You are on page 1of 11

CHAPTER 6: DIFFUSION IN SOLIDS

Gear from case-hardened steel (C diffusion)

Diffusion- Steady and Non-Steady State
Diffusion - Mass transport by atomic motion

ISSUES TO ADDRESS...
• How does diffusion occur? • Why is it an important part of processing? • How can the rate of diffusion be predicted for some simple cases? • How does diffusion depend on structure and temperature? Mechanisms • Gases & Liquids – random (Brownian) motion • Solids – vacancy diffusion or interstitial diffusion

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
• Glass tube filled with water. • At time t = 0, add some drops of ink to one end of the tube. • Measure the diffusion distance, x, over some time. • Compare the results with theory.

Inter-diffusion
• Interdiffusion: In alloys, atoms tend to migrate
from regions of large concentration.
This is a diffusion couple.

Initially
Adapted from Figs. 6.1 - 2, Callister 6e .

After some time

100% 0 Concentration Profiles
MatSE 280: Introduction to Engineering Materials
©D.D. Johnson 2004, 2006-08

2

MatSE 280: Introduction to Engineering Materials

©D.D. Johnson 2004, 2006-08

3

1

atoms also migrate.D.frequency of jumping.Self-diffusion • Self-diffusion: In an elemental solid. Anderson) increasing elapsed time Why should interstitial diffusion be faster than by vacancy mode of diffusion? MatSE 280: Introduction to Engineering Materials ©D. ΔE C A D B ΔE is an activation energy for a particular process (in J/mol. 2006-08 2 . Johnson 2004.D. eV/atom).vacancy concentration . Johnson 2004. Johnson 2004. 2006-08 4 MatSE 280: Introduction to Engineering Materials ©D. (Courtesy P. Substitution-diffusion:vacancies and interstitials • applies to substitutional impurities • atoms exchange with vacancies • rate depends on (1) number of vacancies.D. Johnson 2004. cal/mol. 2006-08 MatSE 280: Introduction to Engineering Materials ©D. MatSE 280: Introduction to Engineering Materials ©D. (2) activation energy to exchange.M. (2) activation energy to exchange. Inter-diffusion across Interfaces • Rate of substitutional diffusion depends on: . 2006-08 Substitution-diffusion Vacancy Diffusion: • applies to substitutional impurities • atoms exchange with vacancies • rate depends on (1) number of vacancies.D. Number ( or concentration*) of Vacancies at T Label some atoms After some time n −k T ci = i = e B N • k BT gives eV * see web handout for derivation.

D. Midland-Ross.) • Result: The "Case" is -hard to deform: C atoms "lock" planes from shearing. 2006-08 MatSE 280: Introduction to Engineering Materials ©D.impurity (B) atoms A = Area of flow • Empirically determined: – Make thin membrane of known surface area – Impose concentration gradient – Measure how fast atoms or molecules diffuse through the membrane ©D.0. Callister 6e .vacancies . Deposit P rich layers on surface. Result: Doped semiconductor regions.. Modeling rate of diffusion: flux • Flux: • Directional Quantity • Flux can be measured for: Fig. Fig. (courtesy of Surface Div. 18.0. 2006-08 silicon MatSE 280: Introduction to Engineering Materials diffused mass M J ∝ slope time MatSE 280: Introduction to Engineering Materials ©D.host (A) atoms . Johnson 2004. 6. Processing using Diffusion • Case Hardening: -Diffuse carbon atoms into the host iron atoms at the surface. Johnson 2004.D.Diffusion Mechanisms • Interstitial diffusion – smaller atoms diffuse between atoms. Heat it. 2006-08 3 .D. silicon 2. More rapid than vacancy diffusion MatSE 280: Introduction to Engineering Materials ©D. Callister 6e . Johnson 2004. .D. -hard to crack: C atoms put the surface in compression. Johnson 2004. -Example of interstitial diffusion is a case hardened gear. 2006-08 Processing using Diffusion • Doping Silicon with P for n-type semiconductors: • Process: 1. 3.

