1- Corrosion Principles

1-1 Introduction:
Corrosion of metals is the deterioration of metallic structures through chemical
and/or Electrochemical Reactions between a metal surface and environment.
Corrosion, derived from Latin word (corrodere) meaning to gnaw to pieces The
Factors governing the rate of Corrosion may be broadly divided into those
relating to The Metal and The environment. The nature of the environment and
the reactions that occur at the Metal/environment Interface. The more
(1)
important factors involved may be summarized as follows (i) the Metal:
composition, the position of the metal in the electrochemical series, detailed
atomic structure, microscopic and, Contact with dissimilar metals, stress
(tensile, compressive, cyclic) (ii) the Environment: chemical nature (The
acidity or alkalinity of the liquid, Relative Humidity), concentrations of reactive
species and deleterious impurities, pressure, Temperature, velocity, Rate of
supply and distribution of oxygen.(iii) Metal/environment interface : kinetics of
metal oxidation and dissolution, Kinetics of reduction of species in solution;
nature and location of Corrosion products; film growth and film dissolution.
Corrosion Costs (2, 3, 4) 4 to 5% of the Gross National Product of the United
States, Corrosion of metals cost the U.S. economy almost $300 billion per
year at 1995 prices. Corrosion of metals is a big problem to chemical and
petrochemical industry; it gives rise to enormous financial losses through (1) Plant
shut downs because of equipment failure, (2) cost of repair and replacement of the
corroded equipments, (3) Maintenance cost, (4) Loss of valuable products such as
foodstuff, dyestuff and drugs because of contamination with corrosion
products,(5) Corrosion decreases equipment efficiency, for instance, the thermal
efficiency of heat exchangers decreases because of the deposition of low thermal
conductivity corrosion products on the heat exchanger tubes.(6) Corrosion Decrease
of Safety and health considerations in handling hazardous materials such as toxic
gases, concentrated acids, ammonia, explosive and flammable materials Corrosion
Engineering(3) is the application of science to prevent or control corrosion
damage economically and safely. So corrosion researches should continue
for better understanding of its mechanism and searching for new methods
for its combating.

1
1-2 why corrosion takes place?

The cycle of iron

Most metals are found in nature as ores, which are typically metallic oxides or
sulphides. Metals are refined from ores by reduction, a forcing of the metal
Ions to give up their charges and become metallic atoms in a regular lattice
array. For this to take place, energy in the form of heat or electricity must be

2
supplied. It is the energy stored in the metal during the refining process that
provides the driving force for corrosion.

Chemical Free Energy:

It can be shown by chemical thermodynamics that the driving force for any
chemical reaction is the chemical free energy. For any spontaneously occurring
reaction, the free energy change is negative. If the calculation shows the free
Energy to be positive, the reaction cannot take place without an external
source of energy. The below table shows the calculated free energy change for
the formation of a number of metal oxides. What these numbers mean is that,
from a free energy standpoint, aluminum will tend to form its oxide very
easily, iron almost as easily, copper only to minor extent, and gold only with
an input of energy. Since steel (iron) is our basic structural metal and its free
energy is so negative, we are continually faced with the tendency of the metal
to return to its oxide.

Free energies of formation of metal oxides (ΔG)

3
In order for corrosion to occur, metal atoms must leave the lattice. Metal
atoms must generally have high energy or lose or gain electrons to leave the
solid.

Voltage Source:
The source of voltage (driving force) in the corrosion process is the energy
Stored during the refining process. Due to the difference of free energy values
of various metals, these voltages are different for each metal.

Electrical Circuits:
The electrical circuit of the corrosion process consists of an anode, cathode,
electrolyte and metallic return path

Corrosion cell

The anode is that portion of the metal surface that is corroded. It is the point
at which metal dissolves, or goes into solution when metal dissolves, the metal
atom loses electrons and is oxidized. The reaction for iron is:
M → M++ + 2e- ------------------------------ (1)
The iron ion goes into solution and two electrons are left behind in the metal
The cathode is that portion of the metal surface where reduction takes place
and does not dissolve. The electrons left behind by the oxidation reaction at
the anode travel through the metallic path to the cathodic surface where they
are consumed by reaction with an oxidizing agent that must be present in the
electrolyte. This consumption of electrons is called a reduction reaction. Two
typical reactions are:

4
 2H+ + 2e-→H2 (pH<4) ------------------------ (2)
Or
½ O2 + H2O + 2e-→2 (OH)- (4<pH<10) ----- (3)
A metallic return path is necessary for the electrons generated at the anode to
travel to the cathode where they are consumed. Electrical current flow is
actually this passage of electrons through the metallic path.

Zinc-Copper Corrosion Cell

5
 1-3 Theory of Corrosion (Mechanism of Corrosion):

Corrosion of metals can be classified into two types, direct chemical corrosion
(dissolution of metals in acids) and electrochemical corrosion or indirect
corrosion.

1-3-1 Direct Chemical Corrosion:

Hydrogen evolution corrosion occurs mainly in acid, sometimes in strongly
alkaline solutions. Even from neutral solutions, the hydrogen evolution is the
main cathodic reaction. The attack by non-oxidizing acid will proceed rapidly
even in the absence of oxygen. The cathodic reaction consists in the
elimination of hydrogen according to equation (2) or the absorption of oxygen
according to equation (3); those are the principle cathodic change in nearly
neutral solutions. Both changes lead to a rise in pH value, but the first is
accompanied by liberation of hydrogen and the second by absorption of
oxygen.
The anodic reaction in either case is shown by equation (1).The e.m.f. driving
the hydrogen evolution type of attack is much smaller than that driving the
oxygen reduction type. If oxygen could be replenished at great speed, its
reduction would be the most probable cathodic reaction, but in acid solutions,
the hydrogen evolution type of corrosion can also occur with considerable
speed, and since the oxygen presence will rarely proceed with sufficient
rapidity to compete with this, the hydrogen evolution type of corrosion usually
predominates.

1-3-1 -A. Evolution of hydrogen as a cathodic reaction:

The liberation of hydrogen becomes important in three situations:
a- The metal which has a very negative normal electrode potential as Mg.
b- The solution which has a high hydrogen ion concentration such as acid.
c- The solution which keeps the concentration of cations (M+n) continuously
low through the formation of complex ions. for many metals this occurs in
alkaline liquids or in Cyanide solution. Impurities In the metal affect the rate
of attack when the cathodic reaction is the evolution of hydrogen than when it
is the reduction of oxygen, since there are some metals which posses a low H2

6
over-potential on which hydrogen is evolved at a potential relatively close to
the reversible value such as Pt, Ni and Fe while on others such as Hg, Pb, Zn
and Cd (metals of high H2 over-potential). It only occurs at potentials far
removed from the reversible value. Certain materials like impure zinc are
attacked slowly at first but the corrosion rate increases with time as a residue
of impurities accumulates, on which the hydrogen can be evolved easily.

1-3-1-B. Reduction of an oxidizing agent as a cathodic reaction:

A different type of corrosion occurs when the acid is itself an oxidizing agent
(HNO3 or hot conc. H2SO4) or when an oxidizing agent is added to a non-
oxidizing acid, a mixture of dilute H2SO4 and potassium chromate will attack a
metal like copper, which is sufficiently noble to dilute H2SO4 acid in absence of
oxygen or an oxidizing agent. In these cases the e.m.f. is higher than that
available when the cathodic reaction is oxygen reduction and the action is
often autocatalytic and the rate increases with time. Although nitric acid and
concentrated sulfuric acid being strong oxidizing agents, they may also
produce films on the metal surface, when such film has appeared, it dissolves
only very slowly in the acid and the attack on the metal dies down, so iron
which is vigorously attacked by dilute nitric acid becomes passive in
concentrated acid. Al exhibits similar behavior in concentrated nitric acid
owing to the formation of Al2O3 film while Pb display passivity in H2SO4 owing
to the formation of an insoluble layer of PbSO4 on the lead surface.

1-2-1-C Prediction of the Corrosion tendency of metals in the acids:

There are three methods by which the tendency of metals to dissolve in acids
can be predicted:
1- The position of the metal in the electromotive series (e.m.s.).
Generally metals lying above H2 in the e.m.s. dissolve in acids with H2
evolution.while metals lying below it don’t dissolve.
2- Thermodynamic free energy change.For metal dissolution in acids to take
place, the free energy (ΔG) of the reaction (M+2H+ → M+++ H2) must be –ve.
The higher the –ve value of ΔG, the higher the dissolution tendency of the
metal.

7
3- The electrochemical theory:Methods 1&2 fail to explain why pure metals
such as Zn, Pb, Sn and Sb which lie above H2 in the e.m.s. don’t dissolve or
slightly dissolve in acids. The electrochemical theory assumes that metal
dissolution in acids takes place through the formation of the galvanic cell:
M /M++ | H+/H2
And for cell reaction:
M+2H+ → M+++ H2

++
To take place, e M|M should be less noble than e H+ | H2
++
i.e. eo-(RT/ZF) ln[ M ] should be less noble than (RT/ZF ln [H+ ] + η H2)

where η H2 Is the H2 over-potential on the dissolving metal.The above equation

shows that metal dissolution in acids is favored by:
Low M++, High acidity,Low η H2 , High value of eo (in the active metal side of
the e.m.s.) Zn, Sb, and Pb dissolve with difficulty in acids because of the high
H2 over-potential (ηH2) on these metals.

8
 Standard Oxidation Potentials for Corrosion Reactions

Oxidation Potential ,eo, (Volt)

Corrosion Reaction vs.
Normal Hydrogen Electrode

K → K+ + e
+2.925
Na → Na+ + e
+2.714
Mg → Mg2+ + 2e
+2.363
Al → Al3+ + 3e
+1.662
Zn → Zn2+ + 2e
+0.763
3+
Cr → Cr + 3e
+0.744
2+
Fe → Fe + 2e +0.440
2+
Cd → Cd + 2e +0.403
2+
Co → Co + 2e +0.277
2+
Ni → Ni + 2e +0.250
Sn → Sn2+ + 2e +0.136
Pb → Pb2+ + 2e +0.126
H2 → 2H+ + 2e 0.000
Sn2+ → n4++ 2e -0.150

Cu → Cu2+ + 2e -0.337

4(OH)- → O2 + 2H2O + 4e -0.401

Fe2+ → Fe3+ + e -0.771

2Hg → Hg24+ + 2e -0.788

-0.799
Ag → Ag+ + e
-0.987
Pd → Pd2+ + 2e
-1.200
Pt → Pt2+ + 2e
-1.229
2H2O → O2 + 4H+ + 4e
-1.498
Au → Au3+ + 3e

9
1-2-1-D Conditions under which noble metals can liberate hydrogen:
The attack of non-oxidizing acid on copper in absence of oxygen will only
continue if the molecular hydrogen and cationic copper are both removed as
quickly as they are formed, so that equilibrium is never attained. This
happens when copper is placed in boiling concentrated HCl acid where simple
copper cations will never accumulate since it passes into the state of complex
anions [CuCl2]- the equilibrium:

[CuCl2]- ↔ Cu+ +2Cl-

Is established when the complex ions vastly exceed the simple Ones.
Evolved hydrogen is continually removed along with bubbies of hydrogen
chloride and water which are being boiled off Thus copper continue to be
attacked by boiling concentrated hydrochloric acid even in absence of
oxygen.

The dissolution of copper in ammonia with or without ammonium salts is also

made possible through the formation of complex ions, but in this case
oxygen is needed, this reaction which is diffusion controlled under certain
conditions.

1-2- 2- Indirect attack (Electrochemical corrosion):

(2-4)
Types of galvanic cells responsible for corrosion
1-2-2-1 Dissimilar Metal Corrosion Cells:
This type of cells takes place when two different metals become in contact in
the presence of an electrolyte. The less noble metal acts as the cell anode
where metal dissolution takes place, the more noble metal acts as the cell
cathode where hydrogen evolution or oxygen reduction takes place depending
on the solution pH, and the reactions involved are:
At the anode can be shown by equation (3), at the cathode can be shown by
equation (1), or equation (2).

10
Based on the e.m.s., iron is protected by contact with a less noble metal such
as Zn metal, while it suffers serious corrosion in contact with a relatively more
noble metal such as copper.A metal containing impurities on the surface as
separate phase, a copper pipe connected to a steel pipe, and a bronze
propeller in contact with the steel hull of the ship are examples of this type of
corrosion. Dissirailar metal corrosion not only takes place when two different
metals becomes in contact in the presence of an electrolyte but also takes
place when the metal contacts a more noble phase such as an oxide or alloy
Dissimilar metals may sometimes cause trouble even when they are not in
electrical contact. If water containing free carbonic acid flows through a copper
pipe and then through a galvanized tank, serious corrosion may be set-up,
such water can take up traces of copper (as copper bicarbonate) and later
deposit metallic copper on the tank.

Cu+2 + Zn = Cu + Zn+2

This will cause the formation of micro-cells of Zn/Cu which will allow the
rapid attack on zinc coating, and when the zinc has disappeared the micro-
cells iron/copper may set up attack on the steel finally causing perforation,
the damage to the copper pipe in such cases will usually be trivial.In the
design of equipments used in the chemical industry care should be taken to
avoid contact between difFerent metals as far as possible.

1-2-2-2 Concentration Cells:

The cell consists of two electrodes of the same metal, each in contact with a
solution of a different composition. There are two types:
A-Differential aeration cell: This takes place when the surface of a submerged
metallic structure is subjected to different concentrations of dissolved oxygen,
the oxygen rich area acts as the cell cathode while the oxygen poor area acts
as the cell anode.This type of cell is responsible for damage at crevices
(crevice corrosion) such as those formed under deposits or at buried steel
pipelines passing through soils of different porosity.

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B-Salt concentration cell :When a copper electrode immersed into
concentrated copper sulphate solution is connected internally and externally to
another copper electrode which is immersed into a dilute copper sulphate
solution, copper dissolves from the electrode in contact with dilute solution
(anode) and deposits on the other electrode (cathode).

1-2-2-3 Differential Strain Cells:

This type of corrosion takes place where there is difference in the degree of
strain on different positions of the metallic structure, when this metal is
exposed to an electrolyte, the more strained part acts as anode and the less
strained part as cathode.The reactions involved are:
At the anode (Strained Part):
M→M++ + 2e
At the cathode (Unstrained Part):
2H+ + 2e-→H2 (pH<4)
or
½ O2 + H2O + 2e-→2(OH)- (4<pH<10)

To avoid this type of corrosion, the residual strains stored in the metal during
fabrication should be removed by annealing before using the structure in
practice.

1-2-2-4 Stray Current Corrosion Cells:

This type occurs when direct current (DC) or alternating current (AC) leaks
from a conductor to a metallic structure. If currents of this kind enter a metal
structure, they cause corrosion at areas in the conductor where the current
leaves to enter the soil and meet buried metallic structure. Damage takes
place also at the location where the current returns back to the conductor.
Sources of DC are commonly electric rail-ways, grounded electric DC power or
cathodic protection systems, while sources of AC are usually grounded AC
power lines.

12
 (1-4)
2-3 Forms of corrosion

2-3-1 Uniform Corrosion:

Uniform attack or general corrosion is the most common form of corrosion. It
is normally characterized by a chemical or electrochemical reaction that
proceeds uniformly over the entire exposed surface or over a large area. The
metal becomes thinner and eventually fails. A prime example of this type is
rusting of metals exposed to the atmosphere.

Schematic view of the effect of uniform corrosion on

a metal Surface.

Macroscopic view of a uniformly corroded surface.

13
Two of the most common forms of corrosion are attack by acids (HCl, H2SO4...)
and attack at elevated temperature by sulfur compounds. Uniform attack
represents the greatest destruction of metal on a tonnage basis, however is
not of too great concern from the technical standpoint because the life of
equipment can be accurately estimated on this basis of comparatively simple
tests. Uniform corrosion is the easiest form of corrosion to measure, and
unexpected failures can usually be avoided by regular inspection.

uniform corrosion on a metal Surface.

2-3-2 Galvanic Corrosion:

This type of corrosion occurs when dissimilar metals are in contact or coupled
electrically in the presence of a corrosive medium (electrolyte). The tendency
of metals to corrode depends on difference in potential (in Volt), which is the
driving force of the corrosion reaction. Arranging the metals according to their
tendency to corrode galvanically in sea water gives the galvanic series of
metals and alloys. Factors affecting the galvanic corrosion are coupling of
metals with large potential differences, conductivity of the corrosive medium,
proximately and anode area relationships. The greater the conductivity the
greater the corrosion will be. For example, distilled water is such a poor
conductor that galvanic corrosion even with metals coupled together with large
potential differences will see very little corrosion, however, water containing
impurities and salts are generally good conductors and galvanic corrosion will

14
proceed rapidly. When metals are closed together or touching, corrosion may
be severe, where small anodic areas are exposed to large cathodic areas,
rapid corrosion will occur at the anode. This phenomenon is often used to the
designer’s advantage when sacrificial anodes made of an inexpensive material
are utilized to increase the life of more expensive parts.

Noble or Active in Corrosion:

What is likely to happen to gold, copper, iron, zinc, titanium and magnesium in
a corrosive environment such as 10 % hydrochloric acid at room temperature?
Use the following Qualitative information?

Metal Corrosion in Hydrochloric Acid (10 wt %)

15
 Galvanic series
Ranks the reactivity of metals/alloys in seawater

16
• Material: Carbon steel, coated with coal tar epoxy.
• System: Sewage treatment plant.
• Part: Skimmer in settling tank.
• Phenomenon: Galvanic corrosion.
• Appearance: Local flaking-off of the coating, with pitting
attack of the steel.
• Time to Failure: ½ year after fitting stainless-steel cap.

• Material: Hot-dip galvanized steel.

• System: Hot water system, 160°C.
• Part: Heating tube from make-up water vessel.
• Phenomenon: Galvanic corrosion (reversal of potential).
• Appearance: Pitting attack.
• Time to Failure: 1 year.

17
Prevention of Galvanic Corrosion:
• Select combinations of metals close together in galvanic series (useful as
first approximation only).
• Provide for complete dielectric insulation of dissimilar metals.
• Avoid unfavorable area ratio effects (i.e., small anodic and large cathodic
areas should be avoided).
• Avoid threaded joints between metals far apart in galvanic series; use
welded, brazed, or fused joints instead.
• Apply coatings, but with caution (coatings contain pinholes!). Do not fully
rely on painting.
• Corrosion inhibitors may be helpful, since they reduce the Aggressiveness of
the environment.
• Prevent access of air and/or water to the joint of the two metals.

2-3-3- Inter-granular Corrosion:

Microscopic cross-section of metal with

Intergranular corrosion at the surface.

