DIFFUSION

Assoc.Prof.Dr. Özlem Kızılırmak Esmer

 Diffusion

The phenomenon of mass transport within the material through

atom transfer is called diffusion.
Diffusion

• Materials of all types are often heat-treated to

improve their properties. The phenomena that
occur during a heat treatment almost always
involve atomic diffusion.
• Often, an enhancement of diffusion rate is
desired; on occasion, measures are taken to
reduce it. Heat-treating temperatures and times
and/or cooling rates can often be predicted by
using the mathematics of diffusion and
appropriate diffusion constants.
Diffusion
• Many reactions and processes that are important in the treatment of
materials rely on the transfer of mass either within a specific solid
(ordinarily on a microscopic level) from a liquid, a gas, or another
solid phase. This is necessarily accomplished by diffusion, the
phenomenon of material transport by atomic motion.
• Diffusion is the basis of the heat treatment processes to which
materials are subjected in order to improve their properties.
 • The phenomenon of diffusion may be demonstrated
with the use of a diffusion couple, which is formed by
Diffusion joining bars of two different metals together so that
there is intimate contact between the two faces.
• This is illustrated for copper and nickel in Figure 5.1a,
which includes schematic representations of atom
positions and composition across the interface.
• This couple is heated for an extended period at an
elevated temperature (but below the melting
temperature of both metals) and cooled to room
temperature.
• Concentrations of both metals vary with position as
shown in Figure 5.1b (bottom). This result indicates
that copper atoms have migrated or diffused into the
nickel, and that nickel has diffused into copper.
• The process by which atoms of one metal diffuse into
another is termed «interdiffusion», or «impurity
diffusion».
• The atoms are transported from high concentration
region to the low concentration region.
• Diffusion also occurs for pure metals, but all atoms
exchanging positions are of the same type; this is
termed «self-diffusion».
• From an atomic perspective, diffusion is just the stepwise displacement
(migration) of atoms from one lattice point to another lattice point. In fact,
atoms in solid materials are in constant motion and change their positions
rapidly.
• For an atom to make such a move, two conditions must be met:
(1) there must be an empty adjacent point, and
(2) the atom must have sufficient energy to break bonds with its neighbor
atoms and for the displacement.
While at a certain temperature, a small part of the atoms can diffuse due to
the vibration energy they have, the number of these atoms increases as the
temperature increases.
DIFFUSION MECHANISMS
• Vacancy diffusion: It involves the interchange of an atom from a
normal lattice point to an adjacent vacant lattice point or vacancy.
• The atoms must have similar sizes. It can occur in the form of self-
diffusion (Al) or inter-diffusion (Cu-Ni example).

Figure 5.2 Schematic representations of

(a) vacancy diffusion
DIFFUSION MECHANISMS

• Interstitial Diffusion : It involves atoms that migrate (transfer) from

an interstitial point to a neighboring one that is empty.

Schematic representations of
(b) İnterstitial diffusion.
Interstitial Diffusion
• Matrix or interstitial impurity atoms are rarely in the interstitial
position, and these atoms are not normally diffused by this
mechanism (interstitial diffusion).
• Small impurity atoms such as hydrogen, nitrogen, oxygen and carbon
are atoms that can settle in the interstitial space, and the diffusion of
these atoms occurs through the interstitial mechanism.
• If the foreign atom diffused into a crystal is much smaller than the
atoms that make up the crystal, interstitial diffusion occurs.

Schematic representations of
(b) İnterstitial diffusion.
Fick Kanunları
• Diffusion always occurs from high concentration to low concentration.
• In 1855, German physiologist Adolf Fick presented mathematical
equations that if each atom moves in random movements, diffusion
occurs in the direction of decreasing concentration.
• 1.Fick's law; If concentration varies depending on distance.
• 2.Fick's law: If concentration varies with both time and distance.
 Diffusion flux
• Diffusion is a time-dependent process—that is, in a macroscopic sense, the quantity
of an element that is transported within another is a function of time.
• Often it is necessary to know how fast diffusion occurs, or the rate of mass transfer.
• This rate is frequently expressed as a diffusion flux (J), defined as the mass (or,
equivalently, the number of atoms) M diffusing through and perpendicular to a
unit cross-sectional area of solid per unit of time.
In mathematical form, this may be represented as
J=M/A.t
where A denotes the area across which diffusion is occurring and
t is the elapsed diffusion time.
• The units for J are kilograms or atoms per meter squared per second (kg/m2 ∙s or
atoms/m2 ∙s).
• The mathematics of steady-state diffusion in a single (x) direction is relatively simple,
in that the flux is proportional to the concentration gradient, dC/dx through the
expression
 Steady-state diffusion (Kararlı yayınma) (Fick’s
1.law)
• If the diffusion flux does not change over
time, but only changes with distance,
there is a "steady-state diffusion".
• Fick’s first law may be applied to the
diffusion of atoms of a gas through a thin
metal plate for which the concentrations (or
pressures) of the diffusing species on both
surfaces of the plate are held constant, as
represented in this figure.
• This diffusion process eventually reaches a
state wherein the diffusion flux does not
change with time—that is, the mass of
diffusing species entering the plate on the
high pressure side is equal to the mass
exiting from the low-pressure surface—such
that there is no net accumulation of Figure 5.3 (a) Steady-state
diffusing species in the plate. This is an diffusion across a thin plate.
example of what is termed steady-state
diffusion.
Steady-state diffusion (Kararlı yayınma) (Fick’s
1.law)
• When concentration C is plotted versus position (or distance) within
the solid x, the resulting curve is termed the concentration profile.
• Concentration gradient is the slope at a particular point on this curve.
In the present treatment, the concentration profile is assumed to be
linear, as depicted in Figure 5.3b.
Steady-state diffusion (Kararlı yayınma) (Fick’s
1.law)
• The mathematics of steady-state diffusion in a single (x) direction is
relatively simple, in that the flux is proportional to the concentration
gradient, dC/dx through the expression;