D.x1 = 1.Steady-state Diffusion: J ~ gradient of c • Concentration Profile. C(x): [kg/m 3] Steady-State Diffusion • Steady State: concentration profile not changing with time. the greater the flux! MatSE 280: Introduction to Engineering Materials ©D. If butyl rubber gloves (0. x • Fick's First Law: D is a constant! • Apply Fick's First Law: • If Jx)left = Jx)right . 6. Johnson 2004.D. Johnson 2004. slope doesn't vary with position)! MatSE 280: Introduction to Engineering Materials ©D.04 cm thick) are used.D. 2006-08 • Result: the slope.C1 x 2 . Johnson 2004. Besides being an irritant. protective gloves should be worn. 2006-08 skin 6D x1 x2 MatSE 280: Introduction to Engineering Materials C2 Jx = -D C2 . 2006-08 Steady-State Diffusion Rate of diffusion independent of time J~ Example: Chemical Protection Clothing dC dx • Methylene chloride is a common ingredient of paint removers.04 cm glove C1 l2 paint remover tb = C1 C1 Fick’s first law of diffusion • • C2 x1 x x2 C2 dC J = −D dx D ≡ diffusion coefficient if linear dC ΔC C2 − C1 ≅ = dx Δx x2 − x1 ©D.D.44 g/cm 3 C2 = 0.16 x 10-5 g cm2 s MatSE 280: Introduction to Engineering Materials ©D. dC/dx. then dC dx  dC  dC   =   dx  left  dx  right Jx = −D • The steeper the concentration profile.02 g/cm 3 – Diffusion distance: x2 – x1 = 0. must be constant (i. Cu flux Ni flux Concentration of Cu [kg/m3] Adapted from Fig. When using. 2006-08 4 .2(c) Concentration of Ni [kg/m3] Position. what is the diffusive flux of methylene chloride through the glove? Data: – D in butyl rubber: D = 110 x10 -8 cm 2/s – surface concentrations: C1 = 0. Johnson 2004.. it also may be absorbed through skin.e.

D. Johnson 2004. changes w/ time. 2006-08 J • (0.6x 10−€ (41.69x 1020 Ni 63 / m 2 • s How many Ni 63 atoms/second through cell? € MatSE 280: Introduction to Engineering Materials ©D. Non-Steady-State Diffusion • Concentration profile.Example: C Diffusion in steel plate • Steel plate at 700 0C with geometry shown: 700 C Knowns: C1= 1. 5. Callister 6e.5Ni 63 / Ni ) (0. D~ 0. so it is a very effective gas-exchange interface. 2006-08 MatSE 280: Introduction to Engineering Materials ©D. • 4 microns below surface Ni 63 /Ni = 48:52 • Lattice constant of Ni at 1000 C is 0. 2006-08 5 .6 x 10 -9 cm 2/sec What is the flux of Ni 63 atoms through a plane 2 µm below surface? C1 = (4Ni / cell )(0. 2006-08 MatSE 280: Introduction to Engineering Materials € Where can we use Fick’s Law? Fick's law is commonly used to model transport processes in • foods. how much carbon transfers from the rich to the deficient side? € 13 m 2 /sec) = −(1.15x 1027 Ni 63 / m 3 • Q: In steady-state.4. • 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 .36x 10−9m )3 / cell = 42.D.36nm )2 = 9 Ni 63 / s ©D. and. Adapted from Fig.8 kg/m 3 at 10mm (1 x 10–2 m) below surface.360 nm. • porous soils. • pharmaceuticals.: 14 MatSE 280: Introduction to Engineering Materials ©D.0016 mm 2/s • Governing Eqn. CO2 in air has D~16 mm 2/s. Johnson 2004. Johnson 2004. • semiconductor doping process.15 − 42. • Experiment shows that self-diffusion of Ni is 1.36x 10−9 m )3 / cell C2 = (4Ni / cell )(0.48Ni 63 / Ni ) (0.D. D = 3 x10 -11 m 2/s at 700 C. • clothing. C(x).D. in water. etc. Johnson 2004.87x 1027 Ni 63 / m 3 = 41.87)x 1027 Ni 63 / m 3 (4 − 0)x 10−6 m = +0. • biopolymers.2 kg/m 3 at 5mm (5 x 10–3 m) below surface. C2 = 0. Example: Diffusion of radioactive atoms • Surface of Ni plate at 1000 0C contains 50% Ni63 (radioactive) and 50% Ni (non-radioactive).

