# Diffusion in Solids

• Phenomenon
– put one drop of ink in a glass of water: you will see ink diffusing away and eventually indistinguishable (the water becomes slightly blue) – pickled vegetable: salt applied on the surface diffusing into the inside – case hardening of steel: put a steel component in a high temperature furnace with a carbonised or nitrogenised atmosphere, and C or N atoms will diffuse from the surface into the component causing hardening of the surface

• Definition
transport of atoms from place to place within a solid material

• Quantitative description
– Fick's first law – Fick's second law – temperature dependence

• What is the mechanism?
– vacancy – interstitial

Reading: Chapter 5 (5th and 6th ed)
436-220 Unit 2: Engineering Materials Dr. K. Xia 1

Diffusion in Solids at a sufficiently high temperature for a period of time Interdiffusion: one type of atoms diffusing into another type. K. most likely driven by composition difference 436-220 Unit 2: Engineering Materials Dr. Xia 2 t .

Diffusion in Solids at a sufficiently high temperature σ for a period of time σ σ Self-diffusion: same type of atoms diffusing among themselves. K. Xia σ t 3 436-220 Unit 2: Engineering Materials . for example driven by stress as in diffusional creep Dr.

Xia 4 . K.Mechanisms Vacancy diffusion Interstitial diffusion 436-220 Unit 2: Engineering Materials Dr.Diffusion in Solids .

K. Xia 5 .Diffusion in Solids .Mechanisms The diffusing atom can jump in any direction that is available An activation energy is needed for the diffusing atom to "squeeze" through to the vacancy next door There are more vacancies and the atoms have more energy (vibrational) at a higher temperature – diffusion is faster with increasing temperature 436-220 Unit 2: Engineering Materials Dr.

x) and observed at a particular moment dC J = −D d x t = to C: concentration (kg/m3 or g/cm3) x: position (dx in m or cm) D: diffusion coefficient (m2/s or cm2/s) t = to x J when dC is plus.Diffusion in Solids Diffusion Rate • Measurement of how fast a diffusion takes place – diffusion flux: mass transported per unit area per unit time M J = At M: mass (kg or number of atoms) A: cross section area (diffusion takes place perpendicular to the cross section) (m2) t: time (s) Fick's law: diffusion flux is proportional to the concentration gradient of the diffusing atoms – for diffusion in a single direction (e. Xia when dC is minus. J is positive (in the direction C + dC of x axis).g. as shown here 6 • x x + dx C when concentration difference is driving diffusion 436-220 Unit 2: Engineering Materials . J is negative (in the opposite direction of x axis) Dr. K.

Diffusion in Solids Steady state diffusion • • Steady state: concentration profile (concentration as a function of location) does not change with time.4 × 10 5 × 10 A B A B CA C C CB 5 mm T = 700°C Dr. i.8 kg/m3 D = 3 x 10-11 m2/s CA Concentration profile of C at steady state CB This can be realised if CA and CB are kept constant x x 7 436-220 Unit 2: Engineering Materials . Xia plate of Fe Concentration profile Example 5.2 J = −D −9 with x but not t = −3 × 10 −11 ⋅ kg/m 2 ⋅ s dx −3 = 2.8 − 1.2 kg/m3 CB = 0. C = C(x) dC C − CA = −D B J = −D • Fick's first law dx xB − x A dC J may change 0.e. K.1 CA = 1.

C = C(x. concentration profile does change with time. numerical solutions are obtained by finite element analysis using computer 436-220 Unit 2: Engineering Materials Dr. i. t) Fick's second law • ∂C ∂ 2C =D 2 ∂t ∂x – this is a partial differential equation – analytical solutions may be found for some boundary conditions – increasingly.Diffusion in Solids Non-steady state diffusion • In general. K. Xia 8 .e.

