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Diffusion

Facultad de Ingeniería Aeronáutica


Solid Solution
Solid solution
https://www.youtube.com/watch?v=Peg1yaB2b
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Solid solution
Solid solution
A) Substitutional solid solution B) Interstitial solid
• T>Tm during cooling solution
• 70g Cu (FCC) + 30g Ni (FCC) in liquid • Small atoms located in
state → new structure with a octahedral sites or
intermediate between Cu and Ni tetrahedral sites.
Solid solution: Hume-Rothery rules
Hume-Rothery rules for the formation of substitutional solid solutions:
1) The same crystal structure
2) Atoms or ions with similar radius
• For ceramics difference < 30%
• For metals difference < 15%
• For differences > 15% limited solubility (<1%)
5) They must have similar electronegativities
6) Valence: In ceramics: They must have the same valence.
Solid solution: Hume-Rothery rules
• If all conditions are fulfilled ⇒ we do not necessarily have total
Solubility

• If one or more conditions are not fulfilled ⇒ partial solubility


Diffusion
• During production and application,
the chemical composition of
engineering materials is often
changed as a result of the
movement of atoms, or solid-state
diffusion.
Diffusion
• In some cases, atoms are redistributed within the microstructure of the
material.

• In other cases, atoms are added from the material’s environment, or atoms
from the material may be discharged into the environment.

• The flow of atoms in engineering materials occurs by the movement of


point defects, and, as a result, the rate of this solid-state diffusion increases
exponentially with temperature.
Diffusion

• Rearrangement of atoms due to high energy of individual atoms


• Requires sufficient activation energy
• Goal: property change, local or bulk
• Applications:
• Electronic transistor manufacturing
• Steel hardening
• Sintering
Diffusion Processes and Bonding Technologies

• Joining technique by which two metal surfaces are joined by high


pressure and temperature
• Sintering -> Ceramics and powder metallurgy (e.g. Titanium, ceramics).
Rate Processes in Solids
• Atom movement within material is called diffusion.
• This movement entails rearrangement of atoms in a new
atomic arrangement.
• This arrangement may be more stable than the initial
one.
• Diffusion occurs due to high energy of individual atoms
(statistical distribution of energy).
• This effect does not change average concentration.
• Properties are changed when concentrational diffusion
Exothermic reaction: new energy level (equilibration) occurs.
below initial one • Moving (reacting) atoms requires sufficient energy to
Endothermic reaction: new energy level
relocate, a threshold energy is a requisite: the activation
above initial one
energy.
Diffusion Mechanisms and Activation Energy

• Diffusion of one element in another


material structure depends on relative
atom size
• Vacancy (substitutional) diffusion for
“equal” size atoms
• Interstitial diffusion for unequal size
atoms
Diffusion Mechanisms and Activation Energy
• Diffusing atoms movement
requires activation energy
• Self-diffusion: atom movement in
absolutely pure materials
• Studied with isotope
migration
• No significant effect on
properties
• Interdiffusion: unlike atoms
Boltzman Equation

• The probability of having one atom of sufficient energy E*, greater than the average energy, E, of all atoms
in a closed system at a particular temperature T is:
Pr obability = Ce−(E*−E) / kT
• C = constant, n
• k = Boltzmann constant = 1.38 x 10-23 J/(atom K) = C e− E*/ kT
Ntotal
• T = absolute temperature (K)
• The fraction of atoms n/N having energies greater than E*
Arrhenius Plot
Arrhenius equation: Expresses the thermal
energy required for atoms to diffuse
Q E
− RT − kT
rate = Ce = Ce
Where:
• Q = activation energy (J/mol; cal/mol)
• E = energy of atom
• R = molar gas constant
• 8.314J/(mol K); 1.987 cal/(mol K)
• k = Boltzman constant
• (k = 13.8 x 10-24 J/atom/K)
• T = absolute temperature (K)
• C = constant
Rate Equation
• The rate equation is rewritten in a logarithmic scale
ln (rate) = ln constant - Q
RT

• And in Boltzman’s terms as:

n E
ln = ln C −
N total kT
• Activation energy is the energy barrier that must be overcome by thermal activation.
Example
• For example, the rate of oxidation of a magnesium alloy is represented by
a rate constant, k. The value of k at 300°C is 1.05 * 10-8kg/(m4 s). At 400°C,
the value of k rises to 2.95 * 10-4kg/(m4 s). Calculate the activation
energy, Q, for this oxidation process (in units of kJ/mol).
Example
• Taking the ratio of rate constants at 300°C (= 573 K) and 400°C (= 673 K),
we conveniently cancel out the unknown preexponential constant, C , and
obtain

or
Steady-State Diffusion: Definition
Steady-State Diffusion: Fick’s First Law
• Concentration gradient, dc/dx

• Diffusion wants to establish equilibrium

• Net flow of atoms moves from higher


concentration to lower concentration.

c
D = diffusion coefficient J = −D
x
Temperature Dependence on Diffusion Coefficient

• Diffusion coefficient depends on


temperature as:
 − Q
D = D0 exp  
 RT 

• D0 is a constant for a specific diffusion


system of two elements, it is called
diffusivity
• Diffusion also dependent on crystal
structure and allotropic transformations.
Bonding and structure dependence on Diffusion Coefficient
Factors Affecting Diffusion

• Diffusion mechanism
• Type of diffusion
• Operational temperature
• Type of crystal structure
• Type of imperfections
• Bonding energy of the matrix atoms
Transient Diffusion: Fick’s 2nd law
• Non-steady state d  dc x 
= (J x )=  D
dc x d

dt dx dx  dx 
• Time-dependent diffusion
cs − c x  x 
= erf  
• Concentration profile as cs − c0  2 Dt 
function of time:
Error Function

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