Vol. 60, No.

6 June 2004

Founded 1945
CORROSION SCIENCE

515 2004 F.N. Speller Award Lecture: Efficacy of Vapor Phase Corrosion Inhibitor
Technology in Manufacturing
B. Miksic, R. Boyle, and B. Wuertz

523 Corrosion Mechanism of Nickel-Containing Stainless Steels in Concentrated

Aqueous Solutions of Sulfuric Acid
J.R. Kish, M.B. Ives, andJ.R. Rodda

538 Detecting External Failures in Coated, Buried Pipelines: Theoretical Model

and Experimental Verification
H. Castaneda and M. Urquidi-Macdonald

548 Corrosion Evaluation of Alloy 800 in Sulfate/Vanadate Molten Salts

C. Cuevas-Arteaga, J. Uruchurtu-Chavan'n, J. Gonzalez, G. Izquierdo-Montalvo,
J. Porcayo-Calderon, and U. Cano-Castillo

561 Electrochemical Study of UNS S32550 Super Duplex Stainless Steel Corrosion
in Turbulent Seawater Using the Rotating Cylinder Electrode
G. Kear, B.D. Barker, and F.C. Walsh

CORROSION ENGINEERING
Microstructural Characterization and Pitting Corrosion Behavior of UNS S30466
573 Borated Stainless Steel
D.A. Moreno, B. Molina, C. Ranninger, F. Montero, and J. Izquierdo

Effect of Climatic Parameters on Filiform Corrosion of Coated Aluminum Alloys

584 N. LeBozec, D. Persson, D. Thierry, and S.B. Axelsen
Development of an Artificial Saliva Solution for Studying the Corrosion Behavior
594 of Dental Alloys
G.S. Duff6 and E. Quezada Castillo
 CORROSION SCIENCE SECTION

2004 F.N. Speller Award Lecture:

Efficacy of Vapor Phase Corrosion Inhibitor
Technology in Manufacturing

B. Miksic, R. Boyle, * and B. Wuertz*

ABSTRACT manufacturing process. Expenditures on cleaning,

blasting, reworking, and disposal combined with
Corrosion is a plight that faces everyone who works with labor-intensive additional processing steps greatly
metals. Its impact on the U.S. economy has been documented affect the bottom line.
to be about 4% of the gross national product. It was esti- To combat the devastating effects of corrosion
mated that about one third of the corrosion damage could be and in an attempt to preserve valuable military
avoided. The avoidable costs were related to the failure to
equipment, the U.S. Navy tested the first volatile cor-
use the best practices available. There are several ways of
combating corrosion. One way that is gaining wider accep- rosion inhibitor (VCI) chemistry for the mothballing
tance is to use vapor phase corrosion inhibitors. Volatile cor- of boilers and similar structures on war ships in the
rosion inhibitors were originally developed to protect boilers late 1940s. The core chemistry at that time was a
and piping systems of ships to be mothballed. Their effective- toxic amine nitrite solution applied to the inside of
ness and ease of application attracted early users. Over the inaccessible spaces. Although a similar nitrite-based
years, the field of usage has increased to cover electronics, chemistry is still widely used today, there is an effec-
packaging, process industries, reinforced concrete, coatings, tive, environmentally sound, and safer alternative.
and metalworking fluids. (Figure 1).
KEY WORDS: vapor phase corrosion inhibitors, manufactur- A new generation of corrosion inhibitors emerged
ing, metals in the late 1970s called vapor phase corrosion inhibi-
tors (VCIs). These new chemistries were developed to
INTRODUCTION utilize state-of-the-art, nontoxic organic inhibitors in
a wide variety of forms. The VCI technology, as de-
A 2002 NACE International study estimated that the scribed below, protects metals from corrosion during
annual cost of corrosion in the United States alone manufacturing, processing, shipping, storage, and
nears 3.1% of the gross domestic product (GDP)—a while in use without any residual contamination to
staggering $340 billion. The real-world implication to the protected metal. The result is a vast line of prod-
metal manufacturing and processing is the added ucts all designed to take the cost of corrosion out of
cost of doing business. Aside from the most visible the metalworking and manufacturing process.
effects, such as product failure and rejection, are
those "hidden" costs that are part of the everyday CORROSION AND VCIs

Presented as the F.N. Speller Award Lecture at CORROSION/ Simply defined, corrosion is the natural process
2004, March 2004, New Orleans, LA. of a material, usually a metal, returning to its origi-
Corresponding author.
Cortec Corporation, 4119 White Bear Parkway, St. Paul, MN nal state through an electrochemical process due to
55110. a reaction with the surrounding environment. Al-
0010-9312/04/000083/$5.00+$0.50/0
Vol. 60, No. 6 © 2004, NACE International 515
CORROSION SCIENCE SECTION

water, chlorides, and other corrosion accelerators.

