
SUCCESSFUL CORROSION PROTECTION UTILIZED
BY MILITARY WORLDWIDE
Anna M. Vignetti
Cortec Corporation
4119 White Bear Parkway
Saint Paul, Minnesota 55110
U.S.A
ABSTRACT
This paper will address the use of successful corrosion
protection solutions for different problems identified by the US
military as well as military worldwide. Various corrosion problems
and solutions being utilized that deal with high tech electronics,
vehicle undercarriages, fluid reservoirs, storage, and cleaning
will be discussed.
Vapor corrosion inhibitor (VCI) products and solutions
give an environmentally friendly, efficient, safe and easy to use
alternative. Effective corrosion prevention is provided with the
benefit of war readiness. Specific laboratory testing presented
in this paper for ASTM and MIL specification standard test procedures
support the successful use of VCIs in field applications. Many solutions
for corrosion protection are now utilized with the incorporation
of VCI systems and products in different delivery systems.
INTRODUCTION
Military organizations worldwide have different
options to choose from for the prevention of corrosion in vehicles,
aircraft, equipment, facilities, and naval vessels. Many existing
and newer VCI products were tested, tried, and recommended for corrosion
control. But even today, some militaries choose not to use any additional
prevention measures due to the fact that war readiness may be jeopardized.
Billions of dollars in assets are lost every year
by the military, as well as industry and just as industry is making
significant changes in the way they do business, so is the military.
Many factors are now being considered when evaluating corrosion
prevention. It is not to losing the war with the enemy. In addition
to war fighting capability, it is necessary to develop a corrosion
control and prevention strategy to be able to fight the war better,
faster, efficiently and economically. Corrosion in its different
forms can contribute to losing the war.
VCI technology provides an effective and relatively
inexpensive method of controlling corrosion in closed systems and
other environments. In the case of precise scientific instruments,
electrical and electronic equipment, VCIs offer a definite advantage
over classical methods of protection. When added in small concentrations,
VCIs effectively check, decrease or prevent atmospheric corrosion
due to the reaction of the metal with the environment. VCIs
can be defined as an individual or combination of chemical compounds
that have significant vapor pressures that allow vaporization of
the molecules and the subsequent adsorption onto metallic surfaces.1,2
"Volatile corrosion inhibitors are secondary electrolyte layer
inhibitors that possess appreciable saturated vapor pressure under
atmospheric conditions, thus allowing vapor-phase transport of the
inhibiting substance", according to Miksic and Miller.3 Two
review papers, written by Fodor4 and Miksic5,
provide a very good overview on the classification/nomenclature,
mechanism and nature of adsorbed VCI compounds.
Types of Prevention|
Today, the many different methods utilized range
from the blockage of moisture and other atmospheric contaminants
on metal with ordinary greases, to silica gel for the absorption
of moisture, to expensive alternatives such as dehumidification.
This paper will further discuss these products and methods.
Water Displacing Products. Typically, these
products are petroleum based. They can be light oils or thixotropic
greases. With the focus on safety and the environment, the interest
in these products by the military and industry decreases everyday.
They are widely used and are relatively inexpensive in a basic form.
Costs increase with the addition of contact inhibitors and other
properties that may be required such as extreme pressure additives.
Aside from these incremental costs, the cost of labor to apply and
remove these products as well as the solvent based cleaners needed,
make this option laborious as well as costly and unsafe to the worker
and ecology. Petroleum based products can be effective to a certain
extent. In addition to water displacement, they can also create
a barrier coating on metal surfaces.
A great deal of time and study has gone into the
perfection of paints and coatings for the prevention of corrosion
on metals which are meant to protect the surface, as well as decorate,
displace water, fluids, and corrosive contaminants. This is an excellent
means of permanent protection. Depending on the coating, applications
may range from easy to extremely difficult and time consuming. So
goes the range in costs. Here also, a great deal of attention is
being given to improving corrosion protection properties as well
as making the products safer and more efficient to use and also
friendly to the environment.
Water Absorption. Silica gel products,
commonly known as desiccants can provide an economical alternative
for temporary protection. In a situation where protection of metal
is strictly related to moisture and the protection time is short
term, this method has its good points. They are now used worldwide
by industry and the military for storage and shipping. Electronic
failures are in most cases caused by moisture and corrosion. Desiccants
prove to be valuable in shipping and storage and in some cases during
electronic and electrical operations.
