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Chapter 6: Diffusion in Solids: Issues To Address..
Chapter 6: Diffusion in Solids: Issues To Address..
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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Concentration Profiles
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MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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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).
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MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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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.)
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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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)!
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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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
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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.:
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MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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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
∂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
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MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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
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MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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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
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MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
C(x i,t i ) − Co x
= 1− erf i
= (constant here)
Cs − Co 2 Dt i
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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.)
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
600
300
T(°C)
(Table 6.2)
10-8
• fcc-Fe: D0=2.3x10 –5(m 2/2)
C
nα
γ-
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
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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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
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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.
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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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
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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.
MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08 MatSE 280: Introduction to Engineering Materials ©D.D. Johnson 2004, 2006-08
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Summary: Structure and Diffusion
Diffusion FASTER for... Diffusion SLOWER for...
• cations • anions
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