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 Cracking of 70-30 brass tube Attack and failure along
the grain boundaries

Corrosion occurs preferentially at grain boundaries, usually with slight or

negligible attack on the adjacent grains. Most alloys are susceptible to inter-
granular attack when exposed to specific environments. This is because grain
boundaries are sites for precipitation and segregation, which make them
chemically or physically different from the grain themselves. Inter-granular
attack is defined as the selective dissolution of grain boundaries or closely
adjacent regions, without appreciable attack of the grain themselves. This is
caused by potential difference between the grain boundary region and any
precipitates, inter-metallic phases or impurities that are formed at the grain
boundaries. Precipitates that are formed as a result of the exposure of metal
at elevated temperatures often nucleate and grow preferentially at grain
boundaries.

Mechanism of Sensitization:
If stainless steel is heated to between 420 to 820°C (800-1500oF); for
example during welding, carbon migrates to the grain boundaries where it
combines with the chromium and precipitates as chromium carbide. The
chromium content adjacent to the grain boundaries is thereby depleted and
makes the metal susceptible to corrosion by specific chemicals, such as boiling
nitric acid or hot organic acids.

19
20
 Corrosion attack occurs not in the weld metal, but in the heat affected
zone as shown on this type 304 stainless steel welded pipe.

Effect of Carbon on Carbide Precipitation

Time required for formation of harmful amount of chromium carbide in

stainless steels with various carbon contents.

21
2-3-4- Stress Corrosion Cracking:
This phenomenon is defined as the cracking of a metal under the combined
effects of stress and corrosion. The stress involved may be either residual or
on the surface which acts as a stress raiser, and the combination of corrosive
attack plus stress result in propagation of the crack. This type of corrosion is
most insidious as it generally occurs without prior warning or any physical
change in size or appearance of the material and is not repairable.

Microscopic cross-section of a typical

stress corrosion crack in metal.

Microscopic cross-section of a stress corrosion

Crack in metal. ASM Handbook, Vol. 13, Corrosion, p. 354.

22
 Stress corrosion cracking in brass

Combinations of some alloys and environments that

have been shown to promote stress corrosion cracking:

Prevention of SCC:
• Select suitably resistant materials of construction.
• Keep stress levels as low as possible (stress-relief where possible).
• Be aware of all of the constituents in the service environment. SCC problems
are often caused by trace impurities.
• Avoid designs that allow stagnant regions where impurities can concentrate
or deposit.
• Use lower operating temperatures if possible.
• Apply cathodic protection (for chloride-induced SCC only).
• Use inhibitors.

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Corrosion fatigue is a special form of stress corrosion cracking. Fatigue
failures occur in the absence of corrodents and are caused by repeated cyclic
stressing. Such failures are common in structures objected to continued
vibration. When susceptibility to fatigue is increased by the presence of
corrodents, the resulting failure is attributed to corrosion fatigue. A metal that
has failed because corrosion fatigue, will usually have visible corrosion
products on fracture. Methods of avoiding a fatigue crack from starting are
design changes and addition of inhibitors.

Schematic diagram of a typical magnified

corrosion fatigue crack cross-section.

Schematic representation of a fatigue fracture surface in a steel shaft, showing

the initiation region, the propagation of fatigue crack (with beach markings),
and catastrophic rupture when the crack length exceeds a critical value at the
applied stress

24
 • Material: Carbon steel.
• System: Dredge.
• Part: Chain link.
• Phenomenon: Corrosion fatigue.
• Appearance: Partly ductile fracture with distinct fatigue
rings and corrosion pitting, partly brittle fracture with pits

• Material: Carbon steel.

• System: Conveyor belt in a cheese store.
• Part: Chains.
• Phenomenon: Low cycle fatigue or strain fatigue.
• Appearance: Cracks and rupture.
• Time to Failure: Several years.

Prevention of Fatigue:
• Minimize or eliminate cyclic stresses.
• Reduce stress concentration or redistribute stress (balance strength and
stress throughout the component).
• Select the correct shape of critical sections.
• Provide against rapid changes of loading, temperature or pressure.
• Avoid internal stress.
• Avoid fluttering and vibration-producing or vibration transmitting design.
• Increase natural frequency for reduction of resonance corrosion fatigue.
• Limit corrosion factor in the corrosion-fatigue process (more resistant
Material /less corrosive environment).

25
2-3-5 Crevice Corrosion:
The environment conditions in crevice can, with time, become quite different
to those on a nearby, clean, open surface. The presence of narrow opening or
gaps gives rise to localized corrosion at these sites. Crevices commonly exist
at gaskets, lap, joints, bolts, rivets, etc. They also created by dirt deposits,
Corrosion products and scratches in paint films. Crevice corrosion is usually
attributed to one or more of the following:
-Changes in acidity in the crevice.
-Lack of oxygen in the crevice.
-Build up of detrimental ion species in the crevice.
Like forms of localized corrosion, crevice corrosion does not occur in all metal
corrodent combinations. Some materials are more susceptible to it than
others, namely those that depends on air formed oxide films to achieve their
corrosion resistance such as stainless steel. These materials can be alloyed to
improve their resistance and with designing it minimize crevices and
maintenance to keep surface clean.

Preference site for Crevice Corrosion

• Crevice corrosion is most common in chloride-bearing solutions, such as

seawater. In seawater coolers, therefore, the water should flow inside the
tubes (as design crevices are more easily avoided there) rather than on the
shell side.

26
• The risk is greatest in stagnant solutions. At flow rates over 1.5 m/s the risk
decreases since there will be no deposit formation and build-up of an
aggressive environment.
• If required, the water should be decalcified. Otherwise, the tubes should be
cleaned regularly.
• Stainless steel should normally not be painted, because a crevice will result
if the paint is damaged.
• Crevice corrosion often occurs at lower temperatures and at lower chloride
concentrations than for pitting corrosion. Up to a certain limit, the risk for
attack increases the more narrow the crevice is.

Mechanism of Crevice Corrosion

Crevice Corrosion of Type 304 Fastener in

Marine Tide after 6 Months

27
 Crevice Corrosion on a Flange Gasket
Contact Surface

Effect of Temperature and Chloride on

Initiation of Crevice Corrosion

28
2-3-6 Pitting Corrosion:
Pitting Corrosion is the formation of holes in an otherwise relatively un-
attacked surface. These holes can have various shapes. The shape of a pit is
often responsible for its continued growth, for the same reasons mentioned
under crevice corrosion. A pit can be considered a self-formed crevice. The
small size of a pit and the small amount of metal that has to be dissolved to
form it make detection in the early stages difficult. Surface cleanliness and
selection of materials known to be resistant to pitting in the given environment
are usually the safest ways of avoiding the problem.

Macroscopic view of pits inside a

pipe. Forms of Corrosion Recognition
and Prevention, Ed. Dale McIntyre,
Vol 2., p. 32.

Pitting occurs in stainless steels in neutral or acid solutions containing

Halides, Primarily chlorides (CI–), for example seawater. The attack
most often takes place at points where the passive layer might be
weakened, e.g.by slag inclusions or surface defects. Once the attack has
started, the material may be completely penetrated within a short time.

29
 Oxygen Pitted Boiler Feed
Water Pipe, 304 stainless steel

• Material: Titanium.
• System: Effluent tank.
• Part: Heating coil.
• Phenomenon: Cavitations corrosion.
• Appearance: Pitting corrosion in the form of
numerous small cavities, the pipe being perforated at
various places.
• Time to Failure: 8 months.

Pitting corrosion forms on passive alloys like stainless steel when the
thin oxide film is broken and does not immediately repassivate. Pits
can become wide and shallow or may rapidly perforate the metal.

30
An example of pitting due to Undercutting of the surface of a stainless steel by
pitting chlorides of an iron-nickel chromium alloy pickling hook.

Critical crevice & pitting corrosion temperature

Pitting Resistance Index, PRE

PRE = %Cr + 3.3(%Mo + 0.5%W) + 30%N

Stainless steels
• Pitting breakdown potential (that potential above which the
anodic current starts to increase); lower pitting potential
implies greater susceptibility.
• Critical pitting temperature (CPT, temperature at which
pitting is observed in aggressive conditions); lower CPT
implies greater susceptibility.
• Pitting Resistance Equivalent (formula based on
composition e.g. (Cr+ 3Mo+30N)gives ranking of alloys.

31
Effect of Temperature and PRE on Pitting

Critical pitting and crevice corrosion temperatures for austenitic

stainless steel related to PRE numbers.

PRE-VALUES
The chromium content of stainless steel grades is important and alloying with
molybdenum and nitrogen has proved very beneficial for the pitting resistance.
From experimental data, relations between elemental composition and pitting
resistance have been developed. PRE = %Cr + 3.3% Mo + 16%N

32
2-3-7- Exfoliation and Selective Leaching:
Exfoliation is subsurface corrosion that begins on a clean surface but spreads
below it. It differs from pitting in that the attack has a laminated appearance.
Selective leaching (parting), also called Dealloying, is the removal of one
element from a solid alloy by corrosion processes. The most common example
is the removal of zinc in copper-zinc alloys (dezincification). The corrosion is
detrimental largely because it yields a porous metal with poor mechanical
properties. The remedy involves the use of non-susceptible alloys.

Microscopic view of typical dealloying.

(The metal left as small islands is rich
in the more noble metal.)

Microscopic dealloying in a brass

screw thread. Metals Handbook, Vol
13, Corrosion, 9th edition, p. 222, 1987.

33
 Dezincification selectively removes zinc from the alloy,
leaving behind a porous, copper-rich structure that has
little mechanical strength–Layer type.

The service conditions generally present where dezincification occurs

include:

• Water with high levels of oxygen and carbon dioxide (uniform attack).
• Stagnant or slow moving waters (uniform attack).
• Slightly acidic water, low in salt content and at room temperature (uniform
attack).
• Soft, low pH and low mineral water combined with oxygen, which forms zinc
oxide (uniform attack).
• Waters with high chloride ion content (uniform attack).
• Neutral or alkaline waters, high in salt content and at or above room
temperature (plug-type attack).
• Relatively high tube-wall temperatures
• Permeable deposits or coatings over the tube surface

34
 • Material: Aluminum-zinc alloy (5 to 6% zinc).
• System: Glasshouse irrigation system.
• Part: Water distributor pipes.
• Phenomenon: Selective leaching (dezincification).
• Appearance: Severe uniform attack with pitting to the point
of leakage.
• Time to Failure: 6 months.

Prevention of Dezincification
• Make environment less aggressive (e.g., reduce O2 content)
• Cathodically protect.
• Use a better alloy (common cure - above not usually feasible).
– Red Brass (<15% Zn) almost immune.
– Admiralty Brass (70 Cu, 29 Zn, 1 Sn)
– Arsenical Admiralty (70 Cu, 29 Zn, 1 Sn, 0.04 As)
– Sn and Sn-As in deposited films hinder redeposition of Cu
• For very corrosive environments likely to provoke dezincification, or for
critical components, use
– Cupronickels (70-90 Cu, 30-10 Ni).

Graphitization:
Another example of Selective leaching is "graphitic corrosion" of (gray)
cast iron, in which the metallic constituents are selectively leached or
converted to corrosion products leaving the graphite intact.

35
• Graphitic corrosion of gray cast iron, whereby a brittle graphite skeleton
remains following preferential iron dissolution.
• The term "graphitization" is commonly used to identify this form of corrosion
but is not recommended because of its use in metallurgy for the
decomposition of carbide to graphite above 425 oC.
• During cast iron graphitic corrosion the porous graphite network, that makes
up 4-5% of the total mass of the alloy, is impregnated with insoluble corrosion
products.
• As a result, the cast iron retains its appearance and shape but is weaker
structurally
• Can be protected by addition of Cr.
• Graphitization is the breakdown of pearlite to ferrite + C at
high temperature)
• Grey cast iron is the cheapest engineering metal
– 2-4% C, 1-3% Si.
• Hard, brittle, easily cast; carbon present as microscopic flakes
of matrix graphite within microstructure.

• Material: Grey cast iron.

• System: Cooling water system.
• Part: Cooling water pump check valve.
• Phenomenon: Selective leaching (graphitic corrosion).
• Appearance: Outer edge black due to graphitic corrosion.
• Time to Failure: 6 years

36
2-3-8- Erosion Corrosion:
Erosion corrosion is the acceleration or increase in rate of deterioration or
attack on a metal because of relative movement between a corrosive fluid and
the metal surface. Generally, this movement is quite rapid, and mechanical
wear effects or abrasion is involved.
Metal is removed from the surface as dissolved ions, or it forms solid corrosion
products that are mechanically swept from the metal surface. Many types of
corrosive mediums could cause erosion corrosion. These include gases,
aqueous solutions, organic systems and liquid metals.
Particles of another phase carried in suspension in a corrosive liquid in
turbulent motion provide the conditions for the conjoint action termed
corrosion erosion,
or impingement attack. The impact of the suspended particles against the
metal tends to remove the protective film and allows corrosion of the metal to
proceed. Most metals and alloys are susceptible to erosion corrosion damage;
many depend upon the development of a surface film of some sort (passivity)
for resistance to corrosion like aluminum, lead and stainless steel. Erosion
corrosion results when these protective surfaces are damaged or worn and the
metal and alloy are attacked at a rapid rate. All types of equipment exposed to
moving fluids are subjected to erosion corrosion. Some of these are piping
systems, bends, elbows, valves, impellers, agitators and heat exchangers
tubing.

Effect of flow of solution containing solids on metal

surface.

37
• Material: Carbon steel.
• System: Soda solution transport system.
• Part: Pipe bend.
• Phenomenon: Erosion corrosion.
• Appearance: Local attack.
• Time to Failure: 2 to 3 months

38
 • Material: Bronze (cast CuSn10).
• System: Chemicals transport system.
• Part: Impeller of centrifugal pump.
• Phenomenon: Erosion corrosion.
• Appearance: The entire surface of the impeller is
attacked with a distinct flow pattern.
• Time to Failure: 21 days continuous.

Factors affecting erosion corrosion are:

1-Surface films: The nature and properties of the protective film that form on
some metals or alloys are very important from the standpoint of resistance to
erosion corrosion. The ability of these films to protect the metals depends on
the speed or ease with which they are formed when originally exposed to
environment, their resistance to mechanical damage or wear and their rate of
reforming when destroyed or damaged Sometimes the nature of the protective
film that formed on a given metal depends upon the specific environment to
which it is exposed and this determines its resistance to erosion corrosion by
that fluid.
2-Velocity: Velocity of the environment plays an important role in erosion
corrosion. Velocity often strongly influences the mechanism of the corrosion
reactions. It exhibits mechanical wear effects at high values and particularly
when the solution contains solids in suspension. Erosion corrosion can occur
on metals and alloys that are completely resistant to a particular environment
at low velocities. Increases in velocity generally result in increased attack,
particularly if substantial rates of flow are involved.
3-Impingement: Many failures are directly attributed to impingement. For
example of this type of failure are steam turbine blades, parts in front of inlet
pipes in tanks, cyclones Solids and sometimes bubbles of gas in the liquid

39
increase the impingement effect. Air bubbles are an important factor in
accelerating impingement attack.
4-Turbulence: Many corrosion failures occur because turbulence or turbulent
flow conditions exist. Turbulence results in greater agitation of the liquid at the
metal surface than in case for laminar flow. Turbulence results in more
intimate contact between the environment and the metal. For example it
occurs in the inlet ends of tubing in condensers and heat and tube heat
exchangers.

5-Caviation damage: Cavitation damage is a special form of erosion corrosion,

which is caused when a fluid's operational pressure drops below its vapor
pressure causing gas pockets and bubbles to form and collapse in a liquid near
a metal surface. Cavitation damage occurs in hydraulic turbines, pump
impellers and other surfaces where high velocity liquid flow and pressure
changes are encountered. Cavitation erosion may occur in absence of
corrosion. Cavitation damage has been attributed to both corrosion and
mechanical effects.

• Material: Carbon steel.

• System: Boiler feedwater system.
• Part: Section of steam dome of two stage deaerator.
• Phenomenon: Cavitation erosion.
• Appearance: Material with sharp edges worn away to the
point of leakage.
• Time to Failure: Unknown.

40
 • Material: Phosphorous deoxidized copper.
• System: Vessel for boiling alcohols.
• Part: Pipe from the heating bundle in the vessel.
• Phenomenon: Cavitation erosion.
• Appearance: All along the upper part of the pipe, a strip of
Material .5-3 cm wide was worn away to the point of
leakage.
• Time to Failure: 2 weeks.

How to Prevent Cavitation Damage:

• Cavitation erosion is best prevented by designing to avoid the formation of

vapor cavities.
• Correct stream lining eliminates turbulence, and uniform heat transfer
prevents local boiling.
• Where cavitation cannot be prevented by design (as in high duty feed
pumps) the provision of cheap readily replaceable inducers minimizes the
cost of erosion.
• The most resistant materials both in fresh and sea water are Stellites
followed by ferritic and austenitic stainless steels.

41
2-3-9-Biocorrosion (Bacteria-Assisted Corrosion):

Macroscopic view of a piece of tube

with tubercules that are caused by
bacterial activity. W. P. Iverson,
ASTM STP 741 p. 40, 1981.

42
 As rust, biofilm or garbage accumulates, oxygen migration
is reduced through the layer. Regions below the layer become
Oxygen depleted and an oxygen concentration cell develops
Tuberculation is a specific type of crevice corrosion.

Microbiologically Influenced Corrosion (MIC), MIC will actively or passively

attack metal.
• Active MIC: Byproducts of Active MIC are acids and/or ammonia. Active MIC
is localized and normally the point in which pinhole leaks are formed.
• Passive MIC: Passive MIC is normally produced by the biological waste
products forming a gel like mass. This mass can extend over large areas,
which will accumulate additional deposits. These deposits will cause flow
obstruction within fire sprinkler systems. Passive MIC will attack large areas
and accounts for the greatest metal loss.

Bacteria related to MIC:

• Acid Producing Fungi.
• Aerobic Slime Formers.
• Iron/Manganese Oxidizing Bacteria.
• Methane Producers.
• Organic Acid Producing Bacteria.
• Sulfate reducing bacteria (SRB).
• Sulfur/Sulfide Oxidizing Bacteria.
There are three major types of bacteria which can cause corrosion:

43
Bacteria Effects – MIC

This is an example of a failure of a type 304 stainless steel pipe due to MIC
caused by Gallionella bacteria in plant waste water service. Note the
tuberculation, that is, the mound of corrosion products from the bacteria, and
the crevice, located on the weld, shown here by an arrow. Leaks at welds were
observed after only 6 months.

44
 Before Cleaning After Cleaning – No Attack

Severe corrosion occurred underneath the bacteria colony.

The 6 mm (1/4 inch) thick walled piping is perforated.

Prevention of MIC in Water:

• Keep The System Clean.
• Keep Water Flow > 2 m/s (6fps).
• Use Bactericide:
– Chlorine
– Chlorine Dioxide
– Hypochloride
– Ozone
– Non-oxidizing
• Remove Heat Tints after Welding.
• Drain and Dry Equipment After Hydrotesting.
• Use Continuous Cleaning.
• Use High Pressure Hydrolancing.
• Use Stainless Steel Scrapers (Hard to Remove of Heavy Deposit).
• Use Alloy Resistant to MIC.