• The constant of proportionality D is called the

diffusion coefficient, which is expressed in
square meters per second (m2/s).
• The negative sign in this expression indicates
that the direction of diffusion is down the
concentration gradient, from a high to a low
concentration.
• This equation is sometimes called Fick’s first
law.
FICK’S SECOND LAW—NONSTEADY-STATE
DIFFUSION
• Most practical diffusion situations are nonsteady-state ones—
• The diffusion flux and the concentration gradient at some particular
point in a solid vary with time, with a net accumulation or depletion
of the diffusing species resulting.
 FICK’S SECOND LAW—NONSTEADY-STATE
DIFFUSION
• This is illustrated in Figure 5.4, which
shows concentration profiles at three
different diffusion times.
• Under conditions of nonsteady state,
use of steady-state equation is not
convenient

Figure 5.4 Concentration profiles for

nonsteady-state diffusion taken at three different
times, t1, t2, and t3.
 FICK’S SECOND LAW—NONSTEADY-STATE
DIFFUSION
• Nonsteady-state diffusion occurs if the
concentration profile changes over
time.
• It shows how the time-dependent
change in concentration is related to
the concentration profile.

Figure 5.4 Concentration profiles for

nonsteady-state diffusion taken at three different
times, t1, t2, and t3.
• Kararsız yayınma şartlarında, Denklem 5.3’ün kullanılması uygun
değildir, bu nedenle Fick’in ikinci kanunu olarak bilinen
aşağıdaki kısmi diferansiyel denklem kullanılır.

denklemine sadeleşir.
FACTORS THAT INFLUENCE DIFFUSION

• Diffusing Species (diffusion coefficient)

• Temperature
• Diffusion mechanism,
• Time,
• Types of interatomic bonding,
• Crystal structure ,
• Concentration of solute element or solvent element
• Diffusion species; The magnitude of the diffusion coefficient D is
indicative of the rate at which atoms diffuse. ! This
comparison also
• The diffusing species and the host material influence the reveals the
diffusion coefficient. difference
between
• The coefficients for self-diffusion and interstial-diffusion for vacancy
various metal diffusion pairs are given in the table. diffusion and
interstitial
diffusion.
While self-
diffusion occurs
by a vacancy
diffusion
mechanism,
carbon does
interstitial
diffusion in iron.
• Temperature: Temperature has a profound influence on the
coefficients and diffusion rates
Diffusion example from Food Engineering
• Migration, one of the food-packaging interactions, also occurs
according to the diffusion mechanism. Migration occurs in
accordance with Fick's second law.
 Difüzyonun Uygulama Alanları
• Sinterleme – Tozların yüksek sıcaklıkta pişirilerek katı parçaları
oluşturacak şekilde birbirleri ile kaynaması.
• Toz metalurjisinde – Toz başlangıç malzemelerinde yekpare makine
parçalarının imali.
• Elektro seramik malzemelerde – elektrik iletken seramiklerin imali.
• Tane büyümesinde – Tane sınır alanlarının azaltılması için tane
sınırlarının hareketi ile büyük tanelerin oluşturulması
• Difüzyon kaynağında – iki yüzeyin basınç ve sıcaklık altında birbirine
birleştirilmesi için kullanılan kaynak tekniği.
• Yüzey sertleştirme – metal yüzeylere sertleştirme kabiliyeti olan
elementlerin emdirilmesi. Çeliğe karbon veya bor emdirilmesi vs.