Paper No.

08213
DESIGN OF NOVEL CORROSION INHIBITING ADDITIVES

Dr. Jeannine Elliott (jelliott@tda.com) and Dr. Ronald Cook (cookrl@tda.com)

TDA Research, Inc
12345 West 52nd Ave
Wheat Ridge, CO 80027

ABSTRACT

While there is widespread use of organic molecules for prevention of corrosion in aqueous solution,
their use in protective coatings has been restricted. Their effectiveness in protective coatings depends
primarily on the carrier used to introduce the organic corrosion inhibitor into the coating, the molecular
features of the corrosion inhibitor and the transport of the corrosion inhibitor to the active corrosion site.
Organic corrosion inhibitors by themselves are difficult to incorporate into protective coatings due to
differences in the specific gravities between the resins, other additives and the organic corrosion
inhibitors themselves. In addition, most of the effective corrosion inhibitors contain functional groups
that react with the resins, locking them into the coating matrix where they are not available to migrate to
the corrosion site. To address this surface modified nanoparticles have been developed as novel
carriers for organic corrosion inhibitors. Also, predictive molecular descriptors for use in designing new
organic corrosion inhibitors has been created.

Keywords: Release-on-demand, corrosion inhibitor, nanoparticles, steel, MIL-DTL-24441

INTRODUCTION

The primary defense against the corrosion of steel is the diligent use of protective organic coatings. In
typical practice, the metal surface(s) are first treated with a chemical agent to passivate or seal the
surface and are then coated with an organic coating (typically an epoxy primer) that contains a
corrosion inhibitor. While the overall durability of protective coatings has improved remarkably in recent
years, thereby reducing material and manpower costs, the development of new corrosion inhibitors has
not kept pace. The most effective and most widely used corrosion inhibitors are still soluble chromates
developed over 50 years ago. The toxic properties and environmental costs of chromates are well
documented and their use and disposal are therefore strictly regulated. In fact, in much of the
developed world, they are being banned outright. Other routes to reducing corrosion include the use of
less toxic heavy metals and development of more corrosion resistant steel alloys. Unfortunately, these
latter approaches are either less effective or more expensive.

One would expect that due to the large number of organic compounds that are available for vapor
phase corrosion inhibition and corrosion inhibition in liquid medium, that many of these compound

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1
would be candidates for protective coating Nanoparticles
applications. That is not the case, however. This is in coating
because organic corrosion inhibitors must meet
multiple necessary criteria to be effective in the Metal Surface
coatings or pretreatment applications. These include Crack formation
limited solubility in organic solvents and some but not
excessive solubility in water, an effective specific Corrosion
gravity of ~2 to 5, absence of deleterious effect on inhibitors are OH-
released from
coating's mechanical properties (e.g. plasticization)
nanoparticle
and most importantly they must not interfere with the
curing process or react with the resin so as to be
locked into the resin and. Organic corrosion inhibitors
generally have functional groups (like amines, thiols, Metal surface OH-

carboxylic acids) that can react with the coating during passivated by
barrier layer
cure, locking them in to the matrix where they are
unavailable for transport to the corrosion site. Corrosion is arrested
Figure 1. Corrosion arrested by release of
Boehmite-based nanoparticle corrosion inhibitors corrosion inhibitor
Use of corrosion prevention coatings is the most effective measure for slowing or preventing corrosion.
These coatings provide a barrier to the (harsh) external environment. In addition, if the coating is
damaged it should also provide active corrosion protection – i.e. corrosion inhibition, even to the now
uncoated area. TDA has developed a patented active corrosion inhibitor that can provide smart
corrosion protection. We have developed a method to surface modify nanoparticles with releasable
corrosion inhibitors. The corrosion inhibitors are anchored to the surface of the nanoparticles and are
released from the nanoparticle surface through a trigger provided by the corrosion process itself. Thus,
the inhibitors remain in the coating until needed and when corrosion occurs they release, migrate to the
metal surface and arrest corrosion (Figure 1). This smart mechanism uses the corrosion inhibitor only
when needed and allows long-term corrosion protection. Current inhibitors are selected to be slightly
soluble in water, and slowly but continually leach out of the coating. In contrast, TDA’s new corrosion
inhibitor additives are released only when needed to arrest corrosion. This smart, release-on-demand
mechanism extends the life of coating, since the inhibitors are not continually being lost.

Nanotechnology offers new ways to create materials promising a degree of property control not
previously possible. Our nanoparticle materials have a very high surface area. When this surface is
functionalized, it can deliver high loadings of organic corrosion inhibitors. Thus, tailored nanoparticles
are the perfect carrier for delivery of the needed level of active corrosion inhibitors. Our nanoparticle
surface functionalization also allows dispersion of nanoparticles into a coating. Nano-sized materials
are, in general, difficult to fully disperse, and when fully dispersed they can cause large increases in
viscosity (making application of the coating difficult or impossible). Because of the patented surface
functionalization of TDA’s nanoparticles, we compatibilize the nanoparticles with the coating. We
achieve a high level of dispersibility (Hegman grind of 6) and good film quality.

