Static Equipment

Refining-Petrochemicals-Chemicals-Engineering
———
CORROSION
— Natural but controllable process —
I - DEFINITIONS AND MECHANISMS ..............................................................................................1

1 - Introduction.........................................................................................................................................1
2 - Economic aspect of corrosion ...........................................................................................................1
3 - Review of chemistry and electrochemistry .......................................................................................2
4 - Primary phenomena of wet corrosion .............................................................................................11
5 - Secondary phenomena of wet corrosion ........................................................................................16
6 - Effects of secondary reactions on the kinematics of wet corrosion ..............................................17
7 - Dry corrosion ....................................................................................................................................29
8 - Measurement and control - Corrosion tests ...................................................................................31
II - THE MANY FORMS OF CORROSION .......................................................................................35

1 - Uniform attack ..................................................................................................................................35
2 - Galvanic corrosion ...........................................................................................................................36
3 - Crevice corrosion .............................................................................................................................38
4 - Pitting ................................................................................................................................................40
5 - Intergranular corrosion.....................................................................................................................42
6 - Stress corrosion cracking ................................................................................................................45
7 - Selective leaching ............................................................................................................................50
8 - Fretting corrosion .............................................................................................................................51
9 - Erosion corrosion .............................................................................................................................52
MX DCA - 02947_A_A - Rev. 2 15/06/2009

© 2009 - IFP Training
I
III - CORROSION PREVENTION .......................................................................................................53

1 - Materials selection ...........................................................................................................................53
2 - Control of process variables ............................................................................................................68
3 - Good engineering design.................................................................................................................70
4 - Inhibitors ...........................................................................................................................................73
5 - Anodic protection..............................................................................................................................75
6 - Cathodic protection ..........................................................................................................................75
7 - Metallic and inorganic coatings .......................................................................................................77
8 - Paints - Organic coatings.................................................................................................................79
IV - HYDROGEN CORROSION..........................................................................................................82
1 - Sources of nascent or atomic hydrogen .........................................................................................82
2 - Hydrogen blistering ..........................................................................................................................83
3 - Hydrogen embrittlement ..................................................................................................................83
4 - Decarburization and hydrogen attack .............................................................................................85
V - CORROSION BY SULFUR DERIVATIVES IN THE ANHYDROUS PHASE.............................88

1 - Corrosion by sulfur compounds.......................................................................................................88
2 - Anhydrous phase H2S corrosion without hydrogen .......................................................................88
3 - H2S corrosion with H2......................................................................................................................89
VI - CORROSION BY COLD HYDROGEN SULFIDE IN A HUMID ATMOSPHERE.......................99

1 - Generalized corrosion......................................................................................................................99
2 - Atomic hydrogen corrosion ..............................................................................................................99
3 - Prevention.........................................................................................................................................99
VII - CORROSION BY COMBUSTION GASES IN FURNACES AND BOILERS............................100

1 - Formation of SO3 ...........................................................................................................................100
2 - Corrosion at high temperatures.....................................................................................................102
3 - Low temperature corrosion............................................................................................................106
VIII - NAPHTHENIC ACIDS CORROSION.........................................................................................114
IX - CORROSION IN DISTILLATION UNITS ...................................................................................118

1 - Corrosive agents in the crude .......................................................................................................118
2 - Study of the reaction mechanisms related to corrosion of atmospheric distillation head
equipment .......................................................................................................................................118
3 - Corrosion combating methods ......................................................................................................119
X - CORROSION BY POLYTHIONIC ACIDS..................................................................................126

1 - Introduction.....................................................................................................................................126
2 - Initiating factors of PSCC...............................................................................................................126
3 - Prevention of polythionic cracking.................................................................................................127
XI - CAUSTIC SODA CORROSION .................................................................................................128
02947_A_A © 2009 - IFP Training

II
XII - BIOCHEMICAL CORROSION....................................................................................................130

1 - Macro-organisms............................................................................................................................130
2 - Micro-organisms.............................................................................................................................130
XIII - CORROSION IN AN AQUEOUS ENVIRONMENT ...................................................................135

1 - Introduction.....................................................................................................................................135
2 - Effect of oxygen concentration ......................................................................................................136
3 - Effect of the solution pH.................................................................................................................137
4 - Effect of strong and weak acids on the iron..................................................................................139
5 - Effect of dissolved salts .................................................................................................................140
6 - Effect of carbon dioxide .................................................................................................................142
7 - Prevention of corrosion by water...................................................................................................144
XIV - ATMOSPHERIC CORROSION..................................................................................................145

1 - Films formed by corrosion products..............................................................................................145
2 - Atmospheric corrosion factors.......................................................................................................145
3 - Remedies for atmospheric corrosion ............................................................................................146
XV - SEA WATER CORROSION .......................................................................................................146

1 - Characteristics of sea water ..........................................................................................................146
2 - Carbon steel corrosion...................................................................................................................147
3 - Corrosion of stainless steels..........................................................................................................148
4 - Corrosion of non-ferrous metals....................................................................................................148
XVI - DRY OXIDATION AT HIGH TEMPERATURE...........................................................................152
1 - Mechanism .....................................................................................................................................152
2 - Oxidation kinetics ...........................................................................................................................155
3 - High temperature materials ...........................................................................................................155
4 - Atmospheres encountered at high temperatures .........................................................................155
XVII - CORROSION BY LIQUID AMMONIUM.....................................................................................159
XIX - REINFORCED CONCRETE CORROSION...............................................................................160

1 - Corrosion of steel structures in a humid environment .................................................................160
2 - Natural protection of steels by cement .........................................................................................160
3 - Weakening of the natural protection of the embedded metal structure: alteration
of the concrete................................................................................................................................160
4 - Prevention.......................................................................................................................................166

1
I- DEFINITIONS AND MECHANISMS

1- INTRODUCTION
Corrosion is the most widespread degradation phenomenon in process units.
It is the cause of most failures and malfunctions of pressure vessels.
It is estimated that corrosion destroys a quarter of the world’s annual production in steel, which
represents approximately 150 million tons per year, or 5 tons per second. In addition, corrosion is not
limited to just steel, but also affects all metals, as well as polymers and ceramics. Here are a few
examples of corrosion phenomena:
- transformation of steel into rust

- cracking of brass in the presence of ammonia
- oxidation of copper electric contacts
- hydrogen embrittlement of a high-resistant steel
- hot corrosion of a super-alloy in a gas turbine
- swelling of a polymer in contact with a solvent
- degradation of PVC by ultraviolet radiation
- attack of a nylon tube by a oxidizing acid
- attack of refractory bricks by slag
- attack of a mineral glass by an alkaline solution
Corrosion is an irreversible interfacial reaction of a material with its environment, which implicates a
consumption of the material or a dissolution in the material of a component of the environment. This
definition includes the positive effects of the corrosion, as well as the absorption of a component of the
environment without consumption of the material. The absorption of hydrogen by steel is, for example,
considered to be a corrosion reaction.
For this reason, wet corrosion, or corrosion at room temperature, is distinguished from dry
corrosion, that is, high-temperature corrosion.
2- ECONOMIC ASPECT OF CORROSION

The direct or indirect effects of corrosion are summarized below:
- cost of the parts to be replaced, the repairs to be made

- cost of maintenance and control (painting, cathodic protection)
- cost due to the use of more noble materials
- enhancement of safety factors
- contamination of the product by corrosion products
- production shutdown
According to the estimates noted in the literature, the yearly cost for corrosion amounts to 4% of the
GDP (Gross Domestic Product), that is, several billion Euros annually for France.
Results of a recent (2002) study show that the total annual estimated direct cost of corrosion in the
U.S. is a staggering $ 276 billion - approximately 3.1% of the nation’s Gross Domestic Product (GDP).
It reveals that, although corrosion management has improved over the past several decades, the U.S.
must find more and better ways to encourage, support and implement optimal corrosion control
practices.

2
The total annual direct cost of corrosion for production and manufacturing is estimated to be $ 17.6
billion.
Mining
Oil and gas 1%
exploration and ($0.1 billion)
production
8%
($1.4 billion)
Petroleum refining
Home appliances 21%
8% ($3.7 billion)
($1.5 billion)
Food processing Chemical

12% petrochemical
($2.1 billion) pharmaceutical
10%
($1,7 billion)
Agricultural
6%
($1.1 billion)
D MAC 1391 A
Pulp and paper
34%
($6 billion)
Annual cost of corrosion in the production and manufacturing category
3- REVIEW OF CHEMISTRY AND ELECTROCHEMISTRY

• Molecule’s structure
The molecule is a structure composed of atoms, and the internal bonds are electrical in nature.
The atoms of an element may be united to form a molecule by setting in common the 2 electrons (case
of H2: H – H, 02: O = O).
+ +
D MAC 2092 B
Nucleus
Electron
Repulsion force
Attraction force
Schematic representation of the Bohr model

3
The atoms of different elements may be united under the same conditions (case of H2O, CO2).
• Ions, anions, and cations
An atom may lose one or more electrons from its peripheral layer. The result is one positive ion or
cation. This positive ion may seize one electron and make an atom:
+
MM +e
An atom can gain one or more electrons. The result is one negative ion or anion. As above, the anion
may lose its additional electron and make an atom:
A + e A–
• Ionization
Water is partially dissociated into ions according to the following equilibrium:
H2O H+ + OH–
+ -
In pure water there are as many H ions as OH ions so that the charge is zero:
[H+] = [OH–] = 10–7 moles per liter
An environment is said to be acid when [H+] is greater than 10-7 in a solution. Otherwise, the
environment is said to be basic.
Definition of pH: pH = Log 1/[H+] = - log [H+ ]
For neutral water, pH = - log [10-7] = 7
• Crystals and ionic solutions
A salt crystal like sodium chloride is a structure resulting from the superposition of polyhedrons at the
+ -
atomic scale (cubes in the case of NaCl) at the summits of which are placed the Na and Cl ions in
equal numbers and regularly distributed so that the crystal is electrically neutral. Cohesion is assured
by electrostatic attraction forces.
0,558 nm
Cl-
Na+
D MAC 2093 B
Diameter of Na+ = 0.196 nm

Diameter of Cl- = 0.362 nm

4
If a sodium chloride crystal is put in water, it dissolves.
In fact, the water molecule presents an electric dissymmetry (positive pole on the hydrogen atoms side
and a negative pole on the oxygen atoms side).
O
- -
D MAC 2116 A
+ +
H H
The Na+ ions of the crystal attract the water molecules by their negative side, while the Cl– ions attract
the water molecules by their positive side. Thus, the water molecules reduce the electrostatic forces.
The crystal is dislocated and the ions are free to move between the water molecule. A dissociation
takes place:
NaCl Na+ + Cl–
• Solid state metal structure
A metal is a compact structure of atoms composed of ions in an electron cloud. Some of the electrons
are relatively free in mass and allow electric conductivity and heat conductivity.
FR FA FR
+ + +
Electrons
+ + +
D MAC 2094 B
+ + +
Positive ions
Schematic representation of the forces intervening in the metal bond: FR = repulsion force of the
positive ions; FA = attraction force between the positive ions and the electron cloud.
• Oxido-reduction phenomena
Earlier, oxidation was defined as the fixation of oxygen on a chemical system and the reduction as
an inverse phenomenon.
Today this concept is generalized and oxidation corresponds to a loss of electrons, while reduction
correspond to a gain of electrons.
Oxidation
Fe Fe++ + 2e
Reduction

5
A system is said to be an oxidant when it may capture electrons.

-
Example: oxygen in water: O2 + 2 H 2O + 4 e 4 OH
A system is said to be a reducer when it may release electrons.

+
Example: sodium in water: Na Na + e
• Behavior of a metal plate in pure water (deaerated or without oxygen)
At the plate’s surface the metal atoms lose electrons and transit from the metal phase to the liquid
phase in the form of positively charged ions. The metal’s electric equilibrium is broken because the
metal which contains an excess of electrons becomes negative, while a cloud of “positive ions” forms
in the solution in the neighborhood of the metal surface.
The electrostatic attraction forces between these charges of opposite signs hold the positive ions and
the electrons formed in the immediate vicinity of the metal surface and the thus-created double layer
generates an electric field of a constant value.
The double electric layer formed at the metal’s surface corresponds to a potential difference between
the metal and the solution (in the immediate vicinity of the metal or interface) and is denoted the
electrode potential”, which depends particularly on the concentration of metal ions in the solution.
The “metal plate + water” system constitutes an electrode.
Layer of dipolar water molecules
e-
+
e-
e- +
e-
e- Solvated cations
+
e-
e- +
e-
e- +
+
e-
Helmholtz
layer
- +
- +
- +
Equivalent capacitor
- +
D MAC 2095 B
- +
- +
Schematic representation of the metal / pure water interface
or electrode with equivalent electric capacitor

6
• Behavior of a metal plate in a solution of one of its salts (this is another electrode)
If a metal place is placed in a solution of one of its salts (case of copper in a copper sulfate solution),
the electrode potential depends on the concentration of metal ions in the solution.
Electrolyte
H2O + CuSO4
Cu2+ Cu2+ 2-
2- SO4
SO4
Cu2+
Cu2+ Cu2+
Cu2+ Cu2+
Cu2+
Cu2+ Cu2+
Cu2+ Cu2+ Cu2+ Cu2+ Cu2+
Cu2+ Cu2+ Cu2+ Cu2+ Cu2+
δ
e e e e
e e e e
e
Metal D MAC 2096 D
e e
e
Cu
Schematic representation of a reversible copper electrode plunged in a copper

sulfate solution; k = Helmholtz layer, compact and adsorbed on surface
-
In the general case where the concentration is [C] and n . e is the ion charge, Nernst has
demonstrated that the electrode potential was equal to:
R: perfect gas constant

T: absolute temperature
RT n: number of electrons exchanged in the
E = Eo + nF log [C]
electrochemical reaction
C: ion concentration in solution
F: Faraday’s constant
-3
This simplified formula is valid only for diluted solutions (concentration less than 10 moles per liter).

