APAS and PCCP
News from APAS and PCCP
The APAS Advisory Committee (AAC) and the PCCP Technical Committee (PTC)
met recently in Melbourne with the following decisions being reached:
APAS & PCCP
Work will commence shortly on
Strategic Planning processes to
consider and review business
objectives including funding
models. It is anticipated that all
stakeholders will be given the
opportunity to comment on what
are the important and unimportant
aspects of each of the schemes.
New cartel laws (in the Trade
Practices Act) have forced a
revision of the structure and
operation of each of the schemes
to ensure compliance. Formal
legal opinion is being sought and
once received this may result
in structural changes in some
areas. In the interim, compliance
with trade barriers legislation
has necessitated the significant
reduction of financial barriers
(subscriptions) for overseas
manufacturers and the imposition
of an equivalent subscription for
local manufacturers.
A generic PowerPoint presentation
of the value to be had from APAS
and PCCP has been produced and
is available to organisations with a
“valid” interest. Interested parties
can contact the Executive Officer for
details.
Both committees agreed that with
the impending retirement of the
Executive Director of the APMF
Michael Hambrook, a formal letter
of appreciation and best wishes be
sent on behalf of all Members.
24 Corrosion & Materials
APAS
Removal of the mandatory
requirement for NATA
accreditation for paint
manufacturer laboratories has
resulted in a significant increase
in the number of overseas
applicants. These are being
processed in order of receipt
and include the requirement
for an APAS manufacturing
audit to ensure standards of
manufacturing equivalent to those
found in Australia.
Work is underway to develop APAS
specifications for fire resistant
coatings, heat reflecting coatings,
seamless flooring products and
anti-corrosive tapes and wraps.
Once acceptable drafts have been
arrived at, they will be circulated
through normal (email) channels
as well as publication on the APAS
web site for public comment.
The AAC also agreed to begin work
on a range of painting specifications
for the water industry. Currently,
each water authority uses its
own specification and these are
essentially similar or nearly
identical. The industry sees benefits
in a generic format that is capable
of easy and quick updating as
required. Again, circulation of a
Ken Lofhelm
draft for public comment will be
Manager, CSIRO Verification Services
part of the process.
Executive Officer, APAS & PCCP
A request from industry for a
surface preparation specification
for concrete was also agreed to
and it is hoped a draft for public
comment will shortly be available.
Technology Supplement Paper
A Statistics Approach for the Prediction of CO2
Distribution of the APAS electronic
List of Approved Products will be
restricted to financial members of
APAS and paint manufacturers with
products listed. This was deemed
necessary to prevent CSIRO cost-
recovery revenue being lost through
potential end-users avoiding annual
subscriptions.
PCCP
The PTC agreed that the value of
the committee would be enhanced
by having greater participation
from direct contractors. A call
for Expressions of Interest from
suitably qualified representative
contractors will be made shortly
once a process is decided upon.
The scheme will be expanded to
add accreditation of contractors
for the application of seamless
flooring products and fire resistant
coatings. Criteria will be developed
and circulated for public comment
including web page uploads.
Training courses – the initial
limiting of course completion
certificates to two years was
modified – courses for hazardous
coatings will remain at two years
but all other courses will be
extended to three years.
the industry. Each model is designed based on certain
Corrosion in Mixed Acid Gases
Yuli Panca Asmara1 , Mokhtar Che Ismail2
1
Department of Mechanical Engineering, of oil and gas environment and the mechanism of the
University of Mataram corrosion reaction.
Jl Majapahit 12, Mataram, NTB, Indonesia
Department of Mechanical Engineering,
2 is important for the prediction of CO2 corrosion. Many of
Universiti Teknologi PETRONAS the oil fields around the world contain this gas. Natural gas
Bandar Seri Iskandar, 31750 Tronoh, Perak, MALAYSIA produced in northern Venezuela, for example, has a H2S
Email: 1YPanca@hotmail.com, 2mokhtis@petronas.com.my
Abstract
Predicting CO2 corrosion is an important element in
Corrosion Design Basis (CDB) which determines material
