TECHNICAL BULLETIN

CORROSION MONITORING IN OILFIELD, PIPELINE,

AND INDUSTRIAL PROCESSES

SUMMARY:
Corrosion monitoring is one of the basic functions required for safe and efficient industrial operations. This
primer presents an overview of the various corrosion measurement technologies that are available for
monitoring industrial process systems. They range from non-direct/non-intrusive to direct/intrusive techniques
and include everything from simple corrosion coupons to sophisticated electrochemical techniques. These
systems should be selected to meet the specific needs of particular plant requirements to minimize downtime
and equipment failures. Major sources of corrosion in industrial processes include dew point corrosion in
overhead systems where an acidic condensate precipitates from a vapor phase. Other conditions that require
monitoring include high temperature non-aqueous corrosion often involving hot combustion gases containing
sulfur impurities, aqueous sulfide corrosion that can produce hydrogen charging and cracking of steels, and
amine solutions used in gas processing equipment. Each process poses a different set of conditions that must
be analyzed.

INTRODUCTION:
There are many purposes for corrosion monitoring in industrial systems. These purposes generally include one
or more of the following:

Diagnoses of corrosion problems.

Monitoring of corrosion control methods (e.g. inhibition, pH control, etc.).
Advanced warning of system upsets leading to corrosion damage.
Invoke process controls.
Determination of inspection and/or maintenance schedules.
Estimation of use service life of equipment.

However, there are several basic aspects of corrosion monitoring that are often over looked. First, corrosion
assessment can be complex since industrial process operations provide a wide variety of dynamic
environments and service conditions. Secondly, no single method will necessarily work or provide optimum
results in all applications. In some cases, multiple technologies may be needed in combination to provide
accurate and reliable corrosion monitoring information that can be used with confidence to make engineering
decisions.

The purpose of this primer is to introduce several of the more common techniques utilized for monitoring
corrosion in industrial process operations and to define their advantages and limitations. Additionally, examples
will be presented on how these techniques are employed for in-plant corrosion monitoring.

TYPES OF CORROSION MONITORING TECHNIQUES SYNERGY WILL UTILIZE:

There are four basic categories of corrosion monitoring methods Synergy will utilize in the field. The first
distinction is based on whether or not the technique is direct or indirectthat is to say, whether the monitoring
technique measures a direct result of corrosion or not. Examples of direct techniques are the three most
common corrosion monitoring methods:

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 TECHNICAL BULLETIN
CORROSION MONITORING IN OILFIELD, PIPELINE,
AND INDUSTRIAL PROCESSES

Corrosion Coupons - Coupons can be weight to determine the extent of mass loss corrosion. In some
cases, valuable information on the mature and distribution of corrosion can also be assessed.
Electric Resistance (ER) technique - ER probes utilize the change in resistance produced by the
change in cross sectional area resulting from corrosion.
Linear Polarization Resistance (LPR) technique - LPR probes utilize the relationship of Potential vs.
Current on a corroding electrode to determine a value of LPR.

Indirect corrosion monitoring techniques measure an outcome of the corrosion process. Two of the most
common indirect techniques are ultrasonic testing and radiography. Both techniques can be used to determine
the remaining wall thickness of a pipe, vessel or other equipment affected by corrosion.

Secondly, the other way to classify corrosion monitoring techniques is if they are intrusive or non-intrusive. An
intrusive technique requires entry into the process stream. Corrosion coupons, ER and LPR probes and on-line
pH or water analysis are intrusive since they have to have access to the inside of the equipment to be
monitored. Examples of non-intrusive techniques are external hydrogen flux probes in H2S containing
environments and analysis of water samples through an existing valve.

