Chapter 6: Diffusion in Solids: Issues To Address..

CHAPTER 6: DIFFUSION IN SOLIDS Diffusion- Steady and Non-Steady State
Gear from case-hardened

steel (C diffusion)
Diffusion - Mass transport by atomic motion
ISSUES TO ADDRESS...
• How does diffusion occur? Mechanisms
• Gases & Liquids – random (Brownian) motion
• Why is it an important part of processing?
• Solids – vacancy diffusion or interstitial diffusion
• How can the rate of diffusion be predicted for
some simple cases?
• How does diffusion depend on structure
and temperature?
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
Simple Diffusion Inter-diffusion

• Interdiffusion: In alloys, atoms tend to migrate
• Glass tube filled with water. from regions of large concentration.
• At time t = 0, add some drops of ink to one end This is a diffusion couple.
of the tube. Initially After some time
• Measure the diffusion distance, x, over some time.
• Compare the results with theory.
Adapted from
Figs. 6.1 - 2,
Callister 6e.
100%
0
Concentration Profiles
2 3
1
Self-diffusion Substitution-diffusion:vacancies and interstitials
• applies to substitutional impurities
• Self-diffusion: In an elemental solid, atoms also migrate. • atoms exchange with vacancies Number (or concentration*)
of Vacancies at T
• rate depends on (1) number of vacancies;
(2) activation energy to exchange. ΔE
n −k T
Label some atoms After some time ci = i =e B
N
C • k BT gives eV
A * see web handout for derivation.
D
B ΔE is an activation energy
for a particular process
(in J/mol, cal/mol, eV/atom).
4
Substitution-diffusion Inter-diffusion across Interfaces

Vacancy Diffusion:
• applies to substitutional impurities
• atoms exchange with vacancies
• rate depends on (1) number of vacancies;
(2) activation energy to exchange. • Rate of substitutional
diffusion depends on:
- vacancy concentration
- frequency of jumping.
(Courtesy P.M. Anderson)
increasing elapsed time

Why should interstitial diffusion be faster than by vacancy mode of diffusion?
2
Diffusion Mechanisms Processing using Diffusion
• Interstitial diffusion – smaller atoms diffuse between atoms. • Case Hardening:
-Diffuse carbon atoms into the Fig. 6.0, Callister 6e.
(courtesy of Surface
host iron atoms at the surface. Div., Midland-Ross.)
-Example of interstitial diffusion

is a case hardened gear.
• Result: The "Case" is

-hard to deform: C atoms
"lock" planes from shearing.
-hard to crack: C atoms put
the surface in compression.
More rapid than vacancy diffusion
Processing using Diffusion Modeling rate of diffusion: flux

• Doping Silicon with P for n-type semiconductors: • Flux:
• Process:
1. Deposit P rich
layers on surface.
• Directional Quantity
silicon • Flux can be measured for:

Fig. 18.0, - vacancies
2. Heat it. Callister 6e.
- host (A) atoms
3. Result: Doped - impurity (B) atoms
semiconductor A = Area of flow
regions. • Empirically determined:
– Make thin membrane of known surface area diffused
– Impose concentration gradient mass J ∝ slope
– Measure how fast atoms or molecules diffuse M
silicon through the membrane time
3
Steady-state Diffusion: J ~ gradient of c Steady-State Diffusion
• Concentration Profile, C(x): [kg/m 3] • Steady State: concentration profile not changing with time.
Cu flux Ni flux Adapted from Fig. 6.2(c)
Concentration Concentration
of Cu [kg/m3] of Ni [kg/m3]
Position, x
• Fick's First Law: D is a constant! dC
• Apply Fick's First Law: Jx = −D
dx
 dC  dC
• If Jx)left = Jx)right , then   = 
 dx  left  dx  right
• The steeper the concentration profile, the greater the flux! • Result: the slope, dC/dx, must be constant
(i.e., slope doesn't vary with position)!
Steady-State Diffusion Example: Chemical Protection Clothing

Rate of diffusion independent of time
dC • Methylene chloride is a common ingredient of paint removers.
J~
dx Besides being an irritant, it also may be absorbed through skin.
When using, protective gloves should be worn.
• If butyl rubber gloves (0.04 cm thick) are used, what is the