7
In a normal solution (concentration equal to 1 mole of ions per liter), each metal assumes a particular
potential, also called a standard or normal potential (E0).
Standard equilibrium potential E0

Reaction with respect to the hydrogen
electrode at 25° C (V)
Au Au3+ + 3 e + 1.50
2 H2O O2 + 4 H+ + 4 e + 1.23
Pt Pt2+ + 2 e + 1.19
Ag Ag+ + e + 0.80
4 OH– O2 + 2 H2O + 4 e + 0.40
Cu Cu2+ + 2 e + 0.34
H2 2 H+ + 2 e 0
Pb Pb2 + 2 e – 0.13
Sn Sn2+ + 2 e – 0.14
Ni Ni2+ + 2 e – 0.25
Cd Cd2+ + 2 e – 0.40
Fe Fe2+ + 2 e – 0.44
Cr Cr3+ + 3 e – 0.74
Zn Zn2+ 2 e – 0.76
Al Al3+ + 3 e – 1.67
Mg Mg2+ + 2 e – 2.37
Na Na+ + e – 2.71
• Electrode potential measurement
A direct measurement is difficult because a potential tap is necessary in the liquid in the immediate
vicinity of the metal.
We prefer measuring the potential difference existing between the electrode studied in a laboratory and
the so-called hydrogen electrode whose potential is equal to 0 under well defined temperature and
pressure conditions.
Practically speaking, reference electrodes are used associating under well defined conditions a metal
and a salt at a fixed concentration (see figure on page 9).

8
The table below gives the correspondences between the diverse reference electrodes.
Electrode Electrolyte Reactions E/V
Calomel KCl, saturated Hg2Cl2 + 2e– = 2 Hg + 2 Cl– 0.241

KCl, 1 M 0.280
KCl, 0,1 M 0.333
Mercury sulfate K2SO4 saturated 2– 0.658

HgSO4 + 2e– = Hg + SO4
Silver chloride KCl, saturated AgCl + e– = Ag + Cl– 0.195
2–
Copper sulfate CuSO4, saturated CuSO4 + 2e– = Cu + SO4 0.316
Hydrogen H2SO4 2 H+ + 2e– = H2 0.000
In the case of the iron electrode, the metal in contact with the deaerated pure water containing the
ferrous ions undergoes the following process:
Fe Fe++ + 2 e–
Nernst law applies and specifies the potential’s value:
E = - 0.44 + 0.029 log [Fe++ ]
which in an E, pH diagram does not depend on the pH, but on the concentration of Fe++ ions. The
straight-line D corresponds to the solubility limit of the ferrous ions vs pH (see page 10).

9
REFERENCE ELECTRODES
Filling orifice
Saturated
KCl solution
CALOMEL Electrode body

Hg 2 Cl 2 + 2e- 2Hg+ Cl-
Mercury (Hg)
Calomel (Hg 2 Cl 2 )
Plug impregnated with
saturated KCl
Excess KCl crystals
SILVER CHLORIDE
Ag Cl + e - Ag + Cl - Porous cap
CU/COPPER SULFATE
Cu 2 + + 2e- Cu
Araldite
Screw
PVC
Rubber washer
Cable Plastic cap
Plastic pad
PVC
Copper rod
PVC
Transparent plastic
cartridge
Excess copper
sulfate crystals
Silver wire
AgCl gel
Tender pine stopper
Fritted glass
D MAC 1276 B
Plug

10
Evolts
0.2
- 0.2
H2
2H +
+2 -
D e
- 0.4
Fe Fe++ + 2e
- 0.44
1
10-2
Fe++ =
10-4
- 0.8
10-6
D MAC 2097 B
- 0.8 PH
0 2 4 6 8 10 12
++
Iron electrode potential vs. pH with respect to the hydrogen electrode Fe/Fe
In any electrolyte, any material in equilibrium assumes a potential called the dissolution potential.
The table below gives the dissolution potential values for diverse materials in a chlorinated solution.
Dissolution potential of diverse metals with respect to the saturated calomel electrode at 20° C in an
aqueous NaCl 3% solution.
Potential in Volt/ECS
Metals
at 20°C
Platinum + 0.30
Gold + 0.22
Passive chromium + 0.20 to + 0.25
Stainless steel (18 - 8) + 0.10
Mercury 0
Silver – 0.05
Copper – 0.18
Hydrogen – 0.25
Nickel – 0.27
Tin – 0.44
Lead – 0.47
Active chrome – 0.60
Iron – 0.60 to – 0.70
Al-Cu alloy – 0.60 to – 0.65
Aluminum – 0.74
Cadmium – 0.78
Al-Mg alloy – 0.77 to – 0.80
Zinc – 1.06
Magnesium – 1.63

11
4- PRIMARY PHENOMENA OF WET CORROSION

• Cathodic electrochemical reactions
Let’s return to our example of the iron electrode in contact with a solution of ferrous salt having a
++
concentration [Fe ]. The following equilibrium results:
Fe Fe++ + 2 e–
leading to a potential:
E = Eo + 0.029 log [Fe++]
Let’s imagine now that the liquid’s potential is held fixed (constant concentration of ions in liquid) and
by means of a suitable apparatus (DC generator connected to the metal and a reference electrode
plunged in the liquid) the metal’s potential is artificially decreased (metal supplied with electrons). The
system is going to alter itself to try to attain the value of the new lower potential.
Since there exists an electric field between the solution and the metal, the positive ions Fe++ are
attracted to the metal and retransit to the atom’s state according to the reaction:
Fe++ + 2 e– Fe
The Fe++ ions have been reduced (gain in electrons) and the metal is said to have been rendered
cathodic.
-
R e
i e-
Ea Ec
e-
Fe++
Cathode
Anode
Fe
D MAC 2098 E
EHN EHN
Fe++
Electrolyte
Fe++
Principle of the apparatus allowing to measure the anodic and cathodic polarization curves
(NHE: Normal Hydrogen Electrode)
Therefore, on a cathode, the reaction which occurs is a reduction.
Example of other cathodic reactions:

- +
- in a deaerated environment: 2 e + 2 H H2
- +
- in an aerated acid environment: 4 e + O2 + 4 H 2 H2O
- -
- in an aerated neutral and alkaline environment: 4 e + O2 + 2 H2O 4 OH
- 2+
- metal depositing: 2 e + Cu Cu
+
H (solvated proton) and O2 (dissolved oxygen) are the 2 main oxidants. They are reduced
by gaining electrons.

12
• Anodic electrochemical reactions
On the other hand, if the metal’s potential is increased (extraction of electrons from the metal) with
respect to the solution, the created electric field goes from the metal to the solution and the already
++
existing Fe ions are repulsed and new iron atoms will be ionized and pass into solution according to
the reaction:
++ -
Fe Fe + 2 e
The metal passes into solution. The iron is said to undergo oxidation or corrosion (loss of electrons
which remain in the metal). The metal is anodic.
R e-
i e-
Ea Ec
e-
Fe++
Corrosion
Anode
Cathode
Fe
D MAC 2098 F
EHN EHN
Fe++
Electrolyte
Fe++
The e– are “pumped” from the anode to the cathode

the Fe potential is increased and iron corrosion results
Therefore, on an anode, the reaction which occurs is oxidation.
Examples of other anodic reactions:
- Zn Zn2+ + 2 e
- Al Al3+ + 3 e

13
• Wet corrosion principles
An examination of the previous experiments allows the following principles to be disclosed:
- an electrochemical corrosion can only occur when the two electrode processes (partial
reactions) are carried out at the same time, that is, one supplies the electrons (partial
oxidation or anodic reaction), while the other consumes them (partial reduction or cathodic
reaction).
cathodic
Reduction of the oxidants reactions
area
Reduction e-
Oxidation
D MAC 1196 B
anodic
Oxidation = corrosion reactions
area
Uniform Localized
Fe Fe2+ + 2 e anodic
2 H+ + 2 e H2 cathodic
————————————————
Fe + 2 H+ Fe2+ + H2 global reaction
The partial anodic and cathodic reactions will explicitly make appear the electrons
unchanged during the oxido-reduction reaction, contrary to the global reaction.
Therefore, an electrochemical reaction is defined to be a chemical transformation which

implicates a transfer of charges at the interface between an electronic conductor, called an
electrode, and an ionic conductor, called an electrolyte.
For any metal M with n valence electrons, the following anodic reaction may be written:
M Mn+ + ne
For iron, Fe Fe++ + 2 e (1)
According to the environment in which the corrosion occurs, that is, according to the
+
electrolyte type, its concentration in H ions (or pH) and its content in dissolved oxygen,
several cathodic reactions may take place, and here are the main ones.

14
+
Deaerated acid environment (pH < 7): 2 H + 2 e H2
Electrolyte
HCl + H2O
H+ H+
Cl-
Cl-
Cl- Cl-
H+
H2
Cl- Fe2+
H+
H+
H+ H+
Cathode Anode
e
D MAC 2096 E
e
Méetal
Fe
Dissolution of the iron in a deaerated solution of hydrochloric

acid. The sites of the anodic and cathodic reactions continually
change so that the iron dissolution is uniformly carried out. The
-
chlorine ions Cl do not participate in the reaction.
Acid environment (pH < 7) containing the dissolved oxygen: O2 + 4 H+ + 4 e 2 H2O
Neutral or basic environment (pH > 7) containing the dissolved oxygen:
O2 + 2 H2O + 4 e 4 OH
Reduction of metal ions: Mn+ + n e M
Electrolyte
HCl + H2O + O2
H+ Cl-
Cl-
O2
Cl- H+
H2O H2O Cl-
Cathode O2 H+
Fe2+ Fe2+
H+ H+ H+ H+ Anode
e e
e e
D MAC 2096 G
Metal
Fe
Corrosion of iron in hydrochloric acid containing dissolved oxygen

15
In an aerated and neutral environment (for example, in salt water), the iron corrosion
product is rust Fe (OH3). The anodic reaction corresponds to equation (1) and the cathodic
reaction to equation (2). The products of both these reactions then react together to yield
ferrous hydroxide, that is:
2 Fe2+ + 4 OH– 2 Fe (OH)2
The ferrous hydroxide precipitates, but since it is unstable, it oxidizes into ferric hydroxide,
commonly called rust, and:
1
2 Fe (OH)2 + H21O + 2 O2 2 Fe (OH)3
- other oxidants
Other oxidants may also corrode the metals, such as:
• oxidizing metal cations: Cu2+, Fe3+, Sn4+

2–
• oxidizing anions: NO2–, NO3–, CrO4 , MnO4–, OCl–
• dissolved oxidizing gases: O3, Cl2, SO3
At high temperatures, some chemical substances normally inoffensive become corrosive.

Among the oxidants responsible for dry corrosions here are a few:
• gaseous oxygen
• steam (water vapor)
• carbon anhydride, CO2
2–
• sulfur compounds: S2, SO2, SO4
- in the case of an electrochemical corrosion, there is always a dissolution of metal at the

anode, while the cathodes are protected against any attack (deposit of metal or release of
hydrogen, or formation of OH- ions in an aerated neutral environment);
- in pure water free of oxygen or deaerated, the only metals liable to be destroyed by
electrochemical corrosion are those whose dissolution potentials are less than the
hydrogen electrode potential;
- in aerated pure water, the metals whose dissolution potentials are less than the oxygen
electrode potential are corroded (this is the case for copper, which does not corrode in a
deaerated environment, but does corrode in an aerated environment).
• Center of cathodic reactions
The diverse reduction reactions occur on cathodic areas which are composed of:
- any more noble metal, electrically coupled with that which is corroded, therefore, having a
higher dissolution potential (which is what occurs in the case of galvanic corrosion)
- any oxide located on a metal’s surface coming from metallurgical elaboration processes.
The oxides generally have more noble potentials than those of the corresponding metal
- in the case of cast irons, graphite has a more noble potential with respect to iron.
Therefore, a dissolution of iron occurs and is known under the name graphitization of the
cast irons

16
5- SECONDARY PHENOMENA OF WET CORROSION

• Description of these phenomena
We have seen that corrosion starts by the transition of the metal into an ion state in the conductor
environment in which it bathes. But then, the ions migrate in the solution, and react with the other ions
already present in the environment.
Thus, in water containing dissolved hydrogen sulfide, we have at average pHs the formation of an iron
sulfur precipitate. In aerated water, we have the formation of hydrated ferric oxide depositing as
a precipitate, etc.
By considering the solubility products, these secondary reactions are of major importance because the
salt deposit thus formed being more or less porous governs the intensity of ionic exchange
phenomena.
• Possibilities of these secondary reactions
In the case of a fundamental aggressive environment, such as water, the possibilities of secondary
reactions define in a pH potential diagram a certain number of areas. Under some conditions, corrosion
phenomena may occur, while under other conditions, the primary corrosion reactions are more or less
inhibited.
Thus, for the iron-water system at 25°C, Pourbaix was able to define an equilibrium diagram in
which the limits separate the regions where diverse reactions may occur. From a purely
thermodynamic approach, these calculations could be worked out. They do not presume the reactional
rate at which the diverse phenomena occur.
E(v) -2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
2,2 2,2
2 2
1,8 1,8
1,6 Fe+++ 02 + 4H+ + 4 e- 2 H2O 1,6

