Paper No.

00405
CORROSION 2000
AN A D V A N C E D A T M O S P H E R I C C O R R O S I O N
M E A S U R E M E N T SYSTEM

Philippe Kempe, Allen Denzine, and Eugen Tiefnig

Cortest, Inc.
3653 Lost Nation Road
Willoughby, OH 44094

ABSTRACT

An atmospheric corrosion probe has been developed to measure corrosion rates under atmospheric
conditions. The corrosivity of the atmosphere as well as the corrosion rate of materials can be accurately
determined.
The performances of this new technology are evaluated with experiments that alternate between wet
and dry exposure conditions. The onset of the dew point is easily detected. These different
measurements show the high sensitivity and high accuracy of these atmospheric corrosion probes. The
outstanding capabilities of these corrosion probes to measure low values of corrosion rate are
demonstrated.

Keywords: corrosion rate measurement, corrosion sensor, corrosion monitoring, atmospheric corrosion,
controlled environment.

INTRODUCTION

A patented corrosion monitoring technology, with the tradename MICROCORrM(I), has been widely
used in oilfield and refmery applications to determine small changes in corrosion rates. The continuing
development of this new metal loss sensor now permits rapid measurements of corrosion rates in
atmospheric conditions. These corrosion probes have a very high resolution and can be used in

MICROCOR and ~COR are registered tradenames of Cortest, Inc.

Copyright
©2000 by NACE International.Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Conferences Division, P.O. Box 218340, Houston, Texas 77218-8340. The material presented and the views expressed in this
paper are solely those of the author(s) and are not necessarily endorsed by the Association. Printed in U.S.A.
conductive and non-conductive environments. Indeed, the response of these corrosion probes does not
vary with changes of the environmental conditions (from conductive to non-conductive liquid or from
liquid to gas). Thus, their applicability has been extended to corrosion monitoring under atmospheric
conditions. An advanced atmospheric corrosion probe has been developed to measure the corrosivity of
the atmosphere and the corrosion rate of materials.

Atmospheric Corrosion

The corrosion of materials in atmospheric conditions is an important degradation process of metallic

structures. Under atmospheric conditions, the exposure conditions are not constant and corrosion rates
vary with fluctuations of temperature and rainfalls. The metal is exposed to changing external conditions
and corrosion rates vary according to these changes. Because of the importance of atmospheric
corrosion on metallic structures, large programs on atmospheric corrosion of different materials have
been conducted with field exposure in various locations [1 ].
The exposure conditions periodically alternate between wet and dry conditions. Previous works [2-5]
on atmospheric corrosion investigated materials corroding under simulated wet and dry conditions.
These studies with alternated wet and dry conditions have shown that corrosion rates are function of the
relative humidity, pH and chemical composition of the electrolyte layer.
In ambient and dry conditions, corrosion of metal plays an insignificant role in atmospheric
corrosion [6]. Atmospheric corrosion takes place only when an aqueous film is present on the metal
surface. Wet corrosion requires a certain level of moisture. A thin aqueous film of moisture is formed
when the relative humidity exceeds a minimal value [7]. The variation from dry to wet conditions may
not be always well defined in atmospheric conditions but the formation of dew represents a situation
where corrosion must be significantly different before and atter the dew formation.

Detection of Dew Point

In atmosphere, dew formation is the result of cooling of exposed surfaces below the dew point of
surrounding air. For a metal element not directly exposed to rain, the corrosion before the dew point
should be very low. When dew is formed on the metal surface, corrosion should significantly increase.
A significant variation of the corrosion rate should be observed before and afler the dew point.