Quantitative structure-property relationships (QSPR) models for non-toxic corrosion

inhibitors

The development of effective and non-toxic alternatives to chromates remains one of the major
objectives of contemporary corrosion inhibitor research efforts. To date, there are no single inorganic or
organic corrosion inhibitors that provide the performance of chromates. However, there are many
molecules that have never been evaluated before and a myriad of combinations between organic and
inorganic molecules that could yield synergies. To develop a robust, non-toxic corrosion inhibiting
package that is truly equivalent or superior to chromates, it is necessary to consider possibilities
beyond what have already been identified. Recently, a very promising approach that uses

2
experimental data and guided virtual (computational) screening to select new low-toxicity corrosion
inhibiting compounds has been developed. These methods can be used to describe the corrosion
inhibiting efficiency of organics corrosion inhibitors from structure when studying new corrosion
inhibitors for steel.

These methods were adapted from the Drug Discovery industry1. For both drugs and corrosion
inhibitors there is need for a delivery vehicle, sufficient solubility so that the compounds can dissolve
and be transported to the active site, binding to the active site and low toxicity. These properties can
be represented by molecular descriptors that are calculated from the two-dimensional structures of the
molecules. Considering the aforementioned needs of the organic corrosion inhibitors we identified
descriptors that are proxies for solubility, partitioning out of the water phase and binding to the metal
surface. As described in the next section these descriptors were found to be good descriptors for both
corrosion inhibitor efficiency and toxicity.

RESULTS

A review of the literature on the action of non-oxidizing organic corrosion inhibitors shows that the
mechanism of their corrosion inhibition is primarily that of a strongly adherent protective film. The best
materials readily displace water and aggressive ions from the metal surface and then provide a barrier
to migration of water, oxygen and electrons through the film to the metal surface. Numerous
quantitative structure-activity relationships (QSAR) studies have shown that various electronic
parameters calculated from the optimized structures of the organic molecules have high correlations
with corrosion protection. These quantum mechanical parameters include the energies of the highest
occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), the HOMO-
LUMO energy gap, the polarizabilty and the dipole moment2-4.

After examining the corrosion inhibitor literature, we decided that the most promising molecular
descriptors for corrosion inhibitors should be: 1) computable from their 2D molecular structures, 2) be
already used in current methods for computing aqueous solubility , oil/water partition coefficients and 3)
be proxies for binding strengths of the corrosion inhibitors to the metal surfaces. As mentioned above,
many QSARs relating quantum mechanical properties computable from the molecular structure to the
corrosion inhibiting efficiencies have been developed. We have combined the orbital energies and their
spacings into a single descriptor to develop a descriptor relating the structure of the organics to their
strength of bonding to the metal surface.

To test the descriptors, we gathered data for the corrosion of steel from the literature and then
calculated the descriptors for the molecular data set. We used the data provided in Zhang et al.3.
Zhang et al. used 34 nitrogen-containing compounds to explore the QSPR relationships. Zhang et al.
used weight loss of cold rolled steel in acid solution as the metric for corrosion efficiency. Using the
molecules described in Zhang et al. we calculated molecular solubility, molecular lipophilicity and the
quantum mechanical descriptors for each molecule and then regressed the molecular parameters
against the corrosion efficiency metrics.

Figure 2 shows the results from the regression analyses for the corrosion inhibitors in Zhang et al.
using the molecular descriptors. The correlation of the predicted corrosion inhibition efficiency with the
experimentally measured corrosion inhibition efficiency in the training set is excellent (r2 = 0.97). In
addition the derived model also predicts out of sample molecules very well (r2 = 0.99). The
effectiveness of the chosen molecular descriptors in predicting corrosion for ferrous metals is therefore
quite good within the small data set that we have trained them with.

In reviewing the scientific literature for QSPRs for toxicity, we saw that solubility, lipophilicity and the
quantum mechanical descriptors are often successfully incorporated into toxicity prediction models.
Therefore we were curious if the same molecular descriptor set that predicted the corrosion inhibitor

3
efficiencies so well could also be effective in correlating the molecular structure of the corrosion
inhibitors to their toxicities.

100 100
y = 0.9314x + 5.2128
R2 = 0.967 y = 0.9474x + 3.2891
90 90 R2 = 0.9887

80 80

GP Predicted Efficiency
GP Predicted CI Efficiency

70 70

60
60

50
50

40
40

A 30
B
30 30 40 50 60 70 80 90 100
30 40 50 60 70 80 90 100
CI Efficiency
CI Efficiency

Figure 2. Prediction of Corrosion Inhibitor Efficiency of Amines for Cold Rolled Steel:
Training set (A), Out of sample test set (B).