90 0. 2006-08 MatSE 280: Introduction to Engineering Materials 6 . Johnson 2004.93 D= x2 erf (z) = MatSE 280: Introduction to Engineering Materials 2 π ∫ z Now solve for D 0 e − y dy 15 2 4 z 2t  x2  (4 x 10−3 m)2 1h ∴D =  2  = = 2.t) concentration of diffusing species is a function of both time and position  ∂c  Fick's Second "Law" ∂c ≈ D 2   2 ∂t   ∂x   • Copper diffuses into a bar of aluminum.7970 So.0 − 0.1 z − 0. CS C(x. 6.0 wt%. t ) − Co 0.8125 − 0. MatSE 280: Introduction to Engineering Materials ©D. ∂C dx = J x − J x + dx ∂t • Using Fick’s Law: → ∂C ∂J ∂J dx = J x − ( J x + x dx ) = − x dx ∂t ∂x ∂x Fick’s 2nd Law D ∂c ∂x      Cs B. C = Co for 0 ≤ x ≤ ∞ at t > 0. If after 49.20 wt% C is carburized at an elevated temperature and in an atmosphere that gives a surface C content at 1.6 x 10−11 m2 /s 2  4z t  (4)(0. what temperature was treatment done? Solution C( x. 2006-08 MatSE 280: Introduction to Engineering Materials ©D.90 0. Johnson 2004. Use interpolation. ∂x Co ∴ erf(z ) = 0.8125.95 − 0.0 mm below the surface.7970 = 0.8209 − 0.20  2 Dt  Using Table 6. Johnson 2004.93) (49. 2006-08 Non-Steady-State Diffusion • Cu diffuses into a bar of Al.8209 • Solution: "error function” Values calibrated in Table 6.90 z 0.D.8125 z 0.D.5 h) 3600 s ©D. C = C S for x = 0 (fixed surface conc.) C = Co for x = ∞ ∂C ∂J ∂  ∂C  = − x = −  −D  ∂t ∂x ∂x  ∂x  Fick's Second "Law" ∂c ∂t =  ∂  ∂x   • If D is constant: ≈D 14       ∂c ∂x 2   2    Adapted from Fig.7970 0.C. Callister & Rethwisch 3e.5.35 − 0. at t = 0.Non-Steady-State Diffusion: another look • Concentration profile.8125 0.35 wt% at a position 4.1 find z where erf(z) = 0.20  x  = = 1 − erf   = 1 − erf ( z ) Cs − Co 1. z = 0. C(x).95 erf(z) 0. changes w/ time.D. Johnson 2004. 2006-08 z= x 2 Dt ©D.D.5 h the concentration of carbon is 0. t) ∂c Fick's Second "Law": ∂c ≈ D ∂t       2   2    Example: Non-Steady-State Diffusion FCC iron-carbon alloy initially containing 0. • Rate of accumulation C(x) Non-Steady-State Diffusion: C = c(x.

C( x. Johnson 2004.50 from • Close agreement. ∴ T= 148.6x10−11 m2 /s) T = 1300 K = 1027°C • Answer: MatSE 280: Introduction to Engineering Materials ©D.D.3 x 10 -5 m2 /s Qd = 148. • How many hours needed to get the same C(x) at 500 C? Key point 1: C(x. ©D.6 x 10−11 m2 /s • Result: Dt should be held constant. we use a rearranged form of Equation (6.3x10−5 m2 /s − ln 2. 2006-08 16 Diffusion Analysis • The experiment: we recorded combinations of t and x that kept C constant. 2006-08 7 .t600C).9a). Data from Diffusion Analysis  x  C(x i.58 • Theory predicts x ~ t0.Example: Processing Solution (cont.D. Key point 2: Both cases have the same C o and Cs.000 J/mol (8.): • To solve for the temperature at which D has the above value. • From Table 6. 2006-08 MatSE 280: Introduction to Engineering Materials 17 MatSE 280: Introduction to Engineering Materials ©D.t i ) − Co i  = 1− erf   2 Dt  Cs − Co  i = (constant here) • Diffusion depth given by: • Experimental result: x ~ t0. Johnson 2004.000 J/mol D = 2.2. Johnson 2004. Johnson 2004. 2006-08 MatSE 280: Introduction to Engineering Materials ©D. t ) − Co Cs − Co  x  = 1− erf    2 Dt  Note D(T) are T dependent! Values of D are provided. for diffusion of C in FCC Fe Do = 2.D. • 10 hours processed at 600 C gives desired C(x). D=D0 exp(-Qd/RT) Qd T = R(lnDo − lnD ) • Copper diffuses into a bar of aluminum.t500C) = C(x.314 J/mol-K)(ln 2.D.

