Addis Ababa Institute of Technology

School of Mechanical and Industrial Engineering

Engineering Materials I
(MEng 2122)
By: Ayalsew Dagnew June, 2022
(MSc. Aeroscpace Eng`g)

Chapter - 5

Diffusion in Solids
 Diffusion in Solids
Overview Application of Diffusion in Mechanical Structures

Carbon diffusion in surface treatment.

Case-hardened gear
 Why Study Diffusion?
The reason why we study the term diffusion is primarily to answer the following
basic questions:

 What does it mean diffusion in general?

 What is diffusion in solids and its principle?
 What are the mechanisms of diffusion? /How diffusion occurs?/
 Why diffusion is important in materials processing and treatment?
 What are the basic factors that influence diffusion?
 How can the rate of diffusion be predicted for some simple cases?
 How does diffusion depend on structure and temperature?
 What real environmental application diffusion has?
 Learning Objectives
After completing this chapter, you should be able to:

 List and describe the two atomic mechanisms of diffusion.

 Distinguish between steady-state and non-steady state diffusion.
 Write Fick’s first and second laws in equation form and define all parameters.
 Note the kind of diffusion for which each of these equations is normally applied.
 Write the solution to Fick’s second law for diffusion into a semi-infinite solid when
the concentration of diffusing species at the surface is held constant. Define all
parameters in this equation.
 Calculate the diffusion coefficient for a material at a specified temperature, given the
appropriate diffusion constants.
 Issues to address

• How does diffusion occur?

• Why is it an important part of processing?

• How can the rate of diffusion be predicted for some simple

cases?

• How does diffusion depend on structure and temperature?

 Introduction to Diffusion
 Diffusion is the phenomenon of material transport by atomic motion.
Diffusion → mass transport by atomic motion.
 Mechanisms: This transfer may be either within a specific solid or from a liquid, a gas, or
another solid phase.
 This is accomplished by diffusion.
 Gases & Liquids – random (Brownian) motion
 Solids – vacancy diffusion or interstitial diffusion
 The process by which atoms of one metal diffuse into another is termed interdiffusion, or
impurity diffusion.
 There is a net drift or transport of atoms from high- to low-concentration regions.
 Introduction cont.
 Interdiffusion: In an alloy, atoms tend to migrate from regions of high conc.
to regions of low conc.
 Introduction cont.
Self-diffusion: In an elemental solid, atoms also migrate.
 Diffusion Mechanisms
 Diffusion is just the stepwise migration of atoms from lattice site to lattice site. → from
atomic perspective.
 The atoms in solid materials are in constant motion, rapidly changing positions.
 For the movement of an atom, two conditions must be met:
1) there must be an empty adjacent site, and
2) the atom must have sufficient energy to break bonds.
 The fraction of diffusion increases with rising temperature.
 Two possible diffusion mechanisms:

o Vacancy diffusion

o Interstitial diffusion
 Diffusion Mechanisms
Vacancy diffusion:
 It is the interchange of an atom from a normal lattice position to an adjacent vacant lattice
site or vacancy.
 Vacancy diffusion – needs presence of vacancies.
 The extent to which vacancy diffusion can occur is a function of the number of these
 defects.
The diffusion of atoms in one direction
corresponds to the motion of vacancies in the
opposite direction.
 Significant concentrations of vacancies may
exist in metals at elevated temperatures.
 Diffusion Mechanisms
Interstitial diffusion:
 It is the migration of atoms from an interstitial position to a neighboring one that is empty.
 This mechanism is found for interdiffusion of impurities such as H, C, N, and O, which have
small atoms.

