section 12

corrosion

corrosion
 section 12

corrosion
section 12 Scomi Oiltools

corrosion defined 2
why does corrosion occur? 2
what environments assist corrosion? 2
main types of corrosion 2
main causes of corrosion 3
main types of corrosion inhibitor 3
mode of operation of corrosion inhibitors 4
the effect of pH on corrosion of metals 5
controlling corrosion in wbm with film-forming
products 6
measurement of corrosion rate 7
corrosion coupon / rings 8
interpreting corrosion coupon analysis 8
Section

12 corrosion

corrosion
corrosion defined
Corrosion is the destruction of any substance, particularly metals, by a reaction with its environment.
Corrosion cannot be stopped, only controlled. Safety and economics are the main considerations when
implementing a corrosion control programme.

why does corrosion occur?

Most metals occur in nature as reacted ones e.g., haematite, iron oxide or pyrites, iron sulphide. The
production of pure metal from these ores requires a large input in energy, thus the pure metal is unstable
and is always trying to return to a low energy ore state. Corrosion is therefore an electrochemical process.

what environments assist corrosion?

For corrosion to occur, three conditions must be satisfied;

ƒ Obviously the metal must be present, e.g. iron.

ƒ A conducting medium must be present, e.g. Brine.
ƒ A dissolved gas must be present, e.g. oxygen.

If any of these three are missing corrosion will not occur. The presence of all three will allow the
following reduction - oxidation reactions to take place.

OXIDATION Fe -> Fe2+ + 2e- ANODE

REDUCTION 02 + H20 + 4e- -> 4OH- CATHODE

The hydroxyl ions will combine with the ferrous ion to produce ferrous hydroxide with subsequent
metal loss from the anode surface.

main types of corrosion

There are many types of corrosion, but of particular interest in connection with the use of drilling
fluids, particularly water based fluids, are:

Uniform Corrosion
This is the most common and desirable form of corrosion caused by continuous shifting of anode and
cathode sites resulting in a uniform metal loss over the entire metal surface.

Pitting Corrosion
One of the most destructive forms, caused by permanent location of anodic and cathodic sites. Since
anodic sites are small in area, this results in the formation of deep pits on the surface at the anodic sites
which ultimately penetrate the metal causing washouts and possible twist-offs.

Crevices Corrosion
Crevices in metal surfaces e.g., tool joints, allow entrapment of fluid which then changes its
composition producing an anodic site where corrosion is concentrated, often resulting in tool joint
failures.

Stress Corrosion
When a metal is subjected to stress, such as at a tool joint by over torquing, the stressed area becomes
anodic and corrosion is concentrated in that area resulting in failures.


Hydrogen Embrittlement
This type of corrosion is seen particularly when hydrogen sulphide is present. The absorption
of atomic hydrogen into the crystal structure of the metal, via intergranular crevices, and the
subsequent combination of hydrogen atoms to form hydrogen molecules, results in embrittlement
of the metal and a loss of tensile strength and ductility.

main causes of corrosion

The main contributors to corrosion in water based muds are as follows.

Dissolved and Entrapped Oxygen

By far the most common cause of corrosion, levels as low as 1 ppm can substantially increase
corrosion rates. The higher the oxygen concentration the faster the rate of corrosion. Oxygen from
the atmosphere is incorporated into the system, especially at the shakers, and via mixing hoppers.
It is a potential problem especially with low solids, high yield point polymer systems. As the mud is
pumped downhole, the temperature rises, oxygen comes out of solution and directly reacts with the
metal surfaces.

Carbon Dioxide
If the pH of the mud is allowed to fall as the result of carbon dioxide intrusion, carbonic acid will
be produced which will directly attack metal surfaces and in the presence of dissolved oxygen the
rate of corrosion will be greatly increased. The type of corrosion occurring will be predominantly
pitting so every effort should be made to prevent or redress a pH drop. The source of carbon dioxide
is redominantly from formations, but may be as a result of the thermal decomposition of mud
additives such as organic polymers.

Hydrogen Sulphide
The presence of hydrogen sulphide, even in very small quantities and particularly in the presence
of dissolved oxygen, may give rise to catastrophic failures of drilling equipment. The source of H2S is
often the formation itself but may be caused by thermal degradation of drilling fluid additives
containing sulphur such as lignosulphonates, or by the action of sulphate reducing bacteria (SRB) on
sulphate scales under anaerobic conditions.

