corrosion corrosion

section 12
corrosion

section 12
corrosion

Section 12
contents
corrosion defined ................................................................................................................1
why does corrosion occur? ..............................................................................................1
what environments assist corrosion? ...........................................................................1
main types of corrosion ....................................................................................................1
main causes of corrosion ..................................................................................................2
main types of corrosion inhibitor ..................................................................................3
mode of operation of corrosion inhibitors ........................................................3
the effect of ph on corrosion of metals...............................................................6
controlling corrosion in wbm with film-forming products .........................7
measurement of corrosion rate ......................................................................................9
corrosion coupon / rings .......................................................................................10
interpreting corrosion coupon analysis ..........................................................11
01 corrosion
Section 12

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.
corrosion 02

Section 12
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
03 corrosion
Section 12

predominantly 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.

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.
corrosion 04

Section 12
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, AMI-FILM, 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.
05 corrosion
Section 12

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, CHALCO-CARB,

zinc oxide, SULF-X and zinc chelates, CHALCO-ZINC. 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, HYDRO-CIDE, KMC-CIDE, are usually

mployed 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
corrosion 06

Section 12
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.

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.
07 corrosion
Section 12

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.
corrosion 08

Section 12
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.
09 corrosion
Section 12

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.
corrosion 10

Section 12
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.
11 corrosion
Section 12

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.

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:

Corrosion rate, lb/ft2/yr =

Weight Loss /(grams)

Exposure Time (hours)
*K

mils per year, mpy = lb/ft2/yr * 24.6

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 12

Section 12
Corrosion Rate (lb/ft2/yr) Severity
0 - 2 Low (acceptable)
2 - 4 Moderate
4 - 6 High
> 6 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.