LIBRO- CORROSION ENGINEERING

The Study of Corrosion

To the great majority of people, corrosion means rust, an almost

universal object of hatred. Rust is, of course, the name which has
more recently been specifically reserved for the corrosion of iron,
while corrosion is the destructive phenomenon which affects almost
all metals. Although iron was not the first metal used by man, it has
certainly been the most used, and must have been one of the first on
which serious corrosion problems were encountered [1].
Greek philosophers viewed the physical world as matter organized
in the form of bodies having length, breadth, and depth that could act
and be acted upon. They also believed that these bodies made up a
material continuum unpunctuated by voids. Within such a universe,
they speculated about the creation and destruction of bodies, their
causes, the essence they consisted of, and the purpose they existed for.
Surfaces did not fit easily into these ancient pictures of the world, even
those painted by the atomists, who admitted to the existence of voids.
The problem of defining the boundary or limit of a body or between
two adjacent bodies led Aristotle (fourth century BC) and others to
deny that a surface has any substance. Given Aristotles dominance in
ancient philosophy, his view of surfaces persisted for many centuries,
and may have delayed serious theoretical speculation about the nature
of solid surfaces [2].
Perhaps the only ancient scientific account of surfaces is to be
found in some passages of the great Roman philosopher Pliny the
Elder (2379 AD) who wrote at length about ferrum corrumpitur, or
spoiled iron. By his time the Roman Empire had been established as
the worlds foremost civilization, a distinction due partly to the
extensive use of iron for weaponry and other artifacts that were, of
course, highly subject to rust and corrosion.
Pliny described corrosion phenomena taking place at the surface
of metals, as well as remedies for minimizing the effects of corrosion.
His reference to the use of oil as a means of protecting bronze objects
against corrosion, as well as of allowing the soldering of lead surfaces,
has been unambiguously verified by modern chemical analysis of
Roman artifacts. According to Pliny, surfaces act as bodies that interact
with each other and external agents. Pliny also speculated on the
causes of metal corrosion (air and fire).
Numerous scientific and engineering discoveries have been made
since then and the general understanding of corrosion mechanisms
has progressed with these. Some of the discoveries that have improved
the field of corrosion are listed in App. A (Historical Perspective). By
the turn of the twentieth century the basic processes behind the
corrosion of iron and steel were relatively well understood. One of
the first modern textbooks on corrosion prevention and control was
published by McGraw-Hill in 1910 [3]. The following are some
excerpts that illustrate the state of knowledge when this landmark
text came out
1. Trethewey KR, Chamberlain J. Corrosion for Science and Engineering. 2nd ed.
Burnt Mill, UK: Longman Scientific & Technical, 1995.
2. Paparazzo E. Surfaceslost and found. Nature Materials 2003; 2: 3513.
3. Cushman AS, Gardner HA. The Corrosion and Preservation of Iron and Steel. New
York: McGraw-Hill, 1910.

Why Metals Corrode

The driving force that causes metals to corrode is a natural consequence

of their temporary existence in metallic form. In order to produce
metals starting from naturally occurring minerals and ores, it is
necessary to provide a certain amount of energy. It is therefore only
natural that when these metals are exposed to their environments they
would revert back to the original state in which they were found.
A typical cycle is illustrated by iron. The primary corrosion product of
iron, for example, is Fe(OH)2 (or more likely FeOnH2O), but the action
of oxygen and water can yield other products having different colors:
Fe2O3H2O or hydrous ferrous oxide, sometimes written as
Fe(OH)3, is the principal component of red-brown rust. It can
form a mineral called hematite, the most common iron ore.
Fe3O4H2O or hydrated magnetite, also called ferrous ferrite
(Fe2O3FeO), is most often green but can be deep blue in the
presence of organic complexants.
Fe3O4 or magnetite is black.
The energy required to convert iron ore to metallic iron is returned
when the iron corrodes to form the original compound. Table 2.1
describes the results of x-ray diffraction of products found on
specimens exposed to real environments where it can be seen that the
metals often revert to naturally occurring mineral forms during the
corrosion process [1]. The amount of energy required and stored in a
metal or that is freed by its corrosion varies from metal to metal. It is
relatively high for metals such as magnesium, aluminum, and iron,
and relatively low for metals such as copper, silver, and gold. Table 2.2
lists a few metals in order of diminishing amounts of energy required
to convert them from their oxides to metal.
The high reactivity of magnesium and aluminum expressed as
energy in Table 2.2 is paralleled by the special efforts that were
historically required to transform these metals from their respective
ores. The industrial process to produce aluminum metal on a large
scale, for example, was only invented at the end of the nineteenth
century and objects made of this metal were still considered to be a
novelty when the 2.85-kg aluminum cap was set as the last piece of
the Washington Monument in 1884. Aluminum was then considered
to be a precious metal.
The energy difference between metals and their ores can be
expressed in electrical terms that are in turn related to heats of
formation of the compounds. The difficulty of extracting metals from
their ores in terms of the energy required, and the consequent
tendency to release this energy by corrosion, is reflected by the relative
positions of pure metals in a list, which is discussed later as the
electromotive series in Chap. 4.