C1 C1 Fick’s first law of diffusion diffusive flux of methylene chloride through the glove?
• Data:
dC – D in butyl rubber: D = 110 x10 -8 cm 2/s
C2 C2 J = −D
dx – surface concentrations: C1 = 0.44 g/cm 3 C2 = 0.02 g/cm 3
– Diffusion distance: x2 – x1 = 0.04 cm
x1 x2 D ≡ diffusion coefficient glove
x C1 l2
tb =
6D
dC ΔC C2 − C1 paint skin C2 - C1 g
if linear ≅ = remover Jx = -D = 1.16 x 10-5
dx Δx x2 − x1 C2
x 2 - x1 cm2 s
x1 x2
4
Example: C Diffusion in steel plate Example: Diffusion of radioactive atoms
• Steel plate at 700 0C with geometry shown: • Surface of Ni plate at 1000 0C contains
50% Ni63 (radioactive) and 50% Ni (non-radioactive).
Adapted from Fig. • 4 microns below surface Ni 63 /Ni = 48:52
700 C 5.4, Callister 6e.
• Lattice constant of Ni at 1000 C is 0.360 nm.
Knowns: • Experiment shows that self-diffusion of Ni is 1.6 x 10 -9 cm 2/sec
C1= 1.2 kg/m 3 at 5mm
(5 x 10–3 m) below surface.
What is the flux of Ni 63 atoms through a plane 2 µm below surface?
C2 = 0.8 kg/m 3 at 10mm (4Ni / cell )(0.5Ni 63 / Ni ) (4Ni / cell )(0.48Ni 63 / Ni )
(1 x 10–2 m) below surface. C1 = C2 =
(0.36x 10−9 m )3 / cell (0.36x 10−9m )3 / cell
D = 3 x10 -11 m 2/s at 700 C. = 42.87x 1027 Ni 63 / m 3 = 41.15x 1027 Ni 63 / m 3
2 (41.15 − 42.87)x 1027 Ni 63 / m 3

= −(1.6x 10−13
€ m /sec)
• Q: In steady-state, how much carbon transfers €
(4 − 0)x 10−6 m
from the rich to the deficient side?
= +0.69x 1020 Ni 63 / m 2 • s
How many Ni 63 atoms/second through cell? J •(0.36nm )2 = 9 Ni 63 / s

€
Where can we use Fick’s Law? Non-Steady-State Diffusion

Fick's law is commonly used to model transport processes in • Concentration profile,
• foods, C(x), changes w/ time.
• clothing,
• biopolymers,
• pharmaceuticals,
• porous soils,
• semiconductor doping process, etc.
• To conserve matter: • Fick's First Law:
Example
The total membrane surface area in the lungs (alveoli)
may be on the order of 100 square meters and have
a thickness of less than a millionth of a meter, so it is
a very effective gas-exchange interface.
CO2 in air has D~16 mm 2/s, and, in water, D~ 0.0016 mm 2/s • Governing Eqn.:
14
5
Non-Steady-State Diffusion: another look Non-Steady-State Diffusion: C = c(x,t)
concentration of diffusing species is a function of both time and position
• Concentration profile,  2
C(x), changes w/ time. ∂c 
Fick's Second "Law" ∂c ≈ D 2 

∂t 

∂x 

• Rate of accumulation C(x) • Copper diffuses into a bar of aluminum.
∂C ∂C ∂J ∂J
dx = J x − J x+dx → dx = J x − (J x + x dx) = − x dx
∂t ∂t ∂x ∂x
Cs
∂C ∂J ∂  ∂C  B.C. at t = 0, C = Co for 0 ≤ x ≤ ∞
• Using Fick’s Law: = − x = −  −D Fick’s
 at t > 0, C = C S for x = 0 (fixed surface conc.)
∂t ∂x ∂x  ∂x  2nd Law
C = Co for x = ∞
   2
∂c ∂ ∂c  ∂c 
• If D is constant: Fick's Second "Law" =  D 

 ≈D



2 
Adapted from Fig. 6.5,
Callister & Rethwisch 3e.
∂t ∂x  ∂x 
 

∂x 

14
Non-Steady-State Diffusion Example: Non-Steady-State Diffusion

FCC iron-carbon alloy initially containing 0.20 wt% C is carburized at an elevated
• Cu diffuses into a bar of Al. CS temperature and in an atmosphere that gives a surface C content 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, what temperature was treatment done?
C(x,t)
Solution
∂c
 2
C( x, t ) − Co 0.35 − 0.20  x 
Fick's Second "Law": ∂c ≈ D
 
