Solidification, solid solutions and

diffusion in solids
• Solidification of metals
• Solidification of a metal or alloy can be
divided into three steps:
•
• the formation of stable nuclei
• the growth of nuclei into crystals
• the formation of a grain structure
• The two main mechanism by which
nucleation of solid particles in liquid
metal occurs are homogeneous
nucleation and heterogeneous
nucleation.
 HOMOGENEOUS NUCLEATION
• In case of homogeneous nucleation the
stable nuclei are provided by the
solidifying metal itself. The question is
how are the stable nuclei obtained? In
general the free energy of a solid is lower
than the free energy of a liquid. The
transformation solid-liquid costs energy,
the transformation liquid-solid provides
energy.
• For the process of nucleation two
kinds of energy must be considered:
• the “volume free energy” released
by the liquid solid transformation
• the “surface energy” required to
form the new solid surface of the
solidified particles.
 VOLUME FREE ENERGY
• The change in volume free energy between the
liquid and the solid per unit volume is given by
Gv, so the change in volume free energy for a
spherical nucleus is given by:
•
4 3
r Gv (this is negative!)
3
• This energy is the driving energy in the
formation of nuclei.
• There is an opposing energy to the formation
of nuclei, the energy required to form the
surface of the particles. The specific surface
free energy to form the surface is given by .
Thus for a spherical nucleus the opposing
energy is:

4 2
r  (this is positive !)
3
 TOTAL FREE ENERGY
• The change in total free energy is now
given by:

GT = 4/3r * Gv + 4r * 

3 2
 CRITICAL RADIUS
• A system can change spontaneously from
a higher to a lower energy level.
• We can see that at the left of r* the
energy drops if we decrease r. This
means that nuclei with r  r* are
unstable. The energy of the system will
be lowered if the nuclei redissolves.
• If r  r* the energy of the system will be
lowered if the nuclei grow.
• r* is called the critical radius
• The greater the degree of undercooling T
below the equilibrium melting temperature
the greater the change in volume free
energy Gv.
• In case of solidification we need a certain
amount of Gv so a certain T is required
(Gv = 0 if T = 0 ). The energy to form the
surface does not change much with
temperature. Therefore the critical radius r*
decreases as the degree of undercool  T
increases.
 HETEROGENEOUS NUCLEATION
• In case of heterogeneous nucleation the nuclei
on which the crystals form are not provided by
the metal itself. The liquid metal solidifies on
insoluble impurities, on the surface of its
container etc. The surface energy to form
nuclei on this material is lower than if the
nuclei are formed in the pure liquid itself. If the
surface energy is lowered the total free energy
is lowered and the critical radius for a stable
nucleus is reduce.
 CRYSTALS
• After stable nuclei have been formed they
grow into crystals. The orientation of each
crystal can vary. The crystals finally join
together and form crystal boundaries.
• Metal containing many crystals is said to be
“polycrystalline”. The crystals are called
“grains” and the surfaces between them,
“grain boundaries”.
 INDUSTRIAL CASTINGS
• In industrial casting large amounts of
undercooling do not occur 0.1 T10C, so
the nucleation must be heterogeneous. In a
lot of cases a fine grain structure is required.
To obtain such a structure “grain refiners” are
added. They provide the surfaces for the
liquid to solidify on and so reduce the critical
radius for stable nuclei. Many stable nuclei
result in a fine grain structure.
 SINGLE CRYSTALS
• Single crystals can also be very important.
For example, solid-state electronic
components such as transistors are made
from single crystals of semi-conducting
elements and compounds. They can be
formed by carefully control the
solidification process. Amongst other
conditions the temperature gradient
must be very low and the melt must be
extremely pure (why?).
 Metallic solid solutions
• A solution can be defined as a
homogeneous mixture in which
atoms of one substance are dispersed
at random in another substance.
Applied to solids we talk about solid
solutions. Alloys can be looked upon
as solid solutions. In general there
are two types of solid solutions
substitutional and interstitial.
 SUBSTITUTIONAL SOLID SOLUTIONS