B.53 eV/atom T = 900 C D=5. Brandes and G.7x10 –10(m 2/2) 10-8 D (m 2/s) 10-14 T(°C) C in γ- Ci nα -Fe Al Fe αFe e i n e F γ -F in Fe • bcc-Fe: in Al 10-20 0.5 1. Diffusion.314 J/mol-K] T = absolute temperature [K] 1 Note: ln D = ln D0 − d   R T  Q Q 1 log D = log D − d   0 2. 2006-08 MatSE 280: Introduction to Engineering Materials ©D. BCC and FCC phase exist over limited range of T (at varying %C). 7th ed.5 1000 K/ T Red octahedral fcc Green + Red octahedral bcc FCC represented as a BCT cell.) Smithells Metals Reference Book .5 1000 K/ T Adapted from Fig. and Stress z-axis (Table 6.7 from E.83 eV/atom T = 900 C D=1.0 1.2x10 –7(m 2/2) Q=0. Brook (Ed. Cannot always have the phase that you want at the %C and T you want! which is why this is all important. Butterworth-Heinemann.3x10 –5(m 2/2) Q=1.D.3 R  T  Al 10-20 0. 6. MatSE 280: Introduction to Engineering Materials ©D.D. with relevant holes.D. BCC diffuses faster due to lower Q.A. • • • • FCC Fe has both higher activation energy Q and D 0 (holes larger in FCC).5 1.. Johnson 2004.) MatSE 280: Introduction to Engineering Materials ©D. at same T.7.D. 6. Johnson 2004.2 ) Diffusion and Temperature • Experimental Data: 1500 600 300 Adapted from Fig.2) • fcc-Fe: D0=2.  Qd  −  D = Do exp   RT  D = diffusion coefficient Do = pre-exponential [m 2/s] (see Table 6. 6.7. Hence. 2006-08 Example: Comparing Diffuse in Fe Is C in fcc Fe diffusing faster than C in bcc Fe? 1500 1000 600 300 Connecting Holes. 2006-08 8 .0 1.Diffusion and Temperature • Diffusivity increases with T exponentially (so does Vacancy conc.). 1992. (Data for Fig. Oxford. Callister & Rethwisch 3e.9x10 –12(m 2/2) D0=6. 1000 T(°C) 10-8 D (m 2/s) 10-14 C in γ- Ci nα -Fe Al Fe αn Fe Fe i e γ -F in Fe Dinterstitial >> Dsubstitutional C in α-Fe C in γ-Fe Cu in Cu Al in Al Fe in α-Fe Fe in γ-Fe Zn in Cu [m 2/s] in Qd = activation energy [J/mol or eV/atom] R = gas constant [8. 2006-08 MatSE 280: Introduction to Engineering Materials ©D. Johnson 2004. Johnson 2004.

2006-08 • The two vacancies cannot accept neighbors because they have wrong charge.D. Johnson 2004.e. there is a net flow of atoms to the right past the markers. NiO There are Schottky defects Cu O Ni O Ni O O Ni Ni O Ni O Ni O Ni O t=0 Zn Mo wire markers Ni2+ O2– Ni O2– Ni O + O Ni O Ni O Ni2+ O2– – Ni Ni2+ O After diffusion Ni O • When diffusion is asymmetric. N = net # e. and ion diffusion needs 2nd neighbors with high barriers (activation energies). Johnson 2004. phonons.D. erf ( − z ) = − erf ( z ) h= κ cV ρ Q = cV ρT  x  Tx − Ts = erf   T0 − Ts  2 ht  ©D.g. • Kirkendall effect driven by vacancies. fcc Cu 70Zn30).g. charges.D.. effective for T > 0. Johnson 2004. the D’s are low unless vacancies are present from non-stoichiometric ratios of atoms.. MatSE 280: Introduction to Engineering Materials ©D. energy ε Solution: Fick’s 2nd Law Assuming DA = DB: For C2x C0 = (C1+C2)/2 Defining thermal conductivity κ (a material property) Or w/ Thermal Diffusivity: Q = −κ dT dx Curve is symmetric about C0. Cu70 Zn 30 Cu concentration Diffusion in Compounds: Ionic Conductors • Unlike diffusion in metals. diffusion in compounds involves second-neighbor migration.… • Charge Flux – j = 1 dq = 1 d ( Ne) q A dt A dt Defining conductivity σ (a material property) Ohm’s Law e = electric chg. interface moves away markers. i. Johnson 2004..D. e. • Symmetry is lost: Zn atoms move more readily in one direction (to the right) than Cu atoms move in the other (to the left). • Since the activation energies are high. x Position. MatSE 280: Introduction to Engineering Materials ©D.cross A Solution: Fick’s 2nd Law Inter-diffusion (diffusion couples) C1 Cu flux Ni flux Cu flux Ni flux C0 interface dV j = −σ dx Concentration of Cu [kg/m3] Concentration of Cu [kg/m3] Concentration of Ni [kg/m3] Concentration of Ni [kg/m3] jq = I 1V V = =σ A AR l  x  Vx − Vs = erf   V0 − Vs 2 σt  C2 Position. x C1x − C0  x  = erf   2 Dt   C1 − C0 • Heat Flux – (by phonons) Q= 1 dH 1 d ( N ε ) = A dt A dt N = # of phonons with avg. 2006-08 Kirkendall Effect: What is DA > DB? • Kirkendall studied Mo markers in Cu-brass (i.e. 2006-08 MatSE 280: Introduction to Engineering Materials MatSE 280: Introduction to Engineering Materials ©D.5 Tmelt. • Analyzing movement of markers determines DZn and DCu. 2006-08 9 .Other Types of Diffusion (Beside Atomic) • Flux is general concept: e.