45
 2 - Corrosion in ammonia plant

2-1 Process description:

Ammonia is formed according to the following stoichiometric equation:

3 H2 + N2 2 NH3
The source of hydrogen is the steam reforming of natural gas and The source of
Nitrogen is the process air, the following block diagram of ammonia production
process show that the natural gas feed stock enters the Desulphurization unit to
remove sulphur compounds which act as catalyst poisons in the primary reformer
and in the LT-shift conversion
R-SH + H2 R-H + H2S
H2S + Zn O Zn S + H2 O

Then the gas reformed in the primary and secondary reformer

CH4 + H2O CO + 3H2

The CO is converted to CO2 in HT and LT shift converters

CO + H2O CO2 + H2

CO2 is removed from the gas in CO2 Removal unit

K2CO3 + CO2 + H2O 2 KHCO3

Before the gas admitted to the ammonia converter CO and CO2 as these two
components constitute strong catalyst poisons in the ammonia synthesis
reaction. Methanation,a process which hydrogenizes carbon monoxide and
carbon dioxide to form methane and, at the same time, removes any oxygen
that might be present.
CO + 3H2 CH4 + H2O
CO 2 + 4H2 CH4 + 2 H2O
O2 + 2H2 2 H2O

46
47
 2– 2 Corrosion in steam system

Water treatment procedures outline of Abu- qir plants

Water is a working fluid of steam system; the raw water contains

contaminants such as turbidity, hardness, alkalinity, color, organic matter,
dissolved solids. So treatment of water must be carried out before water
admitted to boiler.

48
Analysis of process water

49
Integrated steam reformer with steam system flow sheet

50
The demineralized (deionate) water is feed to ammonia plant to deaerator,
preheating and treatment for PH adjustment ,O2 scavenging .Owing to
dissolved oxygen and carbon dioxide in deionate water which causes
corrosion So boiler feed water admitted to deaerator to expelle any dissolved
gasses.

O2 causes oxygen attack : which appears as aggressive localized corrosion

and loss of tube wall, most prevalent near economizer feed water inlet on
Operating boilers. oxygen pitting occurs with the presence of excessive oxygen
in boiler water. It can occur during operation as a result of in-leakage or air at
pumps, or failure of operation of preboiler water treatment equipment. This also
may occur during extended out-of-service periods, such as outages and storage,
If proper procedures are not followed in lay-up. Non- drainable locations of boiler
circuits, such as superheater loops, sagging horizontal superheater and re-heater
tubes, and supply lines, are especially susceptible.
More generalized oxidation of tubes during idle periods is sometimes referred
to as out-of-service corrosion. O2 causes oxidation to magnetite Fe3O4 which is
the passive layer protect the metal from corrosion to less stable Fe2O3 .high
oxygen concentration may cause pitting to carbon steel. When corrosion ash is
present moisture on tube surfaces from condensation or water washing can
react with elements in the ash to form acids that lead to a much more
aggressive attack on metal surfaces.

51
 Oxygen attack in hairpin bend tube used in economizer

The maximum quantity of gas which can be dissolved in cretin volume of

water(x) is proportional to its partial pressure (p) depend on temperature
(Henry's law) X= H * P

Solubility of atmospheric oxygen in water

52
Carbon dioxide causes corrosion
CO2 +H2O--------------- - H2CO3--------H+ +HCO3-

Fe +2H++2H2CO3---------------- Fe(HCO3)2 +H2

Solubility of carbon dioxide in water

Methods of deaeration of water

There are many types but here in fertilizers industry using high pressure
steam use combination of thermal and chemical deaeration .

a- Thermal deaeration: Lp steam is used for heating of B.F.W intodused

into the deaerator tank through tubes submerged in the water .the
stem condense while the water is heated to boiling point gases expelled
from water.
b- Chemical deaeration :the most common material is Hydrazine

N2H4 + O2 -------------→ 2H2O + N2

53
 With efficient thermal deaeration the recommended quantity is
0.5—1.0 g hydrazine per m3 boiler feed water.

Hydrazine requirement for different BFW temperatures

This will not only reduce oxygen content in boiler feed water but also excess
hydrazine will under boiler pressure decomposes into nitrogen and ammonia

3 N2H4 -------------→ 3NH3 + N2

Also primary benefit of hydrazine is that it will repassivate oxidized area of

piping and tube material.

N2H4 +6Fe2O3------------→ 4Fe3O4+N2+2H2O

Ammonia water: it is desirable to alkalize the steam and condensate route to

prevent carbon dioxide corrosion by adjusting PH. the amount of ammonia
needs to be controlled to minimize copper corrosion.

54
Amines: Amines are used to increase the pH of the feed water and the pH of
the condensate in utility and industrial steam systems. There are a number of
different amines, and they vary in basicity and volatility. Among the amines in
common use in the utility industry are cyclohexylamine, morpholine, and
diaminoethanol. Determining which amine to use is in part a function of what
equipment you want to protect and where it is in the condensate cycle.

Flow assisted corrosion

Flow assisted corrosion (FAC) is the localized thinning of a component related to
the dissolution of the protective oxide film and the underlying base metal. The
mechanisms involved in FAC are very complex due to the effect of many
variables, which influence its occurrence. In utility operations FAC is typically
seen in single or two phase water flowing in carbon steel piping. The more
common locations where FAC is detected are: Low pressure system bends in
evaporators, risers and economizer tubes and feed water cycle (due to more
volatile chemistry and lower pH)

Beside oxygen attack, Erosion and Cavitation, takes place erosion caused by
flowing BFW or steam often disrupt passive layer which protect against
corrosion in BFW pump components such as impellers fittings valves housing.
Cavitation results from collapsing bubbles created by pressure change across
surfaces exposed to high velocity water Flow the steam bubbles quickly
collapse producing micro jets that impinging on the metal surface cause
damage of pump components, turbines are subjected to erosion caused by
impingement of solid particles erosion caused by exfoliated oxides, primarily
from superheater and main steam piping. The small particles are carried into
the first stages in the turbine, where they will come into high velocity
contact with the fixed and rotating blade elements. A rotating blade
having suffered material loss on its inlet nose due to solid particle erosion.

55
 Failure of elbow in steam condenser line

Erosion corrosion of stainless alloy pump impeller

BFW pump spacer erosion

56
These scales are composed mainly of magnetite, which is extremely
hard, and has sharp edges. The combined abrasive and impact actions of
these scales cause physical damage to the turbine blades.The boiler feed water
BFW then send to steam drum where blowdown of colloidal silica which has
harmful effect on steam boiler tubes ,damage of turbine blades by it’s erosion
effect.
The BFW is now said to be boiler water BW where the ability to use inexpensive
carbon steel in contact with water at high temperature is due to the reaction
between iron and slightly alkaline water.

Fe + 4H2O ----------- Fe3O4 + 4H2

By which film of magnetite Fe3O4 is formed in the water side surface of the
tubes this layer can passivate the metal by inhibiting the transport of the
reacting species between the metal and it’s environment .this isolation of steel
from boiler water can be maintained for many years of service conversely
rupture of the film by either mechanical or chemical means will promote
corrosion.

In steam Super heater: The construction materials of superheater

tubes can vary from carbon steels to low-chromium ferritic to austenitic
stainless steels. Chromium-containing steels exposed to high pressure steam
at metal temperatures from 550 to 650°C initially from a spinel-type oxide
consisting of two layers whose relative thickness depend on the
chromium content of the steel. In superheaters and reheaters, however,
the inner layer is an iron-chromium spinel type oxide containing the steel
alloying elements. There are two ways in which the normal protective oxide
can break down, exfoliation and SCC.

Exfoliation: The stresses imposed on superheater tubes during shutdown,

startup and cycling duty cause cracks in normal protective oxide as a result
of differences in thermal expansion coefficient between the oxide layer and
tubing.

57
SCC is most commonly associated with austenitic (stainless steel) superheater
materials and can lead to either transgranular or intergranular crack propagation
in the tube wall. It occurs when a combination of high-tensile stresses and a
corrosive fluid are present. The damage results from cracks that propagate from
the ID the source of corrosive fluid may be carry-over into the superheater
from the steam. The tensile stress may be either from operating conditions,
such as thse caused_by thermal expansion and contraction, or inherent in the
metal itself during fabrication and assembly. Common corodents are chlorides
and caustic, which result in transgranular cracks. These contaminants are
usually carried over by steam from the boiler section and deposited on the
metal surface of superheater tubes. Salts of chlorides and sulfates are
hydrolysed by superheated steam at temperatures as low as 440°C.
Sodium hydroxide will lead to severe local attack under the deposits
Especially if the melting point of the deposited salt mixture is lower than
the steam temperature.
in turbines section scc may be one of corrosion mechanisms in steam turbine
are caused by chemical compounds carried out over into turbines with steam.
High temperature ,stress are present during operation Also the ingress of any
impurities into the steam cycle due to leakage can introduce the compounds
which while not dangerous in themselves, can dissociate into ions which will
combine to form harmful compounds. The turbine stages most likely to be
affected by SCC, are those in the low-pre ssure se ct ion w he re mo istu re
of condensation begins to form.

Fatigue
Fatigue is the result of cyclical stresses in the component. Distinct from
thermal fatigue effects, mechanical fatigue damage is associated with
externally applied stresses. Stresses may be associated with vibration due to
flue gas flow or soot blowers (high-frequency low-amplitude stresses), or they
may be associated with boiler cycling (low-frequency high-amplitude stress
mechanism). If any component which is subject to cyclic stress is in addition
contaminated by a corrosive environment, then the ability o f this
component to resist failure is lowered. Damage most often results from in an
OD initiated crack. Fatigue failure most often occurs at areas of constraint,
such as tube penetrations, welds, attachments or supports.

58
Fireside Corrosion Fatigue

Tubes develop a series of cracks that initiate on the outside diameter (OD) surface
and propagate into the tube wall. Since the damage develops over long periods,
tube surfaces tend to develop appearances described as "elephant hide",

Cracking of OD Surface

Transverse view of surface crack

"alligator hide" or craze cracking. Most commonly seen as a series of

circumferential cracks. Usually found on furnace wall tubes of coal-fired once-
through boiler designs,

59
Waterside Corrosion Fatigue ID initiated wide transgranular cracks which
typically occur adjacent to attachments Tube damage occurs due to combination
of thermal fatigue and corrosion. Corrosion fatigue is influenced by boiler design,
water chemistry, boiler water oxygen content and boiler operation. A combination of
these effects leads to the breakdown of the protective magnetite on the ID surface of
the boiler tube. The loss of this protective scale exposes tube to corrosion.

Corrosion fatigue on tube ID adjacent to attachment

Caustic corrosion : Localized wall loss on the inside diameter (ID) surface of the
tube, resulting in increased stress and strain in the tube wall. is caused by caustic
attack occurs when there is excessive deposition on ID tube surfaces. This leads
to diminished cooling water flow in contact with the tube, which in turn causes
local under-deposit boiling and concentration of boiler water chemicals. If
combined with boiler water chemistry upsets of high pH, it results in caustic condition
which corrosively attacks and breaks down protective magnetite. the selective
deposition of corrosion products and NaOH at locations of high heat flux
of water-cooled tubes. The sources of NaOH contamination may be caustic
regeneration of demineralizer or in-leakage from process fluids. As porous deposits
accumulate in high heat input area, NaOH concentrate under film boiling conditions.
The caustic levels can concentrate from less than 100 ppm NaOH
in the bulk water to over 200,000 ppm adjacent to the tube surface.

60
 4NaOH + Fe3O4 --------- → 2NaFeO2 + Na2FeO2 + 2H2O

Concentrated sodium hydroxide can then react with freshly exposed base metal
to yield hydrogen which cause hydrogen attack

Fe + 2 NaOH --------- → Na2FeO2 + 2H+

The high pH level causes the protective magnetite passive layer Fe3O4 to
dissolve, and rapid corrosion occurs. Caustic corrosion is characterized by
localized hemispherical depression as shown in the Figure.

Region of caustic gouging along internal surface

Hydrogen attack:
Intergranular micro-cracking. Loss of ductility or embrittlement of the tube
material leading to brittle catastrophic rupture. Hydrogen damage is most
Commonly associated with excessive deposition on ID tube surfaces, coupled
with a boiler water low pH excursion. Water chemistry is upset, such as what can
occur from condenser leaks, particularly with salt water cooling medium, and leads
to acidic (low pH) contaminants that can be concentrated in the deposit. Under-
deposit corrosion releases atomic hydrogen which migrates into the tube wall
metal, reacts with carbon in the steel (decarburization) and causes intergranular
separation.Hydrogen damage develops from the generation of hydrogen
during rapid corrosion of the internal surface of the tube. Hydrogen may be

61
produced through direct attack of water on bare metal, after acid cleaning,
or during caustic attack or acid corrosion. The atomic hydrogen migrates through
the tube steel, where it can react with iron carbide (Fe3C ) at the grain boundaries
to form methane.

Fe3 C + 4H = CH4 + 3 Fe

Since neither molecular hydrogen nor methane is capable of diffusing through the
steel, these gases accumulate primarily at the grain boundaries. Eventually,
gas pressure will cause separation of the metal at its grain boundaries,
producing iscontinuous intergranular micro cracks as shown in figure.

Discontinuous intergranular microcracks resulting from methane formation in

the grain boundaries (500X).

Failure due to hydrogen damage

62
As microcracks accumulate, tube strength diminishes until stresses imposed
by boiler pressure exceed the tensile strength of the remaining intact
metal .at this point thick walled longitudinal burst may occur.

Protection from Corrosion of Boiler in Standby Condition:

Prevention of corrosion in boilers in standby condition is more difficult than in

operating boilers. The standby corrosion involves the reaction of surface of boiler
with moisture oxygen and carbon dioxide. Dissolved oxygen is 6 to 10 times more
corrosive than carbon-dioxide and where both gases are present together, the
reaction rate may be 10 to 40 per cent greater than the sum of corrosion rates of
two gases acting separately. Dissolved oxygen attack iron piping as follows:

Fe + 2 H2O = Fe (OH) 2 + H2
4Fe (OH) 2 + O 2 + 2H2O = 4Fe (OH) 3
2Fe (OH) 3 = Fe2 O3 + 3 H2 O

From above, it is observed that those key factors responsible for down time
corrosion are water, oxygen and carbon-dioxide and low pH. Elimination of either
water or oxygen and maintaining appropriate pH will prevent appreciable
corrosion.

Short term preservation: If the boiler is to be shut down for a week or two and
it should be kept ready to take load on short notice, the water level in boiler
drum should be kept at normal operating level with deaerated water containing
up to 10 ppm hydrazine and some Ammonia to raise the pH between (9.5 -
10.5). Some positive pressure should be maintained by intermittent firing of
burner so that there should be no air in-leakage. Where intermittent firing is not
possible, boiler and superheater are flooded with treated water as mentioned
above. In this case first fill the superheater (only in case of drainable
superheater) to overflow into the drum, and then fill boiler through normal
filling connection. The Ammonia and hydrazine should be added in such a
manner that results in uniform concentration of these chemicals throughout the
system. During standby some losses of water occur due to leakages which
must be replaced by feed water. The drum water and feed water should

63
regularly be checked and if feed water is oxygen free and have pH between 9.5
to 10.5 conditions leading to corrosion will not develop.
Long term preservation: for shutdown exceeding one month or more, dry
preservation techniques are preferred. These dry techniques fall in two
categories.
1- Open and Dry Preservation: elimination of all moisture is primary objective in
dry preservation, because as long as the boiler and other metal surfaces remain
dry, no significant corrosion can occur. Air in contact with moisture is extremely
corrosive and water leakages into the unit or sweating of surface must therefore
be avoided. The boiler should be drained completely, thoroughly cleaned on
both fire side and water side. All internal surfaces should be dried, by circulating
warm air or some heating device such as heating lamps or resistant heaters in
the boiler drum and furnace. The boiler should be left open for free circulation of
air. During dry preservation, the boiler should be inspected for any
condensation.

2-Closed Dry Preservation: The closed dry preservation is useful when plant

atmosphere contain corrosive fumes and or abrasive dust which could enter the

open dry boiler. It is also generally useful in humid coastal areas. Similarly as

mentioned above under open dry preservation, the boiler and superheater should

be drained and dried with warm air. Trays containing drying agent such as

quicklime (calcium oxide CaO) activated alumina or silica gel should be placed in

boiler drum and furnace to absorb any moisture present. The recommended

amount of drying agent per one cubic meter of boiler volume is 0.907 kg of quick

lime 2.27 kg of silica gel. Silica gel is preferred drying agent, because it can be

easily regenerated by heating 2 to 4 hours at 325 to 350oC, and it has high

moisture absorption capacity. It absorbs 30% its weight of moisture. All manholes

should be closed so that no moisture could enter the boiler. The drying agent

64
should be inspected from time to time and if exhausted must be replaced with

regenerated one.

3-Wet Preservation: For wet preservation the boiler and superheater should be

filled with treated water Containing Hydrazine above 200 ppm and sufficient

Ammonia is added to maintain pH between (9.5 - 10.5). When filling the boiler for

wet preservation, first fill the superheater to overflow into the drum, and then fill

the boiler through normal filling connection. The Ammonia and Hydrazine should

be added in such a manner that results in uniform concentration of these

chemicals throughout the system. It is also recommended that a positive pressure

of Nitrogen gas (approximately 0.4 to 0.7 bar) be maintained on the unit

whenever it is filled for preservation. The drum water and feed water should be

regularly checked. If feed water and drum water are oxygen free and has pH 9.5

to 10.5 conditions leading to corrosion will not exist.

65
Condensate corrosion:

Carbon dioxide related corrosion is found almost exclusively in condensate

systems. CO2 is formed by the decomposition of bicarbonate and carbonate
alkalinity in the boiler, indicated below:
2HCO3 - + heat = CO3- + CO2 + H2O
CO3- + H2O + heat = 2OH- + CO2
Dissolved CO2 in the condensate accelerates corrosion in several ways. The
formation of carbonic acid lowers condensate pH and may cause low pH
corrosion. In addition, carbonic acid leads to the formation of ferrous
bicarbonate which is highly soluble and has no passivating effect.
Fe + 2H+ 2HCO3- = Fe(HCO3)2 + H2
CO 2 carries over with the steam and then redissolves in condensate return
lines
CO2 + H2O = H2CO3
Any oxygen present in the condensate will oxidize the ferrous bicarbonate to
ferric oxide and liberate carbon dioxide to repeat the process.

Control of Condensate Corrosion

A class of inhibitors known as Neutralizing Amines is generally used to

prevent postboiler corrosion caused by low pH. They neutralize carbonic acid

and raise condensate pH.Morpholine and Cyclohexylamine are the most

commonly used neutralizing amines. Selection of the neutralizing chemicals

based on distribution ratio can be very important. If protection of

postboiler condensate lines is required, an amine with a high steam-to-liquid

distribution ratio is the best. Where corrosion prevention in the boiler is more

critical, a more appropriate neutralizing amine is one whose distribution ratio

allows most of it to remain in the boiler water. Often a blend of two amines is

used to provide universal protection. The disadvantages of neutralizing inhibitors

are ineffectiveness against corrosion by dissolved oxygen. Filming Amines

represent an effective and economical approach against oxygen corrosion in

66
condensate system. These products are long chain amines that form a film

on the pipe wall. They provide a physical barrier between the material surface

and the process liquid. The amine group attaches to the metal surface while

the nonpolar organic portion acts as the film.

