EMAT 251: Materials Science

Diffusion
(Chapter 5)

1
 What is Diffusion?
• Mass transport by atomic molecular motion

• Net movement of atoms/molecules from high concentration to low concentration .

2
Diffusion in Solids

heat
→
time

3
 Types of Solid State Diffusion
• Impurity diffusion (“Interdiffusion”): Diffusing atom and host atoms are different

Vacancy

• Self-diffusion: Diffusing atom and host atoms are the Same element

Vacancy

4
 Mechanisms of Solid State Diffusion
Vacancy Diffusion Interstitial Diffusion

j
~

Which mechanism is faster? Why?

Interstitial diffusion is faster because:
mobile
'

-
Interstitial atoms are smaller : more

Many more interstitial positions than vacancies

.
many
What conditions are required for an atom to move?
-

Must be an
open vacancy
on interstitial site adjacent

Atoms must have sufficient energy

to brah bonds
atoms
with neighboring .

5
 Diffusion of different atoms in Iron (Fe)

Diffusing Atomic Host Diffusion Coefficient, Diffusion Diffusion

Species Diameter metal D, (m2/s) @ 500oC Type Mechanism
(nm)
Fe atoms 0.248 . Fe 3.10-21? Self Vacancy
C atoms 0.142 Fe 2. to
-
' 2

Interstitial
Impurity
H atoms 0.100 Fe 1. 10-5 Interstitial
Impurity

6
 Definition of Diffusion Flux
through sectional
Diffusion flux (J) = Mass diffusing a cross area
-

unit time
per

#↳
]

f. A. t

9 [
IT E ]

JET tests

Steady state -

→ J is constant

w/ respect to

time .

7
 Two types of diffusion problems

Concentration of Diffusing Species

Linear
1st Law
Steady state - Fick 's

Position (x)

Concentration of Diffusing Species

Non-steady state - Fick 's 2nd Law Non-Linear

Position (x) 8
 Steady-State Diffusion

I
How is the diffusion flux (J) related to the:
• concentration(s) of the diffusing species? } ¥
• thickness of the membrane?

9
 Steady-State Diffusion
Diffusion Flux (J) is proportional to the concentration gradient ¥
membrane

C 1 CA
•

High Low
Concentration Concentration (kg/m3)
CB C2

0€
xA xB
• •

x
(m)
#
Direction of diffusion
Fick’s first law of diffusion

¥
F- D
deer
-

= =

-
.

10
 Example Problem: Steady-State Diffusion

Find ? J

MYS
"

his D=
'
-

3.10
given : Ca = 1.2kg ,

kg In
3
0.8
CB =

5mm#q
XA =
= 5 .

10-3 m

Carbon-
rich gas 2

www.oo#
-

Carbon-
m
XD = = I .
10

deficient gas

A B F- -

D .

d¥
. "
Ms Cos -

t.DK/n3
F- D 43×5.9-7 z.io
.
.
-
. ,

"

11
 Non-Steady State Diffusion
• The diffusion flux “J” is NOT constant
• The concentration of diffusing species
changes with time and position C = C(x,t)
• In this case Fick’s Second Law is used:

¥ =D .

8¥

• One important solution is for a “semi-infinite solid” in which surface

concentration is held constant

y
12
 Non-Steady State Diffusion: Semi-Infinite Solid
Time = 0
Initial conc. Co Time > 0
Impose a surface
concentration CS

Atoms diffuse into

solid over time

Example: “Case-Hardened” steel gear

• Steel gear exposed to carbon-rich atmosphere at high temp.
• Carbon diffuses into surface.
• Results in higher carbon concentration in outer layer
harder surface!

13
 Non-Steady State Diffusion: Semi-Infinite Solid

Time 0 Time > 0 Time >> 0

Initial Impose a Atoms diffuse

concentration surface into solid over
Co concentration time
CS

To satisfy the semi-infinite solid condition, it is generally required that:

'
k
L > to .

( D. t )

“The material must be thick enough that the concentration at the far end of the
* material does not change (remains at Co)” *
14
 Non-Steady State Diffusion: Semi-Infinite Solid
• Example: Copper diffuses into a bar of aluminum
Alum. bar

-2×2
Surface conc. (CS)
of Cu atoms 0 Initial concentration (Co) of copper atoms

Cs •

⇒ =D .
OI

Distance (x)
Conditions
Bo -

day
I .
@ t -

- O C -

-
Co for O E x E A
,

2 . for t > O ,
C -
-
↳ for X -

- O

3 C Co
.
@ x = A
,
=

15
Solution to Fick’s Second Law for “Semi-Infinite Solid”

C{YI)- =
I -
erf (af⇒ = I - erf ⇐ )

where In
Z =

2. TDE

(x @

terf
C ,
t ) = Concentration @
depth x time

between
O and I
( ) function ranges
⇒ error

CS

C(x,t)

Co

(x)
16
 Lookup Table for “erf”

O
C x, t Co x
1 erf
C s Co 2 Dt

8 so

17
 Non-Steady State Diffusion: Semi-Infinite Solid
For a given impurity concentration C (kg/m3):
C (x .
t )

x
⇒ Constant
⇒

sit
2

.
-

II. .

• Use this relationship to determine effect of changing one variable (x,t,D) on another
• Examples:
• Increase D by a factor of two at half
time is __________
in

• Increase x by a factor of two quadrupled

time is ____________

18
 Example Problem: Semi-Infinite Solid
Given: Diffusion coefficients for copper in aluminum:
300°C: D = 2.6 x 10-17 m2/s Copper
400°C: D = 1.8 x 10-15 m2/s atoms Aluminum
At 400°C, 10 hrs are required to achieve
a certain concentration profile

Determine: Time needed at 300°C to produce the

Concentration (C)
same diffusion result (concentration profile).

+
-

C Cx
,
t ) → Constant •

-
¥ ,
=
×÷ta
Data Dit
Distance (x)
⇒
-

-
'

X .
= Xz ta =
D.I.
Da

if
)
17¥
(
5
ta lohr
'

1.8.10
-
.

tz=692
19
How is diffusion coefficient (D) determined?
Factors that influence diffusion:
Diffusing species
Host material ( crystal structure
, density )
Temperature

20
How is diffusion coefficient (D) determined?
( j¥
D= Do exp )
.

Thot se
Yaku K
Do R K 8.62
-

pm exponential
.
-
-

constant =
8.374 .
or .

lo .

for
Qd = activation
energy T =
absolute te -

praline l KJ
diffusion

-
Vacancy Diffusion

Interstitial Diffusion

21
 Summary

Diffusion is SLOWER for... Diffusion is FASTER for...

crystal
"
"

close parched structures structures

open
-

low density materials

high density materials
smaller diffusing atoms
large diffusing atoms

interstitial diffusion
diffusion
Vacancy
high temperatures
In temperatures

22