Determination of Corrosion Rates under Atmospheric Conditions

In industrial processes, different methods are available to measure corrosion rates. The corrosion
monitoring systems can be divided into two general categories: electrochemical and metal loss
techniques. Under atmospheric conditions, the applicability o f electrochemical techniques as Linear
Polarization Resistance (LPR) or Electrochemical Impedance Spectroscopy (EIS) is very limited
because of the absence of conductive media. The metal loss techniques that are the most widely used
include weight loss coupons and conventional electrical resistance (ER). These techniques are not
sensitive enough to measure corrosion rates over a short period of time. Weight loss coupons provide
reliable results but an extended time is required before meaningful results can be obtained.
The general method used to investigate atmospheric corrosion involves weight loss coupons. The
corrosion attack of metal panels is determined by the difference between the mass of the panels before
and atter exposure. Corrosion products formed on the metal surface are removed with a pickling agent.
This procedure is very laborious and not very sensitive. A significant metal loss can only be measured
when consequent corrosion of the panel has occurred. It means that the test has to be run over a long
time. Moreover, it is well known that corrosion rates are not always constant and may vary with time
[1]. A weight loss coupon gives only the overall corrosion rate at the end of the experiment. A
continuous monitoring of the metal loss is not possible.
Some corrosion microsensors have been developed for corrosion under atmospheric conditions. A
review paper on the recent advancements on atmospheric corrosion sensors (ACM) has been published
by Diwan [8]. These corrosion microsensors are very sensitive but they do not measure the actual
corrosion of the corroding structural member. Moreover, the presence of impurities as dust and salts on
the microsensors alter the results and may damage the microsensors.
On the other hand, the advanced atmospheric corrosion probe provides corrosion measurements with
high resolution and high sensitivity under any kind of environment. The formation of corrosion products
on the metal surface, the constant change of exposure conditions (liquid or gas in contact to the metal
surface) and the deposition of impurities do not alter the measurements. The advanced atmospheric
corrosion probe represents the most valuable technique for corrosion measurements under atmospheric
conditions. It provides a direct measurement of metal loss as a fianction of time.
Aside the much greater resolution of the atmospheric corrosion probe, the other advantage of the
corrosion probe method compared with the weight loss coupon method is that a continuous monitoring
of the metal loss as a fimction of time is possible. The evolution of the metal loss vs. time can follow
different patterns (linear, parabolic or other). The continuous variations of the atmospheric conditions
(humidity, temperature and pollutants) induce significant changes in corrosion.

The purpose of this paper is to demonstrate that metal loss under atmospheric conditions can be
continuously monitored with the atmospheric corrosion probe, that corrosion rates under atmospheric
conditions can be quickly and accurately determined, and that the dew point can be easily detected.

EXPERIMENTAL PROCEDURE

Corrosion Probe

In this investigation, the atmospheric corrosion probe consists of a low-carbon steel element (1010
steel) of l-rail (=0.0254 ram) thickness. The area of the exposed steel element is equal to 19.0 cm 2 (9.5
cm x 2.0 cm). The steel element with the corresponding electrical connections is included in an epoxy
ceramic compound of 13 cm x 7.5 cm x 0.5 cm dimensions. The only corroding element is the 19.0 cm 2
exposed steel surface. The corrosion probe is connected to a transmitter, a power supply of 24 V, a
converter and record/retrieve software.
Measurements provide the remaining metal thickness of the corroding element. Measurements of the
metal thickness of the steel element at different intervals of time give variations of the metal loss with
time.
The response of the measuring steel element is given initially in Probe Life Unit (PLU). The
corroding steel element has a thickness of 1 rail. The effective element thickness, which represents the
half-thickness of the element, is equal to 0.5 mils. The software system displays the PLU as a fimction
of time. The effective element thickness is divided into 256,000 PLU, i.e. 256,000 increments. The
Probe Life Units (PLU) are then transformed into mils and mm for the presentation of results of metal
loss vs. time.
Corrosion Test

To experimentally simulate variations of the atmospheric conditions, the steel element is

alternatively exposed to indoor and outdoor conditions. In outdoor conditions, the steel element is in a
position protected from rain but exposed to air movement by wind.
The atmospheric corrosion probe is initially kept in indoor conditions in a closed room, which is not
under completely dry conditions for 221 hours. The corrosion probe is then placed outdoor in a rain
protected position for 11 hours. It is then replaced in indoor conditions in a completely dry room for 450
hours. The metal thickness of the steel element is recorded every minute. The recording has been
stopped a few times when the steel corrosion probe was in indoor conditions.