Soluble Salts
In combination with dissolved gases soluble salts will invariably increase corrosion rates due to increased
conductivity of the fluid phase up to a limiting point. Above this point an increase in salinity may
reduce corrosion rates due to lower oxygen solubilities. For example the most corrosive concentration
of sodium chloride occurs when the chlorides reach approximately 20,000 mg/l (roughly equivalent to
seawater).

main types of corrosion inhibitor

The two primary types of corrosion inhibitor are oxygen scavengers and film-forming amines.
Chromate and phosphate derivatives have also been used. Other types of chemical which are
added to mud systems primarily to combat different problems but which assist in the prevention of
corrosion are hydrogen sulphide scavengers, biocides and scale inhibitors. Control of pH also
provides corrosion inhibition.


Section

12 corrosion

mode of operation of corrosion inhibitors

oxygen scavengers
Most commonly these are simple chemical compounds such as sodium sulphite or ammonium
bisulphite, OX-SCAV, OX-SCAV S, which dissolve into the drilling fluid to provide an ion in a reduced
state, in these cases sulphite, which will then react with dissolved oxygen in the mud to produce a
stable ion, in these cases sulphate, resulting in the permanent removal of oxygen from the fluid. The
main advantage of this type of product is that it removes the primary cause of most types of corrosion;
very little corrosion can occur in the complete absence of oxygen, the exception being hydrogen
sulphide induced corrosion.

The major drawback of oxygen scavengers is that they also scavenge atmospheric oxygen when
the fluid is in contact with air. For this reason, the best results are obtained when an injection pump
is used to add oxygen scavenger to a mud system in order to prevent the chemical reacting with air
before it can react with dissolved oxygen in the mud. Air is continually being mixed into circulating
mud systems, particularly at the shale shakers and at the hopper and therefore oxygen scavenger
needs to be added on a continual basis which can lead to high treatment costs. Normal practice is to
measure the concentration of the scavenger at the flowline and to maintain an excess of scavenger at
all times. For foam and mist drilling, it is usually economically impractical to add oxygen scavenger.

film-forming amines
These are solutions of organic amines, HYDRO-FILM and HYDRAMINE, which, due to their charged
nature, are attracted to metal surfaces forming a film on them. This film acts as a barrier between the
metal and the dissolved oxygen in the mud. This barrier formation is the main advantage of this type
of product as no other product can achieve the same effect. Some disadvantages do however exist.
If insufficient material is added to completely coat all metal surfaces, corrosion cells can be set up
between protected and unprotected metal surfaces which can actually enhance corrosion.

Most film-forming amines are not soluble in water therefore they must be applied as a solution in
oil/base fluid or some other organic chemical as a carrier. As a result, large treatments can have an
adverse effect on drilling fluid rheology and it may be undesirable / impossible to add the carrier to a
system for environmental reasons.

chromates/phosphates
These chemicals have been used in the past primarily in mist and foam drilling where it is not possible
to use oxygen scavengers. These inhibitors work by chemically interfering with the electrical current
necessary to form corrosion cells.

With present levels of concern about the environment, chromium compounds are now seldom used
and they have been largely replaced by phosphates. Phosphate inhibitors are most effective in low pH,
fresh water systems and solids free systems where field evidence has shown that a concentration of
between 70 and 120 mg/litre is effective in controlling corrosion.

hydrogen sulphide scavengers

H2S has long been recognised as a major contributor to corrosion and a variety of products exist
to remove hydrogen sulphide from a mud system. The majority are based on zinc and work by
releasing zinc ions into the mud which then react with sulphide ions, removing them from the system
as insoluble zinc sulphide. Some iron compounds have been used but these can promote abrasion
due to their hardness and their high density makes them difficult to suspend.


Typical zinc-containing products are zinc carbonate, zinc oxide and zinc chelates. The carbonate and
oxide are relatively insoluble which leads to a fairly slow reaction rate. Zinc chelates are the most
efficient scavengers in terms of reaction rate as they are supplied as solutions and the dissolved zinc
ion is immediately available for reaction with any sulphides present.

biocides
Micro-organisms contribute to corrosion in different ways. Some utilise any available hydrogen and
act as cathodic depolarisers, creating corrosion cells while others form slimes or growths which shield
a portion of the metal and form an oxygen concentration cell. In aerobic environments, the species
thiobacillus accounts for the majority of the corrosion by converting sulphur to sulphuric acid which
stimulates corrosive attack of metals.