  Co = = 1 − erf   = 1 − erf ( z ) ∴ erf(z) = 0.8125
∂t

 ∂x
2 

Cs − Co 1.0 − 0.20  2 Dt 
 
Using Table 6.1 find z where erf(z) = 0.8125. Use interpolation. z erf(z)
• Solution: 0.90 0.7970
z − 0.90 0.8125 − 0.7970 So, z = 0.93 z 0.8125
=
0.95 − 0.90 0.8209 − 0.7970 0.95 0.8209
"error function” Values calibrated in Table 6.1 x x2
Now solve for D z= D=
2 z 2 2 Dt 4 z 2t
erf (z) = ∫ e −y dy  x2  (4 x 10−3 m)2 1h
0 = 2.6 x 10−11 m2 /s
π ∴D =  2  = 2
 4z t  (4)(0.93) (49.5 h) 3600 s
15
6
Example: Processing
Solution (cont.):
• Copper diffuses into a bar of aluminum.
• To solve for the temperature at which D Qd • 10 hours processed at 600 C gives desired C(x).
has the above value, we use a rearranged T = • How many hours needed to get the same C(x) at 500 C?
form of Equation (6.9a); R(lnDo − lnD )
D=D0 exp(-Qd/RT)
Key point 1: C(x,t500C) = C(x,t600C).
Key point 2: Both cases have the same C o and Cs.
• From Table 6.2, for diffusion of C in FCC Fe
Do = 2.3 x 10 -5 m2 /s Qd = 148,000 J/mol D = 2.6 x 10−11 m2 /s • Result: Dt should be held constant.

C(x,t) − Co  x 
= 1− erf  
Cs − Co  2 Dt 
∴ 148,000 J/mol
T=
(8.314 J/mol-K)(ln 2.3x10−5 m2 /s − ln 2.6x10−11 m2 /s) Note
D(T) are T dependent!
Values of D are provided.
T = 1300 K = 1027°C • Answer:
16
Diffusion Analysis Data from Diffusion Analysis

• 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: • Experimental result: x ~ t0.58

• Theory predicts x ~ t0.50 from
• Close agreement.
17
7
Diffusion and Temperature Diffusion and Temperature
• Diffusivity increases with T exponentially (so does Vacancy conc.). • Experimental Data:
1500
1000
Adapted from Fig. 6.7,
600
T(°C)
300
 Qd 
− 10-8
D = Do exp  
RT 
C
D (m 2/s)
in
Ci
nα
γ-
-Fe
Fe Fe i
Dinterstitial >> Dsubstitutional
D = diffusion coefficient [m 2/s]
C in α-Fe Cu in Cu
Fe
Do = pre-exponential [m 2/s] 10-14
n
(see Table 6.2) C in γ-Fe Al in Al
in
α-
Al
Fe in α-Fe
γ -F
Fe
in
Qd = activation energy [J/mol or eV/atom] Fe in γ-Fe
Al
e
Zn in Cu
R = gas constant [8.314 J/mol-K]
10-20
T = absolute temperature [K] 0.5 1.0 1.5 1000 K/T
1 Q Q 1 Adapted from Fig. 6.7, Callister & Rethwisch 3e.
Note: ln D = ln D0 − d   log D = log D − d  
0 2.3R  T 
(Data for Fig. 6.7 from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals
R T  Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)
Example: Comparing Diffuse in Fe Connecting Holes, Diffusion, and Stress

Is C in fcc Fe diffusing faster than C in bcc Fe?
z-axis
1500
1000
600
300
T(°C)
(Table 6.2)
10-8
• fcc-Fe: D0=2.3x10 –5(m 2/2)
C
Q=1.53 eV/atom D (m 2/s) Ci

in
nα
γ-
T = 900 C D=5.9x10 –12(m 2/2) -Fe

Fe e i n
F
Fe
10-14
• bcc-Fe: D0=6.2x10 –7(m 2/2)
in
Al
α-
in
γ -F
Fe
Q=0.83 eV/atom
Al
e
T = 900 C D=1.7x10 –10(m 2/2)