RESULTS

The experimental curve of metal loss as a fimction of time is shown in figure 1. In the first period,
the atmospheric corrosion probe is exposed to indoor conditions. Corrosion of steel is initially low,
indicating that the environment is not very corrosive. Nevertheless, a small corrosion rate is observed at
the beginning of the experiment because the surrounding air is not completely dry. When the
atmospheric corrosion probe is then placed in outdoor conditions, the metal loss increases rapidly. The
significant corrosion rate observed in outdoor conditions is due to the formation of dew. Aqueous
droplets are formed on the steel surface and these droplets provide an electrolyte for the formation of
corrosion microcells on the steel surface. Corrosion rate under wet conditions is much higher than that
under partially dry conditions, as demonstrated by the sharp increase in metal loss in presence of dew.
The atmospheric corrosion probe is then placed in completely dry indoor conditions. Corrosion is then
stopped. The following measurements conducted over 6 days indicate that no significant corrosion can
be detected.

DISCUSSION

Wet and Dry Corrosion

Figure 1 shows the metal loss vs. time curve for the whole experiment. The atmospheric corrosion
probe was placed in outdoor conditions for only 11 hours but a steep slope during the outdoor exposure
shows the higher corrosivity of the environment. The change of external conditions and the dew
formation are clearly seen in figure 1.
The recording of metal loss before and after outdoor exposure may appear like an offset of the
measurement because results are presented over a long time period. Care~l examination of the results
shows that many points were recorded during the outdoor exposure and that steel corrodes steadily
during this period. This fact demonstrates the very high sensitivity of the atmospheric corrosion probe to
changes in exposure conditions.
Figure 2 shows the expanded curve for the cycle of indoor/outdoor exposure. A measurement was
taken every minute. Thus, 660 points were recorded during the outdoor period and the metal loss vs.
time curve appears linear. The corrosion rate is given by the slope of the metal loss vs. time curve. The
corrosion rate in outdoor exposure is equal to 0.21mmpy (-- 8.4 mpy). During the outdoor exposure, the
corrosion rate is precisely estimated, although the corrosion rate is not so high (around 8 mpy = 0.2
mmpy).
 In summary, there is a sharp difference between corrosion rates observed under wet and dry
conditions, i.e. outdoor and indoor conditions. A negligible corrosion is observed under dry conditions
while corrosion under wet conditions is important. A very clear discontinuity appears within 10-15
minutes of implementing changes in exposure. The atmospheric corrosion probe characterizes very well
the corrosivity of the external environment and the corrosion rate of the corroding material.

Sensitivity and Accuracy

The great accuracy and sensitivity of the measurements is illustrated in figure 3. This figure shows
the results obtained during the outdoor exposure for a time period of 4 hours. The complete results for
the outdoor exposure were shown before in figure 2. A metal loss of 10 nm is accurately recorded in less
than 1 hour. The low level of noise is exceptionally good in these measurements. Small amount of metal
loss can be quickly and accurately determined.
The linear relationship of metal loss with time indicates that the corrosion rate is constant. Given that
the area of the corrosion probe is rather large, the level of moisture is probably not uniform on the whole
surface of the probe. Thus, the very good linearity of the experimental curve of metal loss may even be
surprising.
In dry conditions, corrosion rates are very small. Although corrosion rates are almost negligible,
small values of corrosion rates can be determined with good accuracy. A corrosion rate of 0.018 mmpy
(=0.7 mpy) can be measured in a few hours during the indoor conditions, as shown in figure 4.