Toxicity Data With the protective barrier in place, the corrosion cell
Chemical LD50 (mg/kg-rat) cannot form and corrosion is halted. (Figure 2).
Unlike nitrite inhibitors, which do not have
Table salt 3,000
(sodium chloride) sufficient vapor pressure under ambient conditions,
VCI products can actually protect yellow and ferrous
Food preservative/corrosion inhibitor 85 metals as well as soldered parts and alloys. Whereas
(sodium nitrite)
water-displacing, water-absorbing, dehumidification,
Nitrite-based VCI powder 284 and barrier products try to alter an ever-changing
Non-nitrite-based VCI powder 2,100 environment surrounding the metal, VCI technology
passivates the metal's surface. In fact, VCI molecules
FIGURE 1. Toxicity data for some common corrosion inhibitors. actually use the same mechanism that accelerates
corrosion to accelerate the release of protection mol-
ecules—a built-in defense mechanism (Figure 3).

MANUFACTURING WITH VCI PRODUCTS

During the typical manufacture of a metal prod-

uct, the material is cleaned, oiled, blasted, machined,
finished, assembled, painted, and packaged—in some
cases, numerous times before it is sent to the cus-
tomer. By effectively utilizing the benefits of VCI
technology, many of these in-process steps can be
completed eliminated (Figure 4). Other cost savings
result when the disposal and cleanup costs are cal-
culated. Imagine a manufacturing process where the
starting metal structure is processed without need
for secondary oil rust preventatives, rework, rust
removal, blasting, or cleaning.
VCIs in their pure form are usually off-white
powders and can be used in this form for protection
Molecules of
VCt in gaseous phase
of large void spaces (such as the heat recovery steam
generators [HSRGs], boilers, turbines, and pipes
previously coated with amine nitrite inhibitors). Addi-
tionally, VCIs can be incorporated into coatings,
FIGURE 2. VCI molecules vaporize, condense on all metal surfaces, greases, functional fluids, cleaning systems, hydro-
and re-heal and self-replenish through further condensation of the testing solutions, even concrete and plastics. The
vapor. result for a manufacturer utilizing VCI product is
streamlined processes, improved product quality and
acceptance, and overall cost reduction.
though corrosion is a natural process, certain atmo- But how do VCI molecules affect the metal sur-
spheric conditions that a metal is exposed to during face? The VCI molecules are designed specifically to
its manufacture, processing, storage, or shipment prevent reactions on the metal surface. Whereas
can aggressively accelerate the degradation. Most many methods of corrosion protection alter the metal
notable of these factors are sulfur dioxide (typically (i.e., stainless vs carbon steel, cathodic protection,
associated with the burning of coil, oil, and gas), and treatment of metal), VCIs do not alter the surface
acids in packaging materials, and temperature and as the protective ions are adsorbed to the surface
humidity fluctuations during transit. rather than becoming permanently attached.
VCIs are organic compounds that have sufficient A study was conducted on VCI products to
vapor pressure under ambient atmospheric condi- determine how the protective molecules affected the
tions to travel essentially to the surface of the metal exposed ends of fiber optics cables. Three products
by diffusion and to adsorb physically onto the sur- were tested, including VCI-treated anti-stat polyeth-
face. In the presence of moisture, the VCI molecule ylene film, polyurethane foam impregnated with VCI,
becomes polarized and attracted to the anode and and VCI powder contained in high-density vapor per-
cathode of the metal. Once the VCI protective ions meable polyethylene film pouches. The testing
are adsorbed onto the surface, the electrochemical showed that there was no indication of attenuation
process of corrosion is interrupted as the ions create change caused by the corrosion inhibitors. The re-
a protective barrier to contaminants such as oxygen, sults of this study are included in Figure 5.

516 JUNE 2004

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Corrosion Prevention Methods Used by Military Organizations

Corrosion
Prevention
Method Product Type Benefits Disadvantages
Water-displacing products Petroleum-based • Relatively inexpensive • Costs increase with additives
(light oils or thixotropic • Water displacement (e.g., contact inhibitors, extreme-
greases) • Create a barrier coating on pressure additives) needed to
metal surfaces enhance protection
• Excellent permanent protection • High labor and material costs for
application and removal of
product
• Use of solvent-based cleaners
for product removal makes
these products unsafe for the
worker and environment

Water-absorption products Silica gel (dessicants) • Economical alternatives for • Difficult to calculate specific
temporary protection moisture that will be present
• Effective for storage and (i.e., requires more dessicant and
shipping inspection)
• Effective in electronic and • Costs increase with the addition
electrical operations of more dessicant and inspections
• Airtight seal is required but
difficult and expensive to achieve