10-20 1000 K/T
0.5 1.0 1.5
Red octahedral fcc
Green + Red octahedral bcc
• FCC Fe has both higher activation energy Q and D 0 (holes larger in FCC).
• BCC and FCC phase exist over limited range of T (at varying %C).
• Hence, at same T, BCC diffuses faster due to lower Q. FCC represented as a BCT cell, with relevant holes.
• Cannot always have the phase that you want at the %C and T you want!
which is why this is all important.
8
Other Types of Diffusion (Beside Atomic) Inter-diffusion (diffusion couples)
interface
• Flux is general concept: e.g. charges, phonons,… Cu flux Ni flux
• Charge Flux – j = 1 dq = 1 d(Ne) e = electric chg. C1 Cu flux Ni flux
N = net # e- cross A Concentration
q
A dt A dt Concentration
of Cu [kg/m3]
Concentration C0 of Ni [kg/m3]
Concentration
Defining conductivity σ dV Solution: Fick’s 2nd Law
(a material property)
j = −σ of Cu [kg/m3] of Ni [kg/m3]
dx Vx − Vs  x 
= erf 
C2

Ohm’s Law jq =
I 1V V V0 − Vs 2 σt  Position, x
=
A AR
=σ
l Position, x
C1x − C0  x 
• Heat Flux – 1 dH 1 d(N ε ) N = # of phonons with Assuming DA = DB: = erf  C0 = (C1+C2)/2
Q= =
avg. energy ε C1 − C0  2 Dt 
(by phonons) A dt A dt
Defining thermal conductivity κ dT

Q = −κ Solution: Fick’s 2nd Law For C2x Curve is symmetric about C0, erf ( −z ) = −erf ( z )
(a material property) dx
Tx − Ts  x 
Or w/ Thermal Diffusivity:
κ = erf  
h= Q = cV ρT T0 − Ts  2 ht 
cV ρ
Kirkendall Effect: What is DA > DB? Diffusion in Compounds: Ionic Conductors

• Kirkendall studied Mo markers in Cu-brass (i.e., fcc Cu 70Zn30). • Unlike diffusion in metals, diffusion in compounds involves
• Symmetry is lost: Zn atoms move more readily in one direction second-neighbor migration.
(to the right) than Cu atoms move in the other (to the left). • Since the activation energies are high, the D’s are low unless
vacancies are present from non-stoichiometric ratios of atoms.
Cu70 Zn 30 Cu
Cu O Ni O Ni O Ni O
t=0 e.g., NiO
There are Ni O Ni O Ni2+ O2– Ni
concentration
Zn Schottky defects
Mo wire markers O Ni2+ O2– Ni O2– + O
Ni – Ni2+ O Ni O Ni
After diffusion
O Ni O Ni O Ni O
• When diffusion is asymmetric, interface moves away markers, • The two vacancies cannot accept neighbors because they have
i.e., there is a net flow of atoms to the right past the markers. wrong charge, and ion diffusion needs 2nd neighbors with high
• Analyzing movement of markers determines DZn and DCu. barriers (activation energies).
• Kirkendall effect driven by vacancies, effective for T > 0.5 Tmelt.
9
Diffusion in Compounds: Ionic Conductors Ionic Conduction: related to fuel cells
• D’s in an ionic compound are seldom comparable because of size, change
and/or structural differences.
• Molten salts and aqueous electrolytes conduct charge when placed in
• Two sources of conduction: ion diffusion and via e- hopping from ions of variable electric field, +q and –q move in opposite directions.
valency, e.g., Fe 2+ to Fe 3+, in applied electric field.
• The same occurs in solids although at much slower rate.
e.g., ionic • Each ion has charge of Ze (e = 1.6 x 10 –19 amp*sec) ,
• In NaCl at 1000 K, DNa+~ 5D Cl– ,whereas at 825 K DNa+ ~ 50D Cl–! so ion movement induces ionic conduction
• This is primarily due to size rNa+ = 1 A vs r Cl–=1.8 A. • Conductivity σ = nµ Ze is related to mobility, µ, which is
related to D via the Einstein equations: µ = ZeD / k BT
e.g., oxides
• Hence nZ 2 e2 nZ 2 e2
• In uranium oxide, U4+(O2–) 2, at 1000 K (extrapolated), D O ~ 10 7 DU. σ ionic = D= Do e−Q / RT
• This is mostly due to charge, i.e. more energy to activate 4+ U ion. k BT k BT
• Also, UO is not stoichiometric, having U 3+ ions to give UO 2-x, so that the
anion vacancies significantly increase O 2- mobility.  nZ 2 e2  Q So, electrical conduction can be used
log10 σ ionic ~ ln  Do  −
 k BT  2.3RT determine diffusion data in ionic solids.
e.g., solid-solutions of oxides (leads to defects, e.g., vacancies)
• If Fe1-xO (x=2.5-4% at 1500 K, 3Fe 2+ -> 2Fe3+ + vac.) is dissolved in MgO e.g., What conductivity results by Ca 2+ diffusion in CaO at 2000 K?
under reducing conditions, then Mg2+ diffusion increases. • CaO has NaCl structure with a= 4.81 A, with D(2000 K)~10 -14m2/s, and Z=2.
• If MgF2 is dissolved in LiF (2Li+ -> Mg 2+ + vac.), then Li + diffusion increases. 4 cell
= 3.59x10 28 / m 3 nZ 2 e2 1.3x10 −5
All due to additional vacancies. nCa2+ = σ= D~
cell (4.81x10 −10 m)3 k BT ohm − cm
Example: solid-oxide fuel cell (SOFC) Ceramic Compounds: Al2O3