CORROSION COUPONS:
The evaluation of corrosion coupons is one of the most basic methods of corrosion monitoring. Consequently,
coupon testing is often overlooked as an archaic procedure. However, it should be realized that coupons
provide the most reliable physical evidence possible. They yield information on average mass loss corrosion
rate, extent and distribution of localized corrosion. They can also provide information on the nature of corrosion
through analysis of their corrosion products. The biggest drawbacks that coupons have are that they usually
require significant time in terms of labor and they provide time averaged data that can not be utilized for real
time or on-line corrosion monitoring. This not withstanding, corrosion should be utilized to provide periodic
information and their data should be considered a basis from which all other methods are compared.
Procedures for in-plant corrosion coupon testing are given in ASTM G 84. This standard gives methods for
placement, installation and exposure of in-plant corrosion coupons. ASTM G1 gives useful guidelines for
preparation, cleaning, weighing of corrosion coupons. The most common method for evaluating mass loss
corrosion rate is with the following equation:
Corrosion Rate = 354 M/ADT
Where M = mass loss resulting from the difference in initial and final specimen weights (mg), A = coupon
surface area (in2), D = material density (g/cm3) and T = time of exposure (hours). ASTM G46 gives procedures
for analysis of localized corrosion. It is important to document the density (#/area), size (diameter) and depth of
localized attack. A useful parameter is the ratio of maximum localized attack rate versus general corrosion rate
determined by mass loss. In many systems this ratio will be low indicating that the general corrosion rate is an
accurate predictor or corrosion performance. In other cases, such as where oxygen ingress, pitting of stainless
alloys and velocity accelerated corrosion, the local attack rate can be over ten times the general corrosion rate.
Such differences are important when trying to assess the relevance of inspection techniques such as ultrasonic
tests of remaining section thickness.

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CORROSION MONITORING IN OILFIELD, PIPELINE,
AND INDUSTRIAL PROCESSES

ELECTRICAL RESISTANCE MONITORING:

The ER probe is comprised of a sensing element that is basically a loop of material made from a wire or strip
which is used to conduct an electrical signal. When exposed to a corrosive environment, the cross-section of
the loop is reduced which increases the resistance of the sensing element thus producing a change in the
output of the ER meter. Relevant information on this technique can be found in ASTM G96 for in-plant
corrosion monitoring and in NACE Publication 3D170-84.

The main benefit of the ER technique is that it can be utilized in continuous on-line process monitoring. Multiple
probes can be used to access various locations in the process stream. Telemetry can be used to send this
information back to a central location so that corrosion rates and the effects of process changes can be
identified. Typical ER data is shown in Figure 4. It shows an ER output over a period of about 14 days. During
this period the corrosion rate is initially 25 mpy, then becomes very low (3 mpy) and then increases somewhat
to 12 mpy. Probes of varying materials and sensitivities are commonly available. One of the best aspects of the
ER technique is that it does not require a continuous electrolyte current path to make measurements.
Therefore, they work in multiphase environments at contain liquid hydrocarbons and they can be utilized for
monitoring corrosion in non-aqueous and even gaseous process environments.

The limitations of the ER technique are that they provide representative data for general corrosion. They do not
have the ability to accurately detect localized attack. ER probes, while available in varying sensitivity, typically
require several days to determine a reliable corrosion rate trend. Therefore, if the process is prone to rapid
changes in corrosivity, ER probes typically may not provide accurate and reliable corrosion rate data. In some
cases, namely where H2S is present, they can be prone to error due to the presence of conductive sulfide
corrosion products on the sensing element which may lead to non-conservative results. The results of ER
probes should be compared to those obtained from coupon exposures during the same time period. While ER
data may not give reliable indications of the absolute corrosion rate, they can yield useful indications of trends
and changes in plant corrosion activity.

ELECTROCHEMICAL METHODS:
Electrochemical corrosion monitoring is based on the premise that corrosion is basically an electrochemical
process that can be monitored through the measurement of potential and current that characterizes the
corrosion process. In simple terms, corrosion processes can be described as an electrochemical potential
which indicates thermodynamic driving force and a current that indicates the reaction rate or kinetics of the
process. This corrosion current can be converted to a corrosion rate by employing Faraday's Law. This
analysis depends strongly on the ability to measure current flow through the solution. Therefore, it has
limitations in many multiphase (e.g. gas/oil/water) systems and simply can not be used in non-aqueous and
gaseous environments. Even under dew point conditions, where an aqueous phase is being precipitated from
the vapor phase, LPR will not usually work dependably since, in most cases, a continuous electrolyte path from
the working electrode (test specimen) to the counter (current sensing) electrode and reference (potential
sensing) electrode cannot be assured. In some cases, special flush mounted probes are available that utilize a
thin film of condensed liquid as the electrolyte path between electrodes.