Sulphate-reducing bacteria are found in anaerobic environments. These bacteria contribute to

corrosion both by direct attack of iron by hydrogen sulphide, produced by the bacteria, to form iron
sulphide and by cathodic depolarisation. Even in aerobic systems, sulphate-reducing bacteria may be
found within active corrosion pit areas where the oxygen content becomes low.

Broad-spectrum biocides, Isothiazolin and Glutaraldehyde are usually employed in drilling fluids
so that a single treatment is effective against all likely species. Drawbacks of biocides are that they
tend to be expensive and many are adversely affected by temperature, salt concentration and other
treatment chemicals. Compatibility tests with the other mud chemicals should be conducted for all
biocides prior to use.

scale inhibitors
A very wide variety of chemical types are used as scale inhibitors, a typical one being an aqueous
solution of polyacrylate. All these chemicals function by interfering with the deposition of scaling
compounds such as sulphates and carbonates onto the metal surfaces.

These chemicals have a limited ability to protect metal surfaces. They can however make some
contribution to preventing corrosion although none are likely to be as effective as purpose designed
corrosion inhibitors.

the effect of ph on corrosion of metals

pH is the measure of the hydrogen ion concentration in an aqueous system. As hydrogen ions are in
equilibrium with hydroxyl ions the pH can be seen to be directly related to the concentration of both
ions. Hydrogen ions and hydroxyl ions can both play a major part in chemical reactions which result in
corrosion of metal although the relationship between pH and corrosion is complicated.

The importance of the hydrogen ion lies in its ability to interact with a metal surface. Many metals
form an oxidised surface region, the outermost atomic layer of which often contains hydroxide-
like species when water is present. Such a structure would tend to have a dependence on hydrogen
ion concentration. Thus, under a number of conditions, the hydrogen ion concentration can influence
corrosion through the equilibrium that exists between it, water and the hydroxide ion formed on the
metal surface. This interaction often results in a corrosion rate which is proportional to the hydrogen
ion concentration. As pH is measured on a logarithmic scale, this dependence can produce a ten-fold
increase in the rate of corrosion for a change of 1 in pH.


Section

12 corrosion

Iron and carbon steel exhibit a complex dependence of the corrosion rate on pH. At low pH, the rate
of corrosion is dependent not only on the hydrogen ion concentration but also on the counter ions
present. For example, the corrosion rate of steel in sulphuric acid at pH 3 is not the same as in hydrochloric
acid at the same pH.

Under near-neutral conditions (5< pH <9), pH does not in most cases play a direct role in corrosion.
Under more strongly acidic conditions, the oxide or hydroxide layers tend to dissolve thus
exposing fresh metal for attack. At pH levels near neutral, these layers tend to remain on the surface.
The layers have significant structure which tends to be determined by the anions present in solution.
Under these circumstances, the major reaction governing corrosion is the reduction of oxygen present
in solution.

The oxygen ions produced as a result of this reduction then attack metal surfaces. The presence of
chloride ions and oxygen play a much more dominant role than pH under these conditions, possibly
changing the mechanism from one of uniform attack to localised attack. Under near-neutral conditions,
the use of an oxygen scavenger is one of the most effective ways to combat corrosion.

Under more strongly alkaline conditions (pH >9), corrosion mechanisms are somewhat different. The
main mechanism being the formation of soluble metal hydroxides which because of their solubility,
continually expose fresh metal to attack. Metals or alloys which are resistant to corrosion at high
pH levels are usually those which form an insoluble hydroxide layer which then protects the metal
beneath it.

In a number of cases, corrosion rates increase with increasing pH while in others, corrosion occurs
where none was present at lower pH. These two types of behaviour represents most metals and
alloys. Corrosion of iron persists even at high pH and is caused by the formation of soluble iron
tri-hydroxide particularly in the presence of sodium hydroxide. A number of metals exhibit a very
marked increase in rate of corrosion with increase in pH. Among these are aluminium, zinc and lead.
Aluminium corrosion increases very dramatically, increasing by almost two orders of magnitude
between pH 8 and pH 10.

In summary, pH has a direct effect on rates of corrosion at both high and low values. Under these
strongly acidic or alkaline conditions, corrosion can be very severe although it should be remembered
that other factors such as anion type and concentrations can exacerbate or ameliorate this effect. At
intermediate pH values the concentration of oxygen in the system has a much greater effect on
corrosion rate than the direct effect of pH.

controlling corrosion in wbm with film-forming products

Corrosion can be a severe problem when drilling with water-based muds in certain environments.
Recognition of the causes of corrosion has led to the development of numerous techniques for its
control. It is well known that environmental compounds such as oxygen, carbon dioxide, hydrogen
sulphide and dissolved salts accelerate rates of corrosion. Techniques used to offset the effects of these
components include dilution, concentration, precipitation, neutralisation and chemical inhibition.

