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Most metals are melted and then cast into semifinished or finished
shape.
Solidification of a metal can be divided into the following steps:
•Formation of a stable nucleus
•Growth of a stable nucleus.
4πγ r 16 πγ
2 3
⇒ ∆ G T ( r0 ) = = 0
2
3 3 ∆ GV
r0 : critical radius;
* for r < r0 : the growth of the droplet ⇒ ∆GT ↑ ⇒ the embryos
should shrink and disappear!
* for r > r0 : the growth of the droplet ⇒ ∆GT ↓ ⇒ the nuclei
could steadily grow!
γ
∆H f ∆T 2γ Tm
∆GV = ⇒ r0 =
Tm ∆H f ∆T
Where:
-∆Hf = Latent Heat of fusion
∆T = amount of undercooling at which
the nucleus form
Heterogeneous Nucleation
Heterogeneous nucleation is the nucleation that occurs in a liquid
on the surfaces of its container, insoluble impurities or other
structural material (catalyst) which lower the critical free energy
required to form a stable nucleus.
γL-S
Liquid
γL-C = γS-C + γL-S Cosθ
θ
γL-C θ Solid
γS-C
ro
Catalyst
Supersaturated Solutions
• If the liquid is just at the freezing point, only a few molecules stick,
because they have comparatively high energy
• As the liquid is cooled, more molecules can form into nuclei.
• When the nucleus is big enough (because of undercooling) the
supercooled liquid suddenly changes to a solid.
• Metals often experience undercooling of 50 to 500 oC
• Homogeneous nucleation usually only occurs in the lab.
• Impurities provide a “seed” for nucleation
• Solidification can start on a wall.
• It’s like cloud seeding, or water condensing on the side of a glass.
• Adding impurities on purpose is called inoculation
• Nucleation begins
• Chill Zone
• Columnar Zone (a) There may be dendrites in the columnar zone (b)
Grains grow in preferred directions
• Equiaxed Zone
Defects in Solids
Imperfections in Solids
Materials are often stronger when they have defects. The mechanical
and electrical properties of a material are affected by the presence of
defects. The study of defects is divided according to their dimension:
Examples of the large impact of defects:
Gemstones – Hope Diamond blue color due to boron impurities (ppm)
Type of Bonding
Microstructure
Chemical Thermomechanical
Composition Processing
Crystal Structure
0D – point defects: vacancies and interstitials impurities.
1D – linear defects: dislocations (edge, screw, mixed)
2D – planar defects: grain boundaries, surfaces.
3D – extended defects: pores, cracks.
Point Defects (0D)
Vacancies and Self-Interstitials
A vacancy is a lattice position that is vacant because the atom is
missing. It is created when the solid is formed.
They occur naturally as a result of thermal vibrations.
An interstitial is an atom that occupies a place outside the normal
lattice position.
It may be the same type of atom as the others (self interstitial) or an
impurity atom.
In the case of vacancies and interstitials, there is a change in the
coordination of atoms around the defect. This means that the forces
are not balanced in the same way as for other atoms in the solid
(lattice distortion).
Vacancy - a lattice position that is vacant because the atom is missing.
Interstitial - an atom that occupies a place outside the normal lattice
position. It may be the same type of atom as the others (self
interstitial) or an impurity interstitial atom.
The number of vacancies formed by thermal agitation follows an
Arrhenius type of equation:
QV QV
NV = N A exp − NV = N A exp −
k
B T RT
where NA is the total number of atoms in the solid, QV is the energy
required to form a vacancy (per atom or per mole), kB is Boltzmann
constant, R is the gas constant and T the temperature in Kelvin.
Note that kT(300 K) = 0.025 eV (room temperature) is much smaller
than typical vacancy formation energies.
For instance, QV(Cu) = 0.9 eV/atom.
This means that NV/NA at room temperature is exp(-36) = 2.3 × 10-16,
an insignificant number.
Thus, a high temperature is needed to have a high thermal
concentration of vacancies. Even so, NV/NA is typically only about
0.0001 at the melting point.
