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'Diffusion in Solids'': IE-114 Materials Science and General Chemistry Lecture-5

Diffusion is the transport of matter through a medium due to random atomic motions. Diffusion in solids is slower than in liquids or gases due to the restricted atomic movement imposed by atomic bonding in solids. There are two main mechanisms of diffusion in solids: vacancy diffusion, where an atom moves into an empty lattice site, and interstitial diffusion, where a small atom moves between lattice sites. Diffusion rates depend on factors like temperature, crystal structure, and defects.

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76 views

'Diffusion in Solids'': IE-114 Materials Science and General Chemistry Lecture-5

Diffusion is the transport of matter through a medium due to random atomic motions. Diffusion in solids is slower than in liquids or gases due to the restricted atomic movement imposed by atomic bonding in solids. There are two main mechanisms of diffusion in solids: vacancy diffusion, where an atom moves into an empty lattice site, and interstitial diffusion, where a small atom moves between lattice sites. Diffusion rates depend on factors like temperature, crystal structure, and defects.

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Meesala suresh
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© © All Rights Reserved
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Download as PDF, TXT or read online on Scribd
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‘’DIFFUSION IN SOLIDS’’

IE-114 Materials Science and General Chemistry


Lecture-5
Diffusion
 The mechanism by which matter is transported through matter. It is related
to internal atomic movement.

 Atomic movement; Gases > Liquids > Solids


Gases Liquids

 Atomic-scale motion (diffusion) in liquids and gases is rapid and easy to visualize
Diffusion in solids
 The slower diffusion rate in the solid state than in the liquid state.

 Heat Treatment of Metals


 Case hardening of steel (carbon diffusion in steel)
 Oxidation of metals
 Thin film electronics (doping of semiconductors)
 Sintering (fusion of powder particles at solid state)

EXAMPLE : CASE HARDENING OF STEEL

Methods used: Carburizing, Nitriding

Fe + 2CO Fe(c) + CO2


Origin of Diffusion
 Thermal energy
 Concentration gradient (effective in diffusion of impurities)

 In solids, atomic movements are restricted to equilibrium positions due to bondings. If energy is
provided to the solids, it can cause the thermal vibrations of atoms about their equilibrium
position and at sufficient energy vibration may be strong enough to break the bonding and make
the atom move

Types of diffusion in Solids

Self-diffusion Interdiffusion (Impurity diffusion)


1) Self-diffusion
 Diffusion in pure metals
 All atoms exchanging positions are of the same type

Label some atoms After some time

C
A HEAT
D
B
2) Impurity-diffusion (Interdiffusion)
 The process, whereby atoms of one metal diffuse into another
metal
 Upon heating, diffusion of atoms from high concentration to low
concentration takes place

Initially After some time

HEATING

100%

0
Concentration Profiles
COPPER NICKEL
Diffusion Mechanisms
 In atomic point of view diffusion is stepwise migration of
atoms from lattice site to lattice site

 For an atom to make such a move;

a) there must be an empty adjacent site


b) atom that is moving should have enough energy to break bonds with
the neighboring atoms and cause some distortion. The energy is
vibrational in nature.

 There are two types of diffusion mechanisms:

1) Vacancy diffusion
2) Interstitial Diffusion
Vacancy (substitutional) Diffusion

a) Self-diffusion (pure metals) b) Impurity Diffusion

Interstitial Diffusion

a) Self-diffusion (pure metals) b) Impurity Diffusion


1) Vacancy (substitutional) Diffusion
 A host or substitutional atom exchanges places with a vacancy

Activation energy = Act. Ener. (to form a vacancy) + Act. Ener. (to move the atom to the vacancy)
(Both vacancies and required activation energy is provided by thermal energy which results in vibrations of
atoms and impurities)

 Activation energy (Q) as melting temp.


(Stronger bonds exist in higher-melting-temperature metals)

 Rate of diffusion depends on;


 Number of vacancies
 Activation energy to migrate
2) Interstitial Diffusion:
 Atoms move from an interstitial position to another one closeby.
 Migrating atoms should be small in size such as N, C, H and O.
 Interstitial diffusion occurs much more rapidly than diffusion by
the vacancy mode, since interstitial atoms are smaller, and thus
mobile.

• jumping of a smaller atom (black) from one interstitial


site to another in a BCC structure.

e.g. Interstitial diffusion of carbon in iron


Rcarbon=0.071 nm
RFe= 0.124 nm
Activation Energy for Diffusion
 Conditions for atom migration:
- empty adjacent site
- atom must have enough energy to break bonds and cause lattice distortion
during displacement.

 Diffusive motion influenced by atom vibrational energies (kBT)


Diffusion Modeling

1) Steady-State diffusion:
 Diffusion is a time dependent process; the quatity of an element
that is transported within another is a function of time.

 The rate of mass transfer is explained by diffusion flux (J): the


mass of (or, number of atoms) M diffusing through and perpendicular to a unit cross-
sectional area per unit of time

In differential form:
mass

time

crosssectional area

UNIT: kg/m2s or atoms/m2s


 Steady state condition exists when the diffusion flux does not
change with time

Concentrations(pressures) of two species are held constant, PA and PB and PA>PB


 The steady-state diffusion in one (x) direction :

FICK’S FIRST LAW

D: diffusivity or diffusion coefficient (m2/sec or cm2/sec).

The negative sign indicates that the direction of diffusion is


down the concentration gradient.

 Concentration gradient (dC/dx) is the driving force in diffusion reactions.


 The steeper the concentration gradient, the greater will be the diffusion or
the mass transfer
2)Nonsteady state diffusion:

 The diffusion flux and concentration gradient at a selected point vary


with time causing a net accumulation or depletion.

 For nonsteady state diffusion Fick’s first law is not valid.

FICK’S SECOND LAW


Depending on the selected boundary conditions there may be different
solutions for Fick’s second law.

Semi-finite solid in which the surface concentration is held constant.


Assume:
a) before diffusion, diffusing solute concentration is uniform, Co.
b) the value of x is zero at the surface and increases with distance into the solid.
c) the time is zero at the instant before the diffusion begins.

Surface concentration is held constant Gaussian error function

Cx: concentration at depth x after time t.


Cs: concentration at surface
Co: initial concentration
Factors affecting diffusion:
1) Diffusing species:
Different materials have different diffusion coefficient (Do),
which is also the indication of the diffusion rate.

2) Crystal structure (BCC, FCC, ..)


3) Imperfection (grain boundary, dislocation, vacancy, lattice)
4) Temperature: Diffusion is thermally activated process
Temperature dependence can be expressed as follows:
Diffusion coefficient vs 1/T
1200°C 900°C 600°C 400°C

10 -10

10 -12

10 -14
D, m2/s

10 -16

10 -18

10 -20
Fe in bcc Fe
Fe in fcc Fe
C in bcc Fe
10 -22 C in fcc Fe
Mn in fcc Fe
10 -24
0.6 0.8 1 1.2 1.4 1.6

1000/T(K)

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