The use of chemical corrosion inhibitors is an example of the last of these techniques.

Water-based muds present corrosion problems primarily because they are subject to contamination
from corrosion accelerators such as oxygen, carbon dioxide, hydrogen sulphide or salts that are always
present in varying quantities. A recent study has, for example, correlated the amount of pitting corrosion
with oxygen contamination. Examination of the corrosion by-products has in many cases revealed
oxides of iron, clearly indicating the involvement of oxygen in surface corrosion.


Film-forming organic amines are frequently used as corrosion inhibitors. These anionic materials
adsorb strongly onto metal surfaces creating a film which prevents the contact of oxygen and other
gases with the metal, thus preventing corrosion. Experience has shown that these chemicals are
ineffective at low concentrations as partial coverage of metal surfaces leads to the development of
concentration cells.

Ionic concentrations on the metal surface underneath the inhibitor film will be different from the
concentrations on untreated metal surfaces and where the two meet, a corrosion cell will be set up.
Under these conditions, localised corrosion rates can exceed those which would prevail if no inhibitor
was added. In fluids contaminated with oxygen (i.e., most muds), concentration cells act as serious
pitting accelerators. The presence of scale or other barriers on metal surfaces can have the same effect.

Film-forming amines are most effective when applied as a solution in oil directly to the metal surface.
In one study, a corrosion rate of 455 mils per year, mpy, while drilling with untreated mud was reduced
to 88 mpy by pumping 4 gallons of amine inhibitor down the drill string every 30 minutes while
drilling. Because film-forming amines have the ability to displace water in surface pitting and cracks,
they are extremely useful in drilling fluid environments.

One major drawback of this type of chemical is that they will adsorb strongly on the surfaces of solids
in the drilling fluid (both barite and drilled solids) and thereby lose their effectiveness as inhibitors
for metal surfaces. Because of their ionic character, these products can also have a detrimental effect of
drilling fluid rheology if added directly to the mud in significant quantities.

Film-forming products are effective against hydrogen embrittlement as well as preventing oxygen-
induced corrosion. High strength steel under conditions of stress (e.g., rock bit bearings) is particularly
susceptible to hydrogen embrittlement and such steel has been known to fail in as little as five hours
when drilling in hydrogen sulphide contaminated mud. Failure occurs as hydrogen gas penetrate
the metal surface, enters the lattice of metal atoms and weakens the whole structure as a result. A
protective film of organic amine on the surface of the metal has been shown to greatly prolong the life of
steel in a hydrogen-rich environment.

Alternative products are now being produced as filming inhibitors which are non-ionic in character.
They still have a preference to adsorb onto metal surfaces, thus providing the protective film but
have a greatly reduced affinity for other solid surfaces and are also designed to spread evenly on the
metal surface, thus preventing the setting up of localised corrosion cells.

These products are chemically modified amines which have been reacted with functional groups
to give the molecules surfactant as well as filming properties. This ensures that the build up of
molecules on metal surfaces occurs evenly, one layer at a time, thus preventing partial or incomplete
coverage. At concentrations below those required to achieve a uniform mono-molecular layer, the
product does not function as a corrosion inhibitor.

measurement of corrosion rate

Methods of monitoring corrosion fall into two basic categories. Direct measurement of corrosion taking
place can be achieved by the use of corrosion coupons, see below for detailed discussion. Levels of
corrosion inhibitors / corrosive species in the drilling fluid can be monitored by chemical means. Meters
for measuring the concentration of dissolved oxygen are now available although their suitability for use
directly in solids-laden drilling fluids is still not fully proven.

Corrosive components in the mud can be measured by the Garrett Gas Train, hydrogen sulphide, carbon
dioxide, and bacteriological test-kits, to gain an indirect indication of likely corrosion potential.

Sulphite based oxygen scavengers can be measured in muds using a sulphite test-kit.


Section

12 corrosion

corrosion coupon / rings

The placement of corrosion rings in the drill string yields critical information about the corrosive nature
of drilling muds. This is particularly valid since the entire mud system circulates through the ring in the
drill string. Examination of scales, pits or general attack aids in the choice of corrective action. The
drawback of this test method is that long term exposure, minimum 40 hours, is required and accurate
analysis is not usually feasible at the well site. Data obtained is extremely useful in devising long term
corrosion control programmes but does not provide data for daily scavenger / inhibitor requirements.

