Unit 6: Lecture 2- Mass Transport

Dr. Vaibhav S. Kathavate

Assistant Professor (Adjunct),
Department of Metallurgy and Materials Engineering,
COEP Technological University,
(Formerly College of Engineering Pune),
Shivajinagar, Pune 411 005,
Maharashtra, India.
Diffusion in Solids: (i) Self-Diffusion….

• In a lattice, we see continuous movement (motion) of atoms due to the vibration of each atoms
about their normal lattice point.
• There are few unoccupied sites known as “vacancy”.
• Due to the fast and unpredictable movement of atoms, we can see that these vacancies (i.e.,
unoccupied sites) suddenly get occupied (filled) by the surrounding atoms within a fraction of
time.
• At the same time, these atoms will leave behind the other (surrounding) sites, thus again creating
vacancies (see the schematics is next slide)

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Diffusion in Solids: (i) Self-Diffusion….

• Due to the fast and unpredictable movement of atoms, we can see that these vacancies (i.e.,
unoccupied sites) suddenly get occupied (filled) by the surrounding atoms within a fraction of
time.
• At the same time, these atoms will leave behind the other (surrounding) sites, thus again creating
vacancies.

At 𝑡 = 0 At 𝑡 = 𝑡1 At 𝑡 = 𝑡2

The net effect is random motion of atoms there selves: Self-Diffusion

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Diffusion in Solids: (i) Self-Diffusion….

• The rate at which these atoms move (or diffuse) is known as self-diffusion rate.
• This self-diffusion rate can be estimated from “radioactive tracer (or atoms)”.
• The self-diffusion coefficient (𝐷𝑠 ) in simple cubic lattice may be given as;
𝟏
𝑫𝒔 = 𝜹𝟐 𝝑
𝟔

• Here, 𝜹 is the interatomic spacing and 𝝑 is the jump frequency.

• In many instances, the value of jump frequency 𝝑 is estimated to be 𝟏𝟎𝟖 − 𝟏𝟎𝟏𝟎 𝒔−𝟏 from the
measurement of 𝑫𝒔 and 𝜹.
• In the above equation, we are assuming 𝝑 (i.e., atom jump) is random, uncorrelated and
unpredictable.
• This implies that the vacancies can be filled or occupied by any atoms surrounding them (i.e.,
exchange can take place random or just like phantom)
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Diffusion in Solids: (i) Self-Diffusion….

Movement 1 Movement 2

Animation showing the unpredictable and

random movement of atoms within a
phase/material during diffusion.
Ref- Poirier and Geiger, Springer Verlag, (2016). 5
Diffusion in Solids: (i) Self-Diffusion….

• In many instances, the self-diffusion coefficient ( 𝑫∗𝒔 ) calculated from Radioactive Traces
Measurement is slightly lower than true diffusion coefficient (𝑫𝒔 );
𝑫∗𝒔 = 𝒔 × 𝑫𝒔

Crystal Structure Value of "𝒔"

Diamond 0.5
Simple Cubic (SC) 0.655
Body Cantered Cubic (BCC) 0.721
Face Centered Cubic (FCC) 0.781

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Diffusion in Solids: (ii) Diffusion Under the Influence of a Composition Gradient….

• Diffusion of solute atoms at the interstitial sites of solvent lattice/atoms in a material/solution.

• Consider a diffusion of carbon atoms in the interstitials sites of iron lattice.
• Carbon will diffuse within the stationery iron lattice, without distorting the iron lattice (i.e., without
the movement of 𝑭𝒆 atoms).
• However, this mechanism is only possible when solute atoms are significantly smaller in size
than the solvent atoms (Remember Hume-Rothery Rule)
• If the solute atom size is approaching to solvent atom size then this mechanism no longer
applicable

𝑭𝒆 lattice 𝑪 Atoms 𝑪 Atoms occupying the interstitial sites within the 𝑭𝒆 lattice 7
Key Learnings from Today’s Session….

• Self Diffusion vs. Diffusion under an influence of composition gradient ,

(i) Self Diffusion: Vacancies in the material will get occupied by the surrounding atoms
thus leaving behind the adjacent unoccupied sites (Distortion in original lattice
(solvent atoms) is possible.
(ii) Diffusion under an influence of composition gradient: Interstitials sites in solvent
lattice get filled/occupied by solute atoms without disturbing/distorting the solvent
lattice.
• In general,

(i) Heat flow in a medium does not cause the movement of medium 

(ii) Diffusion, in itself, involves the movement of the medium ✓

Therefore, diffusion contributes to the velocity of the medium
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