Physical Metallurgy 2

MMS220803

Ir. Myrna Ariati, M.S

 Lecture 05

Diffusion in Materials

2
Diffusion
Diffusion: the phenomenon of material/mass transport by atomic
motion.
For an atomic to make a motion, there are two conditions that need
to be meet:
 There must be an empty adjacent site
 The atom must have sufficient energy to break bonds with its neighbor
atoms and then cause some lattice distortion during the displacement.
Two mechanisms dominate for metals:
 Vacancy diffusion
 Interstitial diffusion
Diffusion Mechanism: Vacancy
Motion of a host or
substitutional atom

Vacancy

Vacancy
Diffusion Mechanism: Interstice
Position of interstitial Position of interstitial
atom before diffusion atom after diffusion
Steady-State Diffusion, cont…
1 2

Interstitial
Parent lattice

[C] 

x
Assume that on average an interstitial atom jumps 
times per second and that each jump is in a random
direction, i-e, there is an equal probability of the atom
jumping to every one of the six adjacent sites.
If plane (1) contains n1-atoms per m2 the number of
atoms that will jump from plane (1) to (2) in 1 s (J) will
be given by:
1
J  n1 atoms m -2s -1
6

7
At the same time the number of atoms that jump from
plane (2) to (1) assuming  is independent of
concentration, is given by:
1
J  n2 atoms m -2s -1
6
Since n1 > n2, there would be a net flux of atoms from
left to right in which
1
J  J  J  (n1  n2 )
6

8
If the separation of planes (1) and (2) is  the
concentration at the position of plane (1) would be:
n1
C1  atoms m -3

Likewise, at the position of plane (2):

n2
C2  atoms m -3

Thus,
( n1  n2 )   (C1  C2 )

9
From the figure, it can be seen that:
 C 
C1  C2    
 x 
Substitution into previous equation gives:
1 2  C
J     atoms m -2s -1
6  x
This equation is the form of Fick’s first law:
C
J  D
x

10
Diffusion Flux
Flux:
1 dM  kg  atoms
J    or  2 
A dt 2
m s   m s 
Directional Quantity x-direction
y J
y

Jx Unit area A
Jz x through
z which
Flux can be measured for: atoms
vacancies move.
host (A) atoms
impurity (B) atoms
CONCENTRATION PROFILES & FLUX
Concentration Profile, C(x):
[kg/m3] Cu flux Ni flux

Concentration Concentration
of Cu [kg/m3] of Ni [kg/m3]

Position, x
Fick's First Law:
2/s]
Diffusion coefficient [m
flux in x-dir.
[kg/m2-s] dC
J x  D concentration
dx gradient [kg/m4]

The steeper the concentration profile, the greater

the flux!
Steady State Diffusion
Steady State: the concentration profile doesn't
change with time.
Steady State:
J x(left) J x(right) J x(left) =J x(right)
x
Concentration, C, in the box doesn’t change w/time.
dC
Apply Fick's First Law: J x  D
dx
dC  dC
If Jx)left = Jx)right , then     
dx left  dx right

Result: the slope, dC/dx, must be constant (i.e.,

slope doesn't vary with position)!
Steady State Diffusion, example

• Steel plate at
700C with Carbon Steady State =
rich straight line! Adapted
geometry gas from Fig.
Carbon
shown: deficient
5.4,
Callister 6e.
gas
-11m2/s
D=3x10
0 x1 x2
• Q: How much
carbon transfers C2  C1  9 kg
from the rich to J  D 2.4  10
x2  x1 m2s
the deficient side?
Non Steady State Diffusion
dx
Concentration profile,
C(x), changes J (left) J (right)
w/ time. Concentration,
C, in the box
To conserve matter: • Fick's First Law:
J (right)  J (left)  dC dC
 J  D or
dx dt dx
dJ  dC dJ  d2 C (if D does
 D not vary
dx dt dx dx2 with x)
equate
Governing Eqn.:
dC d2C
=D Fick's Second Law
dt dx2
Non Steady State Diffusion, example
Copper diffuses into a bar of
Surface conc.,
aluminum.
C s of Cu atoms bar
pre-existingconc., Co of copper atoms
C(x,t)
Cs

t3
t2
t t1
Co o
position, x
General solution: C(x, t)  C o  x 
 1  erf  
Cs  Co 2 Dt 
"error function"
Values calibrated in Table 5.1, Callister 6e.
Processing Question
 Copper diffuses into a bar of aluminum.
 10 hours at 600C gives desired C(x).
 How many hours would it take to get the same C(x) if we
processed at 500C? D600=5.3x10-13 m2/s, D500 = 4.8x10-14 m2/s
Key point 1: C(x,t500C) = C(x,t600C).
Key point 2: Both cases have the same Co and Cs.
Result: Dt should be held constant.
C (x,t)  Co  x 
=1  erf 