selection and corrosion control strategies. Since CO2
corrosion is a multi species corrosion mechanism, there
are numerous corrosion prediction models developed with
different parameters. However, most of these prediction
models do not consider the combined effect of mixed
gases containing CO2, H2S and acetic acid (HAc) which
limits the corrosion prediction scope. This study analyzes
the effects of mixed gases by using Electronic Corrosion
Engineer (ECE®) corrosion prediction software combined
with a Response Surface Methodology (RSM) statistical
technique. ECE® prediction shows that simultaneous
effects of mixed gases behave differently as compared
to the individual effects. Contrast behavior was observed
for H2S as an individual species and as a mixed species;
corrosion rate depends on concentration level of H2S.
HAc species showed a sharper increase in corrosion in a
mixture than alone. This preliminary analysis of mixed gas
prediction showed multiple mechanisms. Thus, complex
interactions of mixed gases must be studied in more detail
to obtain an accurate prediction.
1. Introduction
Predicting corrosion behavior is a crucial issue in oil and
gas production. Corrosion prediction is one of the tools
to make decisions in selecting material, formulating
guideline for scheduled inspection, and maintaining of
the pipe line structure facilities. Damage to the pipeline
due to a corrosion reaction must be detected for avoiding
loss of production and investment. Therefore, corrosion
control and monitoring methods are important to prevent
the premature failure of industrial facilities and to
increase safety.
In designing a corrosion model, the model must be
concerned with parameters affecting CO2 corrosion as
in the real condition. Predicting models should also be
capable of providing reasonably good agreement between
the experimental observed values and the real condition.
Many CO2 corrosion prediction models are proposed in
mechanisms under certain circumstances. So, in order to
calculate corrosion in oil and gas production environments
accurately, it will be necessary to define the chemistry
Incorporating the role of H2S gas in corrosion calculations
content of 25-80 ppm. In other places like Brazil offshore,
Gulf of Mexico, Norway, and Denmark, have H2S in the
range of 10 ppm – 30 ppm [1-3].
Besides H2S, acetic acid also is suspected for contributing
to corrosion failure. Shell recorded a corrosion failure due
to presence of this organic acid in concentration ranges
from 150 to 700 ppm. A failure was reported in a 10 inch
production flowline in Wytch Farm oil field (UK) was also
reported due to 100mg/l acetate [4].
The role of H2S elemental is believed to influence the
corrosion rate. It was found by Brown [5] that small
concentrations of H2S (less than 30 ppm) in CO2, increased
the corrosion rate compared to solution without H2S.
However, corrosion rate decreased when the condition; H2S
(500ppm), pH(<5), temperature (20°C - 80°C), PCO2 (1 – 7
bar), Velocity (3 m/s) [6]. Kun-Lin [6] working with
10 ppm H2S found that the scale formed on the surface has
a role in inhibiting corrosion rate. Srinivasan [7] revealed
that at 20°C - 60°C, H2S and CO2 produced a competing
film formation bringing a figure of corrosion behavior.
Corrosion rate can increase or decrease depends on the
films properties and mixed compositions. Hunnik et al [8],
stated that the effect of H2S is diminished at concentrations
in excess of 15 ppm in the gas phase, and did not appear
to be dependent upon flow velocity and flow regime. They
concluded, that as the concentration increased up to
10 ppm, corrosion rate decreased significantly.
Crolet and Bonis [9] suggested that the presence of HAc
increased the corrosion in a CO2 environment at pH 4
(particularly at higher temperature), but at pH 6 these
effects will vanish. The effect of HAc on corrosion rate was
studied by many researches [9-13]. They all concluded that,
below the scaling temperature, corrosion rate will increase
for the lower pH conditions. Investigation of HAc’s role
in the corrosion rate and on film formation was done by
George [14]. Analysis on the surface showed that the scale
thickness was similar for solution with and without HAc for
a three day exposure time [15,16].
Based on literature reviews, CO2 corrosion involving
combined effects of HAc, H2S, and CO2 is limited. So the
understanding of the interaction of each species in mixed
gases is important and requires more detailed study.
Vol 34 No 4 August 2009 25
 A Statistics Approach for the Prediction of CO2 Corrosion in Mixed Acid Gases

