Chapter 6. Diffusion

Chapter 6.
Diffusion
6.1. Introduction 6.2. Diffusion mechanisms 6.3. Steady-state diffusion 6.4. Nonsteady-state diffusion 6.5. Factors that influence diffusion 6.6. Other diffusion paths 6.7. Materials processing and diffusion
6.1. Introduction
Diffusion is a phenomenon of material transport by atomic motion.
Inhomogeneous materials can become homogeneous by diffusion. For an active diffusion to occur, the temperature should be high enough to overcome energy barriers to atomic motion.
Interdiffusion or impurity diffusion occurs in response to a concentration gradient.
Heat
Before
After
Self diffusion is diffusion in one-component material, when all atoms that exchange positions are of the same type.
6.2. Diffusion mechanisms

Vacancy diffusion To jump from lattice site to lattice site, atoms need energy to break bonds with neighbors, and to cause the necessary lattice distortions during jump. This energy comes from the thermal energy of atomic vibrations (Eav ~ kT). Materials flow (the atom) is opposite the vacancy flow direction.
Interstitial diffusion Interstitial diffusion is generally faster than vacancy diffusion because bonding of interstitials to the surrounding atoms is normally weaker and there are many more interstitial sites than vacancy sites to jump to. Requires small impurity atoms (e.g. C, H, O) to fit into interstices in host.
6.3. Steady-state diffusion

Diffusion is a process of a quantity of an element that is transported within another as a function of time or the rate of mass transfer. Diffusion flux (J) is defined as the mass (or the number of atoms) M diffusing through and perpendicular to a unit cross-sectional area of solid, A, per unit of time, t.
J=
M At
or
J=
1 dM A dt
with the unit of J is kg/m2s or atoms/m2s. Steady-state diffusion occurs if the diffusion flux does not change with time. Example: diffusion of atoms of a gas through a plate of metal for which concentrations (pressures) of the diffusing species on both surfaces of the plate are held constant.
Concentration profile: concentration of atoms/molecules of interest as function of position in the sample. Concentration gradient: dC/dx (Kg.m-3): the slope at a particular point on concentration profile.
The slope of a particular point on the concentration profile:
concentration gradient =
dC dx
or
concentration gradient =
C x
Sometimes the concentration gradient is called the driving force. Ficks first law
dC J = D dx
where: D is the diffusion coefficient (m2/s). The negative sign indicates that the direction of diffusion is down the concentration gradient, from high to low concentration. Example: purification of hydrogen gas
6.4. Nonsteady-state diffusion

Most of diffusion cases are nonsteady-state ones, which means that the concentration gradient at some particular point vary with time. Ficks second law
C 2C =D 2 t x
Some assumptions are made: 1. Before diffusion, any of the diffusing solute atoms in the solid are uniformly distributed with concentration of C0. 2. The value of a at the surface is zero and increases with distance into the solid 3. The time is taken to be zero the instant before the diffusion process begins. Boundary conditions of Ficks second law:
C x C0 x = 1 erf Cs C 0 2 Dt
where: Cx is the concentration at depth x after time t, C0 is the concentration at time =0, Cs is the concentration at x = 0 (surface concentration), erf(x/2DT) is the Gaussian error function (see Table 6.1).
When a specific concentration of solute is achieved, C1, the left-hand side of Ficks second law equation becomes:
C1 C 0 = constant Cs C0
and the right-hand side of Ficks second law equation becomes:
x = constant 2 Dt
or
x2 = constant Dt
6.5. Factors that influence diffusion

6.5.1. Diffusing species Both diffusing species and host material influence the diffusion coefficient. Smaller atoms diffuse more readily than big ones, and diffusion is faster in open lattices or in open directions.
6.5. Factors that influence diffusion

6.5.2. Temperature Temperature has a big influence on the coefficients and diffusion rates Arrhenius dependence. See examples in Table 5.2.
Qd D = D 0 exp RT
where: D0 is a temperature-independent pre exponential (m2/s), Qd is the activation energy for diffusion (J/mol), R is the universal gas constant (= 8.31 J/mol K), T is the absolute temperature (K). The activation energy is an energy required to produce the diffusive motion of one mole of atoms. Large Qd small diffusion coefficient
In logarithm function:
Graph of log D vs. 1/T has slop of Qd/2.3R, intercept of ln Do
Arrhenius plot of diffusivity data for some metallic systems
6.6. Other diffusion paths

Short-circuit diffusion paths may also occur along dislocations, grain boundaries, and external surfaces. Even the rates are faster than the bulk diffusion, compared the overall diffusion flux, the short-circuit diffusion paths are insignificant.
6.7. Materials processing and diffusion

Heat treatment is a process that involves atomic diffusion and occurs over reasonable time periods at elevated temperatures. The diffusion rate is usually relatively rapid and a common practice for all most materials (metals, ceramics, and polymers). Example: the strength of some steel changes significantly after heat treatment.

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Chapter 6. Diffusion

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Chapter 6.

Interdiffusion or impurity diffusion occurs in response to a concentration gradient.

6.2. Diffusion mechanisms

6.3. Steady-state diffusion

The slope of a particular point on the concentration profile:

6.4. Nonsteady-state diffusion

6.5. Factors that influence diffusion

6.5. Factors that influence diffusion

Graph of log D vs. 1/T has slop of Qd/2.3R, intercept of ln Do

Arrhenius plot of diffusivity data for some metallic systems

6.6. Other diffusion paths

6.7. Materials processing and diffusion

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