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Fall 2009 Lecture 4: Diffusion

Prof. Mitra Taheri

Acknowledgements: Reed-Hill, 4th ed., Udel coursenotes,, and CMU coursenotes.

• Fick’s laws are formulated under the assumption that the driving force for diffusion is a chemical gradient. the driving force is a gradient of chemical potiential. µ x . and most diffusion is “downhill”. to produce a decrease in Gibbs free energy. Specifically.What Is Diffusion? • Controls the rate at which phase transformations occur.

a division of Thomson Learning. . Inc.What IS a concentration gradient (in an A-B Solution)? ©2003 Brooks/Cole. Thomson Learning™ is a trademark used herein under license.

thus making the chemical potential uniform over the whole material (example: A-B solid solution). and M is a constant • We will use the case for an ideal (dilute) solution. unless solution is very concentrated. when it’s only an approximation. dµA/dx is the chemical potential gradient (energy/atom*length). . JA = -MA[dµA/dx] Where J = flux (atoms/area*time).Fick’s First Law • Equilibrium is reached when the gradient has been eliminated.

Schematic: Fick’s 1st Law .

a more detailed insight into the term diffusivity is given. This is explained in terms of the atomic jump frequency. .Atomic Diffusion in Metals ©2003 Brooks/Cole. Thomson Learning™ is a trademark used herein under license. which is highly temperature-dependent. Before going on to look at Fick's 2nd law. a division of Thomson Learning. Inc. It is shown step-by-step how D is related to temperature via the expression: The dependence of diffusion coefficient of Au on concentration. G. where D0 is the frequency factor and QID is equivalent to the enthalpy of interstitial atom migration. Both these terms can be taken as material constants. DHm.

• BUT! Even when c is a function of time. x. you can use the first law at any instant in time. we use Fick’s 2nd law to account for the variation. changes with time. a division of Thomson Learning. ©2003 Brooks/Cole. Fick’s first law is applicable to “steady state” conditions.Fick’s Second Law: Time Dependence of the Concentration • Remember. Inc. is INDEPENDENT of time. • If c at any given position. Thomson Learning™ is a trademark used herein under license. where concentration. c. .

e. this reduces to: . This applies to non steady-sate conditions. The general form of Fick's 2nd law is given by: • For cases in which DB is independent of composition. i.Derivation of Fick’s 2nd Law • A derivation for Fick's 2nd law is given. or where the ranges of composition are very small. CB varies with time. those in which interstitial concentration.

• What happens during diffusion between Cu and Ni? •  We will find out in Lab number 2!  • Calculation of Matano Interface. .

is the area between the profile and Matano interface. whilst dx/dC is the reciprocal of the curve gradient at C. . After removal from the furnace. From this. a concentration profile is generated. the Matano interface is defined as being the plane across which an equal number of atoms have crossed in both directions. The most common method is the Matano analysis. C using the equation: (13) The integral term.Matano Analysis (your 2nd lab) Since Fick's law cannot be directly integrated for variables (need error function solutions : ). A ‘pure’ diffusion couple is created and annealed at a constant temperature for a given length of time. It is shown step-by-step that the interdiffusion coefficient can be obtained by graphical construction for different compositions. from which a plot of versus C can be obtained. Some real data is provided in an additional exercise. values must be obtained experimentally.

Schematic of Matano Interface .

it was a common belief that atomic diffusion took place via a direct exchange or ring mechanism that indicated the equality of diffusion of binary elements in metals and alloys. in his short research career. .The Kirkendall Effect: Marker Movement of a Diffusion Couple (in sectin 12. This article reports how Kirkendall discovered the effect. However.The discovery was a great story! The Discovery and Acceptance of the Kirkendall Effect: The Result of a Short Research Career -Hideo Nakajima In the 1940s. now known as the Kirkendall Effect. Ernest Kirkendall first observed inequality in the diffusion of copper and zinc in interdiffusion between brass and copper.2)…….

Thomson Learning™ is a trademark used herein under license.High Diffusivity Paths • Dislocations. Inc. . Grain Boundaries. a division of Thomson Learning. Free surfaces: ©2003 Brooks/Cole.