As stated, the factors for successful utilization
are restrictive. Desiccants can absorb the moisture out of the atmosphere
creating an atmosphere less conducive to corrosion. The drawback
is that the initial calculation for the amount placed in the container,
package or area is specific. It is difficult to calculate moisture
due to the unpredictable nature of the environment and the climate.
This necessitates the addition of more desiccant and frequent inspections.
Inspections can be costly as well as the replacement of the water-absorbing
product. Another consideration that needs to be addressed with this
option, in most cases, the requirement for an airtight seal or cover
is difficult and expensive to accomplish.
Dehumidification. This method or
process if utilized correctly has proven to be successful, but not
without its limitations. It is more commonly used by the military
and less often by industry. Ultimately, the metal being protected
needs to be sealed so that the air flow is totally restricted, whether
it is the interior of a vehicle such as a tank or a piece of equipment
in some type of container. A dehumidifier is then connected and
then used to extract moisture. Electricity is mandatory which may
be a deterrent in case of remote locations where equipment is prepositioned
for war readiness. Keeping a seal on the object has also proven
to be a challenge. Cost of the dehumidification equipment along
with the upkeep and maintenance required may put a strain on any
budget.
Vapor barrier bags are often used with this method.
Maintaining a seal is the first step and is critical to success.
This multi-layer film is sturdy, and excellent for one time use.
A drawback is high costs of materials and labor associated with
creating airtight protection. In addition, vapor barrier bags are
not recyclable. Again, a good way to protect electronics. In real
world military environments, this would not be the best alternative
during operations.
Vapor Corrosion Inhibitors. There
are three classes of VCI compounds. They are ranked according to
their electrochemical mechanisms. Now, an overused term, VCI corrosion
prevention needs to be carefully considered and analyzed according
to the protective mechanisms.6
Anodic inhibitors prevent metal corrosion
by anodic passivation. An anodic inhibitor will increase the
corrosion potential and decrease the corrosion current density.
A few common inhibitors in this class are sodium nitrite, dicyclohexylamine
nitrite and sodium benzoate. They can be effective given the
right circumstances or requirements but have limitations. In
many cases anodic inhibitors will have a negative effect on
worker safety and the environment.
Cathodic inhibitors can exhibit two
very different effects. They can either slow the cathodic reaction
itself or they can selectively precipitate onto the cathodic
sites, which increase circuit resistance. This circuit resistance
restricts diffusion to the cathodes.
Mixed inhibitors are compounds in which
the electron density distribution causes the molecules to be
attracted to both the anodic and cathodic sites. They are adsorbed
onto the metal surface, creating a monomolecular layer, which
influences the electrochemical activity at both the cathode
and anode.
A monomolecular film serves as a buffer, which
maintains the pH level, at its optimum range for corrosion resistance.
The adsorption process is not instantaneous. It requires a defined
time for the formation of the inhibitor layer.
The necessary molecular binding energy and the
surface area, which the molecules occupy, are important for successful
adsorption. The mixed inhibitor molecules are water-soluble and
possess a binding energy to metal surfaces that is higher than the
binding energy of water dipoles. Strong exothermic reactions are
created, which can displace surface moisture. These inhibitors are
more desirable because of their universal effect on the corrosion
process.6
BENEFITS AND ADVANTAGES TO VCI TECHNOLOGY
The widespread use of VCI type products and systems
is proof that this new technology does have the benefits that the
military and industry require to have successful corrosion prevention
as well as providing key advantages. To recapitulate them:
- Ease of application.
- Efficiency in application and non-removal (removal only if necessary).
- Economics provided:
-Lower cost products
-Reduction of labor in application and removal
-Reduction of exercising and maintenance
-Reapplication of products needed less frequently
-Reduced loss of assets
- Non-removal of products in most cases.
- Enhanced combat readiness.
- Extended life expectancy of equipment
EXPERIMENTAL
- Fingerprint removal properties
Handling of metal components lends itself to corrosion due to
the corrosive nature of the salts in the human skin. Since it
is difficult to ensure that the hands are covered, study was given
to test the ability to remove the fingerprint oils and provide
corrosion protection. A military test and specification was developed
as a result.
Procedure: Per MIL-C-15074, Corrosion preventive, finger print
remover.
1. The synthetic fingerprint solution was prepared according
to the following formulation. (See Table 1)
2. A pad of gauze was placed in a flat dish and
1.5 ml of fingerprint solution was placed on the pad.
