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Zinc Rich Primers for Corrosion

Protection in Marine Environments


J. Peter Ault, P.E.
Elzly Technology Corporation

Zinc-Rich Coating Types


Type 1: Inorganic Zinc Coatings
1-A: Inorganic post-cure (water-soluble)
1-B: Inorganic self-cure (water-reducible)
1-C: Inorganic self-cure (solvent-reducible)

Type 2: Organic Zinc-Rich Coatings


Zinc Rich Epoxy
Zinc Rich Moisture Cure Urethane
Other, less common Organic Zinc-rich

Zinc-Rich Coatings
Coatings with greater than 65% zinc by weight
in the dried film are considered Zinc-Rich
Zinc content is important, SSPC Paint 20 defines 3
levels of zinc in the dried film
Level 1 equal to or greater than 85%
Level 2 equal to 77% to 85%
Level 3 equal to 65% to 77%

Zinc particle size and purity are also issues which


may impact performance

Inorganic Zinc
Powdered metallic zinc
Mixed with a reactive silicate solution
Ethyl Silicate
Potassium Silicate
Other Alkalai Silicates

Zinc becomes part of the film


Not merely encapsulated in a binder

Resists higher temperature 750 F/ 400 C

Inorganic Zinc

Sandblasted
surface

Cross section of IOZ after application


Courtesy of Corrosion Prevention of Protective Coatings, C.G. Munger, 1984, NACE International

Inorganic Zinc: Type 1-A


Two component material zinc powder and
waterborne silicate
Post Cure Cures by subsequent application
of a curing compound
Acidic postcuring solution is common

Limited use today

Inorganic Zinc: Type 1-B


Two component material zinc powder and
waterborne alkali silicate
After water evaporates from coating, carbon
dioxide from the air reacts with the silicate to
cure coating
Surface alkalinity created during cure may
interfere with topcoat adhesion

Inorganic Zinc: Type 1-C


Two component material zinc powder and
solventborne ethyl silicate
Depends on moisture in atmosphere to
complete hydrolysis
Do not cure well at low temperatures or low
relative humidities
Cure may be accelerated by light misting with
water

Organic Zinc-Rich
Available as one, two- or three-package products
Two component epoxy with zinc dust
Moisture cure urethane with zinc dust

Performance related to zinc content in cured dry


film
Must be low enough for binder to create a uniform
film
Greater than 85%/90% recommended
Performance also related to the binder material
Zinc content in dry film is not the same as zinc content
in wet product

Zinc Rich Coatings

NOTE CRITICAL PARTICLE-TO-PARTICLE CONTACT


Courtesy of Corrosion Prevention of Protective Coatings, C.G. Munger, 1984, NACE International

Application Considerations
Zinc Dispersion in Film
Proper mixing during
application

Weathering of Zinc
Primer prior to topcoating
Secondary surface
preparation

Degree of Cure
Especially for IOZ silicate

Resists chemicals, to a
degree (zinc is
amphoteric reacts with
acids and bases)

DoD Specifications for Zinc Rich


Primers

A-A-59745, Commercial Item


Description, Zinc-rich Coatings
Pertinent Characteristics

90% or greater zinc content


Capable of being applied by spraying or brushing
Compatible with CARC primers
Performance Requirements

Accelerated corrosion (cyclic)


Adhesion pull-off
Adhesion cross-cut
Mandrel bend

Typically Moisture Cure Urethane Binder

Zinc Rich Coatings for Navy Ship Use


DOD-P-23236, Type 3 (circa 1982)
Inorganic Zinc
Ch 631 (1982) specified for use in chain lockers, nonfloodable voids and floodable but normally empty
voids
CCIMS lists tanks with zinc rich coatings