2. Methodology .................. (4) Table 2: Randomization of coded experiments and result predictions. The analysis of corrosion regression was carried out
at CO2 concentrations (0-10% mol), H2S concentrations
A. Corrosion Prediction Models No. run Var 1 Var 2 Var 3 Predct. (0.002- 0.1%mol), and HAc concentrations (150–470 ppm).
This investigation will predict corrosion rates under a CO2 βi = [X .X] .X Y ................................................................ (5)
T -1 T
1 -1 -1 -1 1.8 To determine significance effects of the model a F-test
environment. Dependent variables involved are temperature was used. The F-test is formulated by comparing between
Where: 2 1 -1 -1 3.2
(T), pH, CO2, HAc, and H2S. Various experiments were mean sums of squares of predicted models with the mean
conducted with the available prediction model software; Y = predicted response 3 -1 1 -1 1.7 sums of squares of error experiments [19]. From the
ECE® (Electronic Corrosion Engineer) [17]. The software 4 1 1 -1 2.4 variant analysis (Table 3), it can be seen that regression
βo = polynomial coefficient regression
calculated corrosion rate based on method developed 5 -1 -1 1 2.25 models have significant values for 95% of confident level
by de Waard and Milliams and its modified formulas βi = individual (linear) effects of βi (p-value <0.05). The individual effects of CO2 concentration,
recommended by C. de Waard, U. Lotz and A. Dugstad [18]. 6 1 -1 1 3.4 H2S concentration, and HAc concentration show a
βii = secondary regression effects of βii
They proposed a corrosion prediction expression as: 7 -1 1 1 2.1 significant level with the F-test. There are also significant
βij = interaction effects of βij effects of two interactions between CO2/H2S. The three
................................................................... (1) 8 1 1 1 3.2
x = design experiments variables interactions of CO2/H2S/HAc effects are less significant in
9 1.7 0 0 3.1
modeling this regression. Therefore it can be concluded
i, j = independence variables of i and j 10 -1.7 0 0 0.9 that there is a significant correlation between the model
Where: Vcor is rate of corrosion in (mm/year), Vr and Vm
are reaction corrosion and mass reaction, respectively. ε = experiments error 11 0 1.7 0 3.5 and result.
The formulae for their calculation are: Then, 12 0 -1.7 0 3.7 B. Individual Effect of CO2, HAc and H2S Calculated by ECE
. ........................... (2) Y = X.βi ............................................................................ (6) 13 0 0 1.7 3 Figure 2 (a – c) presents the individual effects of the
14 0 0 -1.7 2.4 three gases as predicted by ECE®. It is shown that a
The regression coefficients are calculated by least sum different corrosion trend was observed for each species
square methods using coded matrices calculations to 15 0 0 0 2.8
acting individually. H2S decreased the corrosion rate with
............................................................ (3) predict parameters statistically (Equations 4-6). Table increasing concentration. In contrast with CO2 and HAc, the
1 shows the coded variables which were used during 3. Result and Discussion corrosion rate increased with increasing concentration.
experiments. The following equation is an expression to
A. Analysis of regression model 1.6
t is temperature (°C), pCO2 is pressure (bar), fCO2is fugacity transform the natural variables to the coded variables.
CO2 (bar), pHCO2 is the pH of pure water saturated with CO2 The matrix experimental design to calculate corrosion

