8 Diffusion

Diffusion
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Course content
 Diffusion:
Diffusion Mechanism
laws of diffusion- Fick's I law, II law
inter-diffusion
Kirkendall effect
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Diffusion: An introduction
Diffusion: related to mass transfer -> solid state diffusion
Carburization
Carburization : Carbon concentration in steel surface can be increased by carburization
treatment. Heat the low carbon steel in a carbonaceous atmosphere (packing in C
powder or hydrocarbon gases)
pn junction
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(a) Cross section of a steel sprocket showing showing hardened layers around the teeth.
(b) A single tooth of a case hardened gear showing the unaffected material inside and the hardened
surface layer (the dark spots are produced as a result of hardness measurements).
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Diffusion: Phenomena
• Diffusion: A process of mass transport by atomic movement under the influence of thermal
energy and a concentration gradient.
• Atoms move from higher to lower concentration region.
• If this movement is from one element to another e.g. Cu to Ni, then it is termed inter-diffusion.
If the movement is within similar atoms as in pure metals, it is termed self-diffusion.
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Kirkendall Effect
• If the diffusion rates of two metals A and B in to each other are different, the boundary
between them shifts and moves towards the faster diffusing metal as shown in the
figure. This is known as Kirkendall effect.
• It can be demonstrated experimentally by placing an inert marker at the interface.
• This is a direct evidence of the vacancy mechanism of diffusion as the other
mechanisms do not permit the flux of diffusing species to be different.
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Kirkendall Effect
• Zn diffuses faster into Cu than Cu in Zn. A diffusion couple of Cu and Zn will lead to
formation of a growing layer of Cu-Zn alloy (Brass).
• Same will happen in a Cu-Ni couple as Cu diffuses faster in Ni than vice versa.
• Since this takes place by vacancy mechanism, pores will form in Cu (of the Cu-Ni
couple) as the vacancy flux in the opposite direction (towards Cu) will condense to form
pores
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Fick’s first law of Diffusion
1807 1827 1855 9

Fick’s first law of Diffusion
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Fick’s First Law
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Fick’s first law of Diffusion and Effect of Temperature
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Fick’s second law
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Fick’s second law
Diffusion equation of Fick’s second law in mathematics
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Fick’s second law
This is a partial differential equation. The solution c(x,t)

depends upon the boundary conditions. For one kind of
boundary conditions useful in many problems, e.g.
carburization.
• A solution to this equation can be obtained for a semi-
infinite solid with the following boundary conditions.
• For t = 0, C = Co at 0 ≤ x ≤ ∞. For t > 0, C = Cs (surface
concentration) at x = 0 and C = Co at x = ∞
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Diffusion Mechanism
Interstitial Diffusion
• This mechanism involves migration of atoms from one interstitial site to a neighboring
empty interstitial site.
• This mechanism is more prevalent for impurity atoms such as hydrogen, carbon,
nitrogen, oxygen which are small enough to fit in to an interstitial position.
• For substitution diffusion atoms exchange their places directly or along a ring (ring
diffusion mechanism).
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Diffusion Mechanism
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Diffusion Mechanism
• Diffusion of atoms involves movement in steps from one lattice site to the another. An
empty adjacent site and breaking of bonds with the neighbor atoms are the two
necessary conditions for this.
Vacancy Diffusion
• This mechanism involves movement of atoms from a regular lattice site to an adjacent
vacancy. Since vacancy and atoms exchange position, the vacancy flux is in the opposite
direction.
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Diffusion Mechanism
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The diffusivity values depend on many variables, of which the following are important:
1. The type of diffusion mechanism. Whether the diffusion is interstitial or substitutional will affect the diffusivity.
Small atoms can diffuse interstitially in the crystal lattice of larger solvent atoms. For example, carbon diffuses
interstitially in the BCC or FCC iron lattices. Copper atoms diffuse substitutionally in an aluminum solvent lattice
since both the copper and the aluminum atoms are about the same size.
2. The temperature at which the diffusion takes place greatly affects the value of the diffusivity. As the temperature is
increased, the diffusivity also increases.
3. The type of crystal structure of the solvent lattice is important.
4. The type of crystal imperfections present in the region of solid-state diffusion is also important. More open
structures allow for more rapid diffusion of atoms. For example, diffusion takes place more rapidly along grain
boundaries than in the grain matrix in metals and ceramics. Excess vacancies will increase diffusion rates in metals
and alloys.
5. The concentration of the diffusing species is important in that higher concentrations of diffusing solute atoms will
affect the diffusivity. This aspect of solidstate diffusion is very complex.
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Diffusion path
4. Diffusion along dislocation (Pipe diffusion)

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Steady and unsteady state diffusion
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Steady and unsteady state diffusion
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Diffusion

laws of diffusion- Fick's I law, II law

1807 1827 1855 9

This is a partial differential equation. The solution c(x,t)

3. The type of crystal structure of the solvent lattice is important.

4. Diffusion along dislocation (Pipe diffusion)

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