 Host or substitutional impurity

atoms rarely form interstitials
and do not diffuse by this
mechanism → termed interstitial
diffusion.
 Principle of Diffusion
 Diffusion is a time-dependent process. Fick’s first law — diffusion flux for
 Diffusion flux (J): is the rate of mass transfer. steady-state diffusion: independent of time
 It is the mass or number of atoms diffusing  This is considered as in one direction.
through a unit area per unit time.  The mathematical expression of
 Its mathematical expression is; diffusion flux for steady-state diffusion
M = Diffusing mass (kg) is given by:
D = diffusion coefficient (m²/s)
A = cross sectional area of Minus sign means diffusion
dC
diffusion (m²) J  D toward lower concentrations.
dx
t = time of diffusion (s).
 J is proportional to the concentration
 The unit of J is kg/m²s.
gradient (dC/dx).
dC/dx is → a driving force or concentration gradient.
 Fick’s First Law
 Fick’s first law may be applied to
diffusion of atoms of a gas through a
thin metal plate. → concentrations of
diffusing species on both surfaces
held constant.
 Steady-state diffusion - the
diffusion flux does not change with
time.
 Concentration profile - is the curve
Figure: (a) Steady-state diffusion across a thin plate. (b) A plotted with concentration (C) vs
linear concentration profile for the diffusion situation in (a).
position (x).
 Fick’s First Law
 The slope at a particular point of C-vs-x - The hydrogen selectively diffuses through
curve is called the concentration gradient. the sheet to the opposite side, which is
C may be expressed in → kg/m^3 maintained at a constant and lower
hydrogen pressure.

 Example of steady-state diffusion is found

in the purification of hydrogen gas.
- One side of a thin sheet of palladium metal
is exposed to the impure gas composed of
hydrogen and other gaseous species such as
nitrogen, oxygen, and water vapor.
 Example

1. Methylene chloride is a common ingredient of paint removers. Besides

being an irritant, it also may be absorbed through skin. When using this
paint remover, protective gloves should be worn.
• If butyl rubber gloves (0.04 cm thick) are used, what is the diffusive
flux of methylene chloride through the glove?

Data:
– diffusion coefficient in butyl rubber: D = 110x10^-8 cm2/s
– surface concentrations: C2 = 0.02 g/cm3 C1 = 0.44 g/cm3
Solution
 Fick’s Second Law
Fick’s Second Law – Non-steady State Diffusion
 Non-steady state diffusion occurs when the  Fick’s second law:
diffusion flux and the concentration gradient
at some particular point in a solid is varying
with time.  If the diffusion coefficient (D) is

 Most practical diffusion situations are non- independent of composition, it can be

steady state. simplified as;

 To see the non-steady state diffusion C J Fick’s second law:


t x Diffusion equation
condition - concentration profiles at three for non-steady state
 2C
D diffusion (in one
different diffusion times (t1, t2, and t3) are x 2 direction)

considered (see figure 5.5).

 Fick’s Second Law
Non-steady State Diffusion  Atom needs enough thermal energy to break
bonds and squeeze through its neighbors.

Energy needed energy barrier

called the activation energy Em (like Q)

Figure 5.5: Concentration profiles for

non-steady state diffusion taken at three Diagram for vacancy and interstitial diffusion
different times, t1, t2, and t3. Diffusion  thermally activated process
 Fick’s Second Law

 Solution to Fick’s second law for the

condition of constant surface concentration
→ for a semi-infinite solid:

…..... (5.5)

where Cx represents the concentration at depth x

after time t.

The expression erf(x/2√(Dt)) is the Gaussian

error function.
Figure 5.6: Concentration profile for
non-steady state diffusion; concentration
parameters
 Factors Influencing Diffusion
 Factors that affect diffusion: Temperature:
• Diffusing species • Microstructure  Temperature has a profound influence
• Temperature • Host material on the coefficients and diffusion rates.
 The temperature dependence of the
Diffusing Species:
diffusion coefficients is:
 The magnitude of the diffusion coefficient D is
indicative of the rate at which atoms diffuse.
 The diffusing species and the host material Where, D0 = a temperature-independent preexponential
(m²/s)
influence the diffusion coefficient. Qd = the activation energy for diffusion (J/mol)

.
R = the gas constant, 8.31 J/mol K
 Self-diffusion occurs by a vacancy mechanism, T = absolute temperature (K)

whereas carbon diffusion in iron is interstitial.