Corrosion rate (mm/y)

.................................................... (7) 1.2
at prevailing temperature and pressure. model is summarized in the Table 2 and the results of the
ANOVA are given in the Table 3. Table 3 presents the variant
And Vm is mass transfer representing the main part of the 0.8
analysis of the polynomial model regression as calculated
dependence on flow velocity (U) and pipe diameter (d). Table 1: Correlation between coded and natural variables as inputs by Minitab®[21]. It was used to fit corrosion behavior 0.4
B. Statistical analysis into the corrosion prediction model. calculated by the ECE® program software. The calculation
shows the coefficient determinations. It represented 95.9% 0
The relationship between corrosion rate and factors CO2 H2S HAc 1 3 5 7 9 11
of the overall calculation which means that the model is in
involved in CO2 environment has been published elsewhere Code (%mol) (%mol) (ppm) (a)
error by about 4%.
[7-9]. Majority of the results stated that the corrosion
Var. 1 Var. 2 Var. 3 0.4
rate behaves as a polynomial functions. Therefore, a
Table 3: Analysis of variance for model regression.

Corrosion rate (mm/y)

suitable design to estimate a simple curvature model 1.7 11.2 0.011 470 0.36

regression of CO2 corrosion behavior is a second-degree 1 9 0.009 400 Source DF Seq SS Adj SS Adj MS F P 0.32
polynomial model regression shown by Equation 4 [19]. 0 5. 0.006 300 Regression 9 8.36652 8.36652 0.92961 26.50 0.000 0.28
The regression analysis used is called Response Surface
Methodology (RSM) [20]. RSM with a central composite -1 2.7 0.003 200 Linear 3 5.53070 5.53070 1.84357 52.55 0.000
0.24
technique suggests a design model to calculate the -1.7 0.5 0.0013 130 Square 3 2.72488 2.72488 0.90829 25.89 0.000
0.2
response variables. Central composite design (CCD) is a Interaction 3 0.11094 0.11094 0.03698 1.05 0.411 100 200 300 400 500
widely acceptable experimental design for estimating the Residual Error 10 0.35085 0.35085 0.03509 (b)
second order (quadratic) model without conducting full
Lack-of-Fit 5 0.35085 0.35085 0.07017 0.14
randomized parameters [20]. CCD property must have a
Total 19 8.71737

Corrosion rate (mm/y)

rotatable design (Figure1). Thus, setting variables in the 0.13
experiment should have the length of 1 unit in each factor. Corr. rate (mm/y) = 2.83223+0.587083*CO2-
0.12
Hence, all real variables were transformed to the +1.7 0.115385*H2S+0.208273*HAc-
as a code for high value and -1.7 for the low value. After 0.338661*CO2*CO+0.214973*H2S*H2S- 0.11

coding dependant variables in three levels, all factors were 0.0964461*HAc*HAc-0.0937500*CO2* 0.1
structured in a matrix which has all orthogonal column H2S+0.0187500*CO2*HAc+0.0687500*H2S*HAc
0.09
arrays resulting in 15 experiments running. 0.001 0.003 0.005 0.007 0.009
R-Sq = 95.98%
(c)
Figure 1: Illustration of positions for three variables experiments Figure 2: Illustration of individual effects of CO2 (a), HAc (b), and H2S
in CCD (c) on corrosion rate for conditions: 70oC and total pressure 1 bar.

26 Corrosion & Materials Vol 34 No 4 August 2009 27

 Cathodic Corrosion Protection of Pre-Corroded Steel in Concrete with Galvanic Zinc Anodes

C. Combined Effect of CO2, HAc and H2S Calculated by ECE® 450

Corr rate different compared to its individual effect. In the individual References
2.0 3.0 (mm/y)
< 0.5 effects, H2S at concentrations from 0.001% mol to 0.01%
Effects of HAc and H2S addition to the CO2 gas are [1] E
 . Joseph, Shioya. N., Costa. E., Cynthia. D. A,
400 C02 (% mol) = 8.21288
0.5 — 1.0 decreased the corrosion rate. But, in the combined effects,
presented in Table 4 below. The combined effect of HAc and H2S (% mol) = 436.880 1.0 — 1.5 Monica. O., A Cost Effective Treatment to Mitigate
Corr rate (mm/y) = 3.35016 1.5 — 2.0 this decrease was only at a concentration of 0.006% mol.
H2S was to increase the corrosion rate from 0.52 mm/y to 2.0 — 2.5 Biogenic H2S on FPSO, NACE Corrosion Annual
350 As with CO2, H2S also has a capability to form films which
2.32 mm/y. 2.5 — 3.0 Conf., NACE International, Houston, Texas, Paper no.
> 3.0 can act as a barrier to iron dissolution [22]. But the film
04751, 2004.