Types of Corrosive Atmospheres

While atmospheres have been traditionally classified into four basic

types, most environments are in fact mixed and present no clear
demarcation. Furthermore, the type of atmosphere may vary with the
wind pattern, particularly where corrosive pollutants are present, or
with local conditions (Fig. 9.2) [2].

Industrial
An industrial atmosphere is characterized by pollution composed
mainly of sulfur compounds such as sulfur dioxide (SO2), a precursor to
acid rain, and nitrogen oxides (NOx), the backbone of smog in modern
cities. Sulfur dioxide from burning coal or other fossil fuels is picked up
by moisture on dust particles as sulfurous acid. This is oxidized by some
catalytic process on the dust particles to sulfuric acid, which settles in
microscopic droplets and fall as acid rain on exposed surfaces. The
result is that contaminants in an industrial atmosphere, plus dew or fog,
produce a highly corrosive, wet, acid film on exposed surfaces.
In addition to the normal industrial atmosphere in or near
chemical plants, other corrosive pollutants may be present. These are
usually various forms of chloride which may be much more corrosive
than the acid sulfates. The reactivity of acid chlorides with most
metals is more pronounced than the reactivity of other pollutants
such as phosphates and nitrates.

Marine
A marine atmosphere is laden with fine particles of sea mist carried
by the wind to settle on exposed surfaces as salt crystals. The quantity
of salt deposited may vary greatly with wind velocity and it may, in
extreme weather conditions, even form a very corrosive salt crust,
similar to what is experienced on a regular basis by sea patrolling
aircraft or helicopters [Figs. 9.3(a) and (b)].
The quantity of salt contamination decreases with distance from the
ocean, and is greatly affected by wind currents. The marine atmosphere
also includes the space above the sea surfaces where splashing and
heavy sea spray are encountered. The equipment exposed to these splash
zones are indeed subjected to the worst conditions of intermittent
immersion with wet and dry cycling of the corrosive agent (Fig. 9.4).

Rural
Rural atmospheres are typically the most benign and do not contain
strong chemical contaminants, that is unless one is close to a farm
extremely corrosive to most metals.
Arid or tropical atmospheres are special variations of the rural
atmosphere. In arid climates there is little or no rainfall, but there
may be a high relative humidity and occasional condensation. This
situation is encountered along the desert coast of northern Africa. In
the Tropics, in addition to the high average temperature, the daily
cycle includes a high relative humidity, intense sunlight, and long
periods of condensation during the night. In sheltered areas, the
wetness from condensation may persist long after sunrise. Such
conditions may produce a highly corrosive environment

Indoor
Normal indoor atmospheres are generally considered to be quite
mild when ambient humidity and other corrosive components are
under control. However, some combinations of conditions may
actually cause relatively severe corrosion problems. While there is no

typical contaminant or set of conditions associated with an indoor

atmosphere, any enclosed space which is not evacuated or filled with
a liquid can be considered an indoor atmosphere. If not ventilated,
such an environment may contain fumes, which in the presence of
condensation or high humidity could prove to be highly corrosive.
Even in the absence of any other corrosive agent, the constant
condensation on a cold metallic surface may cause an environment similar
to constant immersion for which a component may not have been chosen
or prepared for. Such systems are commonly encountered in confined
areas close to ground level or, worse, below ground where high humidity
may prevail. Figure 9.5 shows the advanced corrosion of the frame and
contacts in an electric junction box only four years after a building was
completed. While the junction box in this example was only at the ground
level, the wires coming to the box were buried without additional
insulation and in constant contact with much cooler ground than ambient
air in the room. The repeated condensation of ambient humidity on the
electrical box support and on many of its connections caused enough
corrosion in such a short period of time to require the complete replacement
of the system to avoid unscheduled power interruptions.

Deteccin de corrosin en el fondo de un pozo (pag 48)

http://www.slb.com/~/media/Files/resources/oilfield_review/spanish10/sum10/composito.pdf