DEGRADATION OF

MATERIALS
CVE 549
Nov 28th, 2007.
Richard Brown
Chemical Engineering
URI
 Degradation of Materials.
Metals – except for noble metals, they
tend to corrode in wet environments.

M > Mz+ + ze- - Anode- dissolves

Fe -> Fe2+ + 2e-
O2 + 2H2O + 4e- = 4(OH-) – Cathode.

Metal hydroxides form which transform

to oxides. Stability of oxides important.
Unstable oxides – corrosion, stable
oxides no corrosion.
Rust - large volume expansion when it
forms from steel – so unstable on
surface. Chromium and aluminum
oxides reasonably stable, so good
in water environment when no
halides (Cl, F, Br, I).
Rust Expansion
The volume expansion when
rust forms has undesirable
effects. The tensile stresses
formed in reinforced concrete
initiate cracks and eventually
spallation of concrete from the
surface. With paints it will
initiate decohesion and lifts the
paint from the steel, often called
“undercutting”. On nuts, it will
initiate seizure of threads and
make removal of nuts very
difficult.
Note the cracking in the rust,
indicating that it cannot protect
the underlying steel from
moisture.
 Passive Alloys
Potential
(Volts) Passive metals and alloys are
Transpassive region ones that form surface layers
that are stable in the
environment. The vertical
Passive region
region of the Evans diagram –
potential v log current density
shows the passive region of
Epp
low current density and very
low, near zero, corrosion rates.
ηa - activation control

Current Density
1 10 2
icrit µA/cm
Pourbaix Diagram for Iron
Potential – pH diagrams indicate the
combination of electrochemical and
environmental conditions where
unstable and stable films form and
where metals are immune to
corrosion by remaining as an
element rather than reacting to form
an ion.
The Fe region is a region of
immunity.
Fe2+ and 3+ regions represent
corrosion.
Fe(OH)2 and Fe2O3 are passive
regions.
The dashed lines represent where
water will try to initiate corrosion.
Concrete at pH 12.5 falls in a
passive region. (0V SCE and pH
12.5)
Uniform Corrosion
Damp wet environment
initiates corrosion of poorly
painted steel tank. Looks bad,
bud as long as a large area
corrodes, then rate of
penetration low.
 Pitting and Crevice Corrosion
Crevice and Pitting Corrosion.
Localized Corrosion.
Oxides become unstable due to
halides, local attack using same
reactions.

Crevice corrosion on threaded rod, the

problem here is that the retaining nut
comes loose. It is also difficult to detect
as the corroding region is under the
cover of the nut.
Weld Decay
Welding stainless steel can be an
issue is not conducted properly.
The area adjacent to the weld will
corrode and penetration of the
steel will occur rapidly. This can be
avoided by appropriate material
selection and welding techniques.
Filiform Corrosion
Filiform corrosion is surface
corrosion and does not
penetrate into the metal. It
often appears below paint.
The figure on the left shows
filiform corrosion on a steel
component with a clearcoat
applied. Note that although
the corrosion generally
follows the machine
markings, it also does 180
turns, as can be seen in
several locations. Usually
poor paint quality with
porosity or high permeation
“U” turn. rates along with poor
adhesion are reasons for
filiform.
Selective Leaching
A reasonably slow corrosion
process affecting alloys. A
brass screw has de-zincified
in water over a long time.
The zinc is selectively
removed from the bras and
leaves only porous copper. It
was only when to remove
the screw dezincification was
found as the dimensions of
the screw did not change,
but the mechanical
properties were poor.
Better alloy selection would
help.
Erosion Corrosion
Rapid fluid flow of an aggressive
electrolyte removes material, in this
case a 316L stainless steel flange
from a chemical plant. One issue here
is the purity of the fluid flowing in the
pipes as it is now contaminated with
the elements from the stainless steel
in ion form.
Change alloy and slow fluid flow
would help in this case.
 Carbon Fiber Damage
Top figure is unexposed
carbon fiber, the bottom figure
is carbon fiber exposed to a -
0.65V (SCE) voltage.
The white area in a periodic
pattern in the lower figure are
delaminatsion which contan
fliud of pH 11-12 which result
in blisters on carbon fiber
composite surface due to
galvanicinteractions.
These also occur in fiberglass
due to osmotic blistering.
Stress Corrosion Cracking
Brass is liable to stress corrosion crack
when a tensile stress, in this case a
residual stress, and an aggressive
environment are present, in this case
an ammonia based solution.
Stress corrosion cracking requires both
a tensile stress to open up cracks, and
an aggressive environment, which is
material dependent.
 Corrosion Fatigue

Fatigue lives are decreased when

an aggressive environment is
present. The component shown
failed by corrosion assisted fatigue.