HAc (ppm)
300 Hold Values formed by H2S gas, at different concentrations has different
Table 4: Effect of H2S and hac in CO2 corrosion. H2S (% mol) 0.00615
properties [23, 24, 25]. More dense films are formed at the [2] E
 gil.S., H2S Inhibition by Nitrate Injection on the
250 lower H2S concentration [23]. With a concentration more Gulf Field, NACE Corrosion Annual Conf., NACE
CO2 H2S HAc
CR (mm/y) 1.0 than 0.006% mol H2S, iron dissolution controls the reaction International, Houston, Texas, Paper no. 04760, 2004.
(%mol) (%mol) (ppm) 200 rate causing corrosion rate to increase. Figure 4 shows
5 0 0 0.52 [3] T
 ebbal. S., Analysis and Corrosivity Testing of Eight
the effects of HAc on corrosion rate. The combined effect
150 1.5
Crude Oils NACE Corrosion Annual Conf., NACE
5 0.006 0 0.5 2.5 of HAc and CO2 at 0.006% H2S on corrosion rate indicated
International, Houston, Texas, Paper no. 04636, 2004.
2 4 6 8 10 a polynomial model. Effects of HAc showed an increase
5 0.006 300 2.22 C02 (% mol)
of corrosion rate in the range of 100ppm to 400ppm. Both [4] J
 ames A. Dougherty, “A Review of the effect of
5 0 300 2.32 (a) combined and individual effects indicated the same trends. organic acids on CO2 corrosion”, NACE Corrosion
Some studies carried out in the past are consistent with Annual Conf., NACE International, Houston, Texas,
D. Prediction of Corrosion rate calculated by RSM these results [4,13,26]. They related the corrosion rate Paper no. 04376, 2004.
with an increase ion the rate of the cathodic reaction and [5] B
 rown, B., Srdjan Nesic, “CO2 / H2S corrosion under
Figures 3 and 4 below are models of the combination effect with the properties of iron acetate, which was soluble,
of H2S, CO2, and HAc on the corrosion rate calculated by scale forming conditions”, NACE Corrosion Annual
permitting subsequent corrosion. Conf., NACE International, Houston, Texas, Paper no.
ECE®. It shows a different effect compared to the individual 3

effects as shown in Figure 2.

Corr rate (mm/y) 05626, 2005.
2 4. Conclusion
0.011 [6] K
 un-Lin John Lee and Srdjan Nesic, “The effect of
Corr rate
2.5 (mm/y)
1
400 According to the ECE® software, the combined effects of trace amount of H2S on CO2 corrosion investigated by
0.010 C02 (% mol) = 7.51388
H2S (% mol) = 0.0109649
< 1.0 300 variables have changed the corrosion behavior compared using the EIS”, NACE Corrosion Annual Conf., NACE
1.0 — 1.5 0
0.009 Corr rate (mm/y) = 3.41309 1.5 — 2.0 0 200 HAc (ppm) to the individual effects, especially for H2S gas. H2S gas International, Houston, Texas, Paper no. 05630, 2005.
2.0 — 2.5 4
0.008 2.5 — 3.0 8 100 alone reduced the corrosion rate consistently. But, in a
12 [7] S
 rinivasan in Brown, B., Kun-Lin Lee, Srdjan Nesic.
0.007
3.0 — 3.5
C02 (% mol) mixture of gases, H2S reduced the corrosion rate initially.
H2S (% mol)