(b)
1,4 1,4
0 -2 -4 -6
1,2 1,2
1 1
O2
0,8 0,8
O2 +
2H
0,6 2 O + 4e - 0,6
H2O 4 OH -
0,4 0,4
CORROSION
0,2 (a) 0,2
++ PASSIVATION
0 Fe 0
2 H+
- 0,2
+ 2e -
H2 H2 O
Fe(OH)3 - 0,2
H2
- 0,4 - 0,4
Fe (OH)2 -6
- 0,6 -4 - 0,6
- 0,8 0 -2 -4 -6 HFeO2 - 0,8
-1 2 H2O + 2e- H2 + 2 OH- -1

Fe
- 1,2 - 1,2
IMMUNITY
- 1,4 - 1,4
- 1,6 - 1,6
D MAC 2091 B
- 1,8 - 1,8
-2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
pH
Electrochemical equilibrium diagram E, pH of the iron – water system at 25°C

(Only Fe, Fe(OH)2 and Fe(OH)3 are considered to be solid bodies)

17
The equilibrium diagram thus constructed delimits the corrosion and immunity domains of the
environment. The hydroxide precipitation domain is called passivation by assuming the precipitates
are protectors, which is not always the case.
Therefore, we see that a metal may be protected:
- by decreasing the metal’s potential below – 0.62 V; this is the cathodic protection
- by increasing the pH; this is the neutralization of the acid waters
- by adding oxidants at a rather high pH; this is the addition of inhibitors (oxidants)
In the practical usage of such a diagram, do not forget that the position of the
equilibrium straight lines change at the same time as the concentration in Fe++ ions.
6- EFFECTS OF SECONDARY REACTIONS ON THE KINEMATICS OF WET

CORROSION
• Coupling of two different metals
Each metal isolated from the other and plunged in an electrolyte assumes a certain potential with
respect to the solution.
− +
ν
Fe Cu
D MAC 2098 C
R=∞
ν = ECu - EFe i = 0
When the samples are electrically connected, the one with the more negative charge will tend to
become more positive (it is the anode), while the other receiving electrons will tend to become more
negative (it is the cathode).
Α
e- e-
Fe Cu
D MAC 2098 D
ANODE CATHODE
R=0
i = (icorr.) Fe - Cu

18
The anode’s potential is therefore displaced toward more positive values and the cathode’s potential
toward more negative values.
The anodic reaction corresponds to a loss of metal schematized as follows:
M Mn+ + ne–
The electron flow corresponds to an anodic current ia. Like any electrochemical reaction, this reaction
accepts an equilibrium potential Ea for which ia = 0.
The cathodic reaction may be schematized as follows:
oxidant + ne– reducer
The arrival of electrons via the conductor on the cathodic surface corresponds to a current Ic. At
equilibrium, the equilibrium potential Ec corresponds to ic = 0. The cathodic current is considered
negative by definition. The curves E = f (ia) and E = f (ic) are called the anode and cathode
polarization curves, respectively.
a corresponds to the over potential or anodic polarization.

c corresponds to the over potential or cathodic polarization.
Oxidant + ne- reducer

Ec
Cathodic ηc
polarization
M Mn+ + ne-
ηa Anodic
polarization
EA
D MAC 2117 B
Ι
iC iA
Reduction at the cathode Oxidation at the anode

19
• Evans Diagram
Evans proposed a graphic representation of the evolution of the anodic and cathodic potentials in
which the cathodic curve is folded back on the straight section around the ordinate i = 0.
Eoc ioc
ηc
Red
uctio
n
- Potential +
Ecorr.
ation
+ Oxid
ηa
D MAC 2099 C
Eoa
ioa
i i corr.
Log i
Electrode polarization curves: anode and cathode polarization

On the x-axis (abscissas), the current intensity is represented logarithmically
By means of this graphic construction, it is possible to determine by extending the anodic and cathodic
curves the point of intersection which allows determining the dissolution potential or average corrosion
Ecorr assumed by the two metals and corresponding to a corrosion current Icorr, such that:
ioa = - ioc = icorr
This corrosion current allows determining the corrosion rate of metal at the anode by the Faraday law:
m: corroded metal’s weight in g

M: metal’s atomic weight in g
M
m = F . ia . t where : metal’s valence
ia: corrosion current in amperes
T: time in seconds
Therefore, we see that the corrosion rate may be immediately deducted from the knowledge
obtained from the individual polarization curves.
Application
If a metal is coupled to another less noble metal in a conductor environment or electrolyte, the
second constitutes the anode of the battery and the first the cathode. This is the principle of the
cathodic protection method by a reactive anode (iron protected by zinc or magnesium).
• Case of a composite metal
This is the general case which occurs when the same metal is placed in an electrolyte. It is not
possible to plot the Evans diagram since the position of the anodes and cathodes is not known
and thus the value of the current flowing between the electrodes cannot be measured.
However, the graph given in the case of a coupling between two metals assumed to be ideally pure
remains valid and only the measurement Ecc is possible. But another method must be used to
determine the intensity of the corrosion current.

20
The most currently used technique consists of plotting the curve:
E = f (i) or E = f (logi)
where E is the measured potential and i the current supplied by an external source.
galvanometer
ν DC current
source
ν = RI
E Ι
REF
WE CE
D MAC 2100 B
Measurement set-up of a galvanostatic polarization curve;

WE: working electrode, REF: reference electrode; CE: counter-electrode
This curve is called the global polarization curve.
E X
Ec
C
= =
E" E'
Ecorr
A
Ea
D MAC 2101 A
-i ic = icorr. ia = icorr. +i
Ι

21
Under these conditions, at any moment the global current I will be equal to the algebraic (signed) sum
of the anodic current and the cathodic current:
I = ia + ic
In particular, when I =0, that is, when the global polarization curve intersects the potentials axis, then:
ia = – ic = icorr
Therefore, we obtain the corrosion conditions without any external current and, therefore, the corrosion
potential Ecorr.
Special case: When either/both of the reactions is/are governed by an activation polarization, the
individual polarization curves will be easily determined. In this case, we obtain the straight-lines of the
diagram E = f (log I) called TAFEL straight-lines.
E
X
Ec
C TAFEL straightline
E" E'
Ecorr
A
TAFEL straightline Ea
D MAC 2101 C
Y
Log - i ic = icorr. ia = icorr. Log i
Ι

22
We immediately obtain the corrosion current icorr from the abscissa (x-axis value) from either of these
straight-lines corresponding the corrosion potential. Practically speaking, we prefer to use the straight-
line of the cathodic reaction with the corrosion potential to determine the corrosion current icorr.
io, M+/H2
eH+/H2
(+)
l area
(Ec) Tafe
POTENTIAL
Ecorr.
Icorr. Tafe
l area
io, M/M+
Applied current curves
eH/H+
D MAC 2102 B
Anodic
(-)
(Ea) Cathodic
log iapp.
Polarization curve of a metal in an acid environment
Application
Cathodic protection by imposed current. As long as the potential imposed at the electrode is between
Ecorr and Ea, the electrode, even though transported toward a more cathodic potential, is still the center
of an anodic reaction. To protect the sample by an imposed current, it should be lowered to a more
negative potential than the potential Ea.
• Activation polarization
The electrochemical reactions do not instantaneously occur; their kinetics depend, in fact, on certain
intermediary reactions which may momentarily cause one of the products to pass, or one of the
reactants via an activated state (a higher energy state). Let’s take, for example, the reduction
reaction of hydrogen ions which are accompanied by a release of gaseous hydrogen:
2 H+ + 2 e H2
and let’s examine all the phases which allow the H+ ions of the electrolyte to react in this way. In order
to be absorbed at the cathode’s surface, the H+ ion must, first, be combined with an electron. Thus,
H+ + e Hads
This first phase is relatively rapid; however, for the reaction to be completed, it is necessary that two
atoms adsorbed on the surface be sufficiently close to one another to form a hydrogen molecule, that
is:
2 Hads H2
Finally, several molecules must be grouped together to form a bubble with a sufficiently large size to
allow it to escape from the cathode’s surface.

23
In all these phases, this third reaction represents the slowest reaction and, as a result, governs the
global kinetics of the reaction corresponding to the first equation. The reaction’s global kinetics is also
a function of the electrode’s metal, the electrolyte and the temperature.
The anodic reactions may also be the center of an activation polarization. By escaping from the metal’s
crystalline structure, the metal ions transit through an activated state and this reaction may only occur
at a finite rate.
In any case (whether anodic or cathodic reactions), activation polarization is evidenced by an

overvoltage, , determined by the Tafel law as previously seen and repeated below.
Eoc ioc
ηc
- Potential +
Red
uctio
n
Ecorr.
ation
Oxid
ηa
D MAC 2099 D
Eoa
ioa
i i corr.
Log i
Electrode polarization curves: anode and cathode polarization

On the x-axis (abscissas), the current intensity is represented logarithmically
For currents greater than the threshold values i0c at the cathode and i0a at the anode, the cathode’s
potential decreases from its equilibrium value (open circuit), Eoc, while the anode’s potential increases
from Eoc . Thus, for a current I, a cathodic overvoltage c is generated and an anodic overvoltage a.
The variation in the anodic or cathodic overvoltages is governed by the Tafel law for values of i
greater than i0. Thus,
i
= log i
0
where represents the slope of the polarization curves (generally expressed in volt per decade),
E = f (i), when i is represented on a logarithmic scale. In anodic reactions (oxidation), is positive,
while in cathodic reactions (reduction), is negative. The values of depend on the electrolyte’s
characteristics as well as the temperature. The current i0 is called the exchange current (or
exchange curren density if reasoned in terms of surface unit).
The importance of these curves is capital because the higher the absolute values of are, the
higher the corrosion current and, as a result, the lower the corrosion rates.

24
• Diffusion polarization
At the anode the release of positive ions leads to an increase in the concentration of these ions in the
electrolyte; the rate at which they enter the solution is therefore limited by the diffusion rate of the ions
outside of the diffusion layer. This diffusion rate determines the intensity of the limit current ilim.
Diffusion polarization (also called concentration polarization) also occurs in some cathodic reactions
(cathodic reduction of oxygen, for example). In this case, the limit current’s value is a function of the
concentration in oxygen [O2] of the electrolyte; the reaction’s rate is limited by the diffusion of the
oxygen molecules toward the cathode’s surface.
When it is added to the activation overvoltage, the effect of the diffusion overvoltage is to bend the
Tafel straightlines. These bent straightlines tend toward a limit current whose value will be that much
higher as the concentration in O2 is higher in the electrolyte.
Tafel straightlines
O2 + H2O + 4e 4 OH-
Potential +
-
D MAC 2103 B
[O2]1 < [O2]2 [O2]1 [O2]2
(ilim)1 (ilim)2
log i
Schematic representation of diffusion polarization

for the reduction of oxygen
for two oxygen concentrations [O2]; when [O2]1 < [O2]2 (ilim)1 < (ilim)2
• Passivation – Description of the phenomenon
When they are subjected to corrosion, some metals and alloys adopt a behavior quite different from
that described up to now; they become passive; their corrosion rate is thus generally less than
0.001 mm/a. A simple experiment performed by Faraday around the year 1835 focused on this
phenomenon: an iron sample plunged in concentrated nitric acid is subjected to a dissolution
accompanied by a release of hydrogen.
H 2O
Sample scraped or immersed in

diluted acid.
D MAC 2115 B
Fe Fe Fe
(a) HNO3 concentred (b) HNO3 diluted (c) HNO3 diluted

25
In (a) this reaction very rapidly stops and the corrosion rate becomes then almost zero. In (b) if the acid
in which the iron sample is plunged is subsequently diluted with water, the iron remains inert. In (c),
however, when its surface is scraped, a violent release of hydrogen occurs at this spot, which does not
stop.
In addition, a non-passivated iron sample immersed directly in diluted acid is attacked and the reaction
does not stop. When in concentrated acid the corrosion current attains a high value, a passive layer
2+
forms on the metal’s surface, which literally inhibits the Fe ions from entering the solution.
If the thus-passivated iron is then plunged in diluted acid, as long as this passivation layer remains
intact, the iron will not be attacked; however, when this layer is destroyed, it may no longer be
spontaneously reformed, contrary to like it did in the concentrated acid.
Finally, a non-passivated iron sample plunged in diluted acid remains active and is rapidly corroded,
and the reaction is accompanied by a violent release of hydrogen.
In this example, the ratio between the corrosion currents in the active state and in the passive state is
4
on the order of 5 x 10 . Therefore, we see the importance which passivable metals and alloys
represent for all usages where corrosion poses a problem. Iron is passivable only under very
special conditions.
The main passivable metals and alloys are stainless steels, nickel and chromium alloys
(Inconel), cobalt and chromium alloys (Stellite), as well as titanium and its alloys, aluminum,
tantalum, etc.
• Nature of the passive layer
The exact nature of the passive layers is still relatively not well known. Studies rendered possible,
among others, thanks to Auger spectrometry (surface analysis of the first atomic layers) allow
supposing that the passive layers contain oxygen in the form of oxide or hydroxide. The following
reaction may, therefore, occur at the cathode:
M + H2O M (OH) + H+ + e
-
According to this reaction, there will occur on the metal’s surface an adsorption of ions (OH ) and then
the formation of an adsorption compound containing the metal ions. The passive layers are very thin
(on the order of 2 to 3 nanometers), but they constitute an effective barrier which opposes the passage
of metal ions from the metal to the electrolyte; thus, they considerably slow down the corrosion rate.
The passivity of stainless steels, chromium alloys, nickel alloys and cobalt alloys is due mainly
to the formation of an adsorption compound. On the other hand, the passivity of titanium,
niobium and tantalum is attributable to the formation of an oxide layer much thicker than that of
the adsorption compounds.
• Corrosion of passivable alloys
The figure below schematically illustrates the anodic bias curve of a passivable alloy. When the
corrosion potential is greater than E 0a, but less than EF (the Flade potential), the current-potential
relationship obeys the Tafel law and the corrosion current is controlled by anodic and cathodic
overvoltages.
The potential EF corresponds to the critical current icrit. For a potential greater than EF, the corrosion
current amounts to ip (corrosion current at the passive state); from EF and Et this current value
remains constant. When the corrosion potential exceeds Et, the alloy is in the transpassive state and
the corrosion current increases again: as a result, the passive film breaks.