(Dt)500ºC =(Dt)600ºC
Cs  Co 2Dt

5.3x10-13m2/s 10hrs
(Dt)600
Answer: t 500  110hr
D500
4.8x10-14m2/s
Diffusion Demo: Analysis
The experiment: we recorded combinations of
t and xt that kept C constant.
o
t1
t2
t3
xo x1 x2 x3
 
C(xi, ti )  Co x
 1 erf 

i 
 = (constant here)
Cs  Co 2 Dti 

Diffusion depth given by:

xi  Dti
Structure & Diffusion

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

 open crystal structures  close-packed structures
 lower melting T materials  higher melting T
 materials w/secondary materials
bonding  materials w/covalent
 smaller diffusing atoms bonding
 Cations  larger diffusing atoms
 lower density materials  Anions
 higher density materials
Diffusion as a random process
If direction of jumping atom is independent of the
direction of previous jump the process is called as
random walk.
In this case, it can be shown that the displacement, or
jump distance, will be equal to:

Prove it! (see case study #1)

Diffusion due to thermal
Due to the thermal energy of the solid all the atoms will be
vibrating about their position.
Violent oscillation of an interstitial atom, or some chance
coincidence of the movements of the matrix and interstitial
atoms, will result in a jump.
Diffusion coefficient will follow Arhenius equation:

This equation then can be used to determine activation energy for

diffusion.
Solution for Non-Steady-State Diffusion
Homogenization
Thin film solution
Carburization and decarburization
Diffusion from a Finite Source into Semi
Infinite Media
Homogenization
 It is of interest to be able to calculate C
the time taken for an t=0 β0
inhomogeneous alloy to reach
complete homogeneity, for example C
in the elimination of segregation in ’ l t=τ
castings.
 The simplest composition variation
that can be solved is if [C] varies It can be shown that:
sinusoidally with distance in one
dimension as shown in figure.
 In this case B atoms diffuse down
concentration gradient.
Thin film solution
 Thin film solution states that:

 Where

and N is the number of “source” atoms per unit area initially placed at x =
0

 Prove that this thin film solution is indeed a valid solution of Fick’s second
law.
Carburization and decarburization
 Carburization of steel:

 Decarburization
 x 0 1 2 3 4 5 6 7 8 9
ERF Table 0.0
0.1
0.00000
0.11246
0.01128
0.12362
0.02256
0.13476
0.03384
0.14587
0.04511
0.15695
0.05637
0.16800
0.06762
0.17901
0.07886
0.18999
0.09008
0.20094
0.10128
0.21184
0.2 0.22270 0.23352 0.24430 0.25502 0.26570 0.27633 0.28690 0.29742 0.30788 0.31828
0.3 0.32863 0.33891 0.34913 0.35928 0.36936 0.37938 0.38933 0.39921 0.40901 0.41874
0.4 0.42839 0.43797 0.44747 0.45689 0.46623 0.47548 0.48466 0.49375 0.50275 0.51167
0.5 0.52050 0.52924 0.53790 0.54646 0.55494 0.56332 0.57162 0.57982 0.58792 0.59594
0.6 0.60386 0.61168 0.61941 0.62705 0.63459 0.64203 0.64938 0.65663 0.66378 0.67084
0.7 0.67780 0.68467 0.69143 0.69810 0.70468 0.71116 0.71754 0.72382 0.73001 0.73610
0.8 0.74210 0.74800 0.75381 0.75952 0.76514 0.77067 0.77610 0.78144 0.78669 0.79184
0.9 0.79691 0.80188 0.80677 0.81156 0.81627 0.82089 0.82542 0.82987 0.83423 0.83851
1.0 0.84270 0.84681 0.85084 0.85478 0.85865 0.86244 0.86614 0.86977 0.87333 0.87680
1.1 0.88021 0.88353 0.88679 0.88997 0.89308 0.89612 0.89910 0.90200 0.90484 0.90761
1.2 0.91031 0.91296 0.91553 0.91805 0.92051 0.92290 0.92524 0.92751 0.92973 0.93190
1.3 0.93401 0.93606 0.93807 0.94002 0.94191 0.94376 0.94556 0.94731 0.94902 0.95067
1.4 0.95229 0.95385 0.95538 0.95686 0.95830 0.95970 0.96105 0.96237 0.96365 0.96490
1.5 0.96611 0.96728 0.96841 0.96952 0.97059 0.97162 0.97263 0.97360 0.97455 0.97546
1.6 0.97635 0.97721 0.97804 0.97884 0.97962 0.98038 0.98110 0.98181 0.98249 0.98315
1.7 0.98379 0.98441 0.98500 0.98558 0.98613 0.98667 0.98719 0.98769 0.98817 0.98864
1.8 0.98909 0.98952 0.98994 0.99035 0.99074 0.99111 0.99147 0.99182 0.99216 0.99248
1.9 0.99279 0.99309 0.99338 0.99366 0.99392 0.99418 0.99443 0.99466 0.99489 0.99511
2.0 0.99532 0.99552 0.99572 0.99591 0.99609 0.99626 0.99642 0.99658 0.99673 0.99688
2.1 0.99702 0.99715 0.99728 0.99741 0.99753 0.99764 0.99775 0.99785 0.99795 0.99805
2.2 0.99814 0.99822 0.99831 0.99839 0.99846 0.99854 0.99861 0.99867 0.99874 0.99880
2.3 0.99886 0.99891 0.99897 0.99902 0.99906 0.99911 0.99915 0.99920 0.99924 0.99928
2.4 0.99931 0.99935 0.99938 0.99941 0.99944 0.99947 0.99950 0.99952 0.99955 0.99957
2.5 0.99959 0.99961 0.99963 0.99965 0.99967 0.99969 0.99971 0.99972 0.99974 0.99975
2.6 0.99976 0.99978 0.99979 0.99980 0.99981 0.99982 0.99983 0.99984 0.99985 0.99986
2.7 0.99987 0.99987 0.99988 0.99989 0.99989 0.99990 0.99991 0.99991 0.99992 0.99992
2.8 0.99992 0.99993 0.99993 0.99994 0.99994 0.99994 0.99995 0.99995 0.99995 0.99996
2.9 0.99996 0.99996 0.99996 0.99997 0.99997 0.99997 0.99997 0.99997 0.99997 0.99998
3.0 0.99998 0.99998 0.99998 0.99998 0.99998 0.99998 0.99998 0.99999 0.99999 0.99999
3.1 0.99999 0.99999 0.99999 0.99999 0.99999 0.99999 0.99999 0.99999 0.99999 0.99999
3.2 0.99999 0.99999 0.99999 1.00000 1.00000 1.00000 1.00000 1.00000 1.00000 1.00000
Diffusion from a Finite Source into Semi Infinite Media
This is the case when joining by using an interlayer:

