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Defects
Solid State Diffusion
• Planar densities
rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
rCs + 0.170
= = 0.939
rCl− 0.181
Si4+
O2-
• Grain boundaries
• Stacking Faults Planar defects
• Twin Boundaries
• Self-Interstitials
Extra
atom
in
structure
Causes
crowding
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
10
Point defects: impurities
• Substitution defect or impurity
Atom
subs@tuted
(solute)
solvent
• Hume-Rothery rules help to determine solubility of
metals:
– Atomic radii of the solvent and solute must be similar (less than 15%
difference)
– Solute and solvent have identical crystal structures
– A metal prefers to dissolve into a solution with higher valency over a
solution with lower valency
– Solute and solvent have similar electronegativities
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
11
Hume Rothery Rules – additional notes
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
12
Alloys used as biomaterials
• Stainless steel (316L)
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
13
Point defects in ceramics:
vacancies and interstitials
• Electrical neutrality should be maintained
• Shottky defect Missing
anion
– vacancy in both cation and anion to maintain neutrality
– Defects can be far apart
Missing
ca@on
• Frenkel defect
– A vacancy and interstitial pair is created to maintain Extra
ca@on
electroneutrality
– Usually cations, because they are smaller
Missing
ca@on
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
14
Point defects in ceramics: impurities
• Anions generally form substitutional solutions because they are
relatively large, cations can form substitutional or interstitial solutions
because they are smaller
inters@@al
ca@on
subs@tuted
ca@on
Subs@tuted
anion
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
15
Diffusion in solids
• In gases and liquids, diffusion occurs by random Brownian motion
• In the solid state, diffusion of atoms occurs by jumping to
neighboring lattice points or positions
• Self diffusion:
A
B
B
A
C @me C
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
16
Mechanisms of diffusion
• In order for diffusion to occur, a free position (vacancy or interstitial
site) must be present nearby, and the atom must have sufficient
energy to break the bonds with its neighbors (vibrational energy)
• Vacancy diffusion – atom jumps to neighboring position with a
diffusing
atom
vacancy
diffusing atom
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
17
Diffusion in solids
Concentra@on
Diffusion
of
Metal
1
Posi@on
2
different
metals
(ex.
Copper
and
nickel)
placed
next
to
each
other
at
elevated
temperature,
but
below
mel@ng
temperature
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
18
Diffusivity
• The diffusivity of an atom is described by the diffusion coefficient, D
Qd
D = D0 exp(− )
RT
• D0 is a temperature-independent constant (m2/s)
• Qd is the activation energy for diffusion (J/mol, cal/mol, eV/atom)
• R is a gas constant (8.31 J/mol-K, 1.987 cal/mol-K or 8.62 x 10-5 eV/
atom)
• D depends on the temperature and the activation energy for
diffusion, QD
– The larger the activation energy, the smaller the diffusion
coefficient
– The higher the temperature, the higher the diffusion coefficient
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
19
Modeling diffusion: flux
Area
• Flux, J, is the rate of change in mass or number of atoms across an
area over a given time
1 dM
J=
A dt
• Units for J are kg/m2-s or atoms/m2-s
• Flux can be for vacancies, host atoms, or impurities
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
20
Steady-state diffusion
• At steady state, the flux does not change with time or is constant.
• Flux is related to the concentration profile:
Nega@ve
sign
suggests
that
the
dC direc@on
of
diffusion
is
down
the
J = −D Fick’s First Law concentra@on
gradient
dx
A
B
dC CA − CB
=
dx x A − xB
CA
C A − CB
J = −D( )
x A − xB
CB
The steeper the concentration
xA
xB
gradient, the greater the flux
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
21
Non steady-state diffusion
• If diffusion is very slow (as can be the case in solids), it may take a
long time to reach steady state - concentration profiles will change
with time
• Conservation of mass: the rate of change of concentration C in the
box is equal to the flux into the box minus the flux out of the box
dJ J B − J A dC
= =−
dx dx dt
dJ d 2C
@me
= −D 2
JA
JB
dx dx
∂C ∂2 C
=D 2 Fick’s
Second
Law
xA
xB
∂t ∂x
BME111
Design
of
Biomaterials
Spring
2015
April
7
Lecture
3
Slide
22
Solution to Fick’s Second Law
• For the following boundary conditions (a semi-infinite solid)
– At t=0, C throughout the material equals C0
– At t>0, C at the surface (x=0) is Cs and C at x=∞ is C0
Cs
C(x, t) − C0 x
@me
= 1− erf ( )
Cs − C0 2 Dt
BME111 Design of Biomaterials Spring 2015 April 7 Lecture 3 Slide 23