Professional Documents
Culture Documents
Diffusion is relative flow of one material into another (Mass flow process by
which species change their position relative to their neighbours).
Diffusion of a species occurs from a region of high concentration to low
concentration (usually). More accurately, diffusion occurs down the chemical
potential () gradient.
To comprehend many materials related phenomenon (as in the figure below) one must
understand Diffusion.
The focus of the current chapter is solid state diffusion in crystalline materials.
Roles of Diffusion
Oxidation Creep
Metals Some mechanisms
Sintering Aging
Precipitates
Doping Carburizing
Semiconductors Steels
H2 diffusion direction
Ar H2
Movable piston
Piston motion
with an orifice
Piston moves in the
direction of the slower
moving species
Ar diffusion direction
Kirkendall effect
o Let us consider two materials A and B welded together with Inert marker and given a
diffusion anneal (i.e. heated for diffusion to take place).
o Usually the lower melting component diffuses faster (say B). This will lead to the shift in
the marker position to the right.
o This is called the Kirkendall effect.
Example W Mg
A B
Direction of
marker motion
Inert Marker is basically a thin rod of a high melting material, which is insoluble in A & B
Diffusion
Mass flow process by which species change their position relative to their
neighbours.
Diffusion is driven by thermal energy and a gradient (usually in chemical
potential). Gradients in other physical quantities can also lead to diffusion (as in
the figure below). In this chapter we will essentially restrict ourselves to
concentration gradients.
Usually, concentration gradients imply chemical potential gradients; but there are
exceptions to this rule. Hence, sometimes diffusion occurs uphill in
concentration gradients, but downhill in chemical potential gradients.
Thermal energy leads to thermal vibrations of atoms, leading to atomic jumps
In the absence of a gradient, atoms will still randomly jump about, without any
net flow of matter.
Concentration / Chemical potential
Electric
Gradient
Magnetic
Stress
Flux (J) (restricted definition) Flow / area / time [Atoms / m2 / s]
Flow direction
Area (A)
1 dn
J
A dt
Ficks I law As we shall see the law is actually an equation
Flux (J) of atoms* is flow per unit area per unit time Flow/area/time [Atoms/m2/s].
(This is a restricted definition).
dc dc
J J D Ficks first law (equation)
dx dx
1 dn dc
J D
A dt dx Flow direction
A
dn dc
DA dc dJ
dt dx x x
dt dx
Continuity equation
* Could be other species as well
dc
J D
dx
Flow direction
A
As a first approximation assume D f(t)
Steady and non-steady state diffusion D f(c)
Steady state
Under steady state conditions J f(x,t) D = f(c)
dc J Diffusion
0
dt x x t D f(c)
Substituting for flux from Ficks first law Non-steady state
J c J = f(x,t)
D = f(c)
D 0 If D is constant
x x 2c Slope of c-x plot is constant under steady state
D 2 0 conditions
If D is NOT constant x
c
D constant
x
If D increases with concentration then slope (of c-x plot)
decreases with c
If D decreases with c then slope increases with c
1st law 2nd law
x
x1 x2 x3
Ficks II law
The equation as below is often referred to as the Ficks II law (though clearly this is an
equation and not a law).
The equation is a second order PDE requiring one initial condition and two boundary
conditions to solve.
In the form of the equation below D is the diffusivity and is assumed constant (i.e is not a
function of concentration).
c 2
c
D 2
t x
If Jx is the flux arriving at plane A and Jx+x is the flux leaving plane B. Then the
Accumulation of matter is given by: (Jx Jx+x). 2nd law
x
Accumulation J x J x x
J A B
Accumulation J x J x x
x Jx Jx+x
c J Atoms 1 Atoms
m 3 s .m m 2 s J
x J x J x x
t x
c J c c
x x D Ficks first law
t x t x x
c c D f(x) c 2c
D D 2 x1x2x3
t x x t x
c 2c
D 2
t x
c
c
x x
Q D = diffusion co efficient
D0= diffusion co efficient at temp T =
D D0 e kT K= gas const
T= abs temperature in K
Q = activation energy
Arrhenius type
x Dt
ATOMIC MODELS OF DIFFUSION
The diffusion of two important types of species needs to be distinguished:
(i) species sitting in a lattice site
(ii) species in a interstitial void
1. Interstitial Mechanism
Usually the solubility of interstitial atoms (e.g. carbon in steel) is small. This implies that
most of the interstitial sites are vacant. Hence, if an interstitial species wants to jump, most
likely the neighboring site will be vacant and jump of the atomic species can take place.