67
 2-3 Corrosion in cooling water system

Cooling water systems provide an environment where the four main cooling
problems will exist.
Corrosion- Water tends to convert metals (such as carbon steel) to their oxide
states.
Scale- Water impurities, such as calcium and magnesium hardness can precipitate
and deposit Depending on their concentrations, water temperature, pH, alkalinity,
and other water Characteristics.
Microbiological Contamination - Cooling water systems offer a favorable
environment for microorganisms to grow and cause problems.
Fouling-Suspended solids from either external or internal sources can cause
deposits. If left uncontrolled, these problems, either alone or together, can
cause:
-Increased maintenance cost
-Reduced heat transfer efficiency and therefore greater energy losses
-Possible production cutbacks or shutdowns.

Corrosion:
Carbon steel is a commonly used metal in cooling water systems and is very
susceptible to corrosion. It will return to its iron oxide state. For corrosion to
occur, a corrosion cell consisting of an anode, a cathode and an electrolyte must
exist. Metal ions dissolve into the electrolyte (water) at the anode. Electrically
charged particles (electrons) are left behind. These electrons flow through the
metal to other points (cathodes) where electron-consuming reactions occur. The
result of this activity is the loss of metal and often the formation of a deposit.
Copper, aluminum alloys, and stainless steel are subject to corrosion as mild steel
but corrode more slowly than mild steel. However, in some waters these metals
may be subject to severe localized (or pitting) attack. In addition, dissolved
gases, such as H2S or NH3 are frequently more destructive to these metals than to
mild steel.
Galvanic attack can occur when two different metals are in contact. The more
active metal corrodes rapidly. Common examples in water systems are steel and
brass, aluminum and steel, zinc and steel, and zinc and brass. If galvanic attack
occurs, them evitca erommetal first will corrode.

68
Water characteristics that effect corrosion:
- Oxygen and other dissolved gases.

- Dissolved or suspended solids.

- Alkalinity or acidity (pH).

- Velocity.
- Temperature.
- Microbial activity.
Oxygen and other dissolved gases:
- Oxygen dissolved in the water is essential for the cathodic reaction to take
place. So corrosion increases ,oxygen deficient areas becomes anodic
(differential aeration cell)

- Nitrogen aggravates Cavitation corrosion.

- Ammonia selectively corrosive to copper based metals.

NH3 +H2O → NH4OH

NH4OH+Cu2+ → Cu (NH3)2+ + H2O

Copper ammonium complex very corrosive to copper

- Hydrogen sulfide promotes acid attack by decreasing PH, responsible for

formation of iron sulfide which is cathodic to the iron leads to galvanic corrosion.

- Chlorine acid attack promotes by hydrolyzing to HOCl , HCl, strips corrosion

inhibitor films.

- Carbon dioxide reduces PH and promotes acid attack.

CO2+H2O → H2CO3

Dissolved or suspended solids:

Dissolved solids can affect the corrosion reaction by increasing the electrical
conductivity of the water. The higher the dissolved solids concentration, the
greater the conductivity and the more likelihood of corrosion. Dissolved chlorides
and sulfates are particularly corrosive. Suspended solids can influence corrosion
by erosive or abrasive action, and they can settle on metal surfaces to set up
localized corrosion cells.

69
Alkalinity or acidity (PH):
Acidic and slightly alkaline water can dissolve metal and the protective oxide film
on metal surfaces. More alkaline water favors the formation of the protective
oxide layer.
Water velocity:
High-velocity water increases corrosion by transporting oxygen to the metal and
by carrying away corrosion products at a faster rate. High velocity can also cause
erosion of metal surfaces, protective films, and oxides. When water velocity is low,
deposition of suspended solids can establish localized corrosion cells, thereby
increasing corrosion rates.

Temperature:
Below 71°C, every 10°C increase in temperature causes corrosion rates to
double. Above 71°C, additional temperature increases have relatively little effect
on corrosion rates in cooling water systems.
Higher temperature fevers oxygen depolarization, lower hydrogen over voltage,
increase corrosion. As any chemical reaction increase in temperature increase
corrosion rate.

Microbial growth:
Microbial growths promote the formation of corrosion cells. In addition, the
byproducts of some organisms, such as hydrogen sulfide from anaerobic
corrosive bacteria, are corrosive.

Methods used to prevent corrosion:

Corrosion can be prevented or minimized by one or more of the following
methods:
When designing a new system, choose corrosion-resistant materials to minimize
the effect of an aggressive environment.
• Adjust pH.
• Apply protective coatings such as paints, metal plating, tar, or plastids.
• Protect cathodically, using sacrificial metals.
• Add protective film-forming chemical inhibitors that the water can distribute to
all wetted parts of the system.

70
Chemical corrosion inhibitors:

Chemical inhibitors reduce or stop corrosion by interfering with the

corrosion mechanism. Inhibitors usually affect either the anode or the
cathode. Anodic corrosion inhibitors establish a protective film on the
anode. Though these inhibitors can be effective, they can be dangerous: if
insufficient anodic inhibitor is present, the entire corrosion potential occurs
at the unprotected anode sites. This causes severe localized (or pitting)
attack.
Cathodic corrosion inhibitors form a protective film on the cathode. These
inhibitors reduce the corrosion rate in direct proportion to the reduction of
cathodic area.
General corrosion inhibitors protect by filming all metal surfaces
whether anodic or cathodic.

Inhibitors commonly used for cooling water systems:

Mainly anodic, Chromates, Nitrites, Orthophosphates, Silicates, Mainly cathodic

Bicarbonates, Metal cations, Polyphosphates, General Soluble oils Other organics
The choice of treatment is basically a matter of economics. In a once-through
system, a very large volume of water passes through the system only once.
Protection can be obtained with relatively few parts per million of treatment
because the water does not change in composition significantly while passing
through equipment. In an open recirculating system, more chemical must be
present because the water composition changes significantly through the
evaporation process. Corrosive and scaling constituents are concentrated.
However, treatment chemicals also concentrate by evaporation; therefore, after
the initial dosage, only moderate dosages will maintain the higher level of
treatment needed for these systems.
In a closed recirculating system, water composition remains fairly constant. There
is very little loss of either water or treatment chemical.

Fouling: Fouling is the accumulation of solid material other than scale in a way
that hampers the operation of plant equipment or contributes to its
deterioration. The most important factors influencing fouling are:

Water characteristics

• Temperature
• Flow velocity
• Microbial growths
• Corrosion

71
• Contamination

Water characteristics:
Distilled water will not foul. However, most waters contain the dissolved and
suspended materials that can cause a significant fouling problem under certain
conditions.
Temperature:
Increasing temperature increases the fouling tendency. Because heat-transfer
surfaces are hotter, than the cooling water, they accelerate fouling.

Flow rate affect:

At low flow rates (one foot per second or less), fouling occurs due to natural
settling of suspended material. At higher flow rates (three feet per second or
more), fouling can still occur, but usually is less severe.

Microbial growths:
Microorganisms can form deposits on any surface. In addition, corrosive or iron
depositing bacteria cause or utilize corrosion products, which subsequently
deposit as voluminous foulants. All microbial colonies act as a collection site for
silt and dirt, causing a deposit of different foulants.

Fouling of a heat exchanger tube bundle.

72
Corrosion eeffect on fouling:
Corrosion can form corrosion products that migrate and mix with debris,
process contamination, or microbial masses to aggravate fouling.

Process contamination:
Material that leaks from the process side of heat exchange equipment can
cause serious fouling problems in several ways:

• Depositing as insoluble products

• Providing nutrient for microorganisms and causing severe microbial growths
• Reacting with scale or corrosion inhibitors to form insoluble foulants

Microbiological Problems:

The uncontrolled growth of microorganisms can lead to deposit formations which

contribute to fouling, corrosion and scale. Microbial slimes are masses of
microscopic organisms and their waste products. These slimes are usually
characterized by their gooey feeling and can be plant or animal. Some
organisms do not create slime deposits and do not promote metal corrosion. The
presence of large numbers of these harmless organisms, however, indicates that
conditions are ideal for the growth of harmful organisms.The make-up water
supply, wind, and insects can all carry microorganisms into a cooling water
system.

Factors contribute to microbial growth:

The most important factor is the degree of microbial contamination. Next in
importance are:
Nutrients: For instance, hydrocarbons or other carbon sources can serve as food
for slime-forming organisms.

• Atmosphere: Organism growth depends upon the availability of oxygen or

carbon dioxide.

• Location: Such factors as the amounts of light and moisture significantly

affect growth
rates.

• Temperatures: Organisms that make up slime tend to flourish between 40

and 150°F.

Slime can cause or accelerate the rate of scale formation. Slime can cause
treatment chemicals for scale to be ineffective. When deposits form, heat

73
transfer is reduced. This causes possible production cutbacks and higher
energy cost.

Slime masses themselves are foulants. They provide excellent sites for
the deposition of other foulants. Other microorganisms and suspended
solids can become part of the fouling deposit. Although many organisms tend
to die at high temperatures, the remaining debris still fouls metal surfaces.

Slime cause corrosion:

Certain organisms, for example, the sulfate-reducing type, generate
corrosive hydrogen sulfide which causes severe pitting attack. In addition,
slime can accelerate corrosion by depositing on the metal and preventing
protective film formation.

Microbiological contamination on a tube sheet

What types of chemicals are used for microbial control?

Three general classes of chemicals are used in microbial control:

• Oxidizing biocides
• Non-oxidizing biocides
• Biodispersants
A combination of all three generally makes an excellent program.
Chemicals called "oxidizing biocides" literally "burn up" any microbe they come in
direct contact with. Common oxidizers are chlorine, chlorine dioxide, bromine and
ozone.
Chlorine is one of the most widely used, cost-effective biocides, and is available
in liquid, gaseous, or solid form. Its effectiveness is increased when used with
nonoxidizing biocides and biological dispersants.
Non-oxidizing biocides are organic compounds utilized in killing microorganisms.
They are effective in areas or systems where chlorine may not be adequate.

74
Biodispersants:
These chemicals do not kill organisms; they loosen microbial deposits, which can
then flushed away. They also expose new layers' of microbial slime or algae to
the attack of oxidizing, biocides, Biodispersants are an effective preventive
measure, because they make it difficult for the microorganisms to attach to the
metal surfaces to form deposits.

Monitoring and Control

What are the steps in system preparation and start-up?

To begin a cooling water system protection program successfully, the following
preparation and start-up procedures must be followed:

• System cleaning
• Application of special pretreatment chemicals
• Initial high dose application of corrosion inhibitors
• Ongoing application of corrosion inhibitors at maintenance levels

What effect does acid cleaning have on a cooling system?

Acid removes corrosion products and some mineral contaminants, but has little
effect upon organic materials. With improper application it may attack system
metal and cause severe metal attack. Improper flushing will leave metal
surfaces in a highly reactive state, which makes them especially vulnerable to
corrosion attack.
Corrosion Coupons-To establish relative corrosion rates of different metals in
cooling systems, small metal strips called corrosion coupons can be used. These
preweighed coupons are placed in the system for at least 30 days, then removed,
cleaned, and weighed again. The difference in the coupon's weight before and
after exposure is used in calculating the corrosion rate.
The Corrater-An electronic instrument that measures the corrosion and pitting
tendencies in a cooling system. It provides an instantaneous, direct reading of
the system's corrosion rate in mils per year (mpy) when its probe is inserted into
the cooling water.

75
 2-4 Corrosion in CO2 Removal unit

Process Fundamentals
Carbon dioxide is absorbed by an aqueous potassium carbonate solution with
diethanolamine (DEA) added as activator, according to the reaction:

K2CO3 + CO2 + H2O ←

→ 2 KHCO3

Co2 Removal unit flow sheet.

76
Potassium carbonate solution route:
The solution leaves the bottom of absorber 305C001 (54-2201) at
temperature of approx. 110oC and is fed to the top of desorber
305C002 (54-2202) via expansion turbine 305MT01. (54-1601) The
solution is regenerated by flashing in the top of the desorber and
then flowing downwards, counter current to the stripping steam. The
stripping steam required is generated by heat exchange against the
hot process gas in gas cooler 305E001 (steam generator 54-2101)
and in reboiler 305E002. (54-2102) The steam in the flash drum
305D002, 54-200 4 obtained from the intermediate expansion of
the regenerated potassium carbonate solution, is sent to the
desorber via steam ejectors 305A001 to 305A006 (54-2305).
The regenerated solution from the bottom of the desorber is
expanded into flash drum to a temperature of approx. 117 oC, at
which point steam is liberated and, consequently, the temperature of
the flashed solution drops to 104 oC. Flash drum also serves as
pump suction tank.
From the flash drum, the regenerated solution is pumped to the
absorber, via solution pumps. Approximately 80 % of the solution is
fed uncooled to the lower section of the absorber. The remaining
solution is cooled down to approximately 70 oC in solution air cooler
and then fed to the upper part of the absorber. Both solution
streams are distributed evenly over the cross sectional area of the
absorber by means of a distribution tray.

Potassium metavanadate is added as corrosion inhibitor

Because of the corrosive nature of the solution and the selection of
material of construction (carbon steel 35) which have no resistance
To corrosion so corrosion inhibitor must be added to make passive
layer of Fe3O4 (Magnetite) which protect the metal from corrosion.

Fe ------ → Fe2+ +2e'

2+ 5+
Fe +V ------------ → Fe3+ +V4+

77
The potassium metavanadate may be considered as means of anodic
corrosion protection for Benfield solution, its important for the full activity of
potassium metavanadate the ratio V5+/V4+ is increased to more than 0.4 .
Because V5+ is responsible for formation of passive layer.
As any anodic corrosion inhibitor in case of decrease it’s concentration ,very

rabid localized corrosion takes place if the passive layer penetrated the un

passivated area becomes anode ,the large passivated area act as cathode .

Passivation of the carbon dioxide removal unit

The solution cycle must be operating satisfactorily, and a temperature of 100

to 105 °C must have been reached. The initial concentration in the solution
cycle shall be 14 to 15 g/l potassium metavanadate. For a period of approx. 4
to 5 days this solution is circulated at a temperature of 100 to 105 °C. The
concentration of vanadium is to be checked, and maintained by adding
potassium metavanadate, if the minimum value falls below 14 g/l potassium
metavanadate. During these 4 to 5 days carbon dioxide-bearing gas
should not on any account be fed to absorber (54-2201) 305C001.

Fresh potassium metavanadate is all of V5+ valence. It is principally the V5+

that is responsible for the protective film that protects the iron surfaces
against bicarbonate and carbon dioxide corrosion. For good Passivation a
reasonably high concentration of V5+ is of essential importance. The reduced
form V4+ is probably not capable of building a protective film by itself.
After completion of the Passivation process, a concentration of 14 g/l
potassium metavanadate is to be set and maintained constant.

After some time of operation equilibrium is established between V5+ and V4+,
generally with a ratio of about 1 or less. If this ratio goes down to values
smaller than 0.3, there is a danger of abrasion due to packing movement, dirt
in the solution, etc. the protective film can be thinned and lost and the iron
concentration of solution will be increased. Therefore an increase of iron
content is the best indication that the V5+ content of the operating solution is
not correct. Normally the solution will have an iron concentration of 10 to 100
ppm.

78
The operating solution in the bottom of desorber (54-2202), 305C002 is
adjusted to normal level by either adding or draining off some solution. The
concentration of the operating solution is adjusted to set points. Losses of
water due to escaping vapour are made up by adding condensate.
The solids content of the operating solution is to be checked (qualitative
check: allow to settle in beaker). A part-stream of the operating solution is
continuously pumped by filter pump via solution filter 305F004 (54-2306) into
line to flash drum 305D002 (54-2004).
The operating solution is continuously monitored analytically. In particular,
the iron content is checked. Ferric oxide, not removed by the previous
cleaning of surfaces, might now appear in the solution. The pressure in
absorber 305C001 (54-2201 )is maintained by adding nitrogen.
In order to avoid unnecessary losses of DEA during the test period and the
passivation procedure of the unit, The required quantity of diethanolamine is
not to be added to the solution until immediately after gas is fed to the
absorber.
The following is to be observed for the later operation of the carbon dioxide
removal unit.
If the plant has been shut down for a short time (a few days) with no
exposure to air, a restart without revanadation is probably satisfactory. But
24 hours before the process gas is fed into absorber the circulation of the
carbonate solution must be in operation.
On exposure to air or if the coating has dried, the system should be
revanadated before restarting. The solution used previously can be used for
revanadation if the fraction converted (conversion factor 'f') is 0.25 or lower.
The vanadium level should be at a concentration of 14 g/l potassium
metavanadate and fresh potassium metavanadate should be added if
necessary. A reasonably high concentration of the potassium metavanadate
must be in the V5+ form. The procedure described in this Section can be used
for revanadation with the following exception:
The revanadation time can be reduced to 36 hours. The diethanolamine
should already be in the solution and has no effect on revanadation. If, during
the shutdown, plant changes were made that introduced unvanadated carbon

79
steel piping or equipment into the system, a full 4-5 days vanadation
procedure is necessary to insure adequate protection.

Oxidation of solution:
When the solution has a concentration of 14 g/l potassium metavanadate the
ratio between V5+ and V4+ shall be not less than 0.3.
If this ratio goes down to values less than 0.3, than start oxidation of the
solution.
Drain regenerated solution from system to the slop and make-up drum. When
the solution temperature is cooled down close to 50 °C start the slop pump
305P005 (54-1109) cycle and the air injection for approx. 30 min. (KNO2 or
H2O2) can be used).

After this time the ratio V5+/V4+ is increased to more than 0.4 the finished
charge is now pumped back into the system. Instead oxidation of solution
directs from the system you can oxidise solution from the storage tank in the
same way. Pump the prepared solution into the system and replace the
solution in the storage tank by a charge from the system through the slop
drum.
The temperature of the solution during oxidation shall be close to 50 °C to
avoid degradation of DEA which will cause higher losses and corrosion
products.
In case the concentration of potassium metavanadate is 10 g/l respectively
12 g/l the ratio between V5+ and V4+ shall be 0.55 respect 0.45 without any
influence.

80
 2-5 High Temperature Corrosion:

High-temperature corrosion is a form of corrosion that does not require the

presence of a liquid electrolyte. Sometimes, this type of damage is called dry
corrosion or scaling.
• Types of high-temperature corrosion
– Oxidation, Sulfidation
– Carburization, Decarburization, Nitriding
– Hydrogen attack, Halide attack
– Metal Dusting
The term oxidation is ambivalent because it can either refer to the formation
of oxides or to the mechanism of oxidation of a metal (i.e., its change to a
higher valence than the metallic state). Strictly speaking, high-temperature
oxidation is only one type of high-temperature corrosion, but it is the most
important high-temperature corrosion reaction.

High Temperature Oxidation

In most industrial environments oxidation often participates in the high-
temperature corrosion reactions; regardless of the predominant mode of
corrosion Alloys often rely upon the oxidation reaction to develop a protective
scale to resist corrosion attack such as sulfidation, carburization, and other
forms of high temperature attack. In general, the names of the corrosion
mechanisms are determined by the most abundant dominant corrosion
products. For example, oxidation implies oxides, sulfidation implies sulfides,

81
sulfidation/ oxidation implies sulfides plus oxides, and carburization implies
carbides.
Oxidizing environments refer to high-oxygen activities, with excess oxygen.
Reducing environments are characterized by low-oxygen activities, with no
excess oxygen available. Clearly, oxide scale formation is more limited under
such reducing conditions. It is for this reason that reducing industrial
environments are generally considered to be more corrosive than the
oxidizing variety. However, there are important exceptions to this
generalization. At high temperatures, metals can react “directly” with the
gaseous atmosphere. Electrochemical reaction sequences remain, however,
the underlying mechanism of high-temperature corrosion. The properties of
high-temperature oxide films, such as their thermodynamic stability, ionic
defect structure, and detailed morphology, play a crucial role in determining
the oxidation resistance of a metal or alloy in a specific environment.

Scaling Temperatures in Air

Six types of oxidation phenomena:

• At low temperature, diffusion of oxygen and metal species through a
compact oxide film.
• At moderate and high temperatures, a combination of oxide film formation
and oxide volatility.
• At moderate and high temperatures, the formation of volatile metal

82
 and oxide species at the metal-oxide interface and transport through the
oxide lattice and mechanically formed cracks in the oxide layer
• At moderate and high temperatures, the direct formation of volatile
oxide gases.
• At high temperature, the gaseous diffusion of oxygen through a barrier
layer of volatilized oxides.
• At high temperature, spalling of metal and oxide particles.

The Pilling-Bedworth relationship

The volume of the oxide formed, relative to the volume of the metal
consumed, is an important parameter in predicting the degree of protection
Provided by the oxide scale. If the oxide volume is relatively low, tensile
stresses can crack the oxide layers. Oxides, essentially representing brittle
ceramics, are particularly susceptible to fracture and cracking under such
tensile stresses. If the oxide volume is very high, stresses will be set up that
can lead to a break in the adhesion between the metal and oxide. For a high
degree of protection, it can thus be argued that the volume of the oxide
formed should be similar to that of the metal consumed. This argument is the
basis for the Pilling- Bedworth ratio:

Where:
W = molecular weight of oxide
D = density of the oxide
n = number of metal atoms in the oxide molecule
d = density of the metal
w =atomic weight of the metal

• For an oxide to be protective the oxide-metal volume ratio must be

somewhat larger than unity.
– Volume ration < 1, the oxide does not totally cover the metal surface,
permitting free access of the corrosive atmosphere to the metal on certain
locations.

83
– Volume ratio is > 2, compressive stresses will develop in the oxide layer,
which could result in spalling of the oxide and in exposure of the metal to the
corrosive atmosphere.

Oxide-Metal Volume Ratios of Some Common Metals

When considering specific alloys for high-temperature service, it is imperative

to consider other properties besides the corrosion resistance. It would be
futile, for example, to select a stainless steel with high-corrosion resistance
for an application in which strength requirements could not be met. In
general, austenitic stainless steels are substantially stronger than ferritic
stainless steels at high temperatures, as indicated by a comparison of stress
rupture properties.

84
 Ranges of rupture strength (rupture in 10,000 h) for typical ferritic
and austenitic stainless steels.

Oxidation is generally described as the most commonly encountered

form of high-temperature corrosion. Most corrosion and heat resistant
alloys rely on the formation of an oxide film to provide corrosion
resistance. Chromium oxide (Cr2O3, chromia) is the most common
of such films. In many industrial corrosion problems, oxidation does not
occur in isolation; rather a combination of high-temperature corrosion
mechanisms causes material degradation when contaminants (sulfur,
chlorine, vanadium, etc.) are present in the atmosphere. Strictly speaking,
the oxidation process is only applicable to uncontaminated air and

85
clean combustion atmospheres. For a given material, the operating
temperature assumes a critical role in determining the oxidation rate. As
temperature is increased, the rate of oxidation also increases. It has been
argued that thermal cycling in the former causes cracking and spalling
damage in protective oxide scales, resulting in lower allowable operating
temperatures. Some alloys’ behavior (austenitic stainless steels) follows this
argument, whereas others (ferritic stainless steels) actually behave in the
opposite manner Increased chromium content is the most common way of
improving oxidation resistance.
Apart from chromium, alloying additions used to enhance oxidation
resistance include aluminum, silicon, nickel, and some of the rare earth
metals. For oxidation resistance above 1200°C, alloys that rely on protective
Al2O3 (alumina) scale formation are to be preferred over those forming
chromia Increasing the nickel content of the austenitic stainless steels up to
about 30%, can have a strong beneficial synergistic effect with chromium.
Extensive testing of alloys has shown that many alloys establish parabolic
time dependence after a minimum time of 1000 h in air at temperatures
above 900°C. If the surface corrosion product (scale) is removed or cracked
so that the underlying metal is exposed to the gas,
the rate of oxidation is faster. The influence of O2 partial pressure on
oxidation above 900°C is specific to each alloy, as illustrated for some
common alloys in Following Fig.

86
Effect of oxygen partial pressure upon metal penetration of some common
alloys by oxidation after exposure for 1 year at 930°C.

Most alloys do not show a strong influence of the O2 concentration upon the
total penetration. Alloys such as Alloy HR-120, and Alloy 214 even exhibit
slower oxidation rates as the O2 concentration increases. These alloys are rich
in Cr or Al, whose oxides are stabilized by increasing O2 levels. Alloys, which
generally exhibit increased oxidation rates as the O2 concentration increase,
are S30400, S41000, and S44600 stainless steels and 9Cr-1Mo, Incoloy DS,
alloys 617, and 253MA. These alloys tend to form poor oxide scales.

87
Sulfidation:

Sulfidation is a common high-temperature corrosion-failure mechanism.

As the name implies, it is related to the presence of contamination by sulfur
compounds. When examining this form of damage microscopically, a “front”
of sulfidation is often seen to penetrate into the affected alloy. Localized
pitting-type attack is also possible.

Sulfur attack. Pure nickel (100X).

Gaseous environments associated with sulfidation divided into the following

three categories:
-Hydrogen-hydrogen sulfide mixtures or sulfur vapor of a highly reducing
Nature.
- Moderately reducing mixed gas environments that contain mixtures
of hydrogen, water, carbon dioxide, carbon monoxide, and hydrogen
sulfide.
- Sulfur dioxide-containing atmospheres.
In the first category, sulfides rather than protective chromia are
thermodynamically stable. Hydrogen-hydrogen sulfide mixtures are found in
catalytic reformers in oil refining operations. Organic sulfur compounds such

88
as mercaptans, polysulfides, and thiophenes, as well as elemental sulfur,
contaminate practically all crude oils in various concentrations and are
partially converted to hydrogen sulfide in refining operations. Hydrogen
sulfide in the presence of hydrogen becomes extremely corrosive above 260
to 288°C. Sulfidation problems may also be encountered at lower
temperatures. Increased temperatures and higher hydrogen sulfide contents
generally lead to higher degradation rates. For catalytic reforming, the 18Cr-
8Ni austenitic stainless steels grades are considered to be adequately
resistant to sulfidation. The use of stabilized grades is advisable. Some
sensitization is unavoidable if exposure in the sensitizing temperature range
is continuous or long term. Stainless equipment subjected to such exposure
and to sulfidation corrosion should be treated with a 2% soda ash solution or
an ammonia solution immediately upon shutdown to avoid the formation of
polythionic acid, which can cause severe intergranular corrosion and stress
cracking. Vessels for high-pressure hydrotreating and other heavy crude
fraction upgrading processes (e.g., hydrocracking) are usually constructed of
one of the Cr-Mo alloys. To control sulfidation, they are internally clad with
one of the 300 series austenitic stainless steels. In contrast, piping, heat
exchangers, valves, and other components exposed to high-temperature
hydrogen-hydrogen sulfide environments are usually entirely constructed out
of these austenitic stainless alloys.
In some designs alloy 800H has been used for piping and headers. In others,
centrifugally cast HF-modified piping has been used. The effects of
temperature and H2S concentration upon sulfidation of alloys often used in
oil refining services are shown in the following Figure which represent the
metal losses expected after 1 year of exposure .

89
 Effect of H2S partial pressure upon sulfidation corrosion after 1 year in H2-
H2S gases at 34 atm and 540°C.

Increasing the Cr content of the alloy greatly slows the sulfidation, as seen in
progression from 9Cr-1Mo, S41000, S30400, 800H, 825, and 625.
The presence of oxidizing gases such as H2O (steam) or CO2 slow the
sulfidation rate below that expected if only the H2S-H2 concentrations were
considered. This can be important because gases, which are thought to
contain only H2S-H2, often also contain some H2O. For example, a gas, which
has been well mixed and equilibrated with water at room temperature, may
contain up to 2% water vapor in the gas. Sulfidation rate predictions based

90
only upon the H2S-H2 concentrations may overestimate the rate of metal loss.
This slowed corrosion rate is sometimes called sulfidation/oxidation because it
represents a transition between the rapid corrosion of sulfidation and the slow
corrosion of oxidation of alloyed metals containing either Cr or Al.
Atmospheres high in sulfur dioxide are encountered in sulfur furnaces,
where sulfur is combusted in air for manufacturing sulfuric acid. Lower levels
of sulfur dioxide are encountered in flue gases when fossil fuels contaminated
with sulfur species are combusted. It has been pointed out that relatively
little corrosion data exist for engineering alloys in these atmospheres.
A tricky situation can arise when designing equipment that requires
resistance for variable times of exposure to multiple environments such as
oxidizing and sulfidizing conditions. If oxidation times dominate significantly
over sulfidation, it may be prudent to select a high-nickel, high-chromium
alloy. Alloys such as HR-120, HR-160, 602CA, or 45TM belong to this
category. If sulfidation dominates, low-nickel, high-iron, high-chromium
alloys are more appropriate. Increasing the concentration of H2S tends to
increase the sulfidation rate of alloys. High Ni alloys (greater than 35% Ni)
used either as base metals oras welding filler metals are a special concern in
sulfidation conditions.
Sulfidation of high Ni alloys can be especially rapid and yield corrosion rates
greater than 2.5 mm/y if the temperature exceeds 630°C, which is the
melting point of a potential corrosion product that forms as a mixture of Ni
and nickel sulfide. A reasonable approach for high Ni alloys is that they
should not be used in sulfidation conditions when metal temperatures will
approach or exceed 630°C. High Ni alloys with high Cr levels (such as alloys
625 or 825) can be very suitable with low corrosion rates at lower
temperatures.
Alloys that have high concentrations of cobalt are some of the commercially
available alloys that are most resistant to sulfidation at temperatures
in excess of 630°C. The superior resistance of the cobalt-containing alloys is a
result of the higher melting point of the sulfide corrosion products that form
on these alloys, as compared to the lower melting points of iron and nickel
sulfides. Examples of cobalt-containing alloys, 617, HR-160, 6, and 188.

91
Carburization
Carburization is the diffusion of carbon into a metal and the formation of
metallic carbides within the structure of the metal, can occur when metals
are exposed to carbon monoxide, effects of Carburization are important:
1. The carburized area will be hard and brittle at ambient
temperatures.
2. The additional carbon will provide higher strength.
3. The carburized zone will increase in volume.
4. The co-efficient of thermal expansion of carburized material will be
less than that of the base material.
5- Carburized material will be less corrosion resistant, because the
carbon will combine with the protective chromium. (See the Figure)
The protective value of the chromium will be lost and the chromium
carbides will be more easily oxidized.

Carburization.Type 304 stainless steel (100X).600 to 650°C.for

19,000 hr.

In austenitic stainless steels, unexpected atmospheric corrosion can be an

indicator of carburization. If carburization has proceeded far enough to
combine with sufficient chromium, the steel is no longer austenitic and
carburization can be detected by the presence of magnetism methane,
ethane, or other hydrocarbons at elevated temperatures. Carbon from the
environment combines primarily with chromium but also with any other
carbide formers (Nb, Mo, Ti) present in the alloy to form internal carbides.

92
Carbides formed in the microstructure can be complex in composition and
structure and can be found to precipitate on the grain boundaries or inside
the grains. The main undesirable effect of carbide formation is embrittlement
and reduced ductility at temperatures up to 482 to 538°C. By tying up
chromium in the form of stable chromium-rich carbides, carburization also
reduces oxidation resistance. Creep strength may also be adversely affected,
and internal stresses can arise from the volume increase associated with the
carbon uptake and carbide formation. This internal pressure represents
additional stress superimposed on operational stresses. Localized bulging, or
even cracking, of carburized components is indicative of high internal stress
levels that can be generated. Carburization damage is mainly associated with
high-temperature exposure to carbon dioxide, methane, and other
hydrocarbons. Heat treating equipment used for gas carburization (surface
hardening) of steels is also vulnerable. An insidious aspect of carburization is
its nonuniform nature. Just as for other forms of localized corrosion, it is
extremely difficult to predict and model localized carburization damage .As a
rule of thumb, carburization problems only occur at temperatures above
815°C, because of unfavorable kinetics at lower temperatures. Carburization
is therefore not a common occurrence in most refining operations because of
the relatively low tube temperatures of most refinery-fired heaters.
Carburization is more common in the petrochemical industry. A notable
problem area has been the radiant and shield sections of ethylene cracking
furnaces, due to high tube temperatures up to 1150°C. Apart from
temperature, an increase in carbon potential of the gas mix is responsible for
a higher severity of damage. High carbon potentials are associated with the
ethane, propane, naphtha, and other hydrocarbons as reactants that are
cracked. Less severe and frequent carburization damage has been reported
in reforming operations and in other processes handling hydrocarbon
streams or certain ratios of CO/CO2/H2 gas mixtures at high temperature. As
in the case of oxidation and sulfidation, chromium is considered to impart
the greatest resistance to carburization. Other beneficial elements include
nickel, silicon, columbium, titanium, tungsten, aluminum, and molybdenum.
The most important characteristic of a successful alloy is its ability to form
and maintain a stable, protective oxide film. Aluminum and silicon alloying
additions can contribute positively to this requirement. The tubes of
ethylene-cracking furnaces were originally largely manufactured out of the
cast HK-40 alloy (Fe-25Cr-20Ni). Since the mid-1980s, more resistant HP
alloys have been introduced, but carburization problems have not been
eliminated, probably due to more severe operating conditions in the form of

93
higher temperatures. Some operators have implemented a 35Cr-45Ni cast
alloy, with various additions,to combat these conditions. For short residence-
time furnaces with small tubes, wrought alloys including HK4M and HPM,
Alloy 803, and Alloy 800H have been used. Other wrought alloys (e.g., 85H
and HR-160, both with high silicon) have been applied to combat
carburization of trays, retorts, and other components used in carburizing
heat treatments. However, their limited fabricability precludes broad use in
the refining or petrochemical industry. Carburization causes the normally
nonmagnetic wrought and cast heat-resistant alloys to become magnetic.
The resulting magnetic permeability provides a methodology for monitoring
the extent of carburization damage. Measurement devices range from simple
hand-held magnets to advanced multifrequency eddy current instruments.
Carburization patterns can also reveal uneven temperature distributions that
might otherwise have gone undetected. Most alloys tend to have more
carburization penetration with increasing temperatures. The following figure
summarizes carburization after 1 year for some common alloys exposed to
solid carbon and 200 ppm H2S.The time dependence of carburization has
been commonly reported to be parabolic. Removal or cracking of any surface
carbide scale will tend to increase the rate of carburization. One thousand
hours may be required to establish the time dependence expected for long-
term service. Carburization data are properly used when the time
dependence is considered. Increasing the concentration of H2S tends to slow
the carburization rate of alloys.
The effect of H2S is to slow decomposition of the CH4, which adsorbs onto
the metal surface, thus slowing the rate of carburization. Increasing
concentrations will slow carburization until the concentrations become high
enough to cause sulfidation to become the dominant corrosion mechanism.
The conditions for the initiation of sulfidation depend upon the alloy and gas
compositions. High Ni alloys used either as base or welding filler metals are
often used to resist carburizing conditions. Ni slows the diffusion of carbon in
alloys, which is important because carburization is essentially a corrosion
mechanism limited by the rate of carbon diffusion in the alloy. However,
carburization of high Ni alloys can be especially rapid and yield rates greater
than 2.5 mm/y, if the temperature exceeds 980°C.

94
Effect of temperature upon carburization of several alloys exposed to solid
carbon and 200 ppm H2S at 1 atm.

95
Metal dusting

Metal dusting is a form of high-temperature deterioration in which the metal is

penetrated rapidly over isolated areas in the form of pits, generally with an
eroded or washed appearance. The pits contain a dust of loose powdery
corrosion product of graphite, metal carbides and oxides. The dust is magnetic.
Metal dusting occurs in atmospheres containing carbon monoxide, and
generally hydrogen; Metal dusting is manifested at lower temperatures than
carburization, typically between 425 and 815°C. Maximum rates of metal
dusting damage are considered to occur around 650 to 730°C.

The pits are severely carburized, and carburization appears to be the active
reaction in producing dusting. The attack is more pronounced in high
chromium alloys and austenitic stainless steel, because the pits are usually
isolated and unconnected, while the low alloy steels are more uniformly
attacked

Metal dusting. Type 310 stainless steel.

96
 Metal dusting. Type 310 stainless steel (250X).

Carbon activity gives indication for the risk of metal dusting

Ac = (P system /Kp) * ((Yco*YH2)/YH2O*(1+ YH2O))

Where
Ac = carbon activity (f(T))

P system = system pressure

Kp = equilibrium constant (f(T)) for the reaction
CO + H2 = H2O + C

Yco = molar fraction of CO (dry)

YH2 = molar fraction of H2 (dry)

YH2O = molar Ratio of H2O/dry gas

97
Mechanism of metal dusting:
1- Mechanism of metal dusting corrosion of 11/4Cr–1/2Mo and
5Cr–1/2Mo steels

Corrosion mechanism which involves the break-up of M3C and the formation
of ‘pits’ on the surface. If the nature of carbon deposit on the surface of M3C
is mostly amorphous, stress-induced fracturing of M3C could occur in some
regions since amorphous carbon does not provide a pathway for metal atoms
from dissociated M3C to escape. During the formation and growth of M3C,
stresses accumulate and lead the break-up of M3C above a critical stress
level. Once initial fracture of M3C has occurred, corrosion preferentially
continues in the same region. The following Figure shows a region where the
intensity of Fe3C fracture is apparent from the way in which broken pieces are
forced out, generating a ripple effect.

Cross-sectional SEM image showing ripples of fractured Fe3C

after metal dusting of iron at (500 oC) for 7h in 50CO:50H2.

98
2- Mechanism of metal dusting corrosion of 9Cr–1Mo, 13Cr and
20Cr steel

Schematic representation of the progression of low-Cr steel

degradation.

Oxide film rupture:

Consider chromium steels having >9 pct chromium being brought to the
process temperature in a mixed carburizing-oxidizing environment (e.g. CO–
H2), at temperatures that could range from (370–650 oC). Under these
conditions, surface oxidation of the steel occurs leading to a two-layered
oxide morphology. The outer layer is a spinel (M3O4), consisting mainly of Fe
and Cr in the metallic sublattice. Beneath this is an oxide layer, which is
predominantly chromia (Cr2O3) as observed in the 20Cr steel. The formation
of spinel and/or chromia films provides initial protection against carbon
ingress. The steel is protected from carbon ingress in as much as carbon does
not migrate through the oxide films. However, the presence of defects and
differential thermal contraction between steels and an oxide during oxide film
growth could induce stresses that may result in rupture of the oxide film.
Such local rupture of oxide film would lead to carbon migration into the steel.

99
Direct carburization:

Since the diffusivity of carbon is in general much higher than that of oxygen,
carbon rapidly diffuses in, causing the precipitation of the M7C3-type stable
carbide in the steel subsurface region. Such direct carbon entry is a prelude
to the rapid degradation of the steel. The different specific volumes of the
steel and precipitating M7C3-type carbide phase could introduce internal
stresses. carbide precipitation accompanied by volume expansion could
generate internal stresses The sequence of carbide formation and fracture
leads to localized corrosion. Fractured M7C3 undergoes further disintegration
with continued carbon transfer.

M3C formation

Internally precipitated stable M7C3 carbides are rich in Cr. It is observed that
about 25 wt% Cr is partitioned in the M7C3 carbide formed at the surface of
13Cr steel. Therefore, the base steel composition becomes further depleted
in Cr, initially by Cr-rich spinel oxide film formation and rupture on the steel
surface and later by Cr-rich stable carbide precipitation. The steel gets
supersaturated with carbon up to a certain thickness, which depends on
temperature and the chemistry of the carbon-supersaturated gaseous
environment. In the next step in corrosion a surface carbide of M3C forms on
Cr-depleted steel. This carbide is generally stable only in carbon-
supersaturated environments, requiring a carbon activity in excess of unity to
form.

Carbon deposition
In the next stage in the corrosion sequence, carbon, principally graphite,
deposits on the M3C surface, whereby the carbon activity at the carbide/
graphite interface drops to unity. This destabilizes the M3C carbide and leads
to its dissociation into iron particles and graphite. At this stage, metal dusting
is in progress.

Metal dusting
the carbon deposit on Fe3C is essentially a mixture of amorphous
carbon and graphitic carbon. The proportion of graphitic carbon increases

100
with temperature, accounting for nearly 80% of the carbon next to the Fe3C.
Moreover, the graphite planes are oriented more or less perpendicular to the
dissociating Fe3C, facilitating the intercalation of iron atoms into graphite At
the outer surface of the graphite deposit, filamentous carbon is catalyzed by
iron particles. It is thus proposed that metal atoms from the dissociation of
Fe3C intercalate and diffuse out through intergraphitic planes and are
ultimately carried away by filamentous carbon whose formation they catalyze.
This mechanism is schematically illustrated in the Figure.

Schematic illustration of the mechanism of metal dusting

corrosion.

101
Decarburization

• Decarburization is the decrease of the carbon content of (the surface of) a

steel due to interactions with the environment at elevated temperatures.
• The decreasing carbon content causes a degradation of mechanical
properties, as the hardness as well as the strength decrease. However, the
elongation of the metal when subjected to a tensile stress increases.
• Any compound that can influence the carbon level of the steel will influence
the mechanical properties of the steel.

Decarburization by Hydrogen (Hydrogen attack):

• Surface decarburization
Surface decarburization is the formation of hydrocarbons at the metal
surface which causes a migration of carbon atoms to the surface.
Due to surface decarburization the hardness, room temperature strength and
creep strength of a steel decrease, whereas the ductility increases. Surface
decarburization is accelerated by moisture.
• Internal decarburization
Hydrogen permeated into the steel can react with carbon, resulting in
the formation of methane which will accumulate in voids in the metal
matrix. The gas pressure in these voids can generate an internal
stress high enough to fissure, crack or blister the steel (hydrogen
attack). Due to internal decarburization the tensile strength and the
ductility will drop dramatically.
The best documented and most predictable type of high temperature
corrosion is hydrogen attack. The Nelson Chart, now published as API
Publication 941 (6), contains in chart form the failures and some of the
successes in hydrogen service at elevated temperatures. To review, atomic
hydrogen will diffuse into steel and combine with the carbon to form
methane. The methane molecule will occupy a large volume causing
fissures and bursts within the steel. The rate of diffusion and of
hydrogen attack is proportional to the temperature and to the partial
pressure of hydrogen. Resistance to hydrogen attack depends upon the
presence of alloying elements which form stable carbides, such as
chromium, molybdenum, tungsten, columbium, titanium, or vanadium.

102
These carbides resist reduction by hydrogen. The higher the pressure and
temperature, the more alloy is required, but if sufficient alloying element is
present, as in the austenitic chromium-nickel steels, the metal is resistant
to hydrogen attack for any useable combination of temperature and
pressure. The Nelson Chart defines the temperature and pressure at which
attack of carbon and alloy steels will occur.
Hydrogen attack will be evident as decarburization and as cracks and
fissures which can be detected by magnetic particle testing, ultrasonic
testing, or in the early stages by microscopic examination.
There is no time dimension on the Nelson Chart, but supplements to it in
the API Publication show the time necessary for attack to begin for
several materials. The means to avoid hydrogen attack are
straightforward. Define the temperature and hydrogen partial pressure
and select a material according to the Nelson Chart. Cladding a carbon
steel will not protect it against hydrogen attack. Hydrogen will diffuse
through the alloy cladding and attack the base material, if the base
material is not resistant to hydrogen attack.

Hydrogen attack. A-105 carbon steel forging (10X).

103
 Nelson curve defining safe upper limit for steel in hydrogen service.

Operating limits for various steels in high pressure hydrogen service (nelson

curve) to avoid decarburization and fissuring.

104
Time for incipient attack of carbon steel in hydrogen service.

105
Nitriding

is a process in which atomic, or dissociated, nitrogen combines with

components of the alloy to form intermetallic compounds called nitrides. The
source of atomic nitrogen can be dissociated nitrogen from the air, nitrogen
from dissociated ammonia, or as a component of the feed, either as a gas or
an ammonia containing compound Nitriding occurs at temperatures at
temperatures above 340°C below 540°C. The production of ammonia, nitric
acid, melamine, and nylon generate such conditions. Although stainless steels
may have adequate resistance, high-nickel alloys tend to be more resistant
e.g., 18-8 CrNi, 25-20 CrNi or Inconel. Increasing nickel and cobalt contents
are also considered to be beneficial. However, pure nickel has shown poor
resistance. Alloy 600, with 72% nickel, is often used in the heattreating
industry and occasionally in refining and petrochemical applications involving
ammonia at temperatures above 340°C. The nitrided layer will have increased
in volume and will be in compression. For example, austenitic stainless steel
tubes, 0.368 in. O.D. x 0.034 in. wall, nitrided to a depth of 0.0125 in.
(See the following Figure).

Nitriding. Type 304 stainless steel (100X).

106
on the inside surface and to a depth of 0.0021 in. on the outside surface. The
compressive stress from the greater thickness on the inner wall and the volume
change causes a diameter growth of 0.003 in.

The depth and rate of nitriding is significant for thin parts such as wire
mesh where the nitride layer can penetrate all the way through, making it
extremely brittle. Completely nitrided stainless steel behaves like a ceramic
and cannot resist mechanical or thermal stresses.
In ammonia converter service, the amount of nitriding found is spotty,
depending on the temperature and location in the converter. Austenitic
stainless steel ammonia Converter baskets operating at 800°-900°F have
shown the following thickness of nitrided layer: 2 yr., 0.001-0.007 in.; 2 yr.,
0.00375 in.; and 3 yr., 0.005 in.
Austenitic stainless steel internals from the same baskets were nitrided to a
depth of 0.020 to 0.025 in. The nitrided case is very brittle and can cause
difficulties in welding if it is not removed by grinding, but the depths in the
case reported would have no significant effect on the basket integrity. There
is some indication that the rate of penetration of nitriding of austenitic
stainless steels slows down after the initial penetration, as would be expected
in a diffusion-controlled process. Nitriding has also been found on the outside
surface of centrifugally cast 25 Cr 20 Ni, furnace tubes which operate at
1700°-2000°F. These are isolated nitride needles with no significant depth.
The nitrogen from the furnace products of combustion can form stable
nitrides on exposed surfaces at high temperatures, but at a very slow rate.
Fractured surfaces, which exhibit a high surface activity will show nitriding as
isolated needles of nitrides where adjacent "as-cast" surfaces will not. Where
carbides are exposed to the nitrogen-containing atmosphere, nitrogen can
replace part of the carbon, forming carbo-nitrides.
So far, no difficulties with nitrided HK-40 tubes have been reported, either
from external or internal nitriding. In one instance, a tube which had been in
service with a high-nitrogen (9% N2) natural gas feedstock was examined
after two years service. Carburization oxidation attack to a depth of 0.080-
0.120 in. was found, but there was no nitriding either at or near the inside
surface.

107
 3-Corrosion in Urea Plant

Process description:
The production of urea proceeds by a two-stage reaction. Ammonia and carbon
dioxide react to form ammonium carbamate:

Mol

This strongly exothermic reaction reaches equilibrium very rapidly.

The reaction system shown above will hereinafter be referred to the
carbamate equilibrium. In the liquid phase, ammonium carbamate is
next dehydrated to urea and water:

∆H = + 15.5kJ/mol.

This endothermic equilibrium reaction is rather slow compared with the first
one; the system will here in after be called the urea equilibrium.The
Stamicarbon total recycles CO2 stripping process:In the Stamicarbon total recycle
Co2 stripping process almost the whole quantity of unconverted reactants is
returned to the reactor. A large proportion of the reactants are removed from
the reactor solution at the synthesis pressure by contacting this liquid counter
currently with carbon dioxide. By stripping ammonia from the liquid, the
carbamate equilibrium is forced to the left, which results in dissociation of the
carbamate not converted into urea.

108
Urea process flow sheet

109
The reaction heat needed is supplied by external heating of the stripper (HP heat
exchanger) tubes. Owing to the short residence time in the stripper (HP heat
exchanger) and the relatively low temperature, the urea equilibrium is
prevented from establishing, so that the hydrolysis of urea does not get out of
bounds. The stripped reactor solution is flashed off to a much lower pressure
(approx. 4.0 bar) and then subjected to distillative separation to remove
residual ammonia and carbon dioxide. After this, these reactants are pumped
back, dissolved in water, to the synthesis section.

The technical realization of the synthesis process

In addition to the choice and lay-out of the equipment also the interior design
of the equipment items is in a number of cases dictated by the process.
Besides such process parameters as pressure, temperature and the specific
operation of the item in question, also corrosion aspects should be
considered in this connection. This chapter deals with the design of some of
the equipment items that are characteristic of the Stamicarbon urea-
synthesis section.

The HP equipment is protected against corrosion in two ways:

1. by a suitable choice of materials of construction and

2. by the use of oxygen as a corrosion-inhibitor.

Corrosion tends to occur in places where there is a high carbamate

concentration at high temperature, in the absence of oxygen. Materials
getting into contact with corrosive mixtures should have improved corrosion
resistance. Therefore, the high-pressure section is made of stainless steel.
For reasons of economy, the larger part of the equipment consists of carbon
steel with a corrosion-resistant lining.The dissolution of oxygen in carbamate
is a relatively slow physical process. Therefore, in colder spots in the
equipment, where ammonia and carbon dioxide can condense, a corrosive
mixture will be present, while protection will be incomplete owing to the lack

110
of a sufficient quantity of oxygen. It is therefore essential that the equipment
should be insulated in accordance with the pertinent instructions.

Corrosion in urea plant:

Pure urea solutions are not very corrosive, but products containing ammonium
carbamate, an intermediate in urea synthesis, have high corrosiveness. Because
of the corrosiveness of the synthesis solution the materials of construction must
meet severe demands with regard to quality and composition. Design
considerations include both technological aspects and prevention of corrosion. As
a rule, the oxygen content, temperature and composition, of the process liquid
are important tools in avoiding corrosion. Chloride contamination and non-
uniformity of the liquid distribution in the HP heat exchanger can cause corrosion.

Oxygen content:

Stainless steel in a corrosive medium owes its resistance against

electrochemical corrosion to the presence of a protective oxide layer on the
metal. As long as this layer is intact the metal corrodes at a very low rate
(passive corrosion). Corrosion will set in when the oxide layer is destroyed for
one reason or other (Active corrosion). Electrochemical corrosion only occurs
during contact with a liquid phase. Gas filled vessels and gas lines are free of
attack except when local condensation of the gas phase can take place.
Insulation and/or tracing are very important to prevent condensation. The
oxygen concentration in the liquid is determined by the partial pressure of the
oxygen in the adhering gas phase. Adding oxygen and maintaining sufficiently
high oxygen content in the various process streams are essential to avoid
corrosion. The specified oxygen content of the carbon dioxide feed, 0.6 %
(by volume), must be ensured through a reliable flow control of the air
and by analyzing the carbon dioxide for its oxygen content. If the oxygen
content is too low, active corrosion will most probably start after a short
time.

Temperature:

The temperature greatly affects the performance of stainless steel in urea

synthesis. It defines the corrosion rate and, above a certain critical value,
it causes spontaneous activation of passive steel (125 oC). This critical
value depends on the material properties and composition of process

111
liquid. For instance, steam temperatures in the HP heat exchanger higher
than the corresponding condensation temperature at 23bar should not be
used.250 oC It is practically impossible to measure the effect of the
temperature on the material in the passive state because the corrosion
rate is very low while actual conditions may vary so much during
production that the effect of temperature is no longer identifiable.

Process liquid composition:

It is important to ensure that NH3, CO2 and H2O gas mixtures cannot condense
into carbamate solutions where they are not supposed to condense. This is
because, notwithstanding the high oxygen partial pressure, a corrosive
condensate deficient in oxygen is formed in which the oxygen is absorbed at
a relatively slow rate. This accounts for the severe corrosion experienced on
cold spots inside gas lines. However in the HP carbamate condenser, where
an oxygen-rich gas phase is brought in direct contact with the liquid phase,
condensation takes place with significantly higher material film temperatures
by which corrosion can be avoided. Corrosion problems may result not only
from condensation but also from stagnant zones, especially in narrow
crevices into which hardly any oxygen can enter. Another important factor is
the flow velocity of the liquid phase. Obviously, carbamate-containing solutions
are more damaging to the oxide layer at higher flow velocities and are
therefore more liable to initiate corrosion. This can be observed particularly
near constrictions or in sharp bends. The medium in the top part of the HP
heat exchanger tubes has proven to be most aggressive due to its relatively
low partial oxygen pressure and high temperature. Therefore the tubes are
made of stainless steel with improved corrosion resistance, X2CrNiMo 25-22-
2.

Chloride contamination

Chloride ions may cause austenitic stainless steel to corrode depending on

temperature and concentration. Also, urea synthesis solutions containing
chlorides will accelerate overall attack and cause stress corrosion cracking at
elevated concentrations and temperatures in combination with stress.

112
Contamination of the non-process side from steam or condensate can lead to
stress corrosion cracking. It is particularly important to avoid contamination
with chlorides. For this reason the boiler water of the LP steam drum may not
contain more than 0.2 ppm chloride.

Liquid distribution in the HP heat exchanger

The urea solution which flows through the steam heated tubes of the HP heat
exchanger may be regarded as a coolant. Faulty distribution may cause
corrosion. Excessive flow reduces the amount of ascending oxygen, while a
too low flow will lead to disturbance of the liquid film in the tubes resulting in
accelerated corrosion.

Non-uniformity of the liquid distribution may be caused by:

• Leakage between liquid distributors and HP heat exchanger tubes.

• Blockage of the liquid distributor holes by contamination, e.g. packing

material
from pump stuffing boxes, oil, etc.

• Wrong dimensions of some of the liquid distributor holes.

• Overloading of the system, causing liquid to enter via the gas tubes.

After removal of the top manhole, cover blockage of liquid distributor holes
can be checked by means of the air test. Defects in the liquid distribution
system can be traced, except overloading of the system, which is an
operational failure.

Corrosion detection and inspection techniques:

Causes of corrosion can be traced back to:

• equipment fabrication, handling and transport,

• Process operation and maintenance.

When the plant is down, it is usually sufficient to make a visual and

ultrasonic inspection in order to know whether any corrosion is in progress.

113
Parts which cannot be inspected visually can be checked with the help of
instruments:

• heat exchanger tubes in the HP part can be checked by eddy current

testing,

• loose liners by ultrasonic testing

• Overlay welding by magnetic wall thickness testing.

Analyses of corrosion products and oxide layers can be helpful in determining

whether upset conditions such as chloride contamination have occurred or
not. It is also useful to check the insulation material for contamination once in
a while, insulation material applied on austenitic stainless steel equipment must
be analyzed for chloride and insulation material applied on carbon steel for
nitrates because of the risk of external stress corrosion cracking.

Equipment having a loose liner is provided with a reliable leak detection

system to avoid major damage to the carbon steel due to leakage of the
liner.When there is severe overall corrosion (active corrosion) the product will
be found to be brownish. In that case the affected equipment can eventually
be located by determination of the nickel content of the product before and
after the equipment during several measurements. Once the cause has been
established a visual inspection should be made and the equipment repaired if
possible. If active corrosion is found and remedied, it is necessary to
passivate.

Passivation:

Passivation is only required if a real chance exists active corrosion might have
occurred somewhere in the equipment.

A real chance that active corrosion is initiated during operation exists, when
one of the following happens:

• The HP synthesis has been operated without air (oxygen) supply to the
carbon dioxide feed for more than 5 minutes.

114
• In case the HP synthesis has not been drained after a block-in period longer
than 24 hours.

In principle Passivation can be executed by one of the following methods:

Open the equipment to make contact with the atmosphere (oxygen)

• Blow saturated LP steam (wet) and air (approximately 0.5%vol. oxygen

added to the steam) via reactor downcomer into the synthesis;
- Heating up
- Maintain atmospheric pressure
- Drain condensate in the same way as during reactor heating and vent
the air through the HP heat exchanger level control valve.

• Blow in carbon dioxide which is enriched with 0.6 % vol. Oxygen. (This
kind of passivation is merely done in the old designed plants of
Stamicarbon)

In all three kinds of Passivation no duration is connected because the

Passivation is going very rapidly. After that the normal heating procedure
can be followed.

A new material of construction to urea plant (Safurex)

Is duplex stainless steel grade, Good corrosion resistance to carbamate

solutions containing little or no oxygen, At least the same corrosion
resistance to oxygen containing carbamate solutions as X2CrNiMoN 25 22 2
(A4-18005 BC.05), High resistance to Chloride stress corrosion cracking
(S.C.C.),Good microstructure stability, Good weld ability.
Safurex in oxygen free carbamate solution the most challenging goal is to
produce urea in an oxygen free urea plant Numerous tests conducted under
laboratory conditions show indeed that Safurex remains passive under
oxygen free conditions.
The tests have been conducted with carbamate solutions at Urea reactor
conditions temperature 1830C and up. The results of this test are shown in
table:

115
The behavior of different materials which can be used in the HP Synthesis
when using oxygen for Passivation and the effect when reducing the oxygen
content can be learned from the figure. It shows clearly that all known
materials so far cannot maintain their passivity and high (and active or
transpassive) corrosion is the result. Only Safurex shows no reaction when
lowering the oxygen content. The corrosion rate remains constant.

Behavior of typical materials in oxygen free carbamate solutions

116
 4-Corrosion in Nitric acid plant

Process description:

Nitric acid is typically produced by the air oxidation of NH3. This catalyzed

reaction takes place at very high temperatures. The gaseous oxidation

product is condensed to an aqueous liquid of about 65% concentration.

During the high-temperature oxidation, corrosion of the plant materials is of

secondary concern. The elevated operating temperatures dictate that the

high-temperature properties of the materials are the primary design

consideration. Corrosion considerations prevail during and after condensation

and at lower temperatures. The concentration of HNO3 up to 99% requires

secondary processing to remove excess water. The basic materials of

construction used for equipment to carry out the process described above are

reasonably standardized and are listed below:

117
118
 Block Diagram of Nitric Acid Process.

86% is described as fuming. Nitric acid up to 95% is stored and shipped in

Type 304 stainless steel. Concentrated acid above 95% is handled in Aluminum

Association (AA) aluminum alloys 1100 or 3003. The following figure shows

the reason for this; the corrosion rate of type 304 stainless steel increases

rapidly above 95% concentration, while that of aluminum 3003 remains

essentially constant to 100%.

119
Comparison of corrosion of aluminum alloys 3003 and type 304 stainless steel

in HNO 3 .

A new stainless steel containing 4% Si—alloy A-610—shows excellent resistance

to concentrated HNO 3 Unfortunately, this advantage does not extend to lower

concentrations. Nitric acid is a strong oxidizing agent and attacks most metals,

such as iron, by oxidizing the metal to the oxide. A secondary effect of oxidation

is the generation of hydrogen at the metal/acid interface, which can cause

hydrogen embrittlement of some materials, for example, high-strength steels.

Metals and alloys that are able to form adherent oxide films, such as austenitic

stainless steels and aluminum alloys, are protected by their oxide films from

corrosion by HNO3.

120
Effect of silicon content on the corrosion of iron and iron-chromium-nickel

alloy in boiling HNO 3

Metals used in Nitric acid:

Austenitic Stainless Steels. The basic corrosion data for the austenitic
(300-series) stainless steels have been reduced to the corrosion diagram format
at The following figure. This diagram shows the effect of temperature and HNO3
concentration on the corrosion of type 304 stainless steel. Increasing either or
both raises the corrosion rate; nevertheless, there is a large useful area extend-
ing from 0 to 90% concentration and up to the boiling point below 50%
concentration in which the predicted corrosion rate is less than 0.13 mm/yr (5
mils/yr). Experience has shown that, although all austenitic stainless steels
behave in this fashion, types 304 and 304L, when welded, are clearly superior to
the others. Therefore, they are the most popular grades for HNO3 service.
This diagram also applies in general to the cast equivalents of wrought stainless
steels. However, the generally higher carbon content of cast alloys and the
propensity of castings to have high-carbon surfaces often leads to selective
intergranular corrosion in strong HNO3.

121
 Corrosion diagram for annealed type 304 stainless steel in HNO3

Although austenitic stainless steels are commonly used in HNO3, they are not
without problems. One of the most prevalent is selective corrosion associated
with chromium carbides precipitated around grain boundaries in the weld
Because few pieces of industrial equipment are made without welding, this is a
serious shortcoming. There are three methods of avoiding this problem:

• Use low or extra-low carbon content (at The following figure)

• Add carbide stabilizers to the alloy, as in types 32 land 347

• Solution anneal after welding to reduce the chromium carbide gradient

Of these alternatives, solution annealing is frequently not practical, and the

choice of stabilized alloys is not always an option. Therefore, when welding is

122
planned, use of low-carbon stainless steels is the most popular alternative.

Effect of carbon content on corrosion rate of type304 stainless steel in boiling

65% HNO3.

Sensitization of stainless steel refers to the precipitation of chromium carbides

and the resultant depletion of the matrix of chromium as a result of heating from
480 to 760 °C (900 to 1400 °F). Figure 47 shows that the effect of such heating
on corrosion rate in 65% HNC>3 is detrimental in all cases. Sigma phase, which
may also form during prolonged heating of austenitic stainless steels, is
preferentially and rapidly attacked by 65% HNO3. Solution heat treating the
alloy will restore corrosion resistance.
The corrosion of austenitic stainless steels in HNO3 is accompanied by the
formation of hexavalent chromium (Cr +), a complex chromium compound that
increases the corrosivity of HNO3 solutions. The effect of Cr6+ buildup is shown in
the following figure. To be clearly detrimental. In general, the presence of

123
Effect of hexavalent chromium (Cr +) on the corrosion rate of type 304 stainless
steel in HNO3, test duration: 40 h.

Chlorides and fluorides in HNO3 solutions tend to increase the corrosion rate of
stainless steels. Selective corrosion along grain boundaries is common in
austenitic stainless steels exposed to HNO3, especially strong acid. There is some
evidence to support the view that this cannot be entirely prevented; however,
maintaining low carbon and avoiding sensitization will help.
For very concentrated acid (>95%), the addition of silicon to iron and to
austenitic stainless steels is beneficial. Cast iron with 14% Si is very resistant to
acid over 50% concentration. Recently, two new stainless alloys of 4 and 6% Si—
alloys A-610 and A-611—have been produced. These new alloys have
remarkable resistance to HNO3 above 95% .At lower concentrations; they offer
no advantage over type 304.

124
Aluminum, as previously mentioned, shows an advantage over type 304 at acid
concentrations exceeding 95% .However, if acid concentration falls below 80%
or if temperature rises above 40 °C (100 °F), much higher corrosion rates can
be expected. This relationship is clearly shown in the following corrosion
diagram for aluminum. The preferred aluminum alloys for HNO3 service are
alloys 1100 and 3003. If higher strength is required, alloys 5052 or 5454 can
be used.

Corrosion diagram aluminum alloy 1100 in HNO3.

Higher-alloy materials, such as 20Cb-3 stainless steel, Hastelloy C-276,

Chlorimet 3, II-lium 98, and Incoloy 825, are adequately resistant to HNO3,
but are not often used, because the more economical austenitic stainless
steels are just as good. Some exceptions where the higher alloys are useful
include very high velocities, mixed acids (especially HF), or the presence of
other contaminants in the HNO3 tending to in- crease the corrosivity, for
example, Cl-and F- ions.

125
Titanium and titanium-palladium alloys
Resist concentrated HNO3 from 65 to 90% and dilute acid of less than 10%. At
concentrations above 90%, however, titanium is subject to SCC. Titanium is
never used in red fuming HNO3, because a pyrophoric reaction can occur if
water content is less than 1.34% and nitrous oxide (N2O) exceeds 6%.

Corrosion of titanium in boiling HNO3.

Zirconium
is even more resistant to HNOs than titanium is. Zirconium has a corrosion
rate of less than 0.25 mm/yr (1 mil/yr) at all concentrations up to the boiling
point. This corrosion resistance extends to 230 °C (450 °F) at
concentrations under 65%. The response of zirconium to concentrations
exceeding 65% and above the boiling point is uncertain. Unfortunately,
zirconium is subject to SCC in HNOs at high concentrations and therefore
must be used with caution in stronger acids.

126
 5- Corrosion in UAN

Ammonium Urea
Nitrate solution Solution

Mixing tank

Corrosion
Inhibitor

Storage
Tank

Block diagram of UAN production steps

UAN Solution is a nitrogen fertilizer solution composed of urea and

ammonium nitrate. Ammonium nitrate solution of about 92%
concentrations. Urea solution from Abu Qir (I) storage tank, which is about
72% concentration. Urea solution from Abu Qir (III) storage tank, which is
about 83% concentration. The mixing vessel can be divided from inside into
two compartments, the bigger one for mixing and overflowing the solution
to the small compartment to flow it to the cooler. The pH should be

127
continuously measured to be at 7.0, and the ammonia gas could be used to
adjust it. A determined flow rate of hot water, ammonium nitrate, urea
solution and inhibitor should be fed to the mixing vessel (bigger
compartment). After good mixing of all the components, the solution
overflows to the small compartment and then passes to the cooler, where it
is cooled to the required temperature (25 - 35°C) and then flown to the
storage tank. The storage tank is provided with a heating medium to
reheat the product to avoid crystallization (if required).The storage tank is
also provided with two facilities for loading pumps with a connection to feed
the tankers or the ship-vessels and Connection to fill the small packages.
UAN Solution is corrosive so Stainless steel grade 304L is preferably
required and it is used in the most of the unit, the storage tank made of
carbon steel so corrosion inhibitor is added before the UAN Solution is
admitted to storage tank in concentration of 120 ppm which is maintain the
iron concentration as 0.3 ppm in the solution. The corrosion inhibitor used is
may be ammonium phosphate (1% P 2 O 5 ) is added as an inhibitor. The
phosphate material reacts with the mild steal of the tank (used
normal in storage) to form an iron phosphate film, which acts a
protective shield for any tank corrosion.

128
 6 – Case Studies and Discussion
1- Corrosion in the top of Co2 absorber in ammonia plant.

2- Corrosion and failure of ammonia line of UAN unit.

3- Corrosion in oil cooler of generator.

4- Corrosion in Final cooler of synthesis gas compressor.

5- Stress corrosion cracking in the deaerator line.

6- Corrosion of water supply line.

7- High Temperature failure by perforation of Incoloy 800H Pigtail in

Reformer furnace.

8- An unusual case of Hydrogen-induced failure in a refinery Boiler tube.

9- Cracking of Inconel 800H in a steam methane reformer furnace.

10 – Intergranular corrosion in tube sheet of heat exchanger in Nitric Acid

service.

11- Metal dusting of a heat resistance alloy.

12- Stress corrosion cracking of stainless steel heat exchanger tubes in

Ammonia plant.

13- Cracks in the outlet section of steam reformer tubes.

14- Failure of dissimilar metal weld in reformer tubes.

15- Severe cracking of Co2 absorber exit line.

16- Stress corrosion cracking in Ammonia storage tank.

17- Corrosion in NH3 preheater.

18- Nitriding of Thermo well Protection Tubes in Ammonia-Quench Reactor.

19 - Corrosion damage in Waste Heat Boilers.

20- Heavy Corrosion Problem in Benfield-CO2 Removal System of Ammonia

Plant.

129
 7 – Useful information

A-Glossary of Terms
Active-passive Transition: the range of potential between the active (freely
corroding) state and the passive state.

Activity (thermodynamic): the thermodynamic activity of an entity, i, is

a,= exp (ΔG/RT where ΔG is the free energy increase of 1 mol of i when
It is converted from a standard state (defined as when a, = 1) to any
Other activity ai = x.

Alclad: a composite in which a thin layer of aluminium, or an aluminium Alloy

of good corrosion resistance, is bonded metallurgically to a high strength
Aluminium alloy (of lower corrosion resistance) to provide a Combination of
these two properties.

Anion: a negatively charged ion; it migrates to the anode of a galvanic or

voltaic cell.

Anode: the electrode in a galvanic or voltaic cell at which electrochemical

oxidation takes place.

Anode Corrosion Efficiency: the ratio of the actual corrosion rate of the
anode to the theoretical rate according to Faraday’s Law, expressed as a
percentage.

Anode Polarisation: the difference between the potential of an anode

passing current and the equilibrium potential of the electrode having the
same electrode reaction.

Anodic Protection: reduction of the corrosion rate by making the potential

of the metal sufficiently more electropositive by an external source of e.m.f.,
so that the metal becomes passive.

Anaerobic: air or uncombined oxygen being absent.

Anaerobic Bacteria (anaerobes): group of bacteria that are unable to

multiply in an but a minute trace of oxygen
.
Anodizing: the formation of oxide films on metals by anodic oxidation of the
metal in an electrolyte solution. The term can be used for thin dielectric films
but is more particularly applied to thicker films formed on some metals such
as aluminum at higher anodic voltages.

Anolyte: the electrolyte solution adjacent to the anode.

130
Anti-pitting Agent: an addition agent which is used to prevent the
formation of pits or large pores in an electrodeposit.

Austenite: the γ-modification of iron, having an f.c.c. lattice, which is stable

above about 700°C; the term is also applicable to solid solutions of carbon,
chromium, nickel, etc. in γ -iron.

Bainite: a structure produced in carbon and alloy steels by rapid cooling to a

temperature above that at which martensite is formed, followed by
Slower cooling.

Bimetallic Corrosion: corrosion of two metals in electrical contact, in which

one metal stimulates attack on the other and may itself corrode more slowly
than when it is not in such contact; galvanic is often used in place of
bimetallic.

Breakaway Corrosion: a sudden increase in corrosion rate, especially in

high-temperature ‘dry’ oxidation, etc.

Buffer: a substance, or mixture of substances, which when present in an

electrolyte solution tends to diminish fluctuations in pH.

Calcareous Scale: a scale consisting largely of calcium carbonate and

magnesium hydroxide which may be precipitated from a hard water.

Cathode: the electrode of a galvanic or voltaic cell at which electrochemical

reduction takes place.

Cathodic Protection: reduction of the corrosion rate by making the potential

of the metal to be protected more negative, so that the current at any anode
is reduced while that at any cathode is increased.

Cathode Reactant: species which is reduced at a cathode.

Catholyte: the electrolyte solution adjacent to the cathode.

Cation: a positively charged ion; it migrates to the cathode in a galvanic or

voltaic cell.

Caustic Embrittlement: stress-corrosion cracking of carbon steels caused

by the presence of caustic alkali.

Cavitation-corrosion: the wastage of metal caused by the combined action

of cavitation and corrosion.

Cavitation Damage: erosion of a solid surface caused by the collapse of

vacuum bubbles formed in a fluid.

Cementite: the iron-carbon compound of formula very close to Fe3C.

Chemical Conversion Coating: a protective or decorative coating which is
produced deliberately on a metal surface by a chemical environment.

131
Chemical Polishing: improvement in the brightness and levelness of a
surface finish of a metal by a chemical dissolution reaction.

Concentration Cell: a galvanic cell in which the e.m.f. is due to differences

in the concentration of one or more electrochemically reactive constituents of
the electrolyte solution.

Concentration (diffusion or transport) Overpotential: change of

potential of an electrode caused by concentration changes near the
electrode/solution interface produced by an electrode reaction.

Corrosion (of metals): the process of wastage of metals brought about by

electrochemical and/or chemical interaction with their environment. The term
has been defined in many ways by many authors.

Corrosion Control: control of the corrosion rate and form of attack of a

metal of a given metal/environment system at an acceptable level and at an
economic cost.

Corrosion Fatigue: failure by cracking caused by reversing alternating

stress in the presence of a corrosive environment.

Corrosion Potential (mixed potential, compromise potential): potential

resulting from the mutual polarisation of the interfacial potentials of the
partial anodic and cathodic reactions that constitute the overall corrosion
reaction.

Corrosion Product: metal reaction product resulting from a corrosion

reaction; although the term is normally applied to solid compounds it is
equally applicable to gases and ions resulting from a corrosion reaction.

Corrosion Rate: the rate at which a corrosion reaction proceeds. It may be

expressed as a rate of penetration mm/ y, µm /s etc. (inches per year or ipy
is still sometimes used), or as a rate of weight loss per unit area.

Couple (bimetallic, galvanic): two dissimilar metals in electrical contact.

Crevice Corrosion: localized corrosion resulting from the presence of a

crevice in a fabricated component or between two surfaces, at least one of
which is a metal.

Critical Anode Current Density: anodic current density that must be

exceeded in order to produce an active to passive transition (for a given
metal it varies with the nature of the solution, temperature, velocity, etc.).

Critical Humidity: the relative humidity (r-h.) at and above which the
atmospheric corrosion rate of a metal increases markedly.
Critical Pitting Potential: the most negative potential required to initiate
pits in the surface of a metal held within the passive region of potentials (it
varies with the nature of solution, temperature, time, etc.).

132
Current (I): the rate of transfer of electric charge; unit current is the ampere
(A) which is the transfer of 1 coulomb/second.

Current Density (i): the current per unit area (usually geometric) of surface
of an electrode (units: A /m2, A /cm2, mA/ m2 etc.)

Current Efficiency: the ratio of the rate of a specified electrochemical

reaction expressed as a current or current density (anodic or cathodic) to the
total current or current density (anodic or cathodic) flowing. It is usually
expressed as a percentage.

Deactivation: prior removal of the constituent (of a liquid) that is active in

causing corrosion. The term is usually applied to the removal of oxygen by
physical and/or chemical methods.

Dealloying: selective removal by corrosion of a constituent of an alloy.

Depolarization: reduction or elimination (by physical or chemical methods)

of the electrode polarization needed to produce a specified current.

Deposit Attack: localized corrosion (a form of crevice corrosion) under and

resulting from a deposit on a metal surface.

Dezincification: preferential corrosion of zinc from brass resulting in a

copper-rich residue on the surface of the alloy. The term also applies to
preferential loss of the zinc component by evaporation at elevated
temperature.

Differential Aeration: Differences in oxygen concentration in the electrolyte

solution in contact with a metal. Differential aeration stimulates corrosion of
that area where the oxygen concentration is lower, which becomes the anodic
site.

Diffusion: Movement of atoms, ions or molecules under an activity (or

concentration) gradient.

Diffusion Coating: a coating produced by diffusion at elevated

temperatures.

Diffusion Layer: the thin layer of solution adjacent to an electrode through

which transport of species to or from the electrode surface occurs by diffusion
rather than by convection.
Electrochemical Cell: a cell in which chemical energy is transferred into
electrical energy.

Electrolytic Cell: a cell in which electrical energy is used to bring about

electrode reactions and is thus converted into chemical energy. (Note: the
term 'electrochemical cell' is frequently used to describe both types of cells.)

Electrochemical Equivalent: number of moles of substance reacted

electrochemically by the passage of 1 Faraday of charge.

133
Electrode: an electron conductor by means of which electrons are provided
for, or removed from, an electrode reaction.

Electrode Potential (E): the difference in electrical potential between an

electrode and the electrolyte with which it is in contact. It is best given with
reference to the standard hydrogen electrode (S.H.E.), when it is equal in
magnitude to the e.m.f. of a cell consisting of the electrode and the S.H.E
(with any liquid-junction potential eliminated). When in such a cell the
electrode is the cathode, its electrode potential is positive; when the
electrode is the anode, its electrode potential is negative. When the species
undergoing the reaction are in their standard states, E = Eo, the standard
electrode potential.

Electrodeposition: deposition of a metal or alloy onto a substrate by

electrochemical reduction of its ions from an electrolyte under the application
of a cathodic overpotential.

Electrogalvanising: galvanising by electroplating.

Electrolysis: decomposition by the passage of electric current.

Electrolyte: a substance, liquid or solid, which conducts electrical current by

movement of ions (not of electrons). In corrosion science, an electrolyte is
usually a liquid solution of salts dissolved in a solvent, or a molten salt. The
term also applies to polymers and ceramics which are ionically conductive.

Electrolyte Solution: a solution in which the conduction of electric current

occurs by the passage of dissolved ions.

Electrolytic Cleaning: cleaning of a metallic surface obtained by making it

the anode or cathode of a cell containing a suitable electrolyte solution.

Electron Acceptor: a species in solution that accepts one or more electrons

from a cathode for each act of the cathodic reaction and is thus reduced to a
lower valence state. catalysed by the metal deposited.

Electromigration of Ions: movement of ions under an electric field.

Electrophoretic Plating (Electrophoretic Deposition): production of a

layer or deposit onto an electrode by discharge of colloidal particles from a
solution.

Electroplating: deposition of a thin adherent layer of a metal or alloy onto a

substrate by electrochemical reduction of its ions from an electrolyte under
application of a cathodic overpotential.

Electropolishing: surface finishing of a metal by making it the anode in an

appropriate solution, whereby a bright and level surface showing specular
reflectivity is obtained.

134
e.m.f Series: a table of the standard equilibrium electrode potentials of
systems of the type M2+(aq.)+ze = M, relative to the standard hydrogen
electrode, and arranged in order of sign and magnitude.

Epitaxy: the phenomenon whereby a deposit or coating takes up the lattice

habit and orientation of the substrate.

Equilibrium Potential (Eo): the electrode potential of an unpolarised

electrode at equilibrium. At the equilibrium potential there is no net
reaction.The potential is controlled by the same electrode reaction occurring
anodically and cathodically at an equal rate, called the exchange current
density.

Erosion: loss of material mechanically by impact of a liquid, gaseous or

particulate environment.

Erosion-corrosion: the wastage of a material caused by the conjoint action

of erosion and corrosion by a liquid or gaseous environment, with or without
solid particles.

Evans Diagram: diagram in which the E vs. I relationships for the cathodic
and anodic reactions of a corrosion reaction are drawn as straight lines
intersecting at the corrosion potential, thus indicating the corrosion current
associated with the reaction.

Exchange Current Density (io): the rate of exchange of electrons

(expressed as a current per unit area) between the two components of a
single electrochemical reaction when the reaction is in equilibrium. The
exchange current density flows only at the equilibrium potential.

Exfoliation: loss of material in the form of layers or leaves from a solid

metal or alloy.

Faraday Constant (F): the quantity of electric charge involved in the

passage of one Avogadro number (or one mole) of electrons. The value of F
(universal) is 96 485 C/mol.

Faraday's Law: the quantity of charge (Q) passed in an electrochemical

reaction is directly proportional to the number of moles (n) of substance
reacted. Thus Q = zFn, where z is the number of electrons involved in one
molecule of the reaction and F is the Faraday constant.

Fatigue: failure of metal under conditions of repeated alternating stress.

Ferrite: the body-centred cubic form of iron (a-iron) and the solid solutions.

Filiform Corrosion: corrosion in the form of hairs or filaments progressing.

Film: a thin coating of material, not necessarily thick enough to be visible.

135
Flade Potential: the potential at which a metal which is passive becomes
active.

Fogging: reduction of the luster of a metal by a film or particulate layer of

corrosion product, e.g. the dulling of bright nickel surfaces.

Fouling: deposition of flora and fauna on metals exposed to natural waters,

e.g. sea-water.

Frequency Response Analysis: the response of an electrode to an imposed

alternating voltage or current signal of small amplitude, measured as a
function of the frequency of the perturbation. Also called Electrochemical
Impedance Spectroscopy.

Fretting Corrosion: deterioration resulting from repetitive rubbing at the

interface between two surfaces (fretting) in a corrosive environment.

Galvanic Cell: an electrochemical cell having two electronic

conductors(commonly dissimilar metals) as electrodes.

Galvanic Corrosion: corrosion associated with a galvanic cell (often used to

refer specifically to Bimetallic Corrosion).

Galvanostatic Polarisation (intentiostatic): polarisation of an electrode

during which the current density is maintained at a predetermined constant
value.

Galvanic Series: a list of metals and alloys based on their relative potentials
in a given specified environment, usually sea water.

Galvanising (hot dip): coating of iron and steel with zinc using a bath of
molten zinc.

Graphitic Corrosion: corrosion of grey cast iron in which the metallic

constituents are removed as corrosion products, leaving the graphite.

Green Rot: carburisation and oxidation of certain nickel alloys at around

1000oC resulting in a green corrosion product.

Half-cell: one half of an electrochemical cell, comprising one electrode

(anode or cathode) and its immediate electrolyte (anolyte or catholyte).

Hematite: an oxide of iron corresponding closely to Fe2O3, produced during

the oxidation of iron.
Hydrogen Electrode: an electrode at which the equilibrium H+ (aq.) + e - =
H2, is established. By definition, at unit activity of hydrogen ions and unit
fugacity of hydrogen gas the potential of the standard hydrogen electrode = 0

Hydrogen Embrittlement: embrittlement caused by the entry of hydrogen

into a metal.

136
Hydrogen Overpotential (Overvoltage): the displacement of the
equilibrium (or steady-state) electrode potential of a cathode required for the
discharge of hydrogen ions at a given rate per unit area of electrode.

Immunity: the state of a metal whose corrosion rate is low or negligible

because its potential is below (less positive than) that of equilibrium with a
very small concentration (or activity of its dissolved ions. The metal is thus
regarded as thermodynamically stable. Pourbaix has suggested that the
"small" metal ion concentration be10-6 mol dm-3.

Impingement Attack: localised corrosion resulting from the action of

corrosion and/or erosion (separately or conjoint) when liquids impinge on a
surface.

Inhibitor: a substance added to an environment in small concentrations to

reduce the corrosion rate.

Intergranular Corrosion: preferential corrosion at grain boundaries.

Internal Oxidation (subsurface corrosion): formation of particles of

corrosion product (usually oxide) within the metal matrix beneath the metal
surface. The surface may additionally be covered with a film or scale. Internal
oxidation often arises from diffusion of oxygen into the metal matrix at
elevated temperature.

Ion: an electrically charged atom or molecule.

Isocorrosion Chart: a chart having temperature and concentration of the

corrodent as co-ordinates and curves (isocorrosion curves) of various
specified constant corrosion rates of the metal.

Knife-line Attack: severe highly localised attack (resembling a sharp cut

into the metal) extending only a few grains away from the fusion line of a
weld in a stabilised austenitic stainless steel, which occurs when the metal
comes into contact with hot nitric acid and is due to the precipitation of
chromium carbides.

Limiting Current Density: the current density at which change of

polarisation produces little or no change of current density.

Linear Oxidation: oxidation of a metal in such a way that the rate of

oxidation is independent of time.

Linear Polarisation: the linear relationship between potential and current

density that is considered to prevail at potentials very close to the corrosion
potential.

Liquid Metal Embrittlement: the embrittlement of a metal or alloy as a

consequence of contact with a liquid metal, resulting in the formation of
cracks.

137
Local Anodes and Cathodes: the separate anodic and cathodic sites on a
single material immersed in a reactive environment.

Localised Corrosion (or localised attack): accelerated corrosion at certain

sites only of a metal surface, usually induced by spatial separation of the
anodic and cathodic sites. Examples include pitting corrosion, stress corrosion
cracking and intergranular corrosion.

Migration of Ions: movement of ions towards the anode or cathode under

an electric field.

Mil: 0.001 inch or one thousandth of an inch (1 mil = 25.4 pm).

Nernst Equation: the thermodynamic relationship between the equilibrium

potential of an electrochemical reaction and the activities of the species
involved in that reaction.

Open-circuit Potential: the potential of an electrode (relative to a reference

electrode) from which no net current flows, so that the anodic and cathodic
reactions occur at an equal rate.

Overpotential (overvoltage, polarisation): the displacement from the

equilibrium (or steady-state) electrode potential required causing a reaction
to proceed at a given rate.

Oxidation: loss of electrons by a species during a chemical or

electrochemical reaction; addition of oxygen or removal of hydrogen from a
substance.

Oxidizing Agent: a substance that causes oxidation of another species.

Parabolic Oxidation: oxidation of a metal to produce an oxide film in such a

way that the rate of oxidation is proportional to the reciprocal film thickness.
Thus if x is the film thickness at time t, then dx/dt α x -1.

Parting: selective dissolution of one metal (usually the most electro-reactive)

from an alloy leaving a residue of the less reactive constituents.

Passivation Potential: the potential at which a metal in the active state

becomes passive.

Passivator: a substance which in solution causes passivity.

Passivity: the state of a metal in which a low corrosion rate is brought about
By reaction with its environment under a high anodic driving force through
formation of a surface barrier film, usually an oxide.

Patina: a green coating of corrosion products of copper (basic sulphate,

carbonate and chloride) which forms on copper or copper alloys after
prolonged atmospheric exposure.

pH: a measure of the hydrogen ion activity defined by pH = -log aH+

138
where aH+ is the activity of the hydrogen ion.

Pickle, Pickling: a solution (usually acidic) used to remove or loosen

corrosion products from the surface of a metal. Anodic and cathodic pickling
are forms of electrolytic pickling in which the metal is anodically or
cathodically polarised in the pickle.

Pilling-Bedworth Ratio: the ratio of the volume of an oxide film on a metal

to the volume of metal used to form that oxide.

Pitting (pitting corrosion): the formation of small holes in an otherwise

passive metal surface as a consequence of locally accelerated corrosion.

Pitting Potential: minimum potential (least noble or least positive) at which

a metal undergoes permanent pitting corrosion.

Polarisation (overpotential, overvoltage): difference of the potential of

an electrode from its equilibrium or steady-state potential.

Polarisation Curve: A plot of the current density flowing from an electrode

against the electrode potential, often presented on a logarithmic current
density axis.

Polarisation Resistance: slope of the linear plot of overpotential versus

current density measured at potentials close to the corrosion potential, or
the tangent of such a curve at the corrosion potential if the plot is not
linear. If a small change in potential, ΔE, gives rise to a change in current
density, Δi, then the polarisation resistance isRp( Ω m2) = ΔE/Δi .

Potential-pH Equilibrium Diagram (Pourbaix Diagram): diagram of the

equilibrium potentials of electrochemical reactions as a function of the pH of
the solution. The diagram shows the phases that are thermodynamically
stable when a metal reacts with water or an aqueous solution of specified
ions.
Negative potential: a potential more negative than the potential of the
standard hydrogen electrode.

Noble potential: a potential towards the positive end of a scale of electrode

potentials. The potential of an electrode which is made anodic is said to
become ‘more noble’ or ‘more positive’ (preferred term).

positive potential: a potential more positive than the potential of the

standard hydrogen electrode.
Protection Potential for Pitting: potential below which new pits cannot be
initiated nor pre-existing pits continue to propagate.

Rate-determining Step (r.d.s.): the slowest step in the mechanism of a

reaction which thereby controls the rate of the overall reaction. The r.d.s. has
the highest activation energy.

Redox: abbreviation for reduction-oxidation.

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Redox Potential: the equilibrium electrode potential of a reversible
reduction-oxidation reaction.

Redox Reaction: a reversible reduction-oxidation reaction.

Reduction: a chemical or electrochemical reaction in which a species gains

electrons; the removal of oxygen or the addition of hydrogen.

Reference Electrode: an equilibrium (reversible) electrochemical half-cell of

reproducible potential against which an unknown electrode potential can
be measured. Examples of those commonly used in corrosion are the Pt,
H2/H+ (the hydrogen electrode), Hg/Hg2 CI2/Cl- (the calomel electrode),
all with fixed activities of the dissolved ions.

Relative Humidity: the ratio of the amount of water vapor present in the
atmosphere at a given temperature to the amount required for saturation at
the same temperature, expressed as a percentage.

Rusting (rust): corrosion of iron or ferrous alloys resulting in a corrosion

product which consists largely of hydrous ferric oxide.

Scale: a thick visible oxide film formed during the high-temperature oxidation
of a metal (the distinction between a film and a scale cannot be
defined precisely).

Season Cracking: cracking resulting from the combined effect of corrosion

and stress, which is usually confined to the stress-corrosion cracking of brass
in ammoniacal environments.

Sensitisation: susceptibility to intergranular attack in a corrosive

environment resulting from heating a stainless steel at a temperature and
time that results in precipitation of chromium carbides at grain boundaries.

Spalling: the break-up of a surface through the operation of internal

stresses, often caused by differential heating or cooling.

Stray-current Corrosion: corrosion caused by stray currents flowing from

another source of e.m.f. (usually d.c.).

Stress-corrosion Cracking: cracking produced by the combined action of

corrosion and static tensile stress (internal or applied).

Sulphate-reducing Bacteria (S.R.B.): a species of anaerobic bacteria

(devibrio desulphuricans) that is capable of causing rapid corrosion of
iron and steel in near-neutral solutions in the absence of dissolved oxygen.

Tafel Eguation: the linear relationship between the overpotential (or

potential) and the logarithm of the current density for an electrode reaction in
which charge transfer is rate-determining. If η is the overpotential, and
i the current density, then η = a + b log i, or η = b log (i/io) where io is
the exchange current density. b is called the Tafel slope expressed in V.

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Tarnish: dulling, staining or discoloration of metals due to the formation of
thin films of corrosion products. (The term can also be applied to thin
transparent film which may give rise to interference colors.)

Transfer Coefficient a: the transfer coefficient of a cathodic process is the

fraction of the electrical energy difference ZFΔϕ that assists the transfer
of an ion through the double layer towards the electrode and inhibits its
transfer in the reverse direction or vice versa for an anodic process;
frequently experimental values of a are approximately 0.5.

Transport of Ions: the combined motion of ions in an electrolyte (solid or

liquid) under diffusion and migration.

Tuberculation: localized attack in which the corrosion products form wart-

like mounds over the corroded areas.

Uniform Corrosion (general corrosion): corrosion in which no

distinguishable area of the metal surface is solely anodic or cathodic, Ie.
Anodes and cathodes are inseparable, cf. localised corrosion.

Weld Decay: localised attack of austenitic stainless steels at zones near a

weld, which results from precipitation of chromium carbides.

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 B - Symbols and Abbreviations

Quantity Name Symbol

Length meter m
Mass kilogram kg
Time second s
Force Newton N
Work joule J
Current ampere A
Charge coulomb c
e.m.f. Volt v
Conductance Siemens S
Inductance Henry H
Amount of substance mole mole

A.c. Alternating current

Ah ampere hour
aq aqueous, hydrated
b.p. boiling point
C concentration (mol m-3; mol dm-3)
c.d. Current density
O
C degree Celsius (Centigrade)
D diffusion coefficient cm²/s
d day
D.c direct current
e.m.f. electromotive force
Eo standard e.m.f., standard
electrode potential

142
E cell e.m.f. of cell
E a anode potential

E c cathode potential
Ecorr corrosion potential
ηa anode overpotential (V)
ηc cathode overpotential
ηA activation overpotential
F Faraday constant (C mol-1)
G Gibbs free energy (free enthalpy)
(J)
h hour
I current (A)
i current density (Am-1, Acm-1)
i.p.y inches per year (in y-1)
m.p.y. mm y-1
min minute
m.p. melting point
PH - log a H+
p.p.m. parts per million

143
 8 – References

1- L. L Sheir and R. A. Jarman, Corrosion 1 (metal/environment

reactions), 3rd edition, butterworth-heinman, London (1998).

2- Pierre R. Roberge, Hand Book of Corrosion Engineering, McGraw Hill, N.Y

(2000).

3- M .G Fontana, Corrosion Engineering, McGraw Hill, N.Y (1987).

4- S. A. Bradford corrosion control 2nd, casti publishing inc , Canada (2001).

5- L. L Sheir and R. A. Jarman, Corrosion 2 (corrosion control) 3rd edition

Butterworth-Heinemann, London (1998).

6- D .Talbot and J .Talbot, corrosion science and technology, C R C press

,USA (1998).

7- W. Revie. Uhlig's, ,The Corrosion Hand Book, 2nd edition John Wiley &

Sons, New York (2000).

8- R. H. Jones ,stress corrosion cracking, ASM international, USA ( 1993).

15- Linda Garvrerick ,corrosion in the petrochemical industry, ASM

international ,OH USA (1994) .

16- J.O.M Bockris and D B. Mathews, Modern Aspects of Electrochemistry,

Plenum Press,N.Y, 6, 242(1971).

17- U R. Evans, ,Metallic Corrosion Passivity and Protection, Arnold,

London, (1946).

18- D. Steart, ,Principles of corrosion & protection, Macmillan, London

(1960).

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19- L.A. Zeis and J.F. Lancaster, Corrosion at Elevated Temperatures ,the

M.W Kellogg CO. Houston,texas .

20 - R. E. Trerybal ,mass transfer operations,2nd ,Mc Graw-Hill New

York.(1980).

21- American Petroleum Institute API Publication 941, Third Edition ,may
1983,Steels for Hydrogen Service at Elevated Temperature and Pressure.

22 - S. Elsalahy, Abu Qir Fertilizers Experiences in boiler water and

condensate treatment U H D E Fertilizers Symposium 2002.

23- Y. Elsamadisy ,Failure in steam generating systems, Abu Qir Fertilizers

CO, Alexandria , Egyppt.

24- Babcock &Wilcox, Boiler tube analysis, a Mc Dermott Company.

25- B. Nimmo and G. Hinds, Beginners Guide to Corrosion ,NPL ,February

2003.

26- C M C H U N ExxonMobil Research and Engineering Company, USA and

Princeton University, The metal dusting corrosion of steels with

varying concentrations of chromium , USA

27- Nestor Perez, Electrochemistry and Corrosion Science , Kluwer Academic

Publishers ,New York 2004.

28- galp , ARL, INSPECÇÃO ,Crrosion Principles, Refinaria de Sines.

29- Loyd W.Jones ,Corrosion and Water Technology,OGCI publication

Oil and gas consultant international, inc,Tulsa 1992.

30- Ammonia Plant Related Facilities Symposia, volume 3 1993-2005.

145