The corrosion ring is machined to fit in the tool joint box recess. The inside diameter should be the
same as that of the tool joint to minimize turbulence. Unless clearly noted to the contrary the ring will be of
AISI 4130 composition of steel. The ring will be clearly marked with an identification number.

An important information record accompanies each corrosion ring. This takes the form of a packaging
envelope which comes marked with the ring identification number, the initial weight of the ring and the
calibration “K FACTOR” number.

Note: This information record should remain associated with each individual ring. If it is lost any quantitative
data on the ring becomes useless.

For best results the corrosion ring should be exposed to a minimum of 40 hours of mud circulation. If
at all possible more than one ring should be placed in the drill string. One ring is usually placed in the
tool joint at the top of the first stand above the drill collars. An additional ring should be placed in the
kelly saver sub. However, when top drives are used the only place a coupon can be put is in the goose
neck. Care should be taken to insure that the box recess is clean to prevent interference with proper
make up of the joint and to avoid damage to the ring. During installation the ring should be handled with
clean, dry gloves.

The corrosion ring information record must be filled out with the conditions prevalent when the ring
was placed in the drill string. This should include drilling fluid composition, location of the ring in the drill
string, hole depth in, date in, time in, well location, operator and any other required information.

When the corrosion ring is removed from the drill string, drilling fluid residue should be removed from
the coupon by wiping with a cloth. The ring should be visually examined for severity of corrosion or
mechanical damage. If severe corrosion is evident the cause of the corrosion should be determined
promptly so corrective action can be taken. Following the visual observations, immediately coat the
coupon with oil or grease, do not use pipe thread compound. Place the ring in a plastic bag then in the
envelope, and return to the lab for evaluation.

Complete the information record for that numbered ring. This should include the drilling fluid
composition, hole depth out, date out, time out, visual observations and total exposure time in the drill
string.

interpreting corrosion coupon analysis

Upon receipt of the corrosion coupons in the laboratory they will:

ƒ Be tested for the presence of sulphide / carbonate scale.

ƒ Be cleaned and re-weighted to determine the corrosion rate.
ƒ Be microscopically inspected for the presence of pitting corrosion.


The corrosion rate based on weight loss is calculated as follows:

Oilfield units S.I units

Corrosion rate, lb/ft2 /yr = Corrosion rate, kg/m2 /yr =

Mils per year, mpy = 24.6 x lb/ft2 /yr Mils per year, mpy = 5.03 x kg / m2 / yr

K = constant printed on the corrosion ring envelope.

The results obtained will be reported back to the company representative onshore and the mud engineer
on location together with conclusions as to the severity of the problem and recommendations as to
remedial action.

The severity of uniform corrosion rates are characterised as follows: -

Corrosion Rate (lb/ft2 /yr) Corrosion Rate (kg / m2 / yr) Severity

0 - 2 0 - 0.4082 Low (acceptable)
2 - 4 0.4082 - 0.8164 Moderate
4 - 6 0.8164 - 1.225 High
> 6 >1.225 Severe

The presence of pitting corrosion, regardless of the uniform corrosion rate, indicates a severe problem
and, after determining its cause, should be acted upon without delay. Treatment chemicals should be on
standby and used at their recommended dosage levels.

corrosion coupon analysis

The corrosion rate based on weight loss is calculated as follows:

Oilfield units S.I units

Corrosion rate, lb/ft2 /yr = Corrosion rate, kg/m2 /yr =
Weight Loss (grams) [0.2041 x Weight Loss (grams)]
xK xK
Exposure timre (hours) Exposure time (hours)
Mils per year, mpy = 24.6 x lb/ft2 /yr Mils per year, mpy = 5.03 x kg / m2 / yr

K = constant printed on the corrosion ring envelope.

The results obtained will be reported back to the company representative onshore and the mud engineer
on location together with conclusions as to the severity of the problem and recommendations as
to remedial action.

The severity of uniform corrosion rates are characterised as follows: -

Corrosion Rate (lb/ft2 /yr) Corrosion Rate (kg / m2 / yr) Severity

0 - 2 0 - 9.8 Low (acceptable)
2 - 4 9.8 - 19.6 Moderate
4 - 6 19.6 - 29.4 High
> 6 > 29.4 Severe

The presence of pitting corrosion, regardless of the uniform corrosion rate, indicates a severe problem
and, after determining its cause, should be acted upon without delay. Treatment chemicals should be on
standby and used at their recommended dosage levels.