• SOFC is made up of four layers, three of
which are ceramics (hence the name).
• A single cell consisting of these four layers

stacked together is only a few mm thick.
• Need to stack many, many together to

have larger DC current.
Overall: H 2 + 1/2O 2 → H2O
Holes for diffusion
H2 → 2H++2e–
O2– + 2H+ + 2e – → H2O
Image: http://www.ip3.unipg.it/FuelCells/en/htfc.asp
S. Haile’s SOFC (2004 best): Thin-film of Sm-doped Ceria electrolyte (CeO 2, i.e. Sm xCe1-x O 2-x/2)
and BSCF cathode (Perovskite Ba0.5 Sr0.5 Co0.8 Fe0.2 O3-d ) show high power densities – over 1 Unit cell defined by Al ions: 2 Al + 3 O
W/cm2 at 600 C – with humidified H 2 as the fuel and air at the cathode.
10
Summary: Structure and Diffusion
Diffusion FASTER for... Diffusion SLOWER for...
• open crystal structures • close-packed structures
• lower melting T materials • higher melting T materials
• materials w/secondary • materials w/covalent

bonding bonding
• smaller diffusing atoms • larger diffusing atoms
• cations • anions
• lower density materials • higher density materials
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
11

Chapter 6: Diffusion in Solids: Issues To Address..

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Chapter 6: Diffusion in Solids: Issues To Address..

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CHAPTER 6: DIFFUSION IN SOLIDS Diffusion- Steady and Non-Steady State

Gear from case-hardened

Simple Diffusion Inter-diffusion

Substitution-diffusion Inter-diffusion across Interfaces

(Courtesy P.M. Anderson)

increasing elapsed time

-Example of interstitial diffusion

• Result: The "Case" is

Processing using Diffusion Modeling rate of diffusion: flux

silicon • Flux can be measured for:

Steady-State Diffusion Example: Chemical Protection Clothing

• If butyl rubber gloves (0.04 cm thick) are used, what is the

2 (41.15 − 42.87)x 1027 Ni 63 / m 3

How many Ni 63 atoms/second through cell? J •(0.36nm )2 = 9 Ni 63 / s

Where can we use Fick’s Law? Non-Steady-State Diffusion

• Rate of accumulation C(x) • Copper diffuses into a bar of aluminum.

• If D is constant: Fick's Second "Law" =  D 

Non-Steady-State Diffusion Example: Non-Steady-State Diffusion

Do = 2.3 x 10 -5 m2 /s Qd = 148,000 J/mol D = 2.6 x 10−11 m2 /s • Result: Dt should be held constant.

Diffusion Analysis Data from Diffusion Analysis

• Diffusion depth given by: • Experimental result: x ~ t0.58

Example: Comparing Diffuse in Fe Connecting Holes, Diffusion, and Stress

Q=1.53 eV/atom D (m 2/s) Ci

T = 900 C D=5.9x10 –12(m 2/2) -Fe

T = 900 C D=1.7x10 –10(m 2/2)

Defining thermal conductivity κ dT

Kirkendall Effect: What is DA > DB? Diffusion in Compounds: Ionic Conductors

Example: solid-oxide fuel cell (SOFC) Ceramic Compounds: Al2O3

• A single cell consisting of these four layers

• Need to stack many, many together to

Overall: H 2 + 1/2O 2 → H2O

Holes for diffusion

• open crystal structures • close-packed structures

• lower melting T materials • higher melting T materials

• materials w/secondary • materials w/covalent

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials

MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08

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