3.5 — 4.0 “Corrosion in multiphase flow containing small

> 4.0
(b) After that it increased the corrosion rate. HAc did not
0.006 amounts of H2S”, NACE Corrosion Annual Conf., NACE
3.0 Hold Values
HAc (ppm) 300
change the trend of corrosion rate during exposure time.
0.005 Figure 4: Combination effects of HAc and CO2 calculated by ECE® HAc always increased the corrosion rate either alone or in International, Houston, Texas, Paper no. 03341, 2003.
0.004 3.5 presented in 2D (a) and 3D (b) graph show correlations of corrosion combination with other environments.
rate with CO2, at temperature 70ºC, H2S 0.006% and total pressure
[8] H
 unnik, E.W.J. Van B.F.M. Pots, E.L.J.A. Hendriksen
0.003
1 bar. (H2S concentration at the middle of its level) The appropriateness of the model was discussed and the Koninklijke. “The formation of protective FeCO3
0.002 2.0 3.0
model was shown to predict CO2 corrosion prediction. The corrosion product layers in CO2 corrosion”, NACE
4.0
polynomial regression model provided a good agreement Corrosion Annual Conf., NACE International, Houston,
2 4 6 8 10
Considering simultaneous effects of mixed gases, it seems Texas, Paper no. 6, 1996.
C02 (% mol) to the corrosion data calculated by ECE® (96% confidence
that only H2S gave a different effect compared to its sole
(a) level as calculated by RSM). Central composite design [9] C
 rolet and Bonnis, “Carbon dioxide in oil and gas
effect (Figure 2). When H2S was mixed with HAc and CO2,
allowed a more economical design of experiments rather production, Corrosion, Vol. 59, pp. 8, 2003.
H2S showed a different behavior. It reduced the corrosion
than the use of a full randomized design. It reduced
rate, initially, but at a slightly higher concentration (0.08% [10] Garsani in Omkar A. Nafday, “Film formation and
number of experiments significantly. Furthermore, the use
mol), it promoted corrosion. Although the combined effects CO2 corrosion in the presence of acetic acid”, Master
of RSM provided a contour plot which makes it easier to
of H2S and HAc showed a similar trend compared with the Thesis of Fritz.j., Dolores and H.Russ College of
analyze the results of two variables simultaneously.
sole effect of H2S,. the corrosion rate for the mixed gases Engineering and Technology, Ohio University, 2004.
4
Corr rate (mm/y)
was changed. A challenging recommendation is to build a prediction
model involving various modifications using more [11] Joosten in Omkar A. Nafday, “Film formation and
3
Analysis of the interaction effects of those three species on CO2 corrosion in the presence of acetic acid”, Master
parameters and using other regression statistics technique.
2 0.012 corrosion rate are presented at Figure 3. The calculation Thesis of Fritz.j., Dolores and H.Russ College of
However, such a prediction model would still need to be
was done using the ECE® software modified with RSM Engineering and Technology, Ohio University, 2004.
1
0.008 verified and further interpreted. Actual data from real
statistics methodology. The principle important to
0.004 H2S (% mol) service conditions are required for accurate results. [12] Omkar A. Nafday, Srdjan Nesic, “Iron carbonate scale
0
4
emphasize is that the presence of mixed species influenced
8 0.000 corrosion behavior as as shown by Figure 3, and CO2 formation and CO2 corrosion in the presence of acetic
12
C02 (% mol)
increased corrosion rate consistently. However, at the high Acknowledgments acid”, NACE Corrosion Annual Conf., NACE International,
(b) concentration level of CO2 (10% mol), the corrosion rate Houston, Texas, Paper no. 05295, 2005.
The authors are thankful to Universiti Teknologi PETRONAS
was decreased. Compared to the individual effects (Figure for providing grant and facilities for the research. [13] Ismail.Che. Mokhtar, “Prediction CO2 corrosion with
Figure 3: Combination effects of CO2 and H2S calculated by ECE ®
2), there was no significant difference. Thus, it can be the presence of acetic acid”, PhD Thesis, UMIST,
presented in 2D (a) and 3D (b) graphs show correlations corrosion
rate with CO2, H2S at temperature 70°C, HAc 300 ppm and total concluded that CO2 was a dominant factor in determining United Kingdom, 2005.
pressure 1 bar. (HAC concentration at the middle of its level) corrosion behavior [14,15,16]. Effects of H2S were clearly