CONCLUSIONS

The rapid and accurate response of the atmospheric corrosion probe permits fast and precise
detection of any variation of corrosion rates. The onset of dew point is easily detected. The experiments
demonstrated that small variations of the atmospheric conditions can be detected with the atmospheric
corrosion probe and that corrosion rates can be quickly and accurately determined, even for very small
values of corrosion rates. The ability o f the probe to measure precisely very low corrosion rates (0.1
mpy = 0.0025 mmpy can easily be measured) is unique.
This corrosion monitoring technology shows tremendous promises for numerous applications. It
represents an ideal sensor for controlled environments as clean rooms, storage facilities or assembly
areas where any variation of the environment needs to be detected and recorded.

REFERENCES

. Dean, S.W., in Atmospheric Corrosion, ASTM STP 1239, W.W. Kirk and Herbert H. Lawson,
Eds., American Society for Testing and Materials, Philadelphia, (1995).
. Whitton, W.I., Trans. Faraday Society, 46 (1950) p. 927.
3. Evans, U.R., Nature, 206 (1965) p. 980.
4. Stratmann, M., Kim, K.T., and Streckel, H., Corrosion Science, 30, 6-7 (1990) p. 681-734.
5. Stratmann, M., Bohnenkamp, K., and Engell, H.J., Corrosion Science, 23, 9 (1983) p. 969-85.
6. Pohlman, S.L., General Corrosion, in Corrosion, ASM, Editor, 1st Ed., Vol. 13 (1987) p. 80-82.
7. Brown, P.W., and Masters. L.W., in Atmospheric Corrosion, W.J. Ailor, Ed., Wiley, New York,
(1982) p. 31.
. Diwan, R.M., Raman, A., Bhattacharya, P.K., and Lee. R., CORROSION/95 NACE, Houston,
TX, (1995) Paper 227.
 400 ' I ' I ' ' I

350

300

E 250
v IndooJ OutdoOr Indoor
¢/) Conditions Conditions Cond#ions
O
_1 200
partially dry
/ completely, dry
~0 atmosphere atmosphere
150

100

50
Dew Formation
0
100 200 300 400 500 600 700

Time (hours)

Figure l. Atmospheric Corrosion Probe Test

Metal Loss vs. Time

400 I I I f

Dew Formation
350
/
300
Indoor Outdoor Indoor
E Conditions Conditions

O3 250
O3
o
_1
200

150

/ Corrosion Rate
100 CR = 0.2"I mmpy = 8.4 mpy

= i _ i i I L_ , ~ J I i i I _ ~ _ f I r i i i
50
215 220 225 230 235 240
Time (hours)

Figure 2. Indoor/Outdoor Cycles

Metal Loss vs. Time
 r
260 i , [ . ~ - . , , T , .E [ !- 1 [ I . . . . . 1

240 Outdoor
.¢
Conditions
E
co 220 .??,0 '''~
6O
0

200
Corrosion Rate
I
CR = O.21 mmpy = 8. 4 mpy
,.,w, j ~t '=
(linear regression R = 0.9997)
180

.... t,~* L ~ t _ i c ..L _ _ J_ ~ _L J _. £ . . . . . ~ ]. . . . 3.._.; L L • . L . • L- ~ ] . ± [- L : _ _ L .... i L- L .L-. ]

160
224 224.5 228 225.5 226 228.5 22z 22z.5 228
Time (hours)

Figure 3. Metal Loss under Outdoor Conditions

110 =
I

105

100
Indoor I
aq Conditions
o 95
t

1
90
~ ~ o s i o n R a t e Dew Point J

:CR = 0.018 mmpy = O.7 mpy

85

80 " : " L - l . ~ t . b 1 ~ ~ • . E J
J i i _ i • .

170 180 190 200 210 220 230

Time (hours)

Figure 4. Metal Loss under Indoor Conditions