3. The rubber cork was sanded with sandpaper
and rinsed with de-ionized water.
4. 5 steel panels were washed with methanol and
air-dried.
5. Using the rubber cork, the fingerprint solution
was placed on the panels and immediately placed in an oven set
at 121°C for 5 minutes.
6. One panel was placed in boiling methanol for
2 minutes. Another panel was immersed in 1,1,1-trichloroethane
for 1 minute. Three panels were immersed in a VCI product for
2 minutes.
7. All panels were placed in a desiccator with
water for 24 hours.
8. After 24 hours, the dessicator was opened
and the condition of the panels was visually evaluated.
Results are presented on Table 2.
- VCI oil base Coating
There are various ways of evaluating the performance
of coatings. Test methods simulate the environment under which
military equipment may be used or stored. Testing under highly
humid conditions (ASTM D 1748), salt spray (ASTM B117) and cyclic
(ASTM G 85) was carried out using carbon steel panels (SAE 1010).
A VCI Oil Base Coating was tested according to
the following standard test methods:
ASTM D-1748
ASTM B-117
ASTM G-85
- VCI temporary soft coating
Similar to the oil base coating, a VCI soft coating
was run through a battery of testing. The tests carried out for
this coating varied from physical to anticorrosion properties. A
VCI temporary outdoor coating with self-healing properties was tested
according to the following standard method:
MIL-C-16713E Grade 1,Class1
RESULTS
The results for the above mentioned experiments
are reported in the following tables:
Table 2 MIL-C-15074 specification test results.
Table 3 ASTM D-1748, B-117, G-85
Table 4 MIL-C-16173E Grade 1, Class 1
DISCUSSION
The many applications now exemplifying the use
of VCI technology extend throughout the world. Dozens of products
and systems have been tested, approved and documented, which may
be used as references. Following are field applications varying
from simple corrosion protection to more sophisticated systems solutions.
NASA currently uses VCIs in two different areas
and is now in the process of evaluating the corrosion protection
of other critical applications. The first application, although
simple in nature, is potentially catastrophic if not addressed.
The O-rings in the space shuttles are very susceptible to corrosion
due to salt-water atmospheric contamination. With the simple application
of the VCI coating, approved under MIL-C-16173E, Table 4, NASAs
requirement is met in order to eliminate or reduce the corrosion.
The product offers the additional properties of vapor emission of
VCI molecules to nearby areas as well as a self-healing property.
In the protection of electronics, extensive testing
was done at NASA addressing VCI interference with Hyperbolic Ignition
and Lox Mechanical Impact Testing. The VCI emitting products and
spray were tested and approved for use7. By placing the
product in enclosed electronic cabinets or boxes, the VCI is allowed
to form a molecular barrier on the multi-metal surfaces of the electronic
components. The potential adverse effects of molecular layers were
of great concern to NASA and to the US Navy. Based on extensive
testing, it has been proven that VCI products are safe for even
the most sensitive equipment, i.e.: optical coatings and instruments.9
Telecommunication and radar equipment is effectively and economically
protected with VCI products that are located in highly corrosive
atmospheres. The additional property of static dissipation according
to MIL-PRF-81705 may also be required.
The US Navy is a user of the VCI emitting products
for the electronics areas and the USAF also uses the devices in
void spaces. Currently, the emitting devices are used on Naval Aircraft,
Navy ships and Naval Air Stations.2, 8 US Navy usage
extends to other corrosive sites on naval vessels. The ships are
exposed to a salt laden environment continuously. Prevention with
VCIs extends to coatings that are used in areas that may already
be rusted and where appearance is not a factor. Permanent water
base products are also now being tested and used on ships where
aesthetics and the need for a dry and hard coating are more important.
These coatings are especially good due to their environmentally
friendly nature and water clean up of spray equipment. VCI additives
are also used in coatings and oils. For surface preparation, water
base cleaner/degreasers and rust removers are used and that offers
worker safety and low environmental impact.
VCIs used in the protection of weaponry, which
includes cannons, anti-tank rockets, tanks, missiles, ammunition,
charge bags, cartridge cases; military organizations are found to
be a solid, reliable alternative for corrosion prevention. Testing
has been completed to ensure the compatibility of the ammunition
with the VCI.10 Products and systems for protection include:
VCI film and paper for packaging for storage and shipping, lubricating
oils, VCI protective coatings and emitting devices.
