Professional Documents
Culture Documents
1
Overview
4 Results
5 Conclusions
Why Metals Corrode
Metal G*
G
Ore
Corrosion Product
Reaction Coordinate
Corrosion Background
CORROSION CELL
3/2 O2
Water Droplet
n H2O 2 H2O
Rust 2 Fe2+
2
3
Fe2O3 . H2O O2
4 H+
2 Fe 4 e-
Cathodic Region
Iron Substrate 1 Anodic Region
Risk
(Humans)
High Low Low High
Aquatic toxin
Risk
(Environment)
High High Harmful if inhaled High
or swallowed
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EU Driven Legislation on Zinc Compounds
Types of Corrosion
Of concern in coatings…
Lambourne, R. (1999); Paint and Surface Coatings: Theory and Practice, 2 ed.
(Lambourne, R. and Strivens, T.) England: William Andrew Publishing
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Corrosion Inhibitors – What they Do
Corrosion inhibitors - whether inorganic or organic - retard the corrosion rate
by affecting the 2 elements of the corrosion process
e-
Mn+
- + - + - AlPO4
+ + - Ba3(PO4)2
+ Ca3(PO4)2 Hydrolysis
-
Sr3(PO4)2
Zn3(PO4)2 +
Fe2+ H2O
Insoluble
FePO4 Precipitate
Mx(OH)x
Fe
Substrate Anode e- Cathode
• Anodic Reaction
– Slow the reaction rate of anodic dissolution.
– Produce reaction products which form a thin film over anode.
• Cathodic Reaction
– Disrupt the flow of electrons from the anode to the cathode.
– Produce reaction products which precipitate selectively at cathodic sites.
Inorganic Inhibitors
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Inorganic Inhibitors
Coating
5 4
1
Substrate 3 2
Azoles, Calcium Alkyl-aryl Sulfonates , diamines, metal salts of dinonylnapathalene sulphonates, etc.
N
R
O
S
S O-
O Mg++ -O S
O
S
O
O O
OH HO
N N R
N
O
O O
O O OH O- N+ O-
O O
O Zn++ -O
HO O
O N N+ O OH
-
NH2 NH2 NH2 NH2 O O
Adhesion Promotion
Water and corrosion products can cause adhesion loss, delamination,
blistering
Paint Film
CO
O N
Paint Film H H
O H H
CO N
Organic CI
O H H O
H H
H H H H
O O O
O
METAL METAL
• Coatings adhere by mechanical AND polar interactions, (e.g. hydrogen bonding). These
can be displaced by water.
• Fe2O3 nH2O is 2.16 times more voluminous than Fe metal, therefore a stable, continuous
metal oxide film cannot form, leading to “bulging” rust.
Organic Corrosion Inhibitors
• Anodic passivation
– Reduced uniform corrosion & flash rusting
• Improve adhesion
– Reduced blistering
• Increase water resistance
• Form protective films
– Adsorption mechanism
• Increase coating flexibility
• Increase chemical resistance
Galvanic Corrosion Inhibition
Uninhibited
Galvanic & Uniform
Corrosion
Sodium Nitrite
Weld Flash Rust
Seams Inhibited
Organic CI’s
OR H2O OH + ROH
Si Si
RO OR RO OR
Si Si
RO RO
+ ROH
OH + OH OH OH OH O O
Si
RO OR SUBSTRATE SUBSTRATE
3. GELATION (CROSS-LINKING)
POLYMER
O O O
Si Si Si Si Si Si
RO RO
+ H2O + ROH
O O O O O O
SUBSTRATE SUBSTRATE
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Sol-Gel Technology
Inorganic pigments can be trapped both within and underneath the network
formed, thus providing excellent corrosion resistance – SYNERGY!
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Organic Corrosion Inhibitors
Anticorrosive End Use Coatings
Description Composition Function
Mechanisms Applications
Ba3(PO4)2/Ca3(PO4)2
- Higher solubility
- +
+
pigments
- + - + -
+ + -
Sr3(PO4)2/Zn3(PO4)2
+ Lower solubility
- pigments
Passivation
- + - + -
+ + -
Anodic Passivation
+ Inorganic
Ion Scavenging
-
Organic Adhesion
N
Hydrophobicity
S
O O
OH HO
Mechanism II
Increased focus on Analytical Analysis
Terminated at
168 Hrs
1.0E+04
1.0E+03
1.0E+02
1.0E+01
1.0E-01 1.0E+00 1.0E+01 1.0E+02 1.0E+03 1.0E+04 1.0E+05
Frequency (Hz)
30
Bode Plots of 2K Epoxy
• Time zero to 168 hours
Inorganic, CP + Organic AC
No Inhibitor
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Reduced Water Uptake (Barrier)
0.7
0.6
The change in
Capacitance can 0.5
log(Cp/Cp0)/log(80)
be used to
calculate the 0.4
water uptake in a
0.3
coating under
immersion 0.2
conditions. "2% Inhibitor"
0.1
"No Inhibitor
log(CC,0 / CC,24) 0
%v = 100 0 20 40 60 80 100 120
log(80) Time (hours)
Control
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Summary
Indirect Organic
Direct Ion-
Active Scavenging
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