Calculate equilibrium number of vacancies per cubic meter for
copper at 1000oC
Given:
Activation Energy per vacancy = 0.9 eV/atom
atomic weight of copper = 63.5 g/mol
and density at 1000oC = 8.40 g/cm3
Boltzmann’s constant kB=1.38 × 10-23 J/atom-K=8.62 × 10-5 eV/atom-K
Solution:
Determine N, number of atomic sites per cubic meter for Cu
N a ρ ( 6 .023 X 10 23 atoms / mol )(8.40 g / cm 3 )(10 6 cm 3 / m 3 )
N= =
ACu 63 .5g / mol
N = 8 .0 X 10 28 atoms / m 3
Thus , the number of vacancies at 1000 0 C (1273 K ) is equal to
Q
N v = N exp − v
kT
( 0.9eV )
N V = (8 .0 X 10 atoms / m ) exp
28 3
−5
( 8 . 62 X 10 eV / K )(1273 K )
N V = 2.2 X 10 25 vacancies / m 3
Imperfections in Ceramics
Point defects in ionic crystals are charged. Coulombic forces are
large and any charge imbalance wants to be balanced. Charge
neutrality --> several point defects created:
Frenkel defect: a cation vacancy and a cation interstitial or an
anion (negative ion) vacancy and anion interstitial. (Anions are
+
larger so it is not easy for an anion interstitial to form).
Schottky defect: pair of anion and cation vacancies
-
Schottky defect
Frenkel defect
Imperfections in Ceramics
• Frenkel or Schottky defects: no change in cation to anion ratio →
compound is stoichiometric
• Non-stoichiometry (composition deviates from the one predicted
by chemical formula) may occur when one ion type can exist in
two valence states, (e.g. Fe2+, Fe3+). In FeO, usual Fe valence state
is 2+. If two Fe ions are in 3+ state, then a Fe vacancy is
required to maintain charge neutrality → fewer Fe ions → non-
stoichiometry
Impurities in Ceramics
Impurity atoms can exist as either substitutional or interstitial
solid solutions
Substitutional ions substitute for ions of like type
Interstitial ions are small compared to host structure (anion
interstitials are unlikely).
Solubility high if
ion radii and charges
match
Incorporation of
ion with different
Interstitial impurity atom
charge state requires
compensation by
point defects.
Substitutional impurity ions
Impurities in Solids
All real solids are impure. A very high purity material, say
99.9999% pure (called 6N – six nines) contains ~ 6 × 1016
impurities per cm3.
Impurities are often added to materials to improve the properties.
For instance, carbon added in small amounts to iron makes steel,
which is stronger than iron. Boron impurities added to silicon
drastically change its electrical properties.
Solid solutions are made of a host, the solvent or matrix) which
dissolves the solute (minor component). The ability to dissolve is
called solubility. Solid solutions are:
•homogeneous
•maintain crystal structure
•contain randomly dispersed impurities (substitutional or
interstitial)
Solid
Solid Solution
Solution Solids dissolve other solids
C/Fe
For fcc, bcc, hcp structures the voids (or interstices) between the
host atoms are relatively small ⇒ atomic radius of solute should be
significantly less than solvent.
Normally, max. solute concentration ≤ 10%, (2% for C-Fe)
Second Phase: as solute atoms are added, new compounds/structures
are formed, or solute forms local precipitates. Whether the addition of
impurities results in formation of solid solution or second phase
depends the nature of the impurities, their concentration and
temperature, pressure…
Factors for high solubility in Substitutional alloys
(Hume-Rothery Solubility Rules)
•Similar atomic size (to within 15%)
•Similar crystal structure
•Similar electronegativity (otherwise a compound is formed)
•Similar valence
Composition can be expressed in weight percent, useful when
making the solution, and in atomic percent, useful when trying to
understand the material at the atomic level.
Example
Ni is completely miscible in Cu (all rules apply)
Zn is partially miscible in Cu (different valence, different crystal
structure)
Ni - Cu binary isomorphous Limited solubility
alloy (eutectic) alloys
Ni Cu Pb Cu
crystal structure FCC FCC FCC FCC
atomic radius 0.125 0.128 0.175 0.128
2.4% 36.7%
electronegativities 1.8 1.8 1.6 1.8
valence 2+ 2+ 2+, 4+ 2+
3 3
The volume of an FCC cell is
Vol − cell = a 3 = (0.361nm ) = 0.047 nm 3
3