26
Transpassive
state
Et
+
Potential
Passive state
f
-
EF
+ + ne Active state
D MAC 2104 B
M n
Eoa M
log i
Anodic polarization curve of a passivable alloy
Let’s now examine how a passivable alloy (stainless steel, for example) behaves under diverse
corrosion conditions.
The figure below shows the polarization curves of a passivable alloy in three different oxidizing
environments. The cathodic reactions are the same in the three cases; only the oxidizing power of
each of the solutions varies. When the oxidizing power is high (cathodic bias curve C1), the corrosion
potential is less than Et (point A); the passivity is stable.
When the oxidizing power of the electrolyte is higher than that represented by the cathodic bias curve
C1, the corrosion potential attains a value higher than Et. At the transpassive state, the passive film
dissolves faster than it is formed; under these conditions, the corrosion is a pitting corrosion.
ET A
Potentiel +
C1
B
C2
D
-
EF
C3
E
D MAC 2105 A
log i

27
When the oxidation power is low (curve C 3), the corrosion potential attains a value represented by
point F; the corrosion is then major but uniform. Under these conditions, it is obvious that passivation
will not prevail and the anode will undergo corrosion.
On the other hand, when the oxidizing power of the electrolyte is average (curve C2), the passivity is
unstable: as long as the passive film is intact, the metal will remain in the passive state (point B) and
the corrosion rate will be low. However, if the passive film is broken, it cannot be reformed; the
corrosion potential which corresponds to this situation is represented by point E. When the corrosion
potential is equal to EF (point D), the passivity is unstable.
Such a situation is extremely dangerous. In fact, accidentally depassivated areas will be corroded very
rapidly, leading to pitting.
(+)
Potential
Increase
T, (H+)
(-)
D MAC 2106 B
log i
Effect of an increase in temperature and

acid concentration on passivity
+ + ne
Mn
M
(+)
POTENTIAL
Epass
O
2 +2
H2 O
+ 4e
Ipass 4OH -
2H
(-)
2O + 2
e
H
2 + 2O
H-
D MAC 2107 A
Ecorr. 1
ΙL
Ecorr. a 1
Icorr.a 2 3 4 5 6
log i
Effect of deaeration, aeration, agitation on

stainless steel corrosion (active or passive) in neutral sea water

28
1.0
NOBLE
0.8
1.6 0.6
PotentialE(V) ECS
1.2 (3) (2) (1)
0.4
Potential, E(V) ECS
0.8 Fe 0.2
0.4 Fe -10.5 Cr
0
- 0.0
D MAC 2109 B
D MAC 2108 B
ACTIF
- 0.2
- 0.4
- 0.6 - 0.4
10-1 1 10 102 103 104 105 106 - 0.4 100 1 000 10 000
Current density (μA/cm2) Current density (μA/cm2)
Effect of diverse castings and diverse
Anodic polarization of pure iron and an iron alloy samples of the same casting on the
with 10.5 % chromium anodic polarization curve of a stainless steel
304 in H2SO4 1 N, deaerated, at 25° C
1.1
1.0
NOBLE
0.9
NOBLE
1.1 0.8
1 N H2SO4 + IM NaCl
1.0 0.7
Potential E(V) ECS
0.9 0.6
1 N H2SO4
0.8 0.5
Hastelloy C-276
Potential E(V) ECS
0.7 Hastelloy C 0.4

0.6 Hastelloy B
0.3 304 L stainless steel
0.5
0.2 Hastelloy Alloy C
0.4
0.1
0.3 Pitting
0.2 0
ACTIF
0.1 - 0.1
D MAC 2111 B
D MAC 2110 B
0 - 0.2
ACTIF
- 0.1 - 0.3
- 0.2 - 0.4
- 0.3 - 0.5
1.0 10 100 1 000 10 000 1 10 102 103 104
Current density (μA/cm2) Current density (μA/cm2)
Anodic polarization of nickel alloys Effect of chlorides on the

in H2SO4 1 N at room temperature 304 L and a nickel alloy HASTELLOY
ALLOY C in sulfuric acid

29
7- DRY CORROSION
• Dry corrosion (oxidation at high temperatures: T > 260°C)
The dry corrosion of metals is a reaction between them and the gases which surround them. This
reaction is oxidation. In fact, it occurs most often at the metal’s surface, a compound which leads to
an effective loss and a degradation of the metal. This kind of corrosion leads particularly to in-service
strength problems at temperatures clearly higher than room temperature.
In most cases, the oxygen in the air combines with the metal’s atoms to form oxides. In sulfurous
oxidizing atmospheres (SO2), on the other hand, the corrosion products are sulfurs. Finally, the attack
may also be due to halogens (Cl, Br and I) and combustion environments (CO, CO2, H2O, etc.).
• Oxide layer formation process
The oxide layer formation process is a four-phase process schematically illustrated in the figure below.
First, oxygen is chemically adsorbed on the metal’s surface. This adsorption leads to the formation
of bonds between the oxygen and the metal ions which are generally ionic bonds (fig. a).
This phase is favored due to the fact that on the surface the metal bonds of the atoms are not
saturated; this is why these atoms exhibit a strong reactivity.
After a certain incubation period, there is the germination of the oxide on the metal’s surface (fig. b),
and then a lateral growth of the germs, which completely covers the metal’s surface with a film of
oxide (fig. c).
The uniform growth of the oxide then continues perpendicular to the metal’s surface (fig. d). This last
phase is the phase which determines the oxidation kinetics since the oxide layer’s thickness increases
to the detriment of the metal’s.
Chemical adsorption of oxygen Oxide germination

(a) (b)
D MAC 2112 B
Lateral growth of the germs Uniform growth of the oxide

and saturation of the surface (d)
(c)
Metal atom Metal ion (cation) Oxygen ion (anion)
Formation of an oxide layer on a metal’s surface

30
The figure below shows what movements have to be made by the ions and electrons inside the oxide
layer so that it may grow uniformly. For the oxide layer to grow, there must be a diffusion of the ions
(cations or anions) and electrons across this layer.
Therefore, the oxide must be an electric conductor (ionic conductor and electronic conductor). Since
the oxides and the sulfides generally are ionic compounds, their electric conductivity remains always
very low; they may, however, be assured by diverse types of faults, according to the compound’s
stoichiometry. The stoichiometric ratio, R, of a compound of the general form MxOy is:
anions y
R = = x
cations
where x and y are the integers for a perfect stoichiometry.
O2 O2
1 -
- O + 2e O2
O2 MO 2 2
e e
-
O2
Oxide M2+ Oxide
MO
D MAC 2113 B
Metal Metal
Oxide layer growth mechanism: a) Diffusion of metal ions (cations) and electrons to the oxide – gas
interface; b) Diffusion of the oxygen ions (anions) to the metal – oxide interface
re )
b)
e ra t u
i, N
p
h t em
g, L
hig
Formed oxide masses
u at
,M
,C
(F e
(Na
la w
oli c
law
b
P a ra
ear
)
mperature
r o om t e
Lin
u , a t
l, C
F e, A ature
i c la w ( h i g h te m p er
it h m i, a t
Lo gar Cr, S
D MAC 2114 B
Time
Metal oxidation kinematics

31
8- MEASUREMENT AND CONTROL - CORROSION TESTS

The diversity of these tests does not allow developing them here. They are performed either in the
laboratory or on the site or in a pilot factory.
The corrosion rates are evaluated by the measurement of weight losses and by electric and
electrochemical measurements (pitting tendency).
Here are a few of the main tests:
a - For stainless steels
The sensitivity to intergranular corrosion may be evaluated by HUEY and MONYPENNY-STRAUSS

tests.
Huey Test: consists of exposing steel samples for 48 hours in an HNO3 solution (65%) at the boiling
temperature. The sensitized sample becomes black and granular. The grains detach. The sample may
be exposed in a liquid phase or in a vapor phase.
Monypenny Test: a solution of SO4H2 – SO4Cu is used.
b - Salty spray test
The samples are subjected to the corrosive action of a sprayed solution. The vapors condense and the
liquid drops drip down the samples. The environment may be aerated and the temperature is held
constant. The pitting tendency in a chlorinated environment may be tested by this method.
c - Stressed corrosion test
The sample is generally turned on and insulated from the support by alumina joints which prevent
galvanic corrosion.
d - Corrosion tabs
The reference boards are placed in a corrosive environment after polishing and weighing to within
1/10th of a mg. After an exposure of at least four weeks, the boards are removed for observation. The
deposits are analyzed and then removed according to a cleaning method appropriate and carefully
specified in the results. The weight after cleaning allows deducting the corrosion ratio.
e - Measurement of average corrosion by electrical resistance
A probe consisting of a composition filament close to the material subjected to corrosion is

permanently plunged in the aggressive environment. During the read, an alternating current flows
through the filament. The corrosion ratio is connected to the filament’s electrical resistance.
f - Measurement of instantaneous corrosion by linear polarization (polarization resistance

method)
It involves measuring a current across two electrodes of the same composition as the facility’s metal. It
was shown that a minor variation in the potential E on the order of 10 to 20 mV at the corrosion
potential level on an electrode required the application of a current I defined by the following
equation:
l
Icorrosion = K E
The electrodes must be carefully cleaned for each measurement so that no traces persist which could
favor corrosion and falsify the results.
32
g - Analysis of the corrosive environment
For example, the quantity of iron is measured, but the initial contents have to be known before
corrosion occurs.

33
MEASUREMENT OF INSTANTANEOUS CORROSION

BY POLARIZATION RESISTANCE CURVE
DC current source
REF
D MAC 1223 B
AUX WE
Potentiometer
Reference electrode
Auxiliary electrode
Working electrode
20
15
10
ΔEcorr (mv)
ΔE
Slope = = R (ohms)
Iapplied
5
D MAC 1224 B
0
0 2 4 6 8 10
Applied current (ma)
Iapplied K Icorr.
Icorr. = K x E = R(ohms) Corr. rate (mpy) = A x K’

Area of corroding electrode
(square inches)
For iron: 0.46 mpy = 1 A/cm2

2000
For Fe, Co, Ni alloys: corr. rate (mpy) = R(ohms) x A (square inches)

34
h - Measurement of hydrogen penetration in steels
• Hydrogen created damages
The hydrogen atom is one of the main products of corrosion reactions. Normally, these atoms H are
transformed into molecules H2 at the steel’s surface, but it may happen, especially in the presence of
2- 3+ 3+
catalysts such as S , As , or Sn that these H atoms penetrate into the steel. This causes serious
problems in the presence of high stresses. The steel is embrittled and blistered by molecular hydrogen
formed within the metal.
Transfer environment
H Palladium foil (working electrode)
Interior side of Reaction to auxiliary electrode
canalization or device H
Auxiliary electrode
H +
2H + 2e- H2
Corrosion reaction H
Fe Fe2+ + 2e- 2H
+
2H + 2e-
H
Cathodic reaction
+
2H + 2e- 2H H Reference electrode
H Electrolyte
D MAC 1273 B
Reaction to palladium foil sheet
• Operating principle and description
After the metal surface is cleaned, a product allowing the transfer of atoms (paraffin wax) and a
palladium foil 0.25 mm thick are placed on the sheet metal. The electrochemical probe is, in turn,
placed on the thin palladium foil. Tightness is assured by a pair of seals (Viton + Teflon). The palladium
polarized by the instrument acts like a work electrode oxidizing the hydrogen which emerges from the
metal wall:
(2H 2H+ + 2 e)
After a short build-up period, the electric current given by the device corresponds to the hydrogen’s
penetration rate. The penetration rate may be characterized by a diffusion pressure of the gas
across the material. The effect of an inhibitor is evidenced by an almost instantaneous drop in the
diffusion pressure.
Teflon seal
Collar
Viton seal
Vent
Connection of the palladium foil
Palladium foil
Electric connector
Teflon seal
Reference
D MAC 1274 B
Auxiliary electrode
electrode
Cell body

35
II - THE MANY FORMS OF CORROSION

In most cases, the naked eye is sufficient to identify each form but sometimes magnification is helpful or
required.
1- UNIFORM ATTACK
This is the most common form of corrosion, characterized by a reaction which proceeds uniformly over
the entire exposed surface. The metal becomes thinner and eventually fails.
Examples:
- piece of steel or zinc immersed in dilute H2SO4
- rusting of iron in air -saturated water
• initial corrosion rate: 100 mdd (mg/dm2 x day)

• steady-state corrosion: 10 to 25 mdd
- steel in seawater: 25 mdd
a - Rate of uniform attack is reported in
ipy : inch per year

mdd : milligrams per square decimeter per day
mm/year : mm per year
D MAC 2000 A
No corrosion Uniform
mg
weight loss • 87,6

Corrosion rate =
(area) • d • t h
D MAC 2173 A
mm/year mm2 g/cm3

36
b - Metal classification
- < 0.002 ipy (< 0.05 mm/year) Excellent
- 0.02 to 0.005 ipy (0.05 to 0.13 mm/year) Good