Dehumidification • Dehumidifier • Can be successful if air flow to • Dehumidifier

• Vapor barrier bags the metal is totally restricted > Electricity mandatory for
• Vapor barrier bags are dehumidifier and not available
excellent for one-time use (offer in remote locations
a sturdy multilayer film) > Difficult to keep a seal on the
• Good way to protect electronics metal object
> High cost of equipment and
associated upkeep
• Vapor barrier bags
> High costs of materials and
labor needed to create air-
tight protection
> Not a good method to use
during operations

VCIs • Anodic inhibitors (e.g., • Anodic inhibitors • Anodic inhibitors

sodium nitrite [NaNO2], > Prevent metal corrosion > Negative effect on worker
dicyclohexylamine nitrite, • Cathodic inhibitors safety
sodium benzoate) > Slow cathodic reaction > Negative effect on
• Cathodic inhibitors > Precipate onto cathodic sites, environment
• Mixed inhibitors restricting diffusion of corrosive
species
• Mixed inhibitors
> Adsorbed onto metal surface,
creating a monomolecular layer
> Monomolecular film acts as a buffer,
maintaining pH at optimum range for
corrosion resistance
> Provide a universal effect on
corrosion process

FIGURE 3. Advantages and disadvantages of different methods of preservation utilized by military organizations.

PROVING VCI EFFECTIVENESS First, will the compound inhibit corrosion when
it is in direct contact with the metal it is designed to
While there are many methods to test corrosion protect? The "Razor Blade" test is a quick laboratory
inhibiting compounds and methods, the industry test with a pass or fail rating—if corrosion exists af-
standards involve three principle criteria—contact ter the set time frame, the product fails. This test es-
protection, vapor protection, and protection in simu- sentially tests the contact corrosion inhibiting ability
lated environments. There are standardized and in- of a material. In most cases, the test is conducted on
dustry-accepted tests for each. test coupons and on multiple types of metal.

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CORROSION SCIENCE SECTION

FIGURE 4. Flow charts for manufacturing that utilizes and does not utilize VCI coating compounds.

Second, Federal Standard lOlc, the German VIA

A - Water retainer—Aluminum tube
11.4 cm in length, 1.6 cm OD,
test, is used to determine if a corrosion inhibiting
and 1.3 cm ID. The tube shall compound will protect a metal when the compound
have a capacity of 16 ml distilled is never in contact with the metal. For this test, the
water at 24 ± 2°C
corrosion inhibiting compound is placed in
B - Rubber stoppers—Two no. 6 a glass jar. A metal slug is placed in a rubber gasket
1.3-cm rubber stoppers with a
1.3-cm hole bored through attached to the lid, so it is prevented from coming in
centers contact with the corrosion-inhibiting product.
C - Jar lids—Plastic screw-type lid, Figure 5 details the results of the German VIA
with 3-cm holes drilled through test for polyethylene film containing VCI for
the center with two 0.6-cm holes multimetal protection compared to a nitrite-based
2.5 cm apart near the edge.
flexible packaging film. The results are measured on
D - Jars—1-L size, mouth size a scale from 0 to 3 (0 = worst protection, 3 = best
6 cm diameter, 17.7 cm in
height, 13.6cm ID. protection), which detail the severity of corrosion on
E - Insulating sleeve—1.3-cm ID
the metal plug. Since nitrite-based inhibitors lack
rubber tubing, length 3.8 cm. sufficient vapor pressure under ambient conditions,
F - Steel specimen—1.6-cm OD, the products typically do not pass the German VIA
1.3 cm long with 0.9-cm-deep test, nor does the corrosion inhibitor travel to the
Test specimen - flat bottom hole drilled in center metal.
(0.8-cm wall cup).
Enlarged view of "F" Rochester Institute of Technology conducted
extensive testing on several VCI products including
(a)
nitrite-based technologies used by Daubert, Northern
Technologies, Aicello, SKS, as well as barrier film
produced by Intercept and non-nitrite VCI products
manufactured by Cortec Corporation. The results of
these tests are shown in Figure 6.
Simulating environments through ASTM D 1748
Humidity, ASTM Bl 17 Salt Fog, and ASTM D 53
Prohesion also can be an effective means of evaluat-
ing the comparative corrosion protection ability of
VCI products. These tests accelerate the corrosion
process by placing the metal samples (either coupons
or actual parts) in environmental chambers where
atmospheric conditions are monitored and altered.
Figure 7 details the comparative results of several
VCI products under these tests (Figures 7[a] through
[c]).
(b)
Many VCI products also have industry approvals
FIGURE 5. (a) Standard setup for Federa! Standard 101c, German
for use in highly restrictive markets, such as direct
VIA test, (b) Results of the Federal Standard.
and indirect food contact. Polyethylene film contain-

518 JUNE 2004

 CORROSION SCIENCE SECTION

(a)

(b)

(c)

(d) (e)
FIGURE 6. Independent laboratory test results for: (a) carbon steel razor blade test, (b) copper razor blade test, (c) steel
razor blade test, and (d) Federal Standard 101c, German VIA test, (e) Cross reference chart for nitrite vs non-nitrite VCI
inhibitors.