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To see if the descriptors were useful in predicting
5 y = 0.9305x + 0.2068
toxicity we used the same set of molecules modeled in 2
R = 0.9305
Figure 2. First, we calculated the toxicities (14 day LC50 Predicted Log (toxicity) 4

for fish) for the molecules using the EPA program 3

Ecosar contained within the modeling EPA’s E.P.I suite.
The Ecosar toxicities were then regressed against the 2

same descriptors used for the corrosion efficiency 1

modeling. Figure 3 shows the resulting correlation. As

0
seen from Figure 3 the molecular descriptors correlate
quite well (r2 = 0.93) with the toxicity predicted by the -1

Ecosar algorithm. Therefore the same four molecular -2

descriptors can be used to rank molecular structures for -2 -1 0 1 2 3 4 5 6

both corrosion inhibitor efficiency and fish toxicity and Log (toxicity) (from Ecosar)

perhaps other toxicities as well.

Figure 3. Correlation of fish toxicity
calculated from molecular descriptors
Next using structures of standard heterocyclic building
against Ecosar calculated fish toxicity
blocks provided in the Sigma-Aldrich Catalog, we used
the QSPR relationships developed above to calculate
the corrosion inhibition efficiencies and toxicities for a range of heterocyclic structures. The
toxicity/corrosion-efficiency trade-offs of the heterocyclic structures are shown in Figure 4. The y-axis
shows the log of the concentration of the amount of organics needed to cause death for one-half of the
fish population (e.g. LC50). As shown in Figure 4 there are significant differences in the toxicity of
organics that have the same corrosion efficiency (e.g. some materials (e.g. 1 and 21) have similar
corrosion inhibiting toxicities but have four orders of difference in toxicities)). Therefore, using the basic
heterocyclic structures as a guide, we selected several organic corrosion inhibitors for evaluation.

Recent success in the area of nanotechnology stems from the ability to modify the surfaces of the
nanomaterials, tailoring their properties to a specific application. To create corrosion inhibiting
nanomaterials, a suite of patented5 methods to functionalize the surface of boehmite nanoparticles
were developed. This nanoparticle technology is based on process methods that reduce the particle
agglomerates to nanoparticles while at the same time providing a reactive surface in which can tailor
the material properties by functionalizing the surface. For this application we selected heterocyclic

4
structures that are known corrosion inhibitors for steel and attached them to the surface of the boehmite
materials with releasable bonds.

6 1
2
Acridine
Benzimidizole
3 Benzodioxane
4 benzofuran
5 Benzopyran (Chromone)
6 benzothiazole
7 Benzotriazole
42
5 8
9
1-Benzothiophene
2H-1,4-Benzoxazin-3(4H)-on
10 Carbazoles
26 21 27
Predicted Fish Toxicity from Structure

11 Coumarin
24 43 12 Furan
20 49 13 Imidazole
14 14 Imidazoline
4 48
15
16
indazole
indole
30 31 29, 33 17 indoline
44 13 18 isoquinolines
19 22 19 isoxazole
23 36 20
21
morpholine
oxadiazole
9,35 11 32
3 34 45 7 38,40 22 oxazole
2,15 23 oxazoline
25 24 piperizine
25 piperidine
28 46
41 5,12 26 piperidone
27 purine
47 16 17 28 pyran
3 6,18,39
2 29
30
pyrazine
pyrazole
4 37
31 pyridazine
32 pyridine
33 pyrimidine
8 34 pyrrole
10 1 35 pyrrolidine
1 36
37
pyrroline
quinaldine
38 quinazoline
39 quinoline
40 quinoxaline
41 quinuclidine
42 tetrazole
0 43
44
thiadiazole
thiazine
0 10 20 30 40 50 60 70 80 90 100 110 45
46
thiazole
thiazoline
47 thiophene
Predicted Corrosion Inhibitor Efficiency from Structure 48 triazine
49 triazole

Figure 4. Corrosion- Inhibition Toxicity Trade-offs for Base Structures

In order to create nanoparticles that provide active corrosion resistance that responds to corrosion
process itself, we attach the organic corrosion inhibitors via a liable carboxylate bond. The breakage of
this bond is triggered by the products of corrosion. During galvanic corrosion the oxidation of the steel
(anode) and reduction of oxygen (in the presence of water) forms hydroxide (cathode).