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CORROSION MONITORING IN OILFIELD, PIPELINE,
AND INDUSTRIAL PROCESSES

The main benefits of electrochemical methods are that they can provide faster and more dynamic information
coming very close to being able to measure an "instantaneous" corrosion rate in the system. Therefore, it can
identify rapid changes in process corrosivity. Electrochemical techniques can also be used to obtain more
mechanistic information through controlled polarization of the material in the environment. This information
includes identification of transitions between active and passive behavior in stainless alloys and the
mechanisms of and efficacy of chemical inhibition.

Care must be used when electrochemical methods are employed in corrosion monitoring. Standard analyses of
electrochemical data usually assume the measured corrosion rate is the result of general corrosion. In
actuality, many cases are observed where less than 10 percent of the surface of the specimen is actually
corroding as is the case when pitting or other forms of localized corrosion is encountered.

In some environments, non-corrosion electrochemical reactions can lead to the measurement of current that
does not contribute to corrosion. A common situation is that H2S or other soluble sulfur species can complicate
electrochemical measurements since sulfur can be easily oxidized and reduced particularly at elevated
potentials. As in the case with ER probes, electrochemically derived corrosion rates should be compared to
corrosion coupon data. Again, the trends may be meaningful, but the absolute corrosion rate values may be
different. Uncompensated resistance in the service environment can also lead to errors in electrochemical
measurement in low conductivity environments.

LINEAR POLARIZATION RESISTANCE METHOD:

The most popular electrochemical technique utilized for corrosion monitoring is the LPR technique. As
described in ASTM G59, it utilizes a measurement of the slope of the potential versus current plot +20 mV
around the corrosion potential to define a parameter defined as the polarization resistance. Very often
automated corrosion monitoring equipment utilizes a constant (0.12V/decade) of current for both the anodic
and cathodic polarization. The corrosion rate obtained from LPR measurements is inversely proportion to the
polarization resistance (slope of the potential vs. current plot). Therefore, high values of polarization resistance
generally yield low corrosion rates. This yields the ability to determine the corrosion versus time by taking
multiple measurements over short or extended periods. The data can also be transmitted to a central location
using telemetry. Further guidelines for on-line in-plant corrosion monitoring are given in ASTM G96.

OTHER TYPES OF EC MONITORING:

Potential Monitoring. In some systems, it is important to know how the potential of a material changes with
process variations. Two examples of these situations are where either cathodic protection or anodic protection
is being utilized to mitigate corrosion. Variations in the electrochemical potential can indicate if the proper
levels of protection are being maintained or if local changes in corrosion behavior are occurring. For stainless
alloys such measurements may also indicate the influences of process changes or additives on the corrosion
potential relative to the pitting potential for the material. Potential monitoring provides a useful way to
differentiate conditions of active corrosion from passive conditions. However, this is an indirect method of
corrosion monitoring and assesses risk or corrosion not corrosion rate. It also requires the stable reference
electrode that can be used in a field or plant setting. For the evaluation of cathodic protection of steel pipelines
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 TECHNICAL BULLETIN
CORROSION MONITORING IN OILFIELD, PIPELINE,
AND INDUSTRIAL PROCESSES

and equipment, compensation for the IR drop associated with soils of relatively low conductivity must be also
utilized. High solution resistance can also lead to similar problems when electrochemical measurements are
made in high purity water environments use for cooling water in some systems.

Electrical Impedance Spectroscopy. With the increased attention to accurate corrosion monitoring and
methods that are compatible with modern data acquisition technology several new techniques are currently
being utilized. One of these newer techniques is electrochemical impedance spectroscopy (EIS) which utilizes
an AC signal to excite or perturb a corroding specimen. In fact, one convenient way to visualize the EIS
technique is to picture the low frequency limit of EIS as essential the same as the LPR method. In a mechanical
sense, EIS monitors the electric response of the metal/environment interface to the applied AC signal over a
frequency spectrum usually in the range of 10 kHz to 50 micro Hz. In some cases, selected frequencies can be
utilized to reduce the time required for corrosion monitoring.

Most important of these components is the solution resistance in environments of low conductivity which can
be separated from the actual polarization resistance. EIS techniques can also be utilized to examine coated or
inhibited materials much more effectively than with LPR techniques.

