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CORROSION
reaction. The anode and cathode are called electrodes. The anode is the
electrode at which oxidation occurs or where electricity leaves the metal and
enters the electrolyte. For iron, the anode reaction is shown in equation (1),
where iron is oxidized to the ferrous ion.
Fe = Fe++ + 2eH+ = H2 eReduction occurs at the cathode. An example is the reduction of hydrogen ion,
shown in equation (2).
The electrolyte of interest here is water. Its function is not only to carry
corrosive materials to the surface but also to provide a medium of electron
transfer utilizing ions. Any connection, excluding the electrolyte, between the
anode and the cathode is an external connection. Anodes and cathodes both
exist on steel surfaces. The body of the steel serves as an external connection.
The severity of corrosion depends upon the potential generated between the
anode and cathode.
A good example of corrosion is a dry cell. The center carbon electrode is
the cathode. A zinc case serves as anode. These electrodes are separated by an
electrolyte that is essentially ammonium chloride solution. When an external
connection in the form of a flashlight bulb is attached, corrosion occurs as zinc
goes into solution, and the bulb glows. The greater the flow of electricity
through the cell, the greater is the amount of zinc that corrodes. The
relationship between the amount of zinc corroding and the flow of current is
quantitative.
Galvanic corrosion
Galvanic corrosion occurs where two different metals or alloys come in
contact. The severity of galvanic corrosion depends upon the difference in
potential between the two metals, and the relative size of the cathode and
anode areas. The galvanic series for metals and alloys in seawater in table (1).
Active metals are at the top of the series. Coupling a metal near the top with
one near the bottom will cause galvanic corrosion of the more active metal.
If the area of the active metal is very large compared with the area of
less active metal, corrosion will not be so severe. Polarization will also modify the
amount of current flowing during the corrosion reaction.
Water in the Corrosion Process
The presence of water is essential to the low temperature corrosion
process. However, pure water containing no dissolved substances is only very
mildly corrosive to iron. Since iron is anodic to hydrogen in pure water, the iron
corrodes to produce hydrogen gas and ferrous hydroxide, which raises the pH of
the water. The attack proceeds until the solubility of ferrous hydroxide is
exceeded and the ferrous hydroxide deposits on the metal surface in the form
of a film, smothering the corrosion reaction.
Water containing impurities or dissolved substances can be corrosive or
non-corrosive, depending on the nature of the dissolved substances. Chromates
and phosphates are dissolved in water to inhibit or reduce corrosion. Other
substances such as salts, acids, hydrogen sulphite, carbon dioxide, and oxygen
can increase corrosivity of the water. Generally, the water encountered in oil
field operations contains one or more of these substances, which increase its
corrosivity.
In addition to the impurities, which are commonly found in water,
temperature and velocity also influence the corrosivity of water. Seldom is a
corrosion problem encountered where only one of these contributing factors is
present. Generally, the problem is complex because of these various influences
and the manner in which they may interact with each other.
Influence of Dissolved Oxygen
Oxygen dissolved in water is probably the most troublesome corrosion
producing substance. The product of corrosion of iron by oxygen containing
water is a mixture of iron oxides, usually hydrated, and generally referred to as
rust. The following equations illustrate this in the simplest form and in water
containing only dissolved oxygen.
Fe + 2 H
2H
2 Fe
= Fe
++
+ 2 H0
+ O 2 = H 2O
++
+ O2 + H 2 O = 2 Fe+++ + 2 OH
The action of the oxygen is twofold, it depolarizes the cathode, and it oxidizes
the ferrous ions to ferric ions, which form the insoluble (above pH = 3) ferric
hydroxide. If the formation of ferric hydroxide occurs out of contact with the
is
formed
first
in
both
cases.
However,
at
high
oxygen
cathodic
reaction
products
precipitate
calcium
and
magnesium
compounds, which deposit on the iron and shield a part of it from the aerated
solution. Since this shielded area is deprived of oxygen, corrosion occurs here at
the water line.
compositions of essentially the same alloy. A 10 mpy difference has been found
in the corrosion rates of two copper-bearing mild steel samples exposed to
water saturated with the same mixture of oxygen, carbon dioxide, and hydrogen
sulfide. This indicates the possibility of incurring an error in comparing the
corrosivity of two environments on the basis of corrosion of steel tubing or flow
lines without considering the compositions of the steels.