CONCLUSION
In conclusion, the utilization of different VCIs products and preservation
solutions has been developed over the years. Militaries and their
contractors are increasingly testing, identifying, and approving
VCI products as a successful means of protection. Corrosion prevention,
being the ultimate goal, is not enough in this day and age. The
safety of military personnel, environment, elimination of hazardous
waste disposal, labor costs, and war readiness make VCI technology
extremely attractive and interesting to the military. The efficiency
and ease of application along with the benefit of non- removal,
in most cases, makes VCI technology the most desirable alternative
available today.
REFERENCES
- Riggs, Olen L. Jr. (Nathan, C. C. Ed), "Corrosion Inhibitors",
CORROSION 73, (NACE International, 1973).
- Vasanth, K. L., "Vapor Phase Corrosion Inhibitors for Navy
Applications", CORROSION 97, paper no.179, (New Orleans,
Louisiana, NACE International, Louisiana, 1997).
- Miksic, B. A., R. H. Miller, "European Symposium on Corrosion
Inhibitors", 5th Proceedings, 107th
Manifestation of the European Federation on Corrosion, pp. 217-236,
September 1980.
- Fodor, G. E., "Inhibition of Vapor-Phase Corrosion
A Review", Report No. BFLRF-209, Southwest Research Institute,
San Antonio, Texas, September 1985.
- Miksic, B. A., "Use of Vapor Phase Inhibitors for Corrosion
Protection of Metal Products", 11-16-1, NACE Symposium Proc.,
1983.
- Vignetti, A. M., "Vapor Corrosion Inhibitors: Successful
Field Applications in Electronics", CORROSION 2000, paper
no.707, (Orlando, FL, NACE International, 2000).
- NASA Internal Report no. 96-2T0178, September 1996.
- Vansanth, K. L., "Corrosion Inhibition in Naval Vessels",
CORROSION 96, paper no.233, 1996, (NACE International, 1996).
- Creo Electronics Corporation, Burnaby, British Columbia, Independent
Test Report for VCI Sensitivity on Optical Coatings and Instruments,
November, 1989.
- P. Piacun, "Conservation of Weaponry", Cortec Corp.
European Business Meeting, Rome,Italy, 1996.
TABLE 1
Fingerprint Removal Test Solution
Ingredient
|
Quantity
|
Sodium chloride
|
7 grams
|
Urea
|
1 gram
|
Lactic acid
|
4 grams
|
DI water
|
Till 1 liter
|
TABLE 2
MIL-C-15074, Corrosion Prevention, Fingerprint
Removal Test
Material
|
Results
|
Fingerprint Removal
|
Methanol
|
No corrosion
|
100%
|
1,1,1-Trichloroethane
|
Severely corroded
|
0%
|
VCI-327
|
No corrosion
|
100%
|
TABLE 3
VCI-Oil base coating Test Results
ASTM DFT Carbon Steel(1010)
|
Humidity D-1748 2 mils (50 microns) 2000 hr.
|
|
Salt Spray B-117 2 mils (50 microns) 170 hr.
|
|
Prohesion G-85 2 mils (50 microns) 500 hr.
|
TABLE 4
MIL-16173D, Grade 1, Class 1 Results, VCI temporary,
soft coating
Test
|
Test Method
(Section)
|
Result
|
Material
|
3.2
|
Pass
|
Toxicity
|
4.8
|
Pass
|
Film Characteristics
|
4.6.11.7
|
Pass
|
Solvent Distillation Endpoint
|
4.6.1
|
Pass
|
Discernibility
|
3.6
|
Pass
|
Stability
|
4.6.6
|
Pass
|
Recovery from Low Temperature
|
4.6.6.1
|
Pass
|
Uniformity
|
4.6.6.1.2 & 4.6.11.4
|
Pass
|
Storage Stability
|
3.73
|
Pass
|
Flash Point
|
4.6.2
|
Pass
|
Removability
|
4.6.10.1
|
Pass
|
Salt Spray
|
4.6.11.4
|
Pass
|
Weathering, Accelerated
|
4.6.11.5
|
Pass
|
Flow Resistance
|
4.6.15
|
Pass
|
Sprayability
|
4.6.7
|
Pass
|
Corrosion
|
4.6.8.1 & 4.6.8.2
|
Pass
|
Low Temperature Adhesion
|
4.6.12
|
Pass
|
Drying
|
4.6.13
|
Pass
|
|