Initiation Site.
 Corrosion Rates
Uniform or Galvanic Only.
• CR = 0.13 (icorr x EW)
d
• for units of Corr Rate in mils per year, icorr
in mA.cm-2
• EW is the equivalent weight and d is the
density of the metal.
• icorr data available from lab testing.
 Laboratory Data for icorr
Polarization Data
-0.45
Cathode
Reaction
Potentiodynamic test run to find
-0.47
Anode Reaction icorr data from extrapolation.
Potential V (SCE)

-0.49

-0.51

Open Circuit Current Density for

-0.53 Potential calculation
of Corrosion Rate

-0.55
.1 1 10 100
log Current Density
microamps per centimeter squared

Polarization Data
-0.45

-0.47 Raw data from test.

Potential V (SCE)

-0.49

-0.51

-0.53

-0.55
.1 1 10 100
log Current Density
microamps per centimeter squared
 Salt Spray Testing ASTM B117
Salt water Deionzed Water
Salt fog

Water tower and heater Untested steel, steel 1 and steel 2 tested
Salt spray unit, 5% NaCl at 95F and for same time. Steel 2 is best choice.
100% humidity.
Using Corrosion

Weathering steels are a class of steels

that contain copper to stabilize the oxide
layer that forms when steel is exposed
to a wet environment. It modifies the
oxide to avoid the cracking shown
earlier. It can be used but should not be
coated to allow the oxide layer to build
up uniformly.
 Corrosion Protection for Steel
Bridges and Decks.
Sacrificial Coatings on A36 Steel
• Hot dip galvanizing –in plant 4mils thick,
difficult to topcoat, adhesion problems
• Metallizing or Thermal Spray – becoming
more popular as price drops – need to
seal porous coating, 8mils thick. In plant or
on site, repair damage, paint adhesion
OK.
• Paints – zinc rich primers, topcoats.
 Coatings R and D
Cycle Polarization Data of coated Laboratory testing to examine coatings
and uncoated Al 2024-T3 in 0.5N NaCl
involves potentiodynamic scans. The
URI Coating Base Sample Chromate Coating lower the current density for the passive
2.5
region and the larger voltage range
2
1.5
indicate a better coating and also
1 indicate the mechanism of protection.
E (mV)

0.5
0
-0.5
-1
-1.5
-8 -6 -4 -2 0 2 4 6
2
Log i (uA/cm )
 Electrochemical Impedance
Spectroscopy
Long term data available and passive circuit modeling for quantitative analysis

30 days exposure
5.5pH conversion coating

2.0pH conversion coating

Bare sample

Day 1 comparing different surfaces Day 1 compared to day 30 data

 Adhesive Joints-Galvanic Design
Partial interfacial failure after 2 weeks Complete interfacial failure after 4 weeks

Interfacial failure was between the conventional chromate surface treatment and the Ti-6Al-4V alloy
conventional treatment
peroxide-titanate treatment First ply failure after 6 weeks with URI
fit (conventional treatment) non chromate treatment
7000 fit (peroxide-titanate treatment)
6000

5000

4000

3000

2000

1000

0 Voltage between carbon fiber and chromate 0.52V

0 1 2 3 4 5 6

N u mb e r o f W e e k s
Voltage between carbon fiber and URI treatment 0.07V
Removal of galvanic component increased durability of
Failure loads for lap joints after marine exposure.
joint
Why Lamposts Fall.
Lamposts – Failed Coupling
Lamposts - Corrosion Evidence

Different location, note telltale vertical

Vertical rust line on threaded rod
corrosion marking on threaded rod.
indicating cracked coupling
 Lamposts Wrought Aluminum
Coupling

Changing from cast alloy to wrought alloy with copper additionsinduced pitting corrosion
 Cast Iron Coupling
with Resistance Plate
 Polymer Degradation
Ultra Violet exposure – embrittles polymer, these days use clear coats which stop the
process.

Water uptake – polymers such as vinyl esters absorb 1.5% by weight of water can cause
imbalance in propellers.

Water uptake can also cause polymer swelling and delamination.

Dissolution – chemical attack, eg imides in alkaline environment.

 Ceramic Degradation
Acid attack.