Influence of dissolved salts
Salts dissolved in water have a marked influence on the corrosivity of
water. At extremely low concentrations of dissolved salts, different anions and
cations show varying degrees of influence on the corrosivity of the water. The
anions most commonly found in water are chloride, sulphate and bicarbonate. The
effect on the corrosivity of distilled water to steel resulting from the addition
of these ions is shown in figure (1). In the concentration range shown in this
graph, the sulphate ion has a greater effect on the corrosivity of the water
than the chloride ion, and the bicarbonate ion shows inhibitive tendencies. In
solutions containing bicarbonate ion along with either chloride or sulphate ion at
concentrations up to 100 ppm, the bicarbonate ion showed increasing inhibition
with increasing concentration but did not entirely prevent corrosion.
The influence of the anion on corrosivity also depends upon the metal in
question. Waters containing sulphate ion would not seriously corrode lead
because of the formation of lead sulphate on the surface of the lead. The
corrosion rate of stainless steel is greater in 0.1 mole potassium chloride than in
0.1 mole potassium sulphate because of greater penetration of the protective
oxygen or oxide coating by the chloride ion. The order of decreasing penetrating
power of anions has been given as :
chloride > bromide > iodide > fluoride > sulphate > nitrate > monohydrogen
phosphate.
Water solutions containing equal concentrations of salts of the same anion
but different cations show different degrees of corrosivity of mild steel. With
alkali metal chlorides, the corrosion rate is the greatest in potassium chloride
solutions, less in sodium chloride solutions, and lowest in lithium chloride
solutions. The order of decreasing corrosiveness of cations has been given as:
ferric > chromic > ammonium > aluminium > potassium > sodium > lithium > barium >
strontium > calcium > manganese > cadmium > magnesium.
Generally, the corrosivity of waters containing dissolved salts increases
with increasing salt concentration until a maximum is reached,
(NaAlO2) -
and
the
corrosion rate
continues
to
increase
with
increasing
temperature. If the temperature increase is not uniform over the metal system,
the hotter areas
Influence of velocity
The flow of water over a metal surface influences the corrosion rate
chiefly through the effects of water movement on the other factors governing
corrosion. In stagnant waters or waters at zero velocity, the general corrosion
rate is usually low, but localized or pitting corrosion may occur. Generally, some
motion in a corrosive system causes greater uniformity and results in a thinning
type of corrosion rather pitting. Turbulence may occur at high velocities, and it
may result in non-uniform conditions that lead to pitting corrosion.
Corrosion Prevention Techniques
Water treatment
-de-aeration:
problem is often found. Otherwise, the solution to the corrosion problem may
require extensive modification and replacement of equipment or installation of
water treatment equipment.
Many commercially prepared corrosion inhibitors used in the oil field
contain surface active agents. When these are added to a system for the first
time, they remove loose deposits of corrosion products. Precautions should be
taken to prevent these deposits from accumulating in equipment or in injection
wells in order to prevent plugging.
Cathodic protection
Cathodic protection consists of applying an electrical current to the
surface of the metal to be protected in such a way that it will become a
cathodic area. The current is applied externally, so that a net positive current
enters all areas of the metal, including those that were previously anodic.
Cathodic protection is applied to protect steel, brass, lead, copper and aluminium
against corrosion when these metals are immersed in water.
Cathodic protection is particularly useful in protecting the submersed
areas of water tanks and filters. Since only the areas below the water line are
protected, other methods must be used to protect metal above the water line.
Inorganic coatings
Vitreous enamels, cement lining, phosphate coatings and oxide coatings
represent inorganic coatings. Vitreous elements or glass coatings are very
corrosion-resisted but somewhat brittle. Cement coatings are very popular for
lining water flow lines.
Organic coatings
organic coatings are the most widely used means of protecting against
corrosion. These coatings represent a large variety of materials that can be
classified as paint, enamel, lacquer, and plastic linings. In recent years, plastic
linings have found frequent usage in protecting tubing, flowlines, and tanks from
corrosion. The surface preparation and application of these coatings is very
important in the success of the coating.
Use of plastics
Generally, plastics are used in applications where temperatures and
pressures are low. Plastic pipe is frequently used for flow lines with particularly
corrosive oilfield brines.
Metals
Metals resistant to corrosion are available for virtually all corrosive
environments encountered in the oil field. The limitation on the use of many of
these metals, such as platinum and gold, is their cost. There are many other
metals and alloys, whose cost is only slightly more than steel, that are resistant
to corrosion in specific applications.
The choice of a metal to resist corrosion in a specific application is
governed by the nature of the corrosive environment, use of the equipment, and
cost. In the oil field, the greatest use of corrosion resistant metals is for pumps
and meters. Here, the amount of metal required is not large and the ability to
resist corrosion necessary. Whenever a metal other than steel is used and is
joined to steel lines, it is important to take precautions to avoid galvanic
corrosion.