• In substitutional solid solutions, solute

atoms can replace parent solvent
atoms in the crystal lattice
• Basically the crystal lattice remains the
same.
• Difference in atomic radii of the solute
an solvent atoms may distort the
lattice.
 CONDITIONS FOR SULUBILITY
• The diameter of the atoms should not differ
more than 15%
• The crystal structure should be the same
• The electronegativity should not show an
appreciable difference so that compounds will
not form
• The electro valence of the two elements should
be the same.
• If these conditions are satisfied solubility up to
100% can occur.
 INTERSTITIAL SOLID SOLUTIONS
• In interstitial solid solution the solute atoms
fit into the spaces between the parent atoms.
The spaces or voids are called interstices.
Interstitial solid solutions can form if the
solute atoms are much smaller than the
parent atoms
• Due to their dimension oxygen, nitrogen,
hydrogen and carbon can form interstitial
solid solutions.
• Important interstitial solid solutions are
those of carbon in iron. The atomic
radius of – iron with the FCC structure is
0.129 nm and that of carbon 0.075nm.
The atomic radius difference is 42%.
• In spite of this difference a maximum of
2.08% of carbon can dissolve interstitially
in  - iron at 1148C. The voids in BCC  -
iron are much smaller, a maximum of
0.025% of carbon can dissolve at 723 C.
 Diffusion in solids
• Diffusion can be defined as the transport of
matter trough matter.
• In gasses the diffusion rate is very high e.g.
smoke in air. In fluids it is much slower e.g.
dye in water.
• In solids atomic movement is restricted by
their bondings. Thermal vibrations however
do allow some atoms to move.
• Diffusion is important because most solid
state reactions involve atomic movement.
 MECHANISMS OF DIFFUSION
• There are two main mechanisms of
diffusion:
• the vacancy or sustitutional
mechanism
• the interstitial mechanism.
INTERSTITIAL AND VACANCY
DIFFUSION
 VACANCY MECHANISM
• In the vacancy mechanism the diffusing atom
moves to a neighbouring vacancy while creating a
vacancy itself. Two conditions are required.
• The atom must have enough energy and a
vacancy must be present.
• In case the moving atom is the same as the atoms
that form the lattice this is termed “self-
diffusion”. At higher temperatures the number of
vacancies as well as the energy level of the atoms
increases. Therefore the diffusion rate is higher
at higher temperatures.
 INTERSTITIAL MECHANISM
• In the interstitial mechanism the diffusing
atoms move from one interstitial site to
another neighbouring interstitial site. There is
no permanent distortion of the crystal lattice.
The size of the diffusing atoms must be
relatively small compared to the atoms
forming the lattice. Small atoms such as
oxygen, nitrogen, hydrogen and carbon can
diffuse interstitially in some metals
• Carbon can diffuse interstitially in BCC  –iron
and FCC  -iron
 Steady state diffusion.
• In steady state diffusion we consider
diffusion processes in which the
concentration of the solute atoms at a
certain point remains constant through
time.
• e.g At xA the concentration of the solute
atoms is CA, At xB it is CB, If there is no
change in CA and CB with time such
conditions are said to be steady state
conditions.
STEAD STATE DIFFUSION
• If no chemical reaction occurs there will be a
flow of solute atoms from the higher to the
lower concentration. This flow can be calculated
by using “Fick’s first law of diffusion”.

dC J : net flow [atoms/m2s]

J = -D –-- D: diffusion coefficient [m2/s]
dx
dC
: concentration gradient [atoms/m4]
dx
 DIFFUSION COEFFICIENT
• The diffusion coefficient (diffusitivity)
depends on various factors such as:
• the diffusion mechanism
• the temperature at which diffusion takes
place
• the type of crystal structure of the solvent
lattice
Table 5.1. The diffusion coefficients for some solute-solvent systems.

Solute Solvent D0 m2 s2 kJ/mol kcal/mol

Carbon FCC iron 2.0 x 10-5 142 34.0

Carbon BCC iron 22.0 x 10-5 122 29.3
Iron FCC iron 2.2 x 10-5 268 64.0
Iron BCC iron 20.0 x 10-5 240 57.5
Nickel FCC iron 7.7 x 10-5 280 67.0
Manganese FCC iron 3.5 x 10-5 282 67.5
Zinc Copper 3.4 x 10-5 191 45.6
Copper Aluminum 1.5 x 10-5 126 30.2
Copper Copper 2.0 x 10-5 197 47.1
Silver Silver 4.0 x 10-5 184 44.1
Carbon HCP titanium 51.0 x 10-5 182 43.5
 Non-steady state diffusion
• In industry we seldom will encounter
steady state diffusion. Non-steady state
diffusion is a process which occurs much
more frequently.
• Non-steady state diffusion implies that at
any point in the material the
concentration of the solute atoms
changes in time.
NON STEADY STATE DIFFUSION
 NON STEADY SRATE DIFFUSION
• In case the diffusion coefficient is
independent of time the flow of solute
atoms in non-steady state diffusion is
determined by “Fick’s second law of
diffusion”.
dCx d  dCx 
=  D 
dt dx  dx 
• The solution of “Fick’s law” (a
differential equation) for this
example is:

Cs − C x  x 
= erf  
Cs − C0  2 Dt 
• Cs: surface concentration of element in
gas diffusing into the surface
• C0: Initial uniform concentration of element in
solid
• Cx:Concentration of element at distance x
from surface at time t
• X: distance from surface
• D: diffusion coefficient
• t: time
• The error function, erf, is a tabulated
mathematical function.
• Using Fick’s law we are able to calculate
e.g. how much time it takes to obtain a
certain concentration at a certain
distance from the surface.
e 5.2. The tabulated error function erf(z)

z erf z z erf z z erf z z erf z

0 0 0.40 0.4284 0.85 0.7707 1.6 0.9763

0.025 0.0282 0.45 0.4755 0.90 0.7970 1.7 0.9838
0.05 0.0564 0.50 0.5205 0.95 0.8209 1.8 0.9891
0.10 0.1125 0.55 0.5633 1.0 0.9427 1.9 0.9928
0.15 0.1680 0.60 0.6039 1.1 0.8802 2.0 0.9955
0.20 0.2227 0.65 0.6420 1.2 0.9103 2.2 0.9981
0.25 0.2763 0.70 0.6778 1.3 0.9340 2.4 0.9993
0.30 0.3286 0.75 0.7112 1.4 0.9523 2.6 0.9998
0.35 0.3794 0.80 0.7421 1.5 0.9661 2.8 0.9999
 TEMPERATURE DEPENDENCE OF
DIFFUSION COEFFICIENT
• Since diffusion involves atomic
movements it is to be expected that
the temperature will greatly affect
the process. This is taken into
account by the dependence of the
diffusion coefficient of temperature.
 −Q
D = D0e RT

• D: diffusion coefficient [m2/s]

• D0: Constant
• T: temperature [K]
• R: molar gas constant 8.314
[Joule/mole]
• Q: activation energy of diffusing
species [Joule/mol]
Table 5.3. Diffusivity data for some metallic systems.

Diffusivity, m2/s

Solvent 500C 1000C

Solute (host structure) (930F) (1830F)

1. Carbon FCC iron (5 x 10-15) 3 x 10-11

2. Carbon BCC iron 10-12 (2 x 10-9)
3. Iron FCC iron (2 x 10-23) 2 x 10-16
4. Iron BCC iron 10-20 (3 x 10-14)
5.
Nickel FCC iron 10-23 2 x 10-16
6. Manganese FCC iron (3 x 10-24) 10-16

7. Zinc Copper 4 x 10-18 5 x 10-13

8. Copper Aluminum 4 x 10-14 10-
10mt
9.
Copper Copper 10-18 2 x 10-13
10. Silver Silver (crystal) 10-17 10-12m
11.
Silver Silver (grain boundary) 10-11
12. Carbon HCP titanium 3 x 10-1 (2 x 10-11)
 Industrial applications of solid state
diffusion.
• Solid state diffusion is often used as a case
hardening process. Many rotating steel parts,
like gears and shafts, need a hard and wear
resistant surface layer in combination with a
tough inner core for fracture resistance. In
industry we use a low carbon steel which is
machinable and tough. After machining the
parts are placed in a furnace with a methane
(CH4) atmosphere. Carbon will diffuse in the
surface layer. After cooling down the surface
layer becomes hard and wear resistant.
 Example
Surface hardening of a steel
• Consider an alloy initial carbon concentration of
0.25 wt% which is to be treated at a 950C. If
concentration at surface is suddenly brought to and
maintain at 1.20 wt%. How long will it take to
achieve a carbon concentration of 0.8 wt% at a
position 0.5mm below the surface?
• The diffusion coefficient for carbon in iron at this
temperature is 1.6 x 10-11 m2s2.
• Assume the steel piece is semi-infinite.
 S OLUTION
• This is a non steady-state diffusion problem in
which the surface composition is held constant
• Values for all the parameters except time t are
specified in the problem as follows:
• C0 = 0.25 wt% C
• Cs = 1.20 wt% C
• Cx =  0.80 wt% C
• x =  0.50 mm =  5 X 10-4 m
• D= 1.6 X10 -11 m2s-1
Z Erf(Z)

0.35 0.3794

Z 0.4210

0.40 0.4284