α is the thickness of the slab (see case study #2).

Example 1
How long will it take to carburize a 0.20% C steel at
900C so that the carbon content will be 0.40% at a
depth of 1 mm when the carbon concentration at the
surface is assumed to be 1.0%? It has been known that
the value of D0 and Q is 0.21 cm2/s and 33.8 kcal,
respectively.

28
Example 2
A plain carbon steel, 0.85% C, has been heated in air
for 1 h at 900C and as a result the carbon content of the
outermost layer has been reduced practically to zero.
What depth of stock must be removed from the
surface if the permissible carbon concentration in the
outer layer is 0.80%. Take the D value from the
foregoing example.

29
Case study #1
Suppose for a moment you had the misfortune to have me for your thesis
advisor. I has proposed an experiment in which you are to dynamically observe
(using a microscope with a heating stage) the growth of proeutectoid cementite
into austenite in an Fe – 2 wt. % C alloy held isothermally at a temperature of
1,000 °C. The question you need to answer in order to determine if this
experiment will be practicable is: how far will the austenite to cementite
interface move in 30 seconds? As a hint to this question, I suggested to you
that you take a look at the analysis of the growth of ferrite into austenite that I
covered in kinetic class. I also mentioned to you that the diffusivity of carbon in
austenite is 4.7 x 10-11 m2 s-1 at 1,000 °C.
Case study #2
You have now graduated and have taken a job with a company that specializes in providing
consulting services on joining processes. Your new boss has assigned you the following problem.
A customer is using a variant of diffusion bonding to join nickel-base substrates. In this process,
a soft pure copper interlayer is placed between the two substrates to be joined and the diffusion
bond is formed. The interlayer material is then diffused away into the bulk substrates. The
customer’s specification calls for a copper level at the joint center line of not more than 5 wt. %
after bonding. The customer tells you that the copper interlayer is initially 50 μm thick and that
his process operates at a temperature of 1,000 °C. What the customer wants to know is: “How
long do I need to hold at the bonding temperature to meet my specification?” After
thinking about the problem for a while, you guess that the overall rate of the process is limited by
the diffusion of copper into the bulk substrates. By investigating the literature, you find that:
 Copper and nickel form a continuous solid-solution
 For substitutional diffusion of copper in nickel D0 = 4 x 10-5 m2s-1 and Q = 256 kJ mol-1
(R = 8.314 J mol-1 K-1)