Intro
to
Corrosion
Science:
Passivity
Professor
Scott
Lillard
Dept.
of
Chemical
&
Biomolecular
Engineering
University
of
Akron
Sir
Faraday’s
Corrosion
Experiment
add
dilute
nitric
?
English
chemist
1791-‐1867
Fe
acid
Fe
violent
reacDon
add
concentrated
?
Fe
nitric
acid
Fe
nothing
add
water
?
Fe
(dilute)
Fe
Fe
scratch
Conc.
HNO3
nothing
violent
reacDon
Passivity
• Michael
Faraday
deGined
passivity
as
the
loss
of
chemical
reactivity
as
the
result
of
exposure
to
certain
environments:
– Concentrated
nitric
passivates
iron,
dilute
nitric
acid
does
not.
• This
passive
state
protects
the
metal
upon
exposure
to
environments
that
otherwise
would
have
been
corrosive:
– No
corrosion
observed
after
re-‐exposure
to
dilute
nitric.
• We
know
now
that
this
owes
to
the
formation
of
an
oxide
Gilm
on
the
surface
of
the
metal:
– Scratching
the
surface
removes
the
Gilm
and
exposes
the
metal
to
the
dilute
nitric
acid.
Passive
Oxide
Films
• Typically
thin,
1-‐10
nm
in
thickness
(100Å).
• No
long
range
order
….
amorphous.
• Barriers
to
diffusion.
• Anhydrous.
• Chemically
inert.
• Electronic
Properties:
Fe,
Ni,
Cr
are
good
semiconductors
Al,
Ti,
Mg
good
insulators.
The
Active
to
Passive
Transition
• Where
Ecrit
and
icrit
are
the
critical
potential
and
current
for
passivation.
Ecrit
icrit
Passivity
of
Iron
Composition
of
the
Film
on
Fe:
XANES
Characterization
of
Passive
Film
on
Fe
from Schmuki, Issacs,Bohnu, ECS 1999
Behavior
of
Oxide
Film
on
Fe
in
Alkaline
Solution:
XANES
from Schmuki, Issacs,Bohnu, ECS 1999
Behavior
of
Oxide
Film
on
Fe
in
Alkaline
Solution
What
is
Stainless
Steel?
• Austenitic:
austenite
(fcc).
May
contain
18
-‐20%
Cr,
and
8-‐11%
Ni
and
up
to
3%
Mo.
Designated
by
3XX
(302,304,
316
).
Relatively
ductile,
high
fracture
toughness.
• Ferritic:
ferrite
(bcc)
These
steels
contain
iron
and
a
minimum
Cr
concentration
of
17%,designated
by
43X,
44
(430,
446).
Ferritic
steel
is
less
ductile
than
austenitic
steel.
• Martensitic:
martensite,
orthorhombic
Martensitic
steels
are
low
carbon
steels
contain
a
minimum
12%
chromium,
and
0.12%
carbon
designated
by
41X,
42X.
They
may
be
tempered
and
hardened.
Effect
of
Chromium
on
Passivity
What
Makes
Austenitic
Stainless
so
Corrosion
Resistant?
Effect
of
Cr
on
Ecrit
and
icrit
Effect
of
Molybdenum
on
Passivity
Where’s
the
Mo?
XPS
data
for
SS
316L
Effect
of
Structure
on
Corrosion
Properties
Dielectric
Properties
of
Al
Films
• Electric
Field
Strength:
V −V0 ε 0ε
C=
E= ; Al: V0 = −1.3 d
d
• High
Field
Growth
Law,
Mott
&
Cabrera:
! BV $ V
i = A exp " %; =E
# d & d
14Å/V
Oxide
Film
Growth
on
Aluminum:
Anodization
InsulaDng
Oxides
Obey
Ohms
Law
(voltage
limited
thickness)
Vappl
i
aluminum
in
propylene
carbonate
Rsol
Rox
Vappl= i(Rox+Rsol)
V/R
Rox= ρL/A
as L, thickness, increases the voltage
necessary to maintain oxide growth
(i) increases proportionaly.
Al
Film
Types:
1.
Barrier
Layer
Type
2:
Porous
Film
Growth
on
Al
• Applications:
– Membranes
– Filters
– Sensors
– Coatings
(hardness,
color)
Porous
Film
On
Al
TEM
Images
of
Pore
Structure
in
Alumina