e. Ionic Conduction: related to fuel cells • Molten salts and aqueous electrolytes conduct charge when placed in electric field. • Each ion has charge of Ze (e = 1.59 x10 28 / m 3 cell (4. i. DNa+~ 5D Cl– . What conductivity results by Ca 2+ diffusion in CaO at 2000 K? • CaO has NaCl structure with a= 4. having U 3+ ions to give UO 2-x.5 Co0. • Two sources of conduction: ion diffusion and via e.g.g. Haile’s SOFC (2004 best): Thin-film of Sm-doped Ceria electrolyte (CeO 2.e. 2006-08 Unit cell defined by Al ions: 2 Al + 3 O MatSE 280: Introduction to Engineering Materials ©D. Sm xCe1-x O 2-x/2) and BSCF cathode (Perovskite Ba0. Johnson 2004...5 Sr0.D. and Z=2.g. more energy to activate 4+ U ion. Johnson 2004. electrical conduction can be used determine diffusion data in ionic solids.hopping from ions of variable valency. • The same occurs in solids although at much slower rate. • This is mostly due to charge. Johnson 2004. • If MgF2 is dissolved in LiF (2Li+ -> Mg 2+ + vac. e. ionic • In NaCl at 1000 K.D. then Li + diffusion increases.D. D O ~ 10 7 DU. 2006-08 MatSE 280: Introduction to Engineering Materials Example: solid-oxide fuel cell (SOFC) • SOFC is made up of four layers..asp S. vacancies) • If Fe1-xO (x=2.) is dissolved in MgO under reducing conditions.6 x 10 –19 amp*sec) .g. nCa2+ = 4 cell = 3. i. 2006-08 10 .g. Fe 2+ to Fe 3+.. e. +q and –q move in opposite directions..e. at 1000 K (extrapolated).8 Fe0. Johnson 2004.it/FuelCells/en/htfc. with D(2000 K)~10 -14m2/s. 3Fe 2+ -> 2Fe3+ + vac. solid-solutions of oxides (leads to defects.. Overall: H 2 + 1/2O 2 → H2O Ceramic Compounds: Al2O3 Holes for diffusion H2 → 2H++2e– O2– + 2H+ + 2e – → H2O Image: http://www. UO is not stoichiometric. e. All due to additional vacancies. MatSE 280: Introduction to Engineering Materials ©D.5-4% at 1500 K. then Mg2+ diffusion increases.81x10 −10 m )3 σ= nZ 2 e2 1.D.whereas at 825 K DNa+ ~ 50D Cl–! • This is primarily due to size rNa+ = 1 A vs r Cl–=1. • A single cell consisting of these four layers stacked together is only a few mm thick.mobility.8 A. U4+(O2–) 2. oxides • In uranium oxide. e.2 O3-d ) show high power densities – over 1 W/cm2 at 600 C – with humidified H 2 as the fuel and air at the cathode. so that the anion vacancies significantly increase O 2.ip3. e.unipg. which is related to D via the Einstein equations: µ = ZeD / k BT • Hence nZ 2 e2 nZ 2 e2 σ ionic = D= Do e−Q / RT k BT k BT  nZ 2 e2  Q log10 σ ionic ~ ln  Do  −  k BT  2.81 A.3RT So. in applied electric field.). three of which are ceramics (hence the name). change and/or structural differences.g. • Also.3x10 −5 D~ k BT ohm − cm ©D. µ.Diffusion in Compounds: Ionic Conductors • D’s in an ionic compound are seldom comparable because of size. 2006-08 MatSE 280: Introduction to Engineering Materials ©D. so ion movement induces ionic conduction • Conductivity σ = nµ Ze is related to mobility. • Need to stack many. many together to have larger DC current.

Johnson 2004. • close-packed structures • higher melting T materials • materials w/covalent bonding • larger diffusing atoms • anions • higher density materials MatSE 280: Introduction to Engineering Materials ©D..D... 2006-08 11 . • open crystal structures • lower melting T materials • materials w/secondary bonding • smaller diffusing atoms • cations • lower density materials Diffusion SLOWER for.Summary: Structure and Diffusion Diffusion FASTER for..