EIS data can be used to determine the properties of the surface layers such as pore resistance and film
capacitance. Other areas of application for EIS are in the evaluation of corrosion of steel in concrete structures
and in the evaluation of cathodic protection since both applications require significant compensation for
resistive losses. The main limitations of these techniques are that the analysis of the data is complex and its
interpretation is not fully developed for all applications. They require application of a theoretical equivalent
circuit to analyze and interpret the data. Quite often these techniques still require benchmarking with other
more common corrosion monitoring techniques such as corrosion coupons before meaningful data can be
obtained.

Electrochemical Noise. Electrochemical noise (EN) monitoring records the naturally occurring fluctuations in
the corrosion potential and current. Current noise uses current variations between two nominally similar
working electrodes whereas potential noise is based on variations in potential between a working electrode and
a stable reference electrode. As with EIS the technical basis for this technique is still under investigation.
Qualitatively, EN data has been utilized to identify localized corrosion and to differentiate conditions where
general and localized corrosion may occur. The technique is also being explored for use these naturally
occurring fluctuations in potential and current to determine a corrosion rate. However, EN requires monitoring
of very small signal fluctuation which may be prone to extraneous sources of signal noise if improperly used.
Again, EN is most commonly applied to plant applications in combination with the other electrochemical
techniques such as LPR and EIS. These multiprobes have been used to monitoring dew point problems areas
and multiphase environments. They provide a convenient way to compare data from the various techniques
which has been to be prudent since electrochemical methods have been shown to be confused in some
applications. Additionally, these multiprobes have been designed to allow for measurements through thin films
of condensed water and for maintaining controlled temperatures for investigation of dew point corrosion
problems

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CORROSION MONITORING IN OILFIELD, PIPELINE,
AND INDUSTRIAL PROCESSES

HYDROGEN FLUX MONITORING:

A common byproduct of corrosion of steel is atomic hydrogen (Ho). Atomic hydrogen can either recombine to
form molecular hydrogen (H2) and bubble off the metal surface or it can remain in the atomic form and may
diffuse into the steel. The presence of hydrogen sulfide and other compounds called hydrogen recombination
"poisons" promote hydrogen absorption. This can, in turn, lead to problems associated with the various forms
of wet H2S cracking: blistering, hydrogen induced cracking, stress oriented hydrogen induced cracking and
sulfide stress cracking. There have been several intrusive and non-intrusive devices designed to monitor
hydrogen absorption called hydrogen probes. Intrusive probes are actually inserted into the vessel of pipe
section of interest. They consist of a steel sensing element which has a hollow space inside connected to a
pressure sensing devise which monitors the build up of pressure in this hollow space. Atomic hydrogen forms
on the external surface of the probe as a result of sulfide corrosion and diffuses through the steel element.
Once inside of the hollow space, it will recombine to form molecular hydrogen which can not escape. The rate
of hydrogen pressure build-up should be proportional to the severity of hydrogen absorption. Non-intrusive
hydrogen probes have also been designed that utilize an externally applied cell of patch to monitoring the rate
of hydrogen egress from the outer surface of the steel pipe or vessel wall. These non-intrusive devises can
utilize relatively simple sensing elements such as a patch and gauge on the outer surface which traps
hydrogen. Conversely, the more sophisticated probes utilize an electrochemical cell which reacts the hydrogen
as it exists the outer surface of the steel to produce a current signal.

The limitations of hydrogen probe monitoring are numerous, but still, such techniques can be of benefit by
providing at least qualitative information which can be used to monitoring the severity of hydrogen charging and
the potential for hydrogen-related cracking of exposed process equipment.

Most importantly, hydrogen probe data may not correlate with weight loss corrosion since corrosion rate is only
one of the factors involved in defining the severity of hydrogen charging. Secondly, the diffusivity of hydrogen in
steel is changes rapidly with temperature, composition and microstructure which can produce large differences
in hydrogen probe measurements. For more quantitative monitoring applications, such considerations must be
included in the analysis of the data. Finally, non-intrusive probes and in some cases even intrusive probes can
be subject to error or delays in reading transients. This is particularly a problem when non-intrusive techniques
are used to monitor thick walled process equipment since processes can rapidly change in terms of hydrogen
charging severity with plant operating conditions.