Cathodic: ½ O2 + H2O + 2 e → 2OH-

Anodic: Fe → Fe2+ + 2e

In our nanoparticles the carboxylate group that anchors the inhibitor to the nanomaterials is susceptible
to cleavage when exposed to high concentrations of hydroxide (OH-), and the organic corrosion
inhibitors attached to the surface of the boehmite particle are thereby released to arrest corrosion.
When released they are mobile and can migrate to stop corrosion at the metal surface.

Our approach is design the surface modified nanoparticles in such a way so that we can just drop our
nanomaterial additives into an already qualified coating to streamline development of the protective
coating technology. We considered the various naval coating specifications such as the qualified
marine coatings MIL-PRF-23236 and MIL-DTL-24441. MIL-DTL-24441 Formula 20A is a standard
naval marine coating. Because this formulation is widely published and we can formulate this coating in
house from the raw materials, it allows us the greatest degree of control in formulating thed coatings.
The surface-modified nanoparticles were incorporated as a drop-in additive without viscosity increase.
The nanoparticles were incorporated as a drop-in additive with the other pigments in Part B. We
removed the all the talc (Minstron 403) from the standard formulation and 66% of the calcined clay
(Huber 70C) and replaced them with nanomaterials. This keeps the total pigment solids about the
same.

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Coatings were prepared in a Dispermat LC Cowles type disperser and milled to Hegman grind of 4-6
using a zirconium oxide milling media. There were no problems with viscosity increases. The steel test
panels (Q panel R-36, matte bare steel) were blasted to an angular profile of 2-3 mil per military
specification for naval ship coatings. The coatings were applied in a spray booth using a Sharpe Cobalt
high volume low pressure (HVLP) spray gun to a dry thickness of between 4-6 mils to steel panels (Q
panel cold rolled steel). . After the panels were sprayed they were forced cured at 140°F overnight to
remove any variability in cure time so that the differences in the coatings resulted only from the added
corrosion inhibitors. All panels were evaluated for corrosion protection by salt fog testing. Selected
representative panels were evaluated using electrochemical impedance.

Figure 5 shows photographs of the nanoparticle-modified version of a commercial MIL-DTL-24441

Formula 20A coating after testing using ASTM B117 corrosion testing. The salt fog test is an
aggressive, accelerated corrosion test that involves attacking the coatings with a high humidity, high
temperature (95°F) fog containing sodium chloride. Chloride ions are especially aggressive corrosion
agents since they form soluble complexes that are removed from the corrosion site promoting new
metal sites for corrosion. The salt fog results were analyzed according to ASTM method D714-87. One
of the corrosion inhibitors (e.g. D684-32 in Figure 5) was able to significantly reduce blistering and
corrosion in the scribe g, providing increased corrosion protection over the commercial control coating.

Figure 5. Corrosion in scribe after 300 hrs of salt fog testing for control (left) and three
nanoparticle-based corrosion inhibitors.

After 500 hrs, the best nanoparticle-based corrosion inhibitor (e.g.DM684-32) continued to provide very
good corrosion protection with virtually no blistering in the scribe (Figure 6). To check for filliform

Figure 6. Salt fog testing results after 500 hrs commercial MIL-DTL-24441 [left]
compared to TDA coating with DM684-32 nanoparticle modified coating [right] after 500
hrs. The bottom half of the panel was scraped to look for corrosion under the scribe.

6
corrosion and corrosion growing under the coating, we scraped the scribe with a metal spatula. A
close-up of the scribe is shown again with the bottom half of the coating being scraped to remove the
corrosion built up. With the MIL-DTL-24441 control coating, corrosion had occurred under the coating
near the scribe and part of the coating flaked off as shown in Figure 6 (left). With the nanomaterial
coating (DM-684-32), the scribe scraped clean with no loss of integrity of the coating after 500 hrs of
salt fog testing.

CONCLUSION

Structures of organic corrosion inhibitors with both high inhibition efficiency and low toxicity can be
identified using virtual screening (i.e. computational) methods. Descriptors relating solubility, lipophilicity
and quantum mechanical parameters were used to derive molecular structures that had low toxicity and
high efficiency that were then evaluated in protective coatings. In salt fog tests, one of the selected
corrosion inhibitors offered excellent corrosion after 500 hours of salt fog testing.

ACKNOWLEDGEMENTS

This work was funded under NAVSEA SBIR Phase I contract N65538-06-M-0167 with Anthony Eng.
TDA Research, Inc. collaborated in part with International Paint LLC on the incorporation of the
corrosion inhibitors into the epoxy coating.

REFERENCES

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640, 167 and references 9-19 therein.
3. Zhang, S.G., W. Lei, M.Z. Xia, and F.Y. Wang (2006). QSAR study on N-containing corrosion
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4. Cardoso, S. P., E. Hollauer, L. E. P. Borges,and J. A. da C. P. Gomes (2006). “QSPR Prediction
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