CHAPTER 6 – DIFFUSION

6.1 INTRODUCTION
 Many reactions and processes important to the processing of metals rely on the transfer
of mass —> either within a specific solid or from a liquid, a gas, or another solid phase
o This is accomplished by diffusion
 Diffusion = material transport by atomic motion
 Diffusion couple = joining bars of two different metals together, so there is intimate
contact between the two faces
o Used to demonstrate diffusion
o The couple is heated for an extended period of time (high temp but below the
melting points of the two metals) then cooled to room temp

o Results show the two metals will be separated by an alloyed diffusion zone

 Pure respective metals at the extremities and a region with varied

concentrations of both metals —> metal atoms have diffused
 Can observe a change in concentration over time —> net drift of atoms
from high- to low-concentration regions
o INTERDIFFUSION (aka impurity diffusion) = the process by which one metal
diffuses into another
 Diffusion also occurs for pure metals, where all atoms exchanging positions are of the
same type —> this is called SELF DIFFUSION
 o No compositional changes with self diffusion, obviously

6.2 DIFFUSION MECHANISMS

 Diffusion from an atomic perspective = stepwise migration of atoms from lattice site to
lattice site
 Atoms in solids are in constant motion, rapidly changing positions
 For this movement to occur, two conditions must be met:
o (1) there must be an empty adjacent site
o (2) the atom must have sufficient energy to break bonds with its neighbour
atoms and then cause some lattice distortion during the displacement
 Energy of motion is vibrational
 At a specific temperature, some small fraction of the total number of atoms is capable of
diffusive motion by virtue of the magnitudes of their vibrational energies
o This fraction increases with rising temperature**
 Two predominant models for metallic diffusion:
o VACANCY DIFFUSION
 Interchange of an atom from a normal lattice position to an adjacent
vacant lattice site, or vacancy
 Process necessitates the presence of vacancies**
 The extent to which vacancy diffusion can occur is a fn of the number of
these defects present
 There are significantly more vacancies in metals at elevated
temps**
 Diffusing atoms and vacancies exchange positions —> diffusion of atoms
in one directions corresponds to the motion of vacancies in the opposite
direction
 Both self diffusion and interdiffusion occur by this mechanism**
o INTERSTITIAL DIFFUSION
 Atoms migrate from an interstitial position to a neighbouring one that is
empty
 This mechanism is found for interdiffusion of impurities such as H, C, N, O
—> atoms are small enough to fit into the interstitial positions
 Host or substitutional impurity atoms rarely form interstitials and no not
normally diffuse via this mechanism
 In most metal alloys, interstitial diffusion occurs much more rapidly than diffusion by
vacancy mode**
o Interstitial atoms are smaller, thus more mobile
o Also, there are more empty interstitial positions than vacancies
 The probability of interstitial atomic movement is greater than for vacancy diffusion
6.3 FICK’S FIRST LAW
 Diffusion is a time-dependent process —> the quantity of an element that is transported
within another is a function of time
 We often care about rate of mass transfer
o Frequently expressed as DIFFUSION FLUX (J)
 Defined as the mass (or, number of atoms) diffusing through and
perpendicular to a unit cross-sectional area of solid per unit of time

 M = mass
 A = the area across which diffusion is occurring
 t = elapsed diffusion time
o Units of J [=] kg/m2•s or atoms/m2•s
 Steady state diffusion in a single (x) direction: flux is proportional to the concentration
gradient (dC/dx)**

o This equation is called Fick’s first law

o D = constant of proportionality, called the diffusion constant
 Units are m2/s
o Negative sign in this eqn denotes the direction of diffusion is down the
concentration gradient (from high to low concen.)
 Fick’s first law may be applied to the diffusion of atoms of a gas through a thin metal
plate for which concentrations (or pressures) of the diffusing species on both surfaces of
the plate are held constant

o Diffusion process will eventually reach a steady-state

 The mass of diffusing species entering the plate on the high-pressure side
is equal to the mass exiting from the low-pressure surface
 At this point, there is no net accumulation of diffusing species in the plate
 This is an example of STEADY-STATE DIFFUSION
o Figure 6.4(b) depicts the concentration profile graph, where C is plotted against
position within the solid, x
 Concentration gradient = the slope at a particular point on this curve
 Concentration profile is assumed to be linear* (so we can use the
expression below to calc.)