(valve seats, pump shafts, impellers, springs, etc.) for critical parts.
- 0.005 to 0.05 ipy Satisfactory

for tanks, piping, valve bodies, bolt heads, etc.
- 0.05 ipy (0.15 cm/year) Usually Unsatisfactory
c - Prevention
- Uniform corrosion is the easiest form to measure and unexpected failures can usually be
avoided by regular inspection,
- Use of proper materials, including coatings, inhibitors or cathodic protection.
2- GALVANIC CORROSION
May occur when two different metals in contact are exposed to a conductive solution. The larger the
potential difference between the two metals, the greater the probability of galvanic corrosion. The
more "active" metal only corrodes. The less resistant metal becomes anodic (see the dry-cell).
The relative areas of the two metals are also important. A such larger area of the noble, compared to
the active metal, will accelerate the attack and vice versa. Galvanic corrosion can often be recognized
by the increased amount of corrosion close to the junction of the two metals.
More noble metal
Solution
Cu
D MAC 2001 A
Zn
a - Prevention
- select combinations of metals as close together as possible in the galvanic series

- avoid the unfavorable area effect of a small anode and large cathode
- insulate dissimilar metals wherever practicable (use of bakelite)
- apply coatings with caution, keep the coating in good repair
Porosity Tin Zinc

D MAC 2002 A
Steel
- design for the use of readily replaceable anodic parts or make them thicker for longer life
- install a third metal which is anodic to both metals in the galvanic series
- add inhibitors

37
GALVANIC SERIES OF VARIOUS METALS

AND ALLOYS IN FLOWING SEAWATER
(Active) (Noble)
- 1.6 - 1.4 - 1.2 - 1.0 - 0.8 - 0.6 - 0.4 - 0.2 0 0.2
Graphite
Platinum
Ni-Cr-Mo alloy C
Titanium
Ni-Cr-Mo-Cu-Si alloy G
Nickel-ion-chromium alloy 825
Alloy 20 stainless steels, cast and wrought
Stainless steel-types 316,317
Nickel-copper alloys 400, K-500
Stainless steel-types 302, 304, 321, 347
Silver
Nickel 200
Silver-bronze alloys
Nickel-chromium alloy 600
Nickel-aluminium bronze
70-30 copper nickel
Lead
Stainless steel-type 430
80-20 copper-nickel
90-10 copper-nickel
Nickel silver
Stainless steel-type 410, 416
Tin bronzes (G & M)
Silicon bronze
Manganese bronze
Admiraity brass, aluminium brass
50Pb-50Sn solder
Copper
Tin
Naval brass, yellow brass, red brass
Aluminium bronze
Austenitic nickel cast iron
Low-alloy steel
Low-carbon steel, cast iron
Cadmium
Aluminium alloys
D MAC 028 B
Beryllium
Zinc
Magnesium
Galvanic series for seawater. Dark boxes indicate active behavior of active-passive alloys

38
3- CREVICE CORROSION
This type of attack is usually associated with small volumes of stagnant solution caused by holes,
gasket surfaces deposits, crevices under bolts. The deposits (sand, dirt, corrosion products) act as a
shield and create a stagnant condition there under.
a - Mechanism
Na +
O 2– Consider a piece of metal immersed in

OH - aerated water (pH = 7)
Cl - H+ +
M
e D MAC 1225 A
Riveted plate
Electrochemical reaction by differential aeration:

M M+ + e Initially occurs uniformly over the entire
02 + 2H2O + 4e 4 OH - surface
After a short interval, the oxygen within the crevice is depleted because of restricted convection. The
dissolution of metal M continues, because oxygen reduction continues with the external area. This
tends to produce an excess of positive charge M+ which is necessarily balanced by the migration of
chloride ions into the crevice (OH- also migrate but they are less mobile than Cl-).
Secondary reactions
M+ Cl- + H2O M OH + H+ Cl-
The fluid within the crevice possesses a pH = 3 and the corrosion increases.
b - Prevention
- Use welded "butt joints" instead of bolted joints. Sound welds and complete penetration are
necessary to avoid porosity and crevices on the inside (if welded only from one side).
- Design vessels for complete drainage (this facilitates washing and cleaning and tends to
prevent solids from settling on the bottom of the vessel). Avoid sharp corners and stagnant
areas.
- Inspect equipment and remove deposits frequently.
- Remove wet packing materials during long shutdowns.
- Use nonabsorbent gaskets, such as Teflon, wherever possible.

SCHÉMATIC REPRESENTATION OF DIFFERENTIAL AERATION CELL
(EVANS EFFECT)
02947_A_A
Alkali produced
AIR 2H2O + O2 + 4e- —› 4OH-
(+phenolphalein —› pink)
H2O + 3% NaCl
Good access
of oxygen
Rust ring
39
Ferrous salts produced here

2Fe++ + 4e-
(+Fe(CN)6K3 —› blue)
IRON IMMUNE
2Fe
ANODIC ATTACK
D MAC 1363 A
40
4- PITTING
NaCl
Localized attack that results in holes in
O2 Cl O2 the metal. These holes may be small or
large in diameter; sometimes isolated or
so close that they look like a rough
surface.
++ + ++ +
Pitting is one of the most destructive and
Fe+++ insidious forms of corrosion.
Cr++ Chlorides
D MAC 1364 A
Ni++++ The shape of a pit is often responsible for
its continued growth, for the same
reasons mentioned under crevice
Stainless steel corrosion. A pit can, in effect, be
exposed to chloride solution considered as a self-formed crevice.
a - Prevention
- the methods suggested for combating crevice corrosion generally apply also for pitting,
particularly surface cleanliness.
- Increasing velocity, often decreases pitting attack.
- Surface finish improve pitting resistance.
- Ordinary steel is more resistant to pitting than stainless steel alloys.
- Addition of 2% M0 to "304" stainless steel to produce "316" steel results in a very large
increase in resistance to pitting (more stable passive surfaces).
- Materials that show pitting, or tendencies to pit, during corrosion tests should not be used to
build the plant.
- Adding inhibitors may be a dangerous procedure unless attack is stopped completely.
- The following list of alloys may be used as a guide:
• 304 • Hastelloy C
• 316 • titanium
• Hastelloy F

CHEMICAL COMPOSITION, PITTING RESISTANCE AND CREVICE RESISTANCE OF STAINLESS STEELS AND NICKEL ALLOYS
02947_A_A
Designation Producer Type Composition Others PRE PREN1 PREN2 CPT CCT1 CCT2
Cr Ni Mo Cu N °C °C °C
Hastelloy C22 Cabot A 21.0 58.0 13.5 — — 2.5 Co, 3.0 W 65.6 65.6 65.6 114.1 88.8 63.6
Hastelloy C276 Cabot A 15.5 59.0 16.0 — — 4.0 W 68.3 68.3 68.3 119.4 90.2 69.1
Hastelloy C4 Cabot A 16.3 68.0 15.3 — — 66.8 66.8 66.8 116.0 87.4 40.8
Hastelloy G Cabot A 22.0 44.0 6.5 2.0 — 2.0 Cb, 2.5 Co, 1.0 W 43.5 43.5 43.5 63.4 38.8 48.0
Hastelloy G3 Cabot A 22.0 49.0 7.0 1.9 — 1.0 W 45.1 45.1 45.1 67.2 42.6 40.2
Inconel 625 Inco A 21.0 61.0 9.0 — — 3.6 Cb 50.7 50.7 50.7 79.9 54.6 50.9
Incoloy 825 Inco A 21.5 42.0 3.0 2.2 — 0.9 Ti 31.4 31.4 31.4 35.6 10.6 26.3
Uranus SB8 Creusot-Marrel A 25 25 5 1.5 0.20 41.5 44.7 47.5 65.9 39.1 33.0
254 SMO Avesta A 20 18 6.1 0.7 0.20 40.1 43.3 46.13 61.7 31.5 29.8
29-4 C Allegheny F 29 — 4 — — 42.2 42.5 42.2 61.9 42.2 35.4
Cronifer 1925 HMO VDM A 21 25 5.9 — 0.14 40.5 42.7 44.7 60.8 32.5 30.4
AL - 6x Allegheny A 20 25 6.6 — — 41.8 41.8 41.8 59.2 33.2 30.6
A 963 VEW A 17 16 6.3 1.6 0.15 37.8 40.2 42.3 54.2 22.8 27.1
SANICRO 28 Sandvik A 27 31 3.5 1.0 — 38.6 38.6 38.6 53.1 32.0 32.6
41
Nicrofer 3127 LC VDM

Monit Uddeholm F 25 4 4 — — 38.2 38.2 38.2 51.9 29.4 31.4
Ferralium 255 Langley A/F cast 26 6 3 1.3-4 0.1 35.9 37.5 38.9 50.0 26.0 30.8
Uranus 52 N Creusot-Marrel A/F 25 6.2 3 1.5 0.18 34.9 37.8 40.3 50.0 23.7 29.8
Uranus 47 N Creusot-Marrel A/F 25 6.7 3 0.5 0.18 34.9 37.8 40.3 50.0 23.7 29.8

NSCD Ugine-Guegnon A 17 16 5.5 3 — 35.2 35.2 35.2 43.3 15.2 25.8
Uranus B6 Creusot-Marrel
2 RK65 Sandvik A 20 25 4.5 1.5 — 34.9 34.9 34.9 43.2 17.2 27.2
904 L Uddeholm
Uranus 45 Creusot-Marrel
SAF 2205 Sandvik A/F 22 6 3 — — 31.9 31.9 31.9 36.8 12.2 26.8
Cronifer 2205 VDM
Uranus 50 Creusot-Marrel A/F 21.5 6.2 2.5 1.4 0.10 29.8 31.3 32.75 35.0 7.9 25.5
316 — A 17 12 2.5 — — 25.3 25.3 25.3 20.5 – 7.6 21.0
PRE = % Cr + 3.3% Mo (Lorenz & Medavor 1969)

PREN1 = % Cr + 3.3% Mo + 16% N (Truman 1980)
PREN2 = % Cr + 3.3% Mo + 30% N (G. Herbsleb 1982)
CPT = 2.5% Cr + 7.6% Mo + 31.9% N - 41 (Renner & Al 1986)
CCT1 = 3.2% Cr + 7.6% Mo + 10.5% N - 81 (Renner & Al 1986)
CCT2 = % Cr + 1.6% Mo + 4.3%% Cb + 7.0% W (E.L. Hibner 1987)
The critical pitting temperature CPT tests performed by Renner and Al and by E.L. Hibner lead to formulas for estimating the resistance to crevice corrosion by calculating the critical crevice temperature CCT.
CPT°C = 2.5 (% Cr) + 7.6 (% Mo) + 10.5 (% N) – 41
CCT1°C = 3.2 (% Cr) + 7.6 (% Mo) + 10.5 (% N) – 81
CCT2°C = % Cr + 1.6 (% Mo) + 4.3 (% Cb) + 7.0 (% W)
42
5- INTERGRANULAR CORROSION
a - Metallurgical aspects
A B C
DMAC 1365 A
D E F
Diagrammatic representation of various stages

in the process of solidification of a molten metal.
The atoms of a metal are arranged in a regular repeating array. Ferritic steels have a body centered
cubic structure; the austenitics are face-centered cubic.
When a molten metal is cast, its solidification begins at many randomly distributed nuclei.
Each of these grows in a regular atomic array to form a grain. However, because of random nucleation,
the planes of atoms in neighboring grains do not match up. The area of mismatch between the grains
is called a grain boundary.
Grain boundaries are more active chemically and are usually attacked slightly more rapidly than grain
faces when exposed to a corrosive environment.
Intergranular corrosion can be caused by impurities at the grain boundaries, enrichment of one of the
alloying elements, or depleting of one of these elements in the grain-boundary areas.

43
b- Austenitic stainless steels
Grain boundaries
Depletion of chromium in the grain
Chromium boundary regions results in intergranular
depleted corrosion.
zone
The grain boundary phenomena that
causes intergranular corrosion is
sensitive to heat. Susceptibility to
Chromium intergranular attack is usually a by
Carbide product of a heat treatment (e.g. a
D MAC 1366 A
precipitate welding or stress-relieving operation) and
can be corrected by another heat
treatment).
The sensitizing temperature range is 400 to 850°C.
°C
1000
1' 5' 1h 8h 100 h

900
800
Intergranular attack
in boiling 16 % H2SO4
700
+ 6 % CuSO4 solution
D MAC 1367 A
600
500
10 102 103 104 105 106 Seconds
18 Cr 11Ni 0.05%C
Effect of time and temperature
Spot welding, in which the metal is rapidly heated by a momentary electric current followed by a
naturally rapid cooling, does not cause sensitization. Arc welding on the other hand, can cause
damage, the effect being greater the longer the heating time. Sensitizing temperatures are reached
some millimeters away from the weld metal itself.
In the temperature range indicated, Cr23 C6 is insoluble and precipitates out of solid solution if carbon
content is about 0.02% or higher. The chromium depleted zone near the grain boundary is corroded
because it does not contain sufficient Cr to resist attack in many corrosive environments. In a severe
case, entire grains are dislodged due to complete deterioration of their boundaries.

44
When hit with a hammer, the steel gives a dull sound typical of a metal that has suffered intergranular
corrosion, rather than a metallic ring, typical of sound metal.
Weld nugget Unmixed zone

Composite Partially
region melted
zone
Weld decay
zone
D MAC 033 C
Unaffected
base metal True heat-affected zone
Schematic diagram of components of weldment in austenitic stainless steel
Prevention:
- heat-treatment: consists of heating to 1075°C followed by water-quenching. Cr carbide is

dissolved at this temperature and a more homogeneous alloy is obtained.
- adding elements (stabilizers) that are strong carbide formers (cb - titanium). These elements
have a much greater affinity for carbon than does Cr.
- lowering the carbon content to below 0.03% does not permit sufficient carbide to form to
cause intergranular attack in most applications.
c - Ferritic stainless steels
The sensitizing range for ferritic stainless lies above 925°C and immunity is restored by heating for a
short time at 725°C (10 to 60'). In welded sections, damages occur to metal immediately adjacent to
the weld and to the metal itself.
Theory: the much more rapid diffusion rates of chromium and carbon in the body-centered
cubic compared to the face-centered cubic lattice probably explain the shorter times at a given
temperature required in the case of ferritic stainless steel to achieve carbide precipitation in the
first place, and subsequently to reestablish a uniform chromium composition after carbides
have precipitated.