 Factors Influencing Diffusion

 The activation energy is the energy

required to produce the diffusive motion
of one mole of atoms.
 A large activation energy results in a
relatively small diffusion coefficient.
 For evaluating D0 and Qd values:

or

Figure 5.7: Plot of the logarithm of the diffusion

coefficient versus the reciprocal of absolute temperature
for several metals.
 Example

1) If the diffusion coefficient (D) and activation energy (Qd) for Cu in Si at

300ºC are D = 7.8 x 10^-11 m^2/s and Qd = 41.5 kJ/mol. Then determine
the diffusion coefficient at 350ºC. [R = 8.314 J/mol.K]
Solution
 Diffusion in Semi-conducting Materials
 This silicon chip pattern formation is
 Solid-state diffusion is the fabrication of
accomplished by atomic diffusion.
semiconductor integrated circuits (ICs).
 Two heat treatments are used in this
 IC chip is a thin square wafer having
process.
dimensions on the order of 6 x 6 x 0.4 mm.
1) Pre-deposition step, impurity atoms are
 Millions of interconnected electronic devices
diffused into the silicon. From 900˚C and
and circuits are embedded in the chip faces.
1000˚C for < 1h. By eq. 5.5.
 Single-crystal silicon is the base material for
2) Drive-in diffusion, is used to transport
most ICs.
impurity atoms farther into the silicon in order to
 For an efficient ICs - very precise
provide a more suitable concentration distribution
concentrations of impurity must be
incorporated. without increasing the overall impurity content.
 Diffusion in Semi-conducting Materials
 The drive-in diffusion treatment is
where Cs = the surface
carried out up to 1200˚C in an concentration for the predeposition
step, Dp = the diffusion coefficient,
oxidizing atmosphere. and tp = the predeposition treatment

 The solution to Fick’s second law for time.

drive-in diffusion takes the form:

Where, Q0 = total amount of impurities in the

solid → introduced during predeposition
Drive-in diffusion of Profiles after predeposition and
drive-in diffusion treatments for
treatment. semiconductors at three different
semiconductors.
times, t1, t2, and t3.
 Other Diffusion Paths
 Atomic migration may also occur along:

- dislocations,

- grain boundaries, and

- external surfaces.

 These are sometimes called short-circuit diffusion paths in as much as rates are much

faster than for bulk diffusion. However, in most situations short_x0002_circuit

contributions to the overall diffusion flux are insignificant because the

cross_x0002_sectional areas of these paths are extremely small.

 Summary
 Solid-state diffusion is a means of mass transport within solid materials by stepwise
atomic motion.
 The term interdiffusion refers to the migration of impurity atoms; for host atoms, the
term self-diffusion is used.
 Two mechanisms for diffusion are possible: vacancy and interstitial.
- Vacancy diffusion occurs via the exchange of an atom residing on a normal lattice
site with an adjacent vacancy.
- Interstitial diffusion, an atom migrates from one interstitial position to an empty
adjacent one.
 For a given host metal, interstitial atomic species generally diffuse more rapidly.
 Summary
 Diffusion flux is defined in terms of mass of diffusing species, cross-sectional area, and
time.
 Diffusion flux is proportional to the negative of the concentration gradient according
to Fick’s first law.
 Concentration profile is represented as a plot of concentration versus distance into the
solid material.
 Concentration gradient is the slope of the concentration profile curve at some specific
point.
 The diffusion condition for which the flux is independent of time is known as steady state.
 The driving force for steady-state diffusion is the concentration gradient (dC/dx).
 Summary
 For nonsteady-state diffusion, there is a net accumulation or depletion of diffusing
species, and the flux is dependent on time.
 The mathematics for nonsteady state in a single (x) direction (and when the diffusion
coefficient is independent of concentration) may be described by Fick’s second law.
 For a constant surface composition boundary condition, the solution to Fick’s second
law involves the Gaussian error function.
 The magnitude of the diffusion coefficient is indicative of the rate of atomic motion
and depends on both host and diffusing species as well as on temperature.
 The diffusion coefficient is a function of temperature.
 The two heat treatments that are used to diffuse impurities into silicon during integrated
circuit fabrication are predeposition and drive-in diffusion.
 Summary
 Diffusion faster for; open crystal structures, materials with secondary bonding, smaller
diffusing atoms and lower density materials.
 Diffusion slower for; close-packed structures, materials with covalent bond, large diffusing
atoms and higher density materials.

Refer to Callister 9th ed. and known videos like this link for further understanding & related thread; https://youtu.be/j4m0Ye5Qgcg
Thank you!