1 for selected values of erf Cx • Homework: Cx = ? if t = ∞ Surface Dr. K. Xia 9 436-220 Unit 2: Engineering Materials . C = Cs at x = 0 and C = Co at x = ∞ Cs t=0 Co Cx − Co = 1 − erf C s − Co  x     2 Dt  t = to > 0 erf: Gaussian error function See table 5. C = Co at 0 ≤ x ≤ ∞ – for t > 0.Diffusion in Solids Non-steady state diffusion • Analytical solution to Fick's second law equation for a semiinfinite plate with a constant surface concentration with the following initial and boundary conditions – t = 0.

20 − 0 . K.6 x 10-11 m2/s • Require Cx = 0. Xia .20 wt% D = 1.392  436-220 Unit 2: Engineering Materials Surface 0.5 = 0.80 − 0.1 h  0.5  0.5 mm = 0.6 × 10 ⋅ t  Cs CH4 gas at surface to keep Cs Cs = 1.25 5 × 10 −4  = 1 − erf  −11 1.25  2 1.5  2 t=  = 25400 s = 7.e. t = ?) Solution Using equation on the previous page   0.80 wt% C  62.Example Example 5.392 t  62 .4210 = erf    t  62 .2 From table 5.5 mm 10 Dr.Diffusion in Solids .25 wt% C Co t=? C0.25 wt% Cs = 1.25 C steel Co = 0.20 wt% C T = 950°C t=0 Fe-0.1 • Known using interpolation Co = 0.5 mm • How long will it take (i.8 wt% at x = 0.

3794 z − 0.4210 − 0.3794 436-220 Unit 2: Engineering Materials z = 0.35 0. K.35 = 0.4284 − 0. Xia 11 .40 − 0.392 Dr.4210 0.Diffusion in Solids z=? 0.

31 J/mol-K T: absolute temperature (K) 436-220 Unit 2: Engineering Materials log D = log D0 − log D Qd  1    2. Xia 12 .3 R  T  the slope • 1/T Do (the up and down position) and Qd (the slope) dependent on the diffusion system (NOT T!) Temperature has very significant influence on D IMSE: Diffusion coefficients Dr.Diffusion in Solids Diffusion coefficient • D determines how fast a diffusion takes place dC J = −D dx – the higher D is. K. the larger J for the same driving force (dC/dx) Expression for D  Qd  D = Do exp  −   RT  Do: constant for a certain type of diffusion (m2/s) Qd: activation energy for diffusion (J/mol) R: gas constant = 8.

Diffusion in Solids 1 2 E 2 1 3 3 An activation energy is needed for the diffusing atom to "squeeze" through to the vacancy next door There are more vacancies and the atoms have more energy (vibrational) at a higher temperature – diffusion is faster with increasing temperature 436-220 Unit 2: Engineering Materials Dr. K. Xia 13 .

K. Xia 14 .Diffusion in Solids Diffusion system 436-220 Unit 2: Engineering Materials Dr.

28   = −12 .3 R  T  2. Xia 15 Do = 10 −4.8 × 10 −3 = −4.8 × 10 −3 − 1. T2) 1/T x 1000 log Do = log D + Qd  1  194000 ⋅ 0.5 • Known: log D vs 1/T curve • Qd and Do = ? Solution Pick up any two points from the curve (e.T1} & {D2.Diffusion in Solids .3R ·Slope     log D1 − log D2  Qd = −2. T1) Cu diffusion in Au Qd/2.1 × 10 −3  = 194000 J / mol = 194 kJ / mol log D (D1. {D1.3 × 8.3 R    1 1 −   T1 T 2    −12 .28 = 5.g.40 + 2.31    0.45 )  = −2.3R 1 (D2.3 × 8.31 Dr. K.40 − (−15 .T2}) Qd = –2.25 × 10 −5 m 2 / s 436-220 Unit 2: Engineering Materials .Example Example 5.

Xia 16 . K.Summary Phenomenon • mass transport in solids Mechanism • vacancy • interstitial Quantitative description • Fick's first law • Fick's second law • their applications Diffusion coefficient • D – effect of T • Qd and Do – how to determine them 436-220 Unit 2: Engineering Materials Dr.Diffusion in Solids .