45
6- STRESS CORROSION CRACKING
The simultaneous actions of a tensile stress and a

corroding will in some instances result in the cracking of
a metal alloy. The cracks can follow intergranular or
D MAC 1368 A
transgranular paths, and there is often a tendency for
crack branching.
a - Stress effects
Stresses that cause cracking arise from residual cold

work, welding, thermal treatment, corrosion products
which strain a wedging action, or may be externally
applied during service.
The minimum stress required to prevent cracking depends on temperature, alloy composition and
environment. In some cases, it has been observed to be as low as about 10% of the yield stress.
b - Cracking time
Initially, the rate of crack movement is more or less constant, but as cracking progresses the cross-
sectional area of the specimen decreases and the applied tensile stress increases. During later stages,
the crack widens.
c - Environments that may cause stress corrosion of metals
Aluminium alloys NaCl solutions; sea water: air; water vapor; NaCl- H2O2 solution
Copper alloys Ammonia vapors and solutions; amines; water and water vapor.
Inconel Caustic soda solutions.
Monel Fused caustic soda; hydrofluoric acid; hydrofluosilicic acid
Nickel Fused caustic soda.
Ordinary steels NaOH solutions; calcium, ammonium and nitrate soltuions; HCN
solutions; mixed acids (SO4H2 -NO3H); H2S solutions; seawater.
Stainless steels Seawater; H2S; MgCl2 solutions; NaOH-H2S solutions; NaOH-H2O2

solutions; condensing steam from chloride waters.
Titanium alloys Seawater; methanol-HCl; red fuming nitric acid.
In NaCl and similar neutral solutions SCC is observed only if dissolved oxygen is present.

46
d - Metallurgical factors
Time to failure (hr)
1000
The susceptibility to stress-corrosion

cracking is affected by: chemical
composition, preferential orientation of
Cracking
Fissuration grains, composition of precipitates. The
100 figure aside shows the effects of alloy
composition in stainless steels.
g
ac k i n
While generally the use of pure metals is

to c r
often an available way for preventing

ti m e
10 cracking; it should be pursued only with

caution.
im u m
No cracking
The resistance to SCC increases with the
min
amount of ferrite in cast stainless steels.

Pools of ferrite in the austenitic matrix
Ni % tend to block the progress of cracks.
D MAC 2125 B
20 40 60
SCC of FeCrNi in boiling 42 % MgCl2
Solution at 154°C
SCC of iron Cr-Mi in boiling 42% Mg Cl2
e - mechanism
It is not well understood. Some of the operating steps are:
- corrosion plays an important part in the initiation of cracks. A pit or other discontinuity on
the surface of the metal acts as a stress raiser (stress concentration).
- the simultaneous action of stress and corrosion is required (observations have been made
when cathodic protection was applied then removed).
- the rate of tensile stress has been shown to be important in rupturing protective films during
both initiation and propagation of cracks.

47
Alloy Environment Temperature
Hot acid chloride solutions 60°C

Such as MgCl2 and BaCl2 200°C
NaCl - H2O2 solutions
Neutral halides: Br–, I–, F–
Alkaline CaCl2
Austenitic Seawater
Stainless Concentrated caustic solutions > 120°C
Steels NaOH - H2S solutions
Condensing steam from chloride waters
For sensitized alloys:
Polythionic acids (H2SnO6) RT
Sulfurous acid RT
Pressurized hot water containing 2 ppm 300°C
dissolved oxygen
Ferritic H2S, NH4Cl, NH4NO3, hypochlorite. (resistant to

Stainless most environments if free of nickel but may fail by
Steels other modes of corrosion in same media)
Susceptible to same environments as austenitic

Duplex Stainless stainless steels but more resistant (immune to
Steels intergranular SCC in polythionic acid. Also greater
resistance than ferritic stainless steels to other
forms of corrosion)
Martensitic Caustic NaOH solutions (resistant to SCC in hot

Stainless Steel chlorides. Susceptible to hydrogen embrittlement)
Caustic NaOH solutions > 50°C

NaOH - NaSiO2 solutions > 255°C
Calcium, ammonium and sodium nitrate solutions Boiling
Mixed acids (H2SO4 - HNO3) RT
Carbon HCN solutions, acidified Warm
Steels Acidic H2S solutions
Seawater
Anhydrous liquid ammonia RT
Carbonate/bicarbonate
Amines All
CO/CO2 solutions
Environment-alloy combinations know to produce stress corrosion cracking

48
Alloy Environment Temperature
Nickel High temperature chloride solutions aggravating > 205°C

Cr-Fe factors: pH < 4, oxidizing species, such as
Alloys dissolved oxygen, H2, free sulfur
600, 800 Polythionic acids and thiosulfate solutions, RT

690 sensitized alloys with excess carbon
Caustic alkaline solutions 315°C
Ni-Cu Acidic fluoride solutions RT

Monel Hydrofluoric acid RT
Alloy Hydrofluosilici acid RT
400 Susceptible in cold-worked state. Resistant in

stress relieved state
H2S
Nickel Alloy
Caustic alkaline solutions 290°C
200, 201
Copper- Ammonia vapors in water RT
Zinc Amines in water RT

Alloys Nitrites in water RT
(brass) Water, water vapor alone RT

> 15% Zn (45-50% Zn, or + alloys)
Nitrate solutions
Some sulfate solutions
Air with water vapor RT
Potable waters RT
Aluminum Seawater RT
Alloys
NaCl solutions RT
NaCl - H2O2 solutions RT
Red fuming nitric acid RT
Titanium Hot salts, molten salts > 260°C
Alloys N 2O4 30 - 75°C
Methanol/halide RT

49
f - Prevention
• annealing in the case of residual stresses c.s 625°C

(stress relief) s.s 900°C
• reducing the load
• thickening the section
- lowering the stress by:
• annealing in the case of residual stresses

• reducing the load
• thickening the section.
- eliminating the critical species by degasification, demineralization, distillation.
- changing the alloy: use Inconel (raising the Ni content) when 304 is not satisfactory.
Although carbon steel is less resistant to general corrosion, it is more resistant to SCC. For
example, heat exchangers used in contact with seawater are often constructed with ordinary
steel.
- applying cathodic protection (don't forget H2 evolution and embrittlement).
- adding inhibitors: as in all inhibitor applications, sufficient inhibitors should be added to

prevent the possibility of localized corrosion and pitting.
g - Corrosion fatigue
Fatigue is defined as the tendency of a metal to fracture under repeated cyclic stressing. Usually,
fatigue failures occur at stress levels below the yield point. During the propagation of a fatigue crack
through a metal, the frequent cyclic stressing tends to hammer the fractured smooth surface, until the
cross-sectional area of the metal is reduced to the point where the limit is exceeded and rapid brittle
fracture occurs. In general, it is assumed that if a metal is stressed below its fatigue limit, it will endure
an infinite number of cycles without fracture.
Corrosion fatigue is defined as the reduction of fatigue resistance due to the presence of a corrosive
medium. There is usually a large area, covered with corrosion products and a smaller roughened area
resulting from the final brittle fracture. Corrosion fatigue is most pronounced at low stress frequencies;
also influenced by oxygen content, temperature, pH.
For example, steel and stainless steel possess good corrosion fatigue resistance in water, but in
seawater they retain only 75% of their normal resistance. The failure is usually transgranular. It seems
that pitting starts the failure.
Prevention: the same methods as previously seen for SCC. Also, resistance can be improved by
using coating such as electrodeposited zinc, chromium, nickel, copper coatings.

50
7- SELECTIVE LEACHING
This is the removal of one element from an alloy. The most common example is the removal of zinc in
brass alloys (dezincification). The corrosion is detrimental largely because it yields a porous metal with
poor mechanical properties. Similar processes occur in other alloys in which al, Fe, Co, Cr and other
elements are removed.
a - Dezincification
It is readily observed with the naked eye on yellow brass (30 Zn - 70 Cu). The alloy presents a red or
copper color contrasting with the original yellow.
Potable water service
Unaffected
portion
D MAC 1369 A
Dezincified
portion
Corrosion is localized or uniform. The mechanism is not really understood. It seems the zinc is
dissolved. Oxygen also enters into the cathodic reaction and hence increases the rate of attack.
Prevention: Dezincification can be minimized by:
- reducing the aggression of the environment (i.e. oxygen removal),
- cathodic protection,
- addition of 1% tin to a 70-30 brass (admiralty). Further improvements were obtained by

adding small amounts of arsenic, antimony, phosphate as "inhibitors". These elements are
redeposited on the alloy as a film and thereby hinder dezincification.
b - Graphitization
The cast iron appears to become "graphitized" in that the surface layer has the appearance of graphite.
The graphite is cathodic to iron, and an excellent galvanic cell exists. The iron is dissolved leaving a
porous mass consisting of graphite. The cast iron loses strength and its metallic properties. The
surface shows rusting that appears superficial. Graphitization does not occur in nodular or malleable
cast irons, because the graphite network is not present to hold together the residue.

51
8- FRETTING CORROSION
Fretting describes corrosion occuring at contact areas between materials under load, subjected to
vibration and slipping. Is appears as pits or grooves in the metal surrounded by corrosion products. It
is also called "false brinelling" (the resulting pits are similar to the indentations made by a Brinell hard
test). A common case occurs at the interface between a press-fitted ball-bearing race on a shaft.
Load
Cyclic movement
Fretting at tight fits
subject to vibration
D MAC 038 B
Coldweld Contact point
oxidized
D MAC 039 B
particules
Before After
A loss of tolerances and loosening appear. The relative motion necessary to produce fretting corrosion
is extremely small - displacements as little as 1Å cause fretting damage.
Mechanism: either the heat of friction oxidizes the metal and this oxide then wears away, or, the
mechanical removal of protective oxides or corrosi10 - Erosion corrosion 53nued exposure of
fresh surface that continues to actively corrode.
Prevention:
- lubrication reduces friction between bearing surfaces and tends to exclude oxygen
- increase the hardness of both materials
- decrease the load at bearing surfaces (not always successful)
- use gaskets to absorb vibration and to exclude oxygen (Teflon)
- increase load to reduce slipping (effective if it is high enough to prevent slip)
- design of contacting surfaces to avoid slipping completely (e.g. grit sandblasting or
otherwise roughening the surface)
- combination of a soft metal with a hard metal. A sufficiently high loads, soft metals serve to
exclude air at the interface (Sn, Ag, Pb, Cd coated metals in contact with steel)

52
9- EROSION CORROSION
Erosion corrosion is the increase in rate of attack on a metal because of relative movement between a
corrodent fluid and the metal surface. Erosion is usually attributed to the removal of protective surface
films.
(a) (b)
D MAC 2121 B
(c) (d)
Turbulent eddy mechanism for downstream undercutting of erosion-corrosion pits
The attack is characterized by grooves, waves, shallow pits and usually exhibits a directional pattern.
Erosion corrosion thrives on high velocity conditions, turbulence impingement, galvanic effect, which
remove the protective surface films. Fast-moving slurries that contain hard solid particles are also
likely to cause problems. Erosion is frequently seen on pump impellers, piping particularly at elbows,
inlet into exchanger tubes, etc.
a - Prevention
- better material (Ni-Hard is a white cast iron containing about 4% Ni and 2% Cr). It is very
hard (550 Brinell hardness 725) used for pump impellers in slurry services).
- better design-involves: change in shape or geometry, increasing pipe diameter which
decreases velocity, increasing the thickness of material strengthens vulnerable areas).
- environment, filtration, reduce temperature, etc.
- coatings that produce a resilient barrier, elastomer on impellers. Hard facings (stellite for
valves). Repair attacked areas by welding.
b - Cavitation
Cavitation is caused by the formation and collapse of vapor bubbles at the metal surface. Shock
waves may increase up to 4000 bars. This forces can produce plastic deformation. The appearance
of cavitation damage is similar to pitting, except that the pitted areas are closely spaced and the
surface is usually roughened.
Prevention:
- the same techniques used in preventing erosion corrosion.

- smooth do not provide sites for bubble nucleation (smooth finishes on pump impellers).
- available NPSH > required NPSH.

53
III - CORROSION PREVENTION

1- MATERIALS SELECTION
One of the most important factors that must be considered is corrosion resistance. Materials selection
charts presented here, indicate where materials are used for specific range of concentration and
temperature in specific chemicals. Boundary lines for corrosion zones may shift with variations in
aeration, velocity, impurities, etc.
Plastics, as compared with metals and alloys, are much weaker, softer, more resistant to chloride ions
and hydrochloric acid, less resistant to solvents, and have definitely lower temperature limitation.
Fresh Portland cement contains lime (Ca (OH2)) so, it has an high alkalinity (pH = 12.6). Hence
aluminum surfaces in contact with wet concrete may evolve hydrogen visibly. The corrosion rate is
reduced when the cement sets, but continues if the concrete is kept moist or contains deliquescent
salts (e.g. CaCl2).