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CORROSION SCIENCE SECTION

(a)

(c)

(b)
FIGURE 7. (a) Wax, with and without VCI. Test according to ASTM V-117. (b) The addition of VCI materials to a traditional
coating greatly improved performance in ASTM B-117. (c) ASTM B-117 testing of grease with and without VCI additive
package.

ing VCI for multimetal protection, for example, is EXAMPLES OF VCI PRODUCTS IN USE
ideally suited for the shipment and storage of food
processing equipment and has indirect food contact A large telecommunications equipment manufac-
approval from the U.S. Federal Drug Administration turer was shipping high-value enclosures overseas
(FDA). Water-based temporary coatings containing using barrier film, desiccant, vacuum seal, and hu-
VCI for multimetal protection has U.S. Department midity cards yet they were still experiencing nearly
of Agriculture (USDA) approval for use on packaging 85% failure rate due to corrosion. Not only was their
material that is in direct contact with meat or poultry packaging and rust preventative method extremely
food products. Both approvals, as well as many oth- expensive, an even higher cost was borne when the
ers, are evidence that VCI technology can provide a equipment had to be replaced. Additionally, the
cost-effective method of superior corrosion protection packaging was compromised when customs offers
while remaining nontoxic, safe for workers, and with- were forced to open the barrier film to inspect the
out affecting the surface of the protected metal. enclosures.

520 JUNE 2004

 CORROSION SCIENCE SECTION

Initial shipments were established using only

VCI emmitting devices (seen as the small green cup
attached to the right side of the enclosure in Figure
8) and polyethylene film containing non-nitrite-based
VCIs. This polyethylene film contains VCI molecules
throughout the film and is translucent allowing easy
customs inspection. The VCI emitting device quickly
saturate the enclosure with the protective corrosion
inhibiting vapor allowing rapid shipments.
After switching to VCI products, this manufac-
turer was able to eliminate all corrosion claims while
reducing costs by nearly 60%, including a decrease
in material and labor costs.
The U.S. Air Force also has effectively used VCI
technology as part of its war readiness and equip-
ment preservation methods. Vehicles that previously
would have taken nearly a week to clean, drain, reas-
semble, and operate are now wrapped in co-extruded
shrink film containing corrosion inhibitors, flame
retardants, and UV inhibitors, with only the antenna
and battery removed. All fluids in the vehicle, includ-
ing brake, hydraulic, engine, and coolant, incorpo-
rate a VCI additive to the existing fluid. The VCI
additive protects even after the oil or fluid has settled
into the reservoir, as detailed in Figure 9.
A large Power Generation OEM manufactures
FIGURE 8. A large piece of telecommunications equipment that was
their heat recovery steam generators (HRSGs) in
being packaged for shipment utilizing VCI technology.
South East Asia. Historically, these units would be

FIGURE 9. Pipeline section showing active vapor phase corrosion inhibitors at the liquid phase, the vapor phase, the
interface, and partition and emulsion barriers.

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CORROSION SCIENCE SECTION

full of corrosion upon arrival to their customer's site ing is applied to virtually all space rocket booster
due to long shipping periods and large temperature (SRB) structural components and can be used for
and humidity fluctuations. Several years ago, they some limited flight applications.
switched to VCI products to protect the high-value
generators in transit as well as decrease cost and CONCLUSIONS
environmental impact.
United Space Alliance has utilized VCI technol- Corrosion costs industry billions annually and the
ogy successfully in the form of a water-based high- effects on a manufacturing facility can be cata-
performance rust preventative for rocket booster strophic if proper methods of prevention are not uti-
structural components on National Aeronautics and lized. VCI products offer users an effective method
Space Administration (NASA) rockets. The important of protection while maintaining strict adherence to
factors for NASA included rust prevention, cleanli- product quality, environmental considerations,
ness, ability to topcoat, and the VCI product could worker safety, and even throughput and the
not negatively affect the metal surface. The VCI coat- bottomline.

522 CORROSION—JUNE 2004