 For diffusion problems, we often express concentration in terms of mass of diffusing

species per unit volume of solid —> kg/m3 or g/cm3
  DRIVING FORCE = what compels the rxn to occur
o For diffusion rxns, several forces are possible
o For Fick’s first law, concentration is the driving force**

6.4 FICK’S SECOND LAW: NONSTEADY-STATE DIFFUSION

 Most practical diffusion situations are nonsteady-state —> the diffusion flux and the
concentration gradient at some particular point in a solid vary with time
o There is a net accumulation or depletion of the diffusing species

 Under conditions of nonsteady state, we use partial differential equation known as Fick’s
second law

o Used for nonsteady state diffusion in one direction

 If the diffusion coefficient is independent of composition (verify this for every diffusion
situation), the above eqn simplifies to:

 Solutions to this expression  concentration in terms of both position and time

o Sol’ns are possible when physically meaningful boundary conditions are specified
 One important solution: semi-infinite solid where surface concentration is held
constant
o A bar of solid is considered semi-infinite if none of the diffusing atoms reach the
bar end during the time of diffusion**
 A bar of length l is considered to be semi-infinite when l > 10√Dt
o Often, the source of the diffusing species is a gas phase
 Partial pressure is maintained at a constant value
o Following assumptions are made:
  Before diffusion, any of the diffusing solute atoms in the solid are
uniformly distributed with concentration C0
 The value of x at the surface is zero and increases with distance into the
solid
 The time is taken to be zero the instant before the diffusion process
begins
o Thus, initial condition:
For t = 0, C = C0 at 0 ≤ x ≤ ∞
o Boundary conditions:
For t > 0, C = Cs (the constant surface concentration) at x = 0
For t > 0, C = C0 at x = ∞
 Application of these boundary conditions to Fick’s second law eqn yields the solution:

o Cx = the concentration at depth x after time t

o The expression erf(x/2√Dt) is the Gaussian error fn  you get values from a
mathematical table for various x/2√Dt values

 Cx is a function of the dimensionless parameter x/2√Dt, thus may be determined at any

time and position if the parameters C0, Cs, and D are known

16.5 FACTORS THAT INFLUENCE DIFFUSION

 DIFFUSING SPECIES
o The magnitude of the diffusion coefficient D is indicative of the rate at which
atoms diffuse**
o The diffusing species and the host material influence the diffusion coefficient
 TEMPERATURE
o Temperature has a profound influence on the coefficients and diffusion rates
 o The temperature dependence of the diffusion coefficient is:

 D0 = a temperature-dependent preexponential [m2/s]

 Qd = the activation energy for diffusion [J/mol or eV/atom]
 R = gas constant = 8.314 J/mol*K (= 8.62 x 10-5 eV/atom*K)
 T = absolute temperatue [K]
o Activation energy – the energy required to produce the diffusive motion of one
mole of atoms
 Large activation energy results in a relatively small diffusion coefficient**
o D0 & Qd can be found in a table for various host materials and diffusing species
 These two parameters are determined experimentally

o It can be noted that the log of the diffusion coefficient has a linear relationship
with the reciprocal of temperature