28 Corrosion & Materials Vol 34 No 4 August 2009 29

 Cathodic Corrosion Protection of Pre-Corroded Steel in Concrete with Galvanic Zinc Anodes
[14] George in Omkar A. Nafday, “Film formation and
CO2 corrosion in the presence of acetic acid”, Master
Thesis of Fritz.j., Dolores and H.Russ College of
Engineering and Technology, Ohio University, 2004.
[15] Heuer.J.K., J.F. Stubbins, “An XPS characterization of
FeC03 films from CO2 corrosion”, Corrosion Science,
Vol. 41, pp.1231-1243, 1998
[16] Nesic. Srdjan., Kun-Lin., John Lee., “A Mechanistic
model of iron carbonate film growth and the effect Department of Applied Chemistry, parameter to maintain constant height of the probe above
on CO2 corrosion of mild steel”, NACE Corrosion
Annual Conf.,
[17] http://www.intetech.com
[18] de Waard.C., Lotz .U., Dugstad.A., "Influence of liquid
velocity on CO2 corrosion: a semi-empirical model",
NACE International, Houston, Texas, Paper No. 128,1995
[19] Box, G. E. P., Draper.N.R., “Empirical Model Building
and Response Surfaces," John Wiley and Sons, New
York, 1987.
[20] Devore, Peck. Statistics, “The Exploration and is shown by two examples. The first example concerns
Analysis Data”, fifth edition, Thomson Learning,
Belmont, USA, 2005.
Corrosion
& Prevention 2009
The Management of Infrastructure Deterioration
15–18 November 2009
Novotel Pacific Bay Resort
Coffs Harbour
Registration now open invented the first type of a new kind of microscope, the
(see www.corrosion.com.au for details)
30 Corrosion & Materials
[21] Minitab Inc. “Minitab Statistical Software”, Release 15
for Windows, State College, Pennsylvania, 2006.
[22] Houyi Maa, “The influence of hydrogen sulfide on
corrosion iron under different conditions”, Corrosion
Science, Vol. 42, pp. 1669-1683, 2000.
[23] Rudolf H. Hausler, “Contribution to the understanding
of H2S”, NACE Corrosion Annual Conf., NACE
International, Houston, Texas, Paper no. 4732, 2004.
[24] Prakala, Shilpha, “EIS investigation of carbon dioxide
and hydrogen sulfide corrosion under film forming
condition”, Master Theses, Ohio University, 2005.
[25] Agrawal, C. Durr, And G. H. Koch, “Sulfide films and
corrosion rates of aisi 1018 carbon steel in saline
solutions in the presence of H2S and CO2”, NACE
Corrosion Annual Conf., NACE International, Houston,
Texas, Paper no. 04388, 2004.
[26] Veloz, M.A., Gonza´.l., “Electrochemical study
of carbon steel corrosion in buffered acetic acid
solutions with chlorides and H2S”, Electrochemica
Acta, Vol. 48, pp. 135-144, 2002.
This Paper was awarded the Marshall Fordham Best Research Paper Award
at Corrosion & Prevention 2008 for its presentation at Corrosion Control 007.
The Use of Atomic Force Microscopy in
Corrosion Research
B. Kinsella1 & T. Becker2
1
Western Australian Corrosion Research Group,
Curtin University of Technology, Australia
2
Nanochemistry Research Institute (NRI), modes, the constant height mode and the constant current
Curtin University of Technology, Australia
Summary: Atomic force microscopy (AFM), invented in
1986, has found widespread use in science. The technique
enables imaging of material at the molecular level for the
first time. Unlike most other microscopy techniques, the
imaging can be carried out in situ without fear of destroying
the integrity of the inter-phase and the process that is being
measured. The application of AFM to corrosion science
the mechanism of adsorption of carbon dioxide corrosion
inhibitors (surfactant molecules) on steel. The second
example involves an investigation of the mechanism of
stress corrosion cracking of weldable 13 chrome steel.
1. Introduction
Atomic Force Microscopy (AFM) was invented in 1986 and
commercial instruments became readily available in the
early nineties. Development of improved technology and
friendlier user approach has seen the technique flourish in