Light interstitial atoms like hydrogen can diffuse very fast. For a correct description of
diffusion of hydrogen anharmonic and quantum (under barrier) effects may be very
important (especially at low temperatures).
Interstitial Diffusion
Hm
1 2
1 2
At T > 0 K vibration of the atoms provides the energy to overcome the energy
barrier Hm (enthalpy of motion)
frequency of vibrations, number of successful jumps / time
H m
' e kT
2. Vacancy Mechanism
For an atom in a lattice site (and often we are interested in substitutional atoms) jump to a
neighbouring lattice site can take place if it is vacant. Hence, vacancy concentration plays
an important role in the diffusion of species at lattice sites via the vacancy mechanism.
Vacancy clusters and defect complexes can alter this simple picture of diffusion involving
vacancies
Substitutional Diffusion
H f H m H f H m
' e kT
e kT
' e kT
H f H m
D 2 e kT
H m H m
kT
D e 2 kT of the form
D D0 e
Substitutional Diffusion
H f H m H f H m
of the form kT
D e 2 kT D D0 e
Diffusivity for a given path along with the available cross-section for
the path will determine the diffusion rate for that path
Comparison of Diffusivity for self-diffusion of Ag
single crystal vs polycrystal
Schematic
Qgrain boundary = 110 kJ /mole
QLattice = 192 kJ /mole
Log (D)
Polycrystal
Single
crystal
1/T
Increasing Temperature
Applications based on Ficks II law Carburization of steel
Surface is often the most important part of the component, which is prone to degradation.
Surface hardening of steel components like gears is done by carburizing or nitriding.
Pack carburizing solid carbon powder used as C source.
Gas carburizing Methane gas CH4 (g) 2H2 (g) + C (diffuses into steel).
C(+x, 0) = C1
C(0, t) = CS
A = CS
B = CS C1
Solved A 0.2% carbon steel needs to be surface carburized such that the concentration
Example of carbon at 0.2 mm depth is 1%. The carburizing medium imposes a surface
concentration of carbon of 1.4% and the process is carried out at 900C
(where, Fe is in FCC form).
Data: D0 (C in -Fe) 0.7 10 4 m 2 / s Q 157 kJ / mole
x
C ( x, t ) CS (CS -C0 ) erf
2 Dt
C ( x, t ) CS x
= erf
C0 CS 2 Dt
1 2 10-4
erf (2)
3 2 Dt
1
1.4
1 2 10-4
From equation (2) erf
1.2 3 2 Dt
1
1.0
t 2 10-4
erf 1 (0.3333) 0.309
0.8 2 7.14 10 12
t1
%C
0.6 t = t1 = 14580s 2
1 104
t1 12 14580 s
0.4 t = 1000s
t = 7000s 7.14 10 0.33
t =0
0.2
1 1 x1 2 1
erf
2 2 2 Dt 2
x penetration Dt
The depth at which C(x) is nearly C0 is (i.e. the distance beyond which is un-penetrated):
x
0 1 erf Erf(u) ~ 1 when u ~ 2
2 Dt
x
2 x 4 Dt
2 Dt
End
Diffusion in ionic materials
Element Hf Hm Hf + Hm Q
Au 97 80 177 174
Ag 95 79 174 184
c = atoms / volume
c=1/3
concentration gradient dc/dx = (1 / 3)/ = 1 / 4
Flux = No of atoms / area / time = / area = / 2
J ' 4
D 2 ' 2
1 2 (dc / dx)
H m
D 2 e kT
Q
On comparison
with D D0 e kT
Vacant site
D0 2
3. Interstitialcy Mechanism
Exchange of interstitial atom with a regular host atom (ejected from its regular
site and occupies an interstitial site)
Requires comparatively low activation energies and can provide a pathway for
fast diffusion
Interstitial halogen centres in alkali halides and silver interstitials in silver halides
C2
D = f(c)