MSE 225 INTRODUCTION TO

MATERIALS SCIENCE
(SECTION 01-02)

DIFFUSION IN SOLIDS_II

Assoc. Prof. Dr. İlkay KALAY

Materials Science and Engineering Department
Çankaya University Chapter 5 -
 Non-steady State Diffusion
• The concentration of diffusing species is a function of
both time and position C = C(x,t)
• In this case Fick’s Second Law is used C  2
C
D 2
t x

Fick’s second law - The partial differential equation

that describes the rate at which atoms are
redistributed in a material by diffusion Chapter 5 - 2
 Non-steady State Diffusion
• Copper diffuses into a bar of aluminum.
Surface conc.,
Cs of Cu atoms bar
pre-existing conc., Co of copper atoms

Cs

Adapted from
Fig. 5.5,
Callister &
Rethwisch 8e.

B.C. at t = 0, C = Co for 0  x  
at t > 0, C = CS for x = 0 (constant surface conc.)
C = Co for x = 
Chapter 5 - 3
Chapter 5 - 4
Chapter 5 - 5
 Solution:
C x , t   Co  x 
 1  erf  
Cs  Co  2 Dt 

C(x,t) = Conc. at point x at CS

time t
erf (z) = error function
2 z C(x,t)

y 2
 e dy
 0
Co
erf(z) values are given in
Table 5.1
Adapted from Fig. 5.5,
Callister & Rethwisch 8e.

Chapter 5 - 6
Non-steady State Diffusion
C( x, t )  Co  x 
 1  erf  
Cs  Co  2 Dt 

Chapter 5 - 7
Factors that influence diffusion

Temperature

• Diffusion coefficient increases with increasing T.

 Qd 
D  Do exp 
 RT 

D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]
Chapter 5 - 8
Fick’s Second Law
Sample Problem: An FCC iron-carbon alloy initially containing 0.20 wt% C
is carburized at an elevated temperature and in an atmosphere that gives a
surface carbon concentration constant at 1.0 wt%. If after 49.5 h the
concentration of carbon is 0.35 wt% at a position 4.0 mm below the surface,
determine the temperature at which the treatment was carried out.

Chapter 5 -
Parts carburized in nitrogen-methanol atmosphere

Chapter 5 -
Sample Problem: An FCC iron-carbon alloy initially containing 0.20 wt% C
is carburized at an elevated temperature and in an atmosphere that gives a
surface carbon concentration constant at 1.0 wt%. If after 49.5 h the
concentration of carbon is 0.35 wt% at a position 4.0 mm below the surface,
determine the temperature at which the treatment was carried out.

Chapter 5 -
Non-steady State Diffusion
C( x, t )  Co  x 
 1  erf  
Cs  Co  2 Dt 

Chapter 5 - 12
Sample Problem: An FCC iron-carbon alloy initially containing 0.20 wt% C
is carburized at an elevated temperature and in an atmosphere that gives a
surface carbon concentration constant at 1.0 wt%. If after 49.5 h the
concentration of carbon is 0.35 wt% at a position 4.0 mm below the surface,
determine the temperature at which the treatment was carried out.

Read the values from the

corresponding columns!!!

Chapter 5 -
Sample Problem: An FCC iron-carbon alloy initially containing 0.20 wt% C
is carburized at an elevated temperature and in an atmosphere that gives a
surface carbon concentration constant at 1.0 wt%. If after 49.5 h the
concentration of carbon is 0.35 wt% at a position 4.0 mm below the surface,
determine the temperature at which the treatment was carried out.

Chapter 5 -
Chapter 5 - 15
 DIFFUSION
• The experiment: we recorded combinations of
t and x that kept C constant.

 
C(x i , t i )  Co x
 1 erf 

i 
 = (constant here)
Cs  Co 2 Dt i 

• Diffusion depth given by:

Chapter 5 - 17
 DIFFUSION

 
C(x i , t i )  Co x
 1 erf 

i 
 = (constant here)
Cs  Co 2 Dt i 

• Diffusion depth given by:

Chapter 5 - 17
Factors that influence diffusion

• Temperature

• Diffusing species

• Type of Crystal Structure

• Imperfections in Crystal

Chapter 5 - 18
Factors that influence diffusion

Temperature

• Diffusion coefficient increases with increasing T.