6.6 DIFFUSION IN SEMICONDUCTING MATERIALS

 Fabrication of semiconductor integrated circuits (ICs) applies stead-state diffusion
 Single-crystal silicon is the base material for most ICs
 In order for these IC devices to function properly, very precise concentrations of an
impurity (or, impurities) must be incorporated into minute spatial regions on the silicon
chip —> this is accomplished through atomic diffusion
 Typically, two heat treatments are used in this process
o (1) Predeposition step
 Impurity atoms are diffused into the silicon
 Often from a gas phase – partial pressure is maintained constant
 The surface composition of the impurity this remains constant over
time**
 The impurity concentration within the silicon is a function of position and
time according to Fick’s Second Law:

 Predeposition treatments are normally carried out within the temp range
of 900ºC to 1000ºC for typically less than 1 h
o (2) Drive-in diffusion
 Transports impurity atoms farther into the silicon in order to provide a
more suitable concentration distribution without increasing the overall
impurity content
 This treatment is carried out at a higher temp – up to ~1200ºC
 Carried out in an oxidizing atmosphere to form an oxide layer on the
surface
 Diffusion rates through this SiO2 layer are relatively slow, so very few
impurity atoms diffuse out and escape from the silicon**
6.7 OTHER DIFFUSION PATHS
 Atomic migration may also occur along dislocations, grain boundaries, and external
surfaces
o These are sometimes called short-circuit diffusion paths
o Rates are much faster than for bulk diffusion
 In most situations, short-circuit contributions to the overall diffusion flux are insignificant
o B/c cross-sectional area of these paths is extremely small**

6.8 DIFFUSION IN IONIC AND POLYMERIC MATERIALS

 IONIC MATERIALS
o For ionic materials, diffusion is more complicated than for metals
o Need to consider diffusive motion of two types of ions that have opposite
charges
o Diffusion usually by vacancy diffusion**
 Ion vacancies occur in pairs
 Vacancies form in nonstoichiometric compounds
 Vacancies are created by substitutional impurity ions having different
charge states from the host ions
o Vacancy behaviour arises from the need to maintain charge neutrality in an ionic
material**
o Associated with the diffusive motion of a single ion is the transference of
electrical charge
 In order to maintain localized charge neutrality in the vicinity of this
moving ion, another species having an equal and opposite charge must
accompany the ion’s diffusive motion**
 Possible charged species include: another vacancy, an impurity atom, or
an electronic carrier (a free electron, or hole)
o Rate of diffusion of these electrically charged couples is limited by the diffusion
rate of the slowest-moving species**
o When an external electric field is applied across an ionic solid, the electrically
charged ions diffuse in response
 This ionic motion gives rise to an electric current
o The mobility of ions is a function of the diffusion coefficient
 POLYMERIC MATERIALS
o In polymeric materials, we often care about the diffusion of small foreign
molecules between the molecular chains
 Ex. O2, H2O, CO2, CH4
o A polymer’s permeability and absorption characteristics relate to the degree to
which foreign substances diffuse into the material
o Penetration of these foreign substances can lead to swelling and/or chemical rxns
with the polymer molecules and often a degradation of the material’s
mechanical and physical properties
o Rates of diffusion are greater through amorphous regions than through
crystalline regions**
 Amorphous regions have more “open” structure
o Diffusion mechanism is analogous to interstitial diffusion in metals**
o Foreign molecule size affect the diffusion rate
 Smaller molecules diffuse faster than larger ones
o Diffusion is more rapid for foreign molecules that are chemically inert than for
those that react with the polymer
o The diffusion properties of polymers are often characterized in terms of a
permeability coefficient (PM)
o Steady-state diffusion through a polymer membrane modelled by Fick’s first law:

 J = diffusion flux of gas through the membrane [cm3STP/cm2*s]

 PM = permeability coeff.
 ∆x = membrane thickness
 ∆P = difference in pressure of gas across the membrane
o For some applications, low permeability rates through polymeric materials are
desirable
 Ex. food and beverage packaging, automotive tires
o Polymer membranes are often used as filters to selectively separate one chemical
species from another
 Ex. desalination of water
 In these cases, permeation rate of the substance to be filtered is
significantly greater than for the other substance(s)