CASE HISTORIES IN CORROSION MONITORING:

Corrosion monitoring is a vital part of any plant corrosion control program. It should be integrated with other
programs designed optimize the process conditions, chemical injection and inspection to recognize the full
potential to successfully management plant operations.

CHEMICAL INJECTION
Typical oilfield, pipeline, and industrial process plants may have dozens of process additives including
antifoulants, corrosion inhibitors, neutralizers, emulsion breakers, biocides and scale inhibitors. Due to the
number of additives and the complexity and dynamic nature of process environments it is very difficult to
properly simulate these situations to optimize performance or to identify potential interactions or complications.
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CORROSION MONITORING IN OILFIELD, PIPELINE,
AND INDUSTRIAL PROCESSES

Therefore, in-plant corrosion monitoring is essential in most processes so that protection and long terms
serviceability of equipment can be assured. This approach is gaining in popularity as plant operators are
focusing on maintaining capital assets, minimizing equipment damage, downtime and lost production in an
effort to maximizing profits.
Suitable corrosion monitoring devises need to be utilized which are compatible with the nature of the process
media. An evaluation of the process and the intended corrosion monitoring requirements needs to be
conducted. For example, the locations of injection and distribution of the aqueous phase and the injected
chemicals through the system are important conditions. This will usually dictate the proper location and type of
equipment required for optimum results. Corrosion monitoring locations should be located in sites where water
will condense, pool or impinge since corrosion is usually the worst in these locations. Coupons should be
installed for long term (e.g. on overlapping 30 to 90 day intervals) baseline corrosion rates as some locations.
The exposure interval (in days) for coupons should be typically between 80 to 300 times 1/C.R. in mpy where
C.R. is the anticipated corrosion rate.

DEW POINT
Overhead systems are a particular problem area due to the potential for precipitation and the influence of acidic
and chloride-containing condensates. Effective corrosion monitoring can take many forms and in most cases
involves multiple sources of data. These range from inspections during a unit turnaround. A visual observation
of corrosive damage is valuable information since prediction of the exact location of highest corrosivity and the
effectiveness of injected chemicals used for neutralization and corrosion inhibition. This information may be
useful in the verification that the present corrosion monitoring sites are adequate or for identification of other
more appropriate corrosion monitoring sites. Samples of corrosion deposits can also be analyzed to determine
the nature of the corrosion and the reactive species causing the attack.

Retractable corrosion coupons and ER probes are valuable only if placed in a region of potential corrosion. For
example, corrosion rates are generally higher before coolers and lower after the condenser, presumably due to
the removal of water by the condenser. One complication is that the location and severity of corrosion may vary
with feedstock and plant operating conditions since these can influence the location and amount of water
precipitated and the amounts of corrodants.

This often places some degree of uncertainty in dew point corrosion monitoring. Therefore, corrosion data at
fixed sites is usually supplemented by ultrasonic inspection, radiography and visual examination, where and
when possible.

One way to reduce the need for multiple corrosion monitoring sites is to utilize modern corrosion monitoring
technology. A more sophisticated corrosion monitoring probe can be employed which has multiple sensors
types and where the temperature of the sensing element can be controlled while making corrosion
measurements.

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 TECHNICAL BULLETIN
CORROSION MONITORING IN OILFIELD, PIPELINE,
AND INDUSTRIAL PROCESSES

Copyrighted Information

Disclaimer of Liability: Synergy Services, Inc. (Synergy) warrants to purchasers, but no third parties or others, the specifications for the
product shall fall with a generally recognized range for typical properties established by Synergy when the product departs from
Synergys point of origin and that any services shall only be performed in WARRANTY OF MERCHANTABLITILY OR FITNESS FOR A
PARTICULAR PURPOSE, REGARDING ANY SERVICES PERFORMED OR PRODUCT SUPPLIED. Synergy will give purchaser the
benefit of Synergys best judgment in making interpretations of data, but does not guarantee the accuracy or correctness of such
interpretations. Synergys recommendations contained herein are advisory only and without representation as to the results. Synergy
shall not be liable for any indirect, special, punitive, exemplary or consequential damages or losses from any cause whatsoever
including but not limited to its negligence.