TYPES AND COMPOSITIONS OF WROUGHT STAINLESS STEELS
02947_A_A
— American Iron and Steel Institute —
AISI Cr Ni C Mn P S Si Other elements Remarks

Type N° (max) (max) (max) (max)
Class: Austenicit (face-centered cubic, nonmagnetic, not heat treatable)
201 16.0-18.0 3.5-5.5 0.15 max 5.5-7.5 0.06 0.03 1.0 0.25 N (max)
202 17.0-19.0 4.0-6.0 0.15 max 7.5-10 0.06 0.03 1.0 0.25 N (max)
301 16.0-18.0 6.0-8.0 0.15 max 2.0 0.045 0.03 1.0
302 17.0-19.0 8.0-10.0 0.15 max 2.0 0.045 0.03 1.0
302 B 17.0-19.0 8.0-10.0 0.15 max 2.0 0.045 0.03 2.0-3.0 Resistant to high-temp. oxidation
54
303 17.0-19.0 8.0-10.0 0.15 max 2.0 0.20 0.15 min 1.0 0.6 Mo (max) Easy machining, nonseizing
303 Se 17.0-19.0 8.0-10.0 0.15 max 2.0 0.20 0.06 1.0 0.15 Se (min) Easy machining, nonseizing

304 18.0-20.0 8.0-10.5 0.08 max 2.0 0.045 0.03 1.0
304 L 18.0-20.0 8.0-12.0 0.03 max 2.0 0.045 0.03 1.0 Extra low carbon
305 17.0-19.0 10.5-13.0 0.12 max 2.0 0.045 0.03 1.0 Lower rate of work hardening than
302 or 304
308 19.0-21.0 10.0-12.0 0.08 max 2.0 0.045 0.03 1.0

309 22.0-24.0 12.0-15.0 0.20 max 2.0 0.045 0.03 1.0
309 S 22.0-24.0 12.0-15.0 0.08 max 2.0 0.045 0.03 1.0
310 24.0-26.0 19.0-22.0 0.25 max 2.0 0.045 0.03 1.5
310 S 24.0-26.0 19.0-22.0 0.08 max 2.0 0.045 0.03 1.5
314 23.0-26.0 19.0-22.0 0.25 max 2.0 0.045 0.03 1.5-3.0
316 16.0-18.0 10.0-14.0 0.08 max 2.0 0.045 0.03 1.0 2.0-3.0 Mo
316 L 16.0-18.0 10.0-14.0 0.03 max 2.0 0.045 0.03 1.0 2.0-3.0 Mo Extra low carbon
317 18.0-20.0 11.0-15.0 0.08 max 2.0 0.045 0.03 1.0 3.0-4.0 Mo
321 17.0-19.0 90-12.0 0.8 max 2.0 0.045 0.03 1.0 Ti 5 X C (min) Stablized grade
347 17.0-19.0 9.0-12.0 0.08 max 2.0 0.045 0.03 1.0 Cb-Ta: 10 X C (min) Stabilized grade
348 17.0-19.0 9.0-13.0 0.8 max 2.0 0.045 0.03 1.0 Cb-Ta: 10 X C (min) Stabilized grade 0.1 Ta (max)
when radiation conditions require
low Ta
02947_A_A
TYPES AND COMPOSITIONS OF WROUGHT STAINLESS STEELS
— American Iron and Steel Institute —
AISI Cr Ni C Mn P S Si Other elements Remarks

Type N° (max) (max) (max) (max)
Class: Austenicit (face-centered cubic, nonmagnetic, not heat treatable)
403 11.5-13.0 — 0.15 max 1.0 0.04 0.03 0.5 Turbine quality
55
410 11.5-13.5 — 0.15 max 1.0 0.04 0.03 1.0

414 11.5-13.5 1.25-2.5 0.15 max 1.0 0.04 0.03 1.0
416 12.0-14.0 — 0.15 max 1.25 0.06 0.15 min 1.0 0.6 Mo (max) Easy machining, nonseizing

416 Se 12.0-14.0 — 0.15 max 1.25 0.06 0.06 1.0 0.15 Se (min) Easy machining, nonseizing
420 12.0-14.0 — Over 0.15 1.0 0.04 0.03 1.0

431 15.0-17.0 1.25-2.5 0.20 max 1.0 0.04 0.03 1.0
440 A 16.0-18.0 — 0.6-0.75 1.0 0.04 0.03 1.0 0.75 Mo (max)
440 B 16.0-18.0 — 0.75-0.95 1.0 0.04 0.03 1.0 0.75 Mo (max)
440 C 16.0-18.0 — 0.95-1.2 1.0 0.04 0.03 1.0 0.75 Mo (max) Highest attainable hardness
Class: Ferritic (body centered cubic, magnetic, not heat treatable)
405 11.5-14.5 — 0.08 max 1.0 0.04 0.03 1.0 0.1-0.3 Al

430 16.0-18.0 — 0.12 max 1.0 0.04 0.03 1.0
430 F 16.0-18.0 — 0.12 max 1.25 0.06 0.15 min 1.0 0.6 Mo (max) Easy machining, nonseizing
430 F, Se 16.0-18.0 — 0.12 max 1.25 0.06 0.06 1.0 0.15 Se (min) Easy machining, nonseizing
446 23.0-27.0 — 0.20 max 1.5 0.04 0.03 1.0 0.25 N (max) Resistant to high temperature
oxidation
56

57
MATERIALS SELECTION CHART FOR PLANT PHOSPHORIC ACID
Temperature (°F)
320
280 Atmospheric boiling 4

point curve 3
240
2
200
5 7
160
120
1 6
80
D MAC 1371 A
40
0 10 20 30 40 50 60 70 80 90 100 110 120
Plant phosphoric acid (wt.%)

1 Haveg 41 6
Ceramics Epoxys Ceramics
Hostelloy B*, C Glass Hastelloys B*,C
Durimet 20 Cl. polyether Durimet 20
R-55 Impervious graphite R-55
Type 316* Type 316*
Lead (to 205 F.) 3 Copper (air free)
Copper (air free) Ceramics Monel (air free)
Monel (air free) Hostelloys B*,C Duriron*
Duriron* Durimet 20 Rubber (to 85 F.)
Impervious graphite R-55 PVC (to 85 F.)
Haveg 41 Impervious graphite Glass
Rubber (to 150 F.) Glass Ni-O-nel alloy 825
PVC (to 150 F.) Duriron*
Polyesters (65%) Ni-O-nel alloy 825 7
Epoxys Ceramics
Polyethylene (to 140 F.) 4 Hastelloys B* (to 400 F.)
Glass Ceramics Durimet 20
Cl. polyether Duriron* R-55
Saran (to 75 F.) Glass Type 316*
Ni-O-nel ally 825 Monel (air free)
5 Glass
2 Ceramics
Ceramics Hastelloys B*,C
Hostelloys B*,C Durimet 20
Durimet 20 R-55
R-55 Type 316* Notes
Type 316* Duriron* Ta, Mo & W
Duriron* Polyesters 0.85% to 375 F.
Ni-O-nel alloy 825 Glass Zr
Lead (to 205 F.) Ni-O-nel alloy 825 0-50% to 375 F.
* Subject to attack by fluorine compounds

58
MATERIALS SELECTION CHART FOR SODIUM HYDROXIDE
Temperature (°F)
600
500
Stress cracking boundary
400
Atmospheric
boiling 4
point curve
300
5
30 mpy
3
200
2 1 mpy
100
1 Melting point curve
D MAC 1372 A
0
0 20 40 60 80 100
Sodium hydroxide (wt.%)
1 2 Inconel
Steel and cast iron Nickel Hastelloys
Most plastics Monel 400 Ni-o-nel
Stainless steels Hastelloys B, C
Nickel Inconel 4
Copper alloys Stainless steels Nickel
Monel 400 Zirconium Silver
Saran Ni-o-nel alloy 825 Cast iron
Cl.polyether (to 30%) Haveg 60, 61
Rubber Neoprene 5
Epoxies Steel
Haveg 60,61 3 Nickel
Polyethylene Nickel Stainless steels
PVC Monel 20 alloys

59
CORROSION RESISTANCE OF MATERIALS TO HYDROCHLORIC ACID
240
Boiling point
200
5
4
Temperature (°F)
160
120
80
D MAC 1373 A
10 20 30 40
Concentration HCI %

60
CODE FOR HYDROCHLORIC ACID CHART
Zone 3
Zone 1
Chlorimet 2
Chlorimet 2 Glass
Glass Silver
Silver Platinum
Platinum Tantalum
Tantalum Hastelloy B (Chlorine Free)
Hastelloy B Durichlor (FeCl3 Free)
Durichlor (Fe Cl3 free) Haveg
Haveg Saran
Saran Rubber
Rubber Molybdenum
Silicon Bronze (Air Free) Zirconium
Copper (Air Free) Impervious Graphite
Nickel (Air Free)
Monel (Air Free) Zone 4
Zirconium
Tungsten Chlorimet 2
Titanium - up to 10% HCl at room température Glass
Worthite -up to 2% HCl at room température Silver
Platinum
Tantalum
Hastelloy B (Chlorine Free)
Zone 2 Durichlor (FeCl3 Free)
Monel (Air Free) up to 0.5% HCl)
Chlorimet 2 Zirconium
Glass Impervious Graphite
Silver Tungsten
Platinum
Tantalum Zone 5
Hastelloy B
Durichlor (FeCl3 Free) Chlorimet 2
Haveg Glass
Saran Silver
Rubber Platinum
Silicon Bronze (Air Free) Tantalum
Zirconium Hastelloy B (Chlorine Free)
Molybdenum Zirconium
Impervious Graphite Impervious Graphite
Materials in shaded zones having reported corrosion rate less than 0.020" per year

61
CORROSION RESISTANCE OF MATERIALS TO SULFURIC ACID
600
500
10
400
Temperature (°F)
9
Avoid hastelloy B and D in
the range at boiling point
300
Boiling point
200
1
3
2
5
100
D MAC 1374 A
8
4
20 40 60 80 100
Concentration H2SO4 (%) 103,5

62
CODE FOR SULFURIC ACID CHART
Zone 1 Zone 3 Zone 6

10% Aluminum Bronze (Air Free)
Illium G Glass Glass
Glass Silicon Iron Silicon Iron
Hastelloy B and D Hastelloy B and D Hastelloy B and D (0.020" to 0.050")
Durimet 20 Durimet 20 (up to 150°F) Tantalum
Worthite Worthite (up to 150°F) Gold
Lead Lead Platinum
Copper (Air Free) Monel (Air Free)
Monel (Air Free) Impervious Graphite Zone 7
Haveg 43 Tantalum Glass
Rubber (up to 170°D) Gold Silicon Iron
Impervious Graphite Platinum Tantalum
Tantalum Zirconium Gold
Gold Molybdenum Platinum
Platinum
Silver Zone 4 Zone 8
Zirconium
Nionel Steel Glass
Tungsten Glass Steel
Molybdenum Silicon Iron 18 Cr-8 Ni
Type 316 Stainless (up to 10% Hastelloy B and D Durimet 20
Aerated) Lead (up to 96% H2SO4) Worthite
Durimet 20 Hastelloy C
Zone 2 Worthite Gold
Glass Ni Resist Platinum
Silicon Iron Type 316 Stainless (above 80%)
Hastelloy B and D Impervious Graphite (up to 96% H2SO4 ) Zone 9
Durimet 20 (up to 150°F) Tantalum
Worthite (up to 150°F) Gold Glass
Lead Platinum 18 Cr-8 Ni
Copper (Air Free) Zirconium Durimet 20
Monel (Air Free) Worthite
Haveg 43 Zone 5 Gold
Rubber (up to 170°F) Platinum
10% Aluminum Bronze (Air Free) Glass
Ni Resist (up to 20% at 75°F) Silicon Iron Zone 10
Impervious Graphite Hastelloy B and D
Tantalum Durimet 20 (up to 150°F) Glass
Gold Worthite (up to 150°F) Gold
Platinum Lead (up to 175°F and 96% H2SO4 ) Platinum
Silver
Impervious Graphite (up to 175°F and
Zirconium
96% H2SO4)
Nionel
Tungsten Tantalum
Molybdenum Gold
Type 316 Stainless (up to 25% at Platinum
75°F) Aerated

63
CORROSION RESISTANCE OF MATERIALS TO HYDROFLUORIC ACID
250
Boiling point
225
200
175
Temperature (°F)
6
4
150
5
3
125
100
75 7
1 2
D MAC 1375 A
10 20 30 40 50 60 70 80
Concentration (HF %)

64
CODE FOR HYDROFLUORIC ACID CHART
Zone 1 Zone 4
Monel (Air Free) MONEL (Air Free)

Copper (Air Free) 70 CU-30 Ni (Air Free)
70 CU-30 Ni (Air Free) Copper (Air Free)
Lead (Air Free) Lead (Air Free)
Nickel (Air Free) Hastelloy C
Alloy 20 Platinum
Ni Resist Silver
Hastelloy C Gold
Platinum Impervious Graphite
Silver Haveg 43
Gold
Impervious Graphite Zone 5
Haveg 43
Rubber Monel (Air Free)
25 Cr-20 Ni Steel 70 Cu-30 Ni (Air Free)
Lead (Air Free)
Zone 2 Hastelloy C
Platinum
Monel (Air Free) Silver
70 Cu-30 Ni (Air Free) Gold
Copper (Air Free) Impervious Graphite
Lead (Air Free) Haveg 43
Nickel (Air Free)
Alloy 20 Zone 6
Ni Resist
Hastelloy C Monel (Air Free)
Platinum Hastelloy C
Silver Plainum
Gold Silver
Impervious Graphite Gold
Rubber Haveg 43
Haveg 43
Zone 7
Zone 3
Carbon Steel
Monel (Air Free) Monel (Air Free)
70 Cu-30 Ni (Air Free) Hastelloy C
Copper (Air Free) Platinum
Lead (Air Free) Silver
Alloy 20 Gold
Hastelloy C Haveg 43
Platinum
Silver
Gold
Impervious Graphite
Haveg 43
Rubber

