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Challenges in the Corrosion World
Risk
(Humans)
High Low Low High
Aquatic toxin
Risk
(Environment)
High High Harmful if inhaled High
or swallowed
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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.
Inhibitive Pigment Classification
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Inorganic Inhibitors
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Inorganic Inhibitors
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Mechanism(s) of Organic Inhibitors
Coating
5 4
1
Substrate 3 2
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
Hybrid Corrosion Inhibitors
1. SILICONE ESTER HYDROLYZES TO FORMS SILANOL
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
Water-based
Organic Acid Long- term, flash Acrylics,
Organic B Anodic
Amine Complex rust, adhesion Polyurethanes, UV,
Polyester Alkyds
Humidity Water-based
Silane based resistance, barrier Acrylics,
Hybrid Adhesion
sol-gel properties, Polyurethanes, UV,
adhesion Polyester Alkyds
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Tips to Formulating
- + - + -
+ + -
Anodic Passivation
+ Inorganic
Ion Scavenging
-
Organic Adhesion
N
Hydrophobicity
S
O O
OH HO
Mechanism II
Accelerated Test Methods
• Salt Spray (ASTM B-117)
• QUV (ASTM 6154)
• Prohesion (ASTM G85 – Annex A5)
• QUV/Prohesion (ASTM 5894 -5)
• Humidity (ASTM 2247)
• SAE J2334
• Filiform Corrosion (Controlled Humidity)
ASTM D 2803
• EIS (Electrochemical Impedance Spectroscopy)
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ASTM B117 Water Base Acrylic
Terminated at
168 Hrs
Inorganic + Organic A
Inorganic + Hybrid
Inorganic
Control
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Bode Plots of 2K Epoxy
• Time zero to 168 hours
Inorganic + Organic A
Control
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Bode Plots of 2K Epoxy
• Time zero and 168 hours
Inorganic + Organic A
Control
Reduced Water Uptake (Barrier)
No 4% BTTSA-amine
0 Inhibitor
WATER0 0
PERMEATION OF 2K-EPOXY PRIMERS
3 2
4
5 5
3
0
Volume fraction of water 0 5 1 1 2 2 3
0 5 0 5 0
TIME (days)
ASTM B117: Medium Oil Alkyd – 504 Hrs.
Inorganic + Organic B
Control
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Summary
Indirect Organic
Direct Ion-
Active Scavenging
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