Unit 6: Lecture 3- 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: (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• If the solute atom size is approaching to solvent atom size then this mechanism no longer
applicable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 2
Diffusion in Solids: (ii) Diffusion Under the Influence of a Composition Gradient….

𝑨𝒖 lattice 𝑵𝒊 lattice
• Consider an example of Gold and Nickel bar joined
together so that they will form a diffusion couple.
• The changes in the concentration distribution of both
the lattices is represented schematically in Fig. X.
Shift due
• Let us consider that the 𝑨𝒖 atoms diffuse more rapidly to 𝑨𝒖
𝒍
than 𝑵𝒊 atoms, and therefore, boundary slightly shifts
𝒍
towards right side (i.e., shift due to 𝑨𝒖 atoms).
• In order to maintain the uniform concentration Figure X

gradient, the bar of 𝑨𝒖 must shorten by some length

while at the same time the bar of 𝑵𝒊 must lengthen by
the same length (i.e., 𝒍).

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

𝑨𝒖 lattice 𝑵𝒊 lattice
• In the same way, the diffusion of 𝑵𝒊 atoms is also
obvious, thereby shifting the bars towards left.
• This will shorten the length of 𝑵𝒊 bar while lengthen
the 𝑨𝒖 bar by same amount (i.e., 𝒍).
Shift due
• The net result is “𝑲𝒊𝒓𝒌𝒆𝒏𝒅𝒂𝒍𝒍 𝑺𝒉𝒊𝒇𝒕” or to 𝑨𝒖
𝒍
“𝑲𝒊𝒓𝒌𝒆𝒏𝒅𝒂𝒍𝒍 𝑬𝒇𝒇𝒆𝒄𝒕”. This implies that the diffusion 𝒍
of atoms under the influence of compositional gradient Shift due
to 𝑵𝒊
also depends on the diffusion rate (or diffusivity). 𝒍
𝒍
Net shift

Figure X
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Diffusion in Solids: (iii) Temperature Dependent Diffusion and Arrhenius Equation….

• Temperature has a pronounced influence on the diffusion in solids.

• Arrhenius proposed an equation that related the diffusion coefficient with temperature.

𝑸ൗ
𝑫 = 𝑫𝒐 𝒆−( 𝑹𝑻) (Equation X)

• Here, “𝑸” is the activation energy, “𝑫𝒐 ” specifies frequency factor, “𝑹” represents the universal

gas constant, and “𝑻” is the temperature.

• Both “𝑸” and “𝑫𝒐 ” are constant over a wide range of temperatures.

• Activation Energy: Minimum energy required to activate/cause a process (say chemical

𝒌𝑱
reaction). It’s unit is .
𝒎𝒐𝒍

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 Diffusion in Solids: Concept of Activation Energy….

• The term Activation energy was first proposed by a Swedish scientist Svante Arrhenius.
• The term activation energy is sometimes also known as “potential barrier/activation
barrier/energy barrier”.

• Initially ball had certain amount of

Activation Energy (𝑸)
potential energy (P. E.) and once the
Potential
Energy (P.E.) ball roll up the hill, there will be
Change in P.E.
change in the P. E.
• However, to make this process
The ball need to come out of certain barrier happen, we need certain amount of
(i.e., energy barrier). We call it as “Activation energy (i.e., pushing the ball up the
Barrier” and energy corresponding to that barrier hill).
(level) is “Activation Energy”. 6
Diffusion in Solids: (iii) Temperature Dependent Diffusion and Arrhenius Equation….

• A few studies have been in the past indicated that jump process is an activated one (process).

• Recall the formula for self diffusion coefficient;

𝟏 𝟐
𝑫𝒔 = 𝜹 𝝑
𝟔

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

• The jump frequency in terms of Gibbs Free Energy required for the activation (∆𝑮), vibrational

frequency of an atom in the lattice (𝝑𝟎 ), and coordination number (𝒁) can be expressed as;

−∆𝑮ൗ
𝝑 = 𝝑𝟎 𝒁𝒆 𝑹𝑻

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Diffusion in Solids: (iii) Temperature Dependent Diffusion and Arrhenius Equation….

• We can modify equation X as;

∆𝑯ൗ )
𝑫 = 𝑫𝒐 𝒆 ( 𝑹𝑻

• Where 𝑫𝒐 turns out to be;

𝜹𝟐 𝝑𝟎 𝒁 ∆𝑺ൗ
𝑫𝟎 = 𝒆 𝑹
𝟔

• Here, ∆𝑯 is analogous to 𝑸, while 𝝑𝟎 , ∆𝑺, and 𝜹 does not change with the temperature

significantly.

• Therefore, net result is; 𝑫𝟎 do not vary much with the temperature (or varies slightly).

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Diffusion in Solids: (iii) Temperature Dependent Diffusion and Arrhenius Equation….

Ref- Poirier and Geiger, Springer Verlag,

(2016).

Diffusion coefficient decreases with a decrease in temperature (or an

increase in inverse of temperature)
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Key Learnings from Today’s Session….

• We have discussed herein “volume diffusion effects” so far (i.e., diffusion in bulk) and not the

surface diffusion.

• In many instances, volume diffusion dominates, but grain boundary diffusion (or surface diffusion

effects) can also be important in polycrystalline metals and in thin films at relatively low

temperatures.

• Surface diffusion is of vital importance during sintering process (in case of powder metallurgy)

and in the growth of thin films.

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Concluding Remarks….

…..By Dr. Sarvepalli Radhakrishnan

Thank you very much for your kind attention…..

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