not created or destroyed by
dislocation climb.
3. Substitutional Diffusion-Diffusion in Binary alloys and Darken’s Equations
 3. Substitutional Diffusion-Diffusion in Binary alloys and Darken’s Equations

Fig. 12. Climb of an edge dislocation. (a)Before and (b) after the atom jumps into vacancy. (c) Jogged Dislocation
 3. Substitutional Diffusion-Diffusion in Binary alloys and Darken’s Equations

Extra atomic planes are created in B rich side and destroyed in A rich side, if climb of dislocations or other
mechanism operates . Fig. 13. shows such a process.

Fig.13. Flux of Vacancies causing the atom causing the atomic planes to move through the specimen
3. Substitutional Diffusion-Diffusion in Binary alloys and Darken’s Equations
3. Substitutional Diffusion-Diffusion in Binary alloys and Darken’s Equations
Numerical-3
 3. Substitutional Diffusion-Kirkendall Effect

In previous section we have seen that there is movement of lattice planes in the
welded diffusion couple towards B rich side.

Smigelskas and Kirkendall in 1947 observed the displacement of inert

wires(Molybdenum) in their experiment in which a block of α brass (Cu-30 wt. %Zn)
wound with Molybdenum wires and encapsulated in a block of pure Cu, was
annealed at high temperature for a particular duration.

After annealing at high temperature it was found that the distance between markers
had decreased. This is because DZn > Dcu . Zn atoms diffused out of the central block
at a rate higher than the rate at which those atoms were replaced by Cu atoms
diffusing in the opposite directions.

In general it is found that atoms with the lower melting point possess a higher D.
Fig. 14. Experimental set up to show
Kirkendall effect
 3. Substitutional Diffusion- Composition Dependence of Diffusion Coefficients

Fig. 15. The relationship between the various diffusion coefficients in the Cu‑Ni system at 1000 °C
(After A.G. Guy, Introduction to Materials Science, McGraw-Hill, New York, 1971.)
 4. Factors affecting Diffusion

(4.1) Influence of the path along which atoms diffuse

At any temperature, Diffusion rate through the free surface is higher than the diffusion rate through grain boundaries(GBs)
and diffusion rate through GBs is higher than the diffusion rate through interior of crystal or lattice.
Ds>DGB>Dl
Ds,DGB and Dl are the Surface, GB and Lattice Diffusion coefficients.

Atom packing is disordered and less dense in GBs

Measured Diffusion Coefficient has contributions from both Lattice Diffusion and GB Diffusion.

Fig. 16. The combined effect of GB and volume diffusion.

 4. Factors affecting Diffusion
(4.2) Effect of temperature on DGB and Dl

Fig. 17. Diffusion in polycrystalline silver. (From data of Hoffman, R. E., and Turnbull, D. J., Jour. Appl. Phys., 22 634 [1951].)

DGB>Dl at all temperatures and difference increases as the temperature decreases. This is because the activation energy for
diffusion along GBs (QGB) is lower than that for diffusion along lattice diffusion (Ql)

At higher temperatures the apparent Diffusion coefficient (Dapp) has greater contribution from diffusion through lattice.
 4. Factors affecting Diffusion

(4.3) Effect of bonding and crystal structure on Diffusion rate

• Interstitial Diffusion with a lower activation energy usually occurs much faster than vacancy or substitutional diffusion.
• Activation Energy depends upon the strength of atomic bond. It is higher for diffusion of materials with higher melting
point.
• Activation energy depends upon the size of the anions. In NaCl, activation energy for diffusion of Cl - is twice that for
diffusion of Na+ ions.
• Covalently bonded materials such as C and Si have usually higher activation energies for self diffusion because they have
strong atomic bonds.

Fig. 18. The activation energy for self-diffusion increases as the melting point of the metal increases.
 4. Factors affecting Diffusion

Fig. 19. Diffusion in ionic compounds. Anions can only enter other anion sites. Smaller cations tend to diffuse faster.

• In Ionic materials such as some of the oxide ceramics, a diffusing ion only enters site having same charge. The
diffusing ion must physically pass by region of opposite charge and move a relatively long distance. Consequently,
activation energies are high and rate of diffusion are lower for ionic materials than those of metals.
5.Sintering-Industrial application of Diffusion processes

Bonding and Densification of particles by the application of heat below the melting point of the material. The changes that
occur during sintering is shown in Fig. 20.

Driving force for sintering

Driving force for sintering arises from the pressure difference at the curved surfaces. The driving force for sintering is the
reduction in surface energy.

Fig.20. Changes that occur during sintering

 5.Sintering-Industrial application of Diffusion processes

The paths for material transfer are shown in Fig.20 and Table 1
Table 1 Mechanisms of material transfer as shown in Fig. 20

Mechanis Transport Path Source of Size of Matter

m Number
Matter
1 Surface Diffusion Surface
2. Lattice Diffusion Surface
3. Vapour Transport Surface
Neck
4. Boundary Diffusion GB
5. Lattice Diffusion GB
6. Lattice Diffusion Dislocations

Neck
Fig.21. Alternate paths for material
transport during initial stages of
sintering
5.Sintering-Industrial application of Diffusion processes
 5.Sintering-Industrial application of Diffusion processes

Remarks
1. These results indicate that the growth of bond formation between particles increases as a one-fifth power of time (a
result which has been experimentally observed for a number of metal and ceramic systems) and that the shrinkage
of a compact densified by this process should be proportional to the two-fifths power of time.

Stages of Sintering

1. Sintering process starts with bonding among particles as the material heats up. Bonding involves diffusion of atoms
where there is intimate contact between adjacent particles lea leading to the development of grain boundaries. This
stage results in a relatively large increase in strength and hardness, even after short exposures to an elevated
temperature.(See Fig. 22)

2. In the next stage, the newly formed bond areas called ’necks’ grow in size followed by pore rounding.

3. The last stage is pore shrinkage and eventual elimination. This stage is rarely complete since the temperatures
And times required are impractical
 5.Sintering-Industrial application of Diffusion processes

Fig.22. Schematic illustration of a three-sphere sintering model: (a) original point contacts, (b) neck
growth, (c) and (d) pore rounding. (From J. S. Hirschhorn. "lntroduction to Powder Metallurgy," American
Powder Metallurgy Institute, New York, 1969.)
 References

1. Phase Transformations in Metals and Alloys, Third Edition, CRC Press, David A Porter, Kenneth E Easterling and
Mohamed Y Sherif.
2. Physical Metallurgy Principles, Fourth Edition, Reza Abbaschian, Lara Abbaschian and Robert E-Reedhill, Wadsworth
Publishing Co Inc
3. Askeland D R, Wright W J , "Science and Engineering of Materials", Cengage Learning India Pvt Ltd, New Delhi, 2017.
4. Introduction of Physical Metallurgy, Sidney H Avner, McGRAW-HILL BOOK COMPANY, 1974