many areas of scientific investigation. This paper provides
a description of the AFM technique and various modes of
operation and its application to corrosion research. Two
examples are given – an investigation of the mechanism of
adsorption of carbon dioxide corrosion inhibitors and the
mechanism of stress corrosion cracking of stainless steel.
2. Scanning Probe Microscopy (SPM)
Scanning Probe Microscopes allow researchers to
investigate the topography of a specimen in great detail with
a resolution down to the atomic level. The basic principle of
these microscopes is a sharp probe that is precisely scanned
across the surface of the sample. The probe is moved using
a scanner tube made of piezoelectric material that allows
accurate positioning. Typically, the scanner tube consists
of two parts, one for the lateral and one for the vertical
movements. An important advantage of all SPM techniques
is the ability to be used in fluid environments, enabling
researchers to study samples in-situ, for example biological
specimen or the formation of surfactant layers on a sample.
2.1 Scanning Probe Microscopy (SPM)
In 1981 Gerd Binnig and Heinrich Rohrer at IBM, Zurich,
Scanning Tunneling Microscope [STM] (1). Five years later,
in 1986, they received the Nobel Prize “for their design of
the Scanning Tunneling Microscope”. The STM utilises the
quantum-mechanical tunneling effect, where a sharp tip
(i.e. an etched tungsten wire) is brought in close contact
with an electrically conductive or semi-conductive sample.
A bias voltage is applied between tip and sample and
for a tip-sample (probe-sample) separation of <1 nm a
tunneling current of the order of 10-9A can be measured.
The tunneling current depends exponentially on the probe-
sample separation and can thus be used as a feedback
the surface. STMs can be operated in two different imaging
mode. In constant height mode, the probe is scanned at a
constant z-position and the tunneling current varies with
topography and with the local surface electronic properties
of the sample. In constant-current mode, the microscope
uses an electronic feedback to adjust the z-position of
the probe relative to the sample in order to maintain a
constant tunneling current. In the latter case, the x-, y- and
z-data of each point of the scan results in a 3-dimensional
topography map of the sample surface.
In 1986, Binnig, Gerber and Quate presented a new form of
Scanning Probe Microscope, the Atomic Force Microscope
(AFM) (Figure 1). The principle of the AFM is a combination
of STM and a stylus profilometer (2). The AFM uses a sharp
probe (typical radius of curvature 5-10 nm) mounted on a
flexible spring, the so-called cantilever. The deflection of
the cantilever is proportional to the force between tip and
sample (Hooke’s law). Depending on application and imaging
mode, cantilevers with a spring constant ranging from
0.01 N/m to 100 N/m are commercially available. The
deflection of the cantilever is detected using the beam
deflection principle. Here, a laser diode generates a laser
beam that is projected on the back of the cantilever and is
reflected onto a four-segment photo detector. This technique
allows the detection of intermolecular forces such as van
der Waals forces. Whereas the STM requires electrically
conductive or semi-conductive samples, the AFM is also
capable of investigating insulators. AFMs are operated in
three different imaging modes: Contact Mode, Intermittent
Contact or Tapping Mode and Non-Contact Mode. Contact
Mode and Tapping Mode are the relevant imaging modes for
the present paper and will be discussed in section 2.2.
laser
piezoelectric
scanner (PZT)
split
photodetector
x, y
z z
probe
x
sample
Figure 1: schematic set-up of an Atomic Force Microscope (AFM).
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