MIL-DTL-24441, formula 159


Epoxy zinc rich
Approximately 91% zinc in dry film by weight

Pre-construction primer
Thin film build, lower zinc loads

Performance Of Zinc Rich Coatings in


a Marine Environment

5-Year Marine Exposure


W/ Zinc Primer

W/O Zinc Primer

19-Months Simulated Catapult Trough


Zinc Containing Primer

Without Zinc Containing Primer

Zinc Rich Primers for Vehicles


Two organic zinc rich coatings (MCU) under
conventional CARC coating system
GM 9540P testing of panels with coating damage
9-year exposure of 5-ton truck doors at Cape
Canaveral
Zinc-Rich
Epoxy/CARC

Zinc-Rich
CARC

Epoxy/CARC
Control

Zinc-Rich
Only

18

Zinc Rich Primers for Vehicles


Epoxy Primer Only

Zinc Rich A

Zinc Rich B

Galvanized Sheet

Zinc Rich Primers for Vehicles

1 year

Zinc-Rich
Epoxy/CARC

Zinc-Rich
CARC

Epoxy/CARC
Control

Zinc-Rich
Only

9 years

Zinc Rich Primers for Vehicles

1 year

Zinc-Rich
Epoxy/CARC

Zinc-Rich
CARC

Epoxy/CARC
Control

Zinc-Rich
Only

9 years

How Do Zinc Rich Coatings Work?


????
Sacrificial
Barrier

22

Electrochemical Data
Perform a variety of
experiments
Polarization resistance
Open Circuit Corrosion
Potential
Electrochemical
Impedance Spectroscopy
Galvanic Current
(Interaction with steel)

23

Effect of Environment

Current - mA

Galvanic Current Flow


0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

Seawater
Tap Water

10

15

20

25

Elapsed Time - Days

24

Effect of Environment
Tap Water Cell
1
0.8
0.7
E(off), zinc

0.6
0.5

0.4

0.9

0.3

0.8

10

15

Elapsed Time - Days

20

Volts vs SCE

Volts vs SCE

0.9

Seawater Cell

E(off), steel
Couple Potential

25
0.7
E(off), zinc

0.6
0.5

E(off), steel

0.4

Couple Potential

0.3
0

10

15

20

25

Elapsed Time - Days

25

Polarization Behavior
(9 days in seawater)
Potential vs SCE - Volts

0.000
-0.200
-0.400

Galvanized

-0.600

Zinc A

-0.800

Zinc B
Zinc C

-1.000

Zinc D

-1.200
1.E-07

1.E-06

1.E-05

1.E-04

1.E-03

1.E-02

1.E-01 1.E+00

Current - Amps

26

Evans Diagram of Steel-Zinc Couple


0

Potential, mV vs Ag/AgCl

-200

-400

-600

zinc
steel
1/100 zinc

-800

-1000

-1200
1.E-03

1.E-02

1.E-01

1.E+00

1.E+01

1.E+02

1.E+03

Current - mA

Based on data in "Atlas of Polarization Diagrams for Naval Materials in


Seawater," Harvey P. Hack, April 1995

27

Effect of Metallic Surface Area Ratio


Effect of Area Ratio
(Zinc Surface as percent of Steel Surface)
0.6
0.17%

0.5

0.44%
0.44%

Steel Polarization - V

0.4

0.7%
1.8%

0.3

2.7%
7.1%

0.2

7.1%
0.1

11%
28%

44.4%
0

-0.1

10

15

20

25

30

35

100%

Time - Days

28

How Much Zinc is Effectively


Protecting the Steel?
Many Variables

Binder type
Packing factor
Zinc content
Defect geometry
Zinc coating thickness
Electrolyte conductivity
Zinc particle purity
Zinc particle size
Surface chemistry
29

Electrochemical Observations
Lower resistivity electrolyte
Better sacrificial protection, shorter life

Over time, steel polarization decreases


Indicative of zinc consumption

Zinc coatings behave differently


Need to determine sources of differences

Is specifying zinc content sufficient?


30

Summary/Conclusions
Zinc rich coatings can help increase coating
service life in marine atmosphere exposure
Zinc rich coatings have unique issues which
must be considered
Todays coating community is more sophisticated
than 30 years ago