 Qd 
D  Do exp 
 RT 

D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]
Chapter 5 - 19
Factors that influence diffusion

Temperature

interstitial
Chapter 5 -
Factors that influence diffusion
Temperature D has exponential dependence on T
1500

1000

600

300
T(C)
10-8

D (m2/s) Dinterstitial >> Dsubstitutional

C in a-Fe Al in Al
10-14 C in g-Fe Fe in a-Fe
Fe in g-Fe

10-20
0.5 1.0 1.5 1000 K/T

Adapted from Fig. 5.7, Callister & Rethwisch 8e. (Date for Fig. 5.7
taken from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals
Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)

Chapter 5 - 21
Example: At 300ºC the diffusion coefficient and activation energy for Cu in Si
are
D(300ºC) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350ºC?

D transform ln D
data

Temp = T 1/T

Qd æ1ö Qd æ1ö
lnD2 = lnD0 - çç ÷÷ and lnD1 = lnD0 - çç ÷÷
R è T2 ø R è T1 ø
D Q  1 1
 lnD2  lnD1  ln 2   d   
D1 R  T2 T1 
Chapter 5 - 22
 Example (cont.)
 Qd  1 1 
D2  D1 exp    
 R  T2 T1 

T1 = 273 + 300 = 573K

T2 = 273 + 350 = 623 K

11 2   41,500 J/mol  1 1 

D2  (7.8 x 10 m /s) exp    
 8.314 J/mol - K  623 K 573 K 

D2 = 15.7 x 10-11 m2/s

Chapter 5 - 23
 Factors that influence diffusion

• The diffusing species, host material and temperature

influence the diffusion coefficient.
• For example, there is a significant difference in magnitude
between self-diffusion and carbon interdiffusion in α iron
at 500 °C.
Chapter 5 -
 ATOMIC PACKING FACTOR: BCC
• APF for a body-centered cubic structure = 0.68

3a

R
a 2a

Chapter 5 - 8
 ATOMIC PACKING FACTOR: FCC
• APF for a body-centered cubic structure = 0.74

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a

Chapter 5 - 10
Fast Tracks for diffusion !
eg. self-diffusion of Ag :
-Areas where lattice is pre-
strained can allow for faster
diffusion of atoms
-Less energy is needed to
distort an already strained
lattice !

Chapter 5 -
Fast Tracks for diffusion !
eg. self-diffusion of Ag :
-Areas where lattice is pre-
strained can allow for faster
diffusion of atoms
-Less energy is needed to
distort an already strained
lattice !

Chapter 5 -
 Factors That Influence Diffusion
• 1. Temperature
- Increasing T, increases D
- Large Qd,smaller D; slower diffusion
• 2. Diffusion species (atoms)
Smaller atoms diffuse more rapidly than bigger atoms
Ex: self diffusion (Fe in BCC Fe) : D1 (substitutional)
Carbon interdiffusion in BCC Fe : D2 (interstitial)

At the same T (ex. 900C), D2 is greater than D1!!!!

Why???
Smaller atoms diffuse more
rapidly than bigger atoms
Chapter 5 - 29
 Factors That Influence Diffusion

• 3. Type of Crystal Structure

Ex: C in BCC Fe : D1
C in FCC Fe: D2

D1 is greater than D2!!!! Why???

FCC is more packed structure, has greater density

(slower diffusion rate)
APF (FCC) is greater than APF (BCC)

Chapter 5 - 30
 Factors That Influence Diffusion

4. Type of Crystal Imperfections

Dsurface >Dgrain boundary>Dvolume

Qd surface<Qdgrain boundary<Qdvolume

5. Type of Bonding
6. Type of Diffusing Species

Chapter 5 - 31
Size Impact on Diffusion

Smaller atoms diffuse faster

Chapter 5 -
 Important
• Temperature - diffusion rate increases with
increasing temperature (WHY ?)
• Diffusion mechanism – interstitials diffuse faster
(WHY ?)
• Diffusing and host species - Do, Qd is different for
every solute - solvent pair
• Microstructure - grain boundaries and dislocation
cores provide faster pathways for diffusing species,
hence diffusion is faster in polycrystalline vs.
single crystal materials. (WHY ?)

Chapter 5 -
 Summary
Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• materials w/secondary • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials

Chapter 5 - 34