65
CORROSION RESISTANCE OF MATERIALS TO MIXED ACIDS

AT ROOM TEMPERATURE
100 % H2O
2
5
D MAC 1376 A
100 % H2SO4 100 % HNO3

66
CODE FOR MIXED ACIDS CHART
Zone 1 Zone 4
Steel 18 Cr-8 Ni
Durimet 20 Durimet 20
Worthite Worthite
Glass Glass
Silicon Iron Silicon Iron
Tantalum Tantalum
Platinum Platinum
Gold Gold
Lead
Zone 5
Zone 2
18 Cr-8 Ni
Cast Iron Durimet 20
Steel Worthite
18 Cr-8 Ni Glass
Durimet 20 Silicon Iron
Worthite Tantalum
Glass Platinum
Silicon Iron Gold
Tantalum Aluminum
Platinum
Gold
Lead
Zone 3
Durimet 20
Worthite
Glass
Silicon Iron
Tantalum
Platinum
Gold

67
Remarks concerning some materials used in the charts
Karbate: graphilor: graphite with resin impregnation
Haveg: phenolic resin
Saran: copolymer of vinylchloride and vinylidene chloride
Lead (ch): chemical lead (0,06% Cu)
Lead (Sb): hard lead (3 at 18% Sb)
Duriron: ferrous alloy 82% Fe, 15% Si, 0.95% C
Alloys 20: 20% Cr, 29% Ni, 3.25% Cu, 2.25% Mo, < 0.07% C
Durimet 20 - cast
carpenter 20 - wrought
worthite: 20 Cr, 24 Ni, 3 Mo, 3 Si, 2 Cu
Ni-resist: cast-iron 15% Ni + 3% Cr (the hardest grey cast iron)
Illium - Ni alloy (21% Cr, 5% Mo, 6% Fe, 4% Cu, 1% Mn)
Uranus 65: %C < 0.03, 25,5% Cr, 20% Ni, 0.25% Nb

68
2- CONTROL OF PROCESS VARIABLES

a - Concentration of major constituents
The rate of corrosion of a given material usually

increases as the concentration of the corrodent
increases (example: iron in hydrochloric acid).
Corrosion rate
Corrosion does not always increases with

concentration (iron in sulfuric acid and in nitric
D MAC 1377 A
acid.
80 % Here, hydrogen ions concentration increases but
at the higher levels, it decreases again.
Acid % weight
Ambient temperature
b - Effect of impurities
Beneficial effects are dependent upon the same rules as the inhibitors. Chloride ion is deleterious
because it interferes with the anodic reaction. Chlorides can be particularly effective at destroying
passivity in material such as the stainless steels (Pitting).
Impurities form complex ions and cause rapid corrosion (conversion of copper into copper-ammonia
complexes when ammonia in the presence of oxygen, is present as an impurity).
Ferric ions Fe3+ are deleterious to iron, but can be beneficial to stainless steel. There may be
interference between impurities to reduce corrosion. The first step to mastering impurities is knowing
what they are, how much is present, and where they come from.
c - Temperature
An increase in temperature will usually increase the rate of corrosion. There are a few exceptions due
to a decrease in oxygen content of the solution (particularly near the boiling point). Oxygen is needed
to depolarize the cathodic reaction.
Also, corrosion problems appear at the dew point temperature.
d - pH effect
Acidity of a solution is designated by pH .
The Pourbaix diagram relates the possibility of corrosion.
2 2 2
0 0 0
2 2 2
7 14 7 14 7 14
D MAC 1378 A
Tantalium Titanium Aluminium
Passivation Corrosion Immunity

69
e - Influence of aeration
Metals that do not show passivity and that are corroding will generally do so at a faster rate if the
oxygen content of the solution is increased. Corrosion rate of materials that show passivity, depends
of the state in which they are (active, passive).
f - Velocity
Has been seen before.
Velocity acts on the following ways :
- remove deposits,
- erosion,
- concentration polarization.
g - Startup and shutdown procedures
Startup problems are related to too high operating temperature, corrodent concentration, incomplete
oxygen removal.
Downtime problems are related to inadequate cleaning procedures for removing process residues.
This can be deleterious in promoting localized corrosion (pitting of dirty stainless steel tubes left to
drain slowly without cleaning).
Improper cleaning can cause problems if the wrong reagents or inadequate rinsing procedures are
used (cleaning stainless steel with HCl acid is a particularly dangerous practice).

70
3- GOOD ENGINEERING DESIGN
GOOD INGINEERING DESIGN
BAD GOOD
WELDS
Crevice
Drainage deposits
Acid
Corrodent concentration
Acid
Hot gas
Hot gas
Condensation
Métal A
Weld
Dilution
of metalB
Tube métal B by A at weld
Pad
of metal B
Turbulent flow
Inlet
Inlet
Impingement Tube
Tube
D MAC 001 B
métal A Galvanic
métal B corrosion

71
Faulty designs and good design
t
6.5 mm
Concrete
Beam t
Steel rods and
25 x 3 mm stirrups
Inadequate access
Faulty design in renforced concrete.
for maintenace painting
The concrete cover is too thin to exclude
water, which permeater through it and Tubeplate Seal-weld
causes corrosion of the steel
Flow direction Erosion damage
Shellside
Erosion/corrosion downstream of a butt weld Tube/tube plate crevice
with too much root penetration (exaggerated in scale) Tube
Water and dirt
Channels and angles

Poor
Drainage hole
Better
Even coating
Thin protection
D MAC 003 B
Poor Better
Contour used in construction

72
Pipewall
Crevices
bad
Seal weld
Crevices
Crevices at screwed joint
bad Bad
Seal weld
Crevices
Mauvais
Seal weld
Good
Vessel wall
Branch on
Seal weld vessel
Crevice
Good situation
Pipe butt Thermocouple

welded sheath
to flange
D MAC 002 B
Good Bad
Crevices. Formed (a) by the incomplete penetration of a butt weld, (b) by the use of a screwed flange and (c) by the use of a socket-
welding flange. (d) Crevice-free slip-on-welding flange type, (e) crevice-free welding-neck flange type, (f) crevices created by choice of
wrong size or wrong standard gasket for duty, (g) correct configuration if crevice corrosion is thought likely, (h) crevice situation
created by too small a clearance between thermosheath and the containing branch, (i) crevice formed at the back of a tubeplate and
(j) and (k) variants of sealing the tube/tubeplate crevice.

73
4- INHIBITORS
An inhibitor is a substance which, when added in small concentrations to an environment, decreases
the corrosion rate. It is possible to classify inhibitors according to their mechanism and composition.
a - Adsorption, inhibitors
In general, these are organic compounds which adsorb on the metal surface and suppress metal
dissolution and reduction areas. They adsorb on the cathode and anode areas and stifle the reaction.
They are commonly used in acid solutions (pickling operations, storage, etc.).
b - Anodic inhibitors
They retard the anodic reaction:
- film formers: that precipitate insoluble films on the anode area (alkalis, phosphates,
silicates, benzoates),
- oxidizing: (chromates, nitrates, ferric salts) that promote passivity.
Anodic inhibitors are often dangerous. If a small anode area is not protected, it will corrode very rapidly
(pitting).
E-v
E-v
r 2 H+ + 2
e –› H
hibito
No in i 2
E-v
i
D MAC 1379 A
c - Cathodic inhibitors
They retard the cathodic process
- oxygen scavengers: they remove oxygen from the solution, and so prevent it from
depolarizing the cathode. Examples are:
• sodium sulfide: 2 Na2 SO3 + O2 2 Na2 SO4

• hydrazine: 2 N2 H2 + O2 2 N2 + 2 H2O
They are used in closed systems like boiler waters. They can be deleterious with stainless-
steel operations where the conditions are borderline between active and passive corrosion.

74
- hydrogen evolution poisons: ions Arsenic, Antimony, Bismuth retard hydrogen

depolarization 2H+ + 2 e H2
They are useful with acid solutions, but ineffective when the major cathode reaction is
oxygen reduction. In some cases, they cause hydrogen embrittlement (H into the metal
instead of H2 evolution).
- Insoluble films: they form in the cathode and reduce its effective area.
Example 1: Addition of calcium bicarbonate to iron in neutral water converted in insoluble

calcium carbonate.
Example 2: Tension-active [R – N3]+ is a polar group. They form an adsorbed monolayer

on the metal surface. An other layer may appear on the preceding one (constituted for
instance by hydrocarbons).
Hydrocarbon
+ N-R
+ ++
Fe
H 3
+ +
- - -
D MAC 1380 A
- -
e e e e e
d - Vapor phase inhibitors
They have high vapor pressures that enable them to spread into the atmosphere and then adsorb into
the metal surfaces. Used for metal parts in storage or during shipment.
Care should be taken:
- to use enough inhibitor,

- they may contaminate environment.
When two or more inhibitors are added, the inhibiting effect is sometimes greater than that which would
be achieved by the two substances alone. This is called a synergistic effect.

75
5- ANODIC PROTECTION
Pontentiostat
ΔE
Insolated - + Steel tank
plug
Auxilary H2SO4
D MAC 1381 A
cathode
Reference
electrode
Storage tank containing sulfuric acid
Ev Anodic protection is based on the formation of a

protective film on metal by externally applied
Applied anodic current. This appears for metals with
i current active-passive transitions such as Ni, Fe, Cr, Ti
E and their alloys. a potentiostat is an electronic
device which maintains a metal at a constant
D MAC 008 B
potential with respect to reference electrode

i (CALOMEL).
This system is used in sulfuric producing plant.
6- CATHODIC PROTECTION
The purpose of a cathodic protection system is to apply a direct current, through an electrolyte such as
earth or water, uniformly to the surface of a buried or immersed metal structure in order to stop
corrosion.
In cathodic protection, we make the metal behave entirely as a cathode. It has no anode areas and so
does not corrode.
Ev Current used in excess of that required does no

Ec good, however, and may do harm to amphoteric
metals or to coatings.
The horizontal line at 0.62 V (S.H.E.), of the

Ι applied Pourbaix diagram means that iron will not
Ea corrode below this value to form a solution >
10-6 M Fe++ (M: molality).
D MAC 010 B
10-6 M Fe++ means 0.056 mg of Fe++ per liter. In fact there is no corrosion at 10-3 M Fe++ = 10-3 ion
gram per liter. This means – 0.85 volts versus copper/copper sulfate. The potential of a structure is
determined with a high-resistance voltmeter.

76
a - Impressed current
_ +
e- I
a.c line
Transformer
C 1,5m
Scrap
iron
A anode
Steel pipe
D MAC 012 C
Carbonaceous + -
backfill
Impressed current Rectifier
The direct electrical current is applied by connecting a d.c source to the corroding metal and an anode
(scrap iron, carbon, etc.). The anode is buried in backfill such as coke to improve electrical contact.
Example: Pipe - 300 kms = 300 mm

6 rectifiers (4 to 13 A)
metal potential – 1.5 to – 2 v
total consumption = 0.85 kwh
It was a new pipe very well insulated.
b - Sacrificial anode
The basis is the inherent difference in the tendency to ionize of different metals. This is reflected by
the relative position of the different metals in the galvanic series. Materials for sacrificial anodes are
limited to those metals which are anodic to the metal of the structure (Mg, Zn, Al).
EXAMPLES: pipe 85 kms - 300 mm

(GDF) (1/3 in marshy ground electrolyte-resistivity = 4 m)
20 anodes Mg (350 kg) - (18 to 880 mA)
metal potential – 0.85 to – 1 v
Cost: 1/800 of investment.
Ground level
Coated The principal difference in the two systems lies
copper in the fact that, with impressed current system,
wire adverse environmental conditions can more
H easily be overcome through the selection of the
Mg output voltage of the rectifier and the current
anode output per anode can be pushed to higher
D MAC 012 B
levels.

77
The most dramatic problems are the possible effects of stray currents on the corrosion of adjacent
metal structures. A remedy is to connect electrically the structures.
- +
Steel Anode
tank
D MAC 011 B
Remedy = insulated connection
7- METALLIC AND INORGANIC COATINGS

Hundreds of different coatings are available. This can make coating selection confusing. So, it is
useful to separate coatings into a number of groups. Relatively, these coatings can provide a
satisfactory barrier between metal and its environment (from 1μ to 0.5 mm depending on the method
used).
a - Electrode position (or electroplating)
Consists of immersing an article to be coated in a solution of the metal to be plated and passing a
direct current between the part and another electrode. It is common to plate several different metals in
sequence to obtain optimum coatings (example: copper for adhesion, Ni for corrosion and Cr primarily
for appearance).
Zn, Ni, Sn and Cd are very often plated by electrode position. With a noble coating (Ni, Ag, Cu, Cr, Pb
more noble than the metal being coated) extra care must be taken to avoid porosities or scratches (in
service).
b - Metallizing or metal spraying
This process involves the application of a spray of molten-metal droplets. Thicknesses are usually in
the range of 0.05 mm to 2.5 mm. In the wire and powder techniques, the coating metal is fed into the
spray gun, where it is melted. Compressed air then atomizes and sprays to molten particles into the
prepared surfaces to be coated.
c - Cladding
The bonding of two materials is most commonly done by hot rolling or welding, cladding of steel with
stainless steel, copper, Ni alloys, titanium is the most popular. Problems of diffusion are encountered
when austenitic stainless steel are clad to carbon steel. Carbon that diffuses from the steel can cause
intergranular corrosion (due to chromium carbide formation) in the stainless steel, particularly when a
vessel has to be stress-relieved at about 600°C (development of very low carbon stainless steels).
d - Hot dipping
Immersion of the part to be coated into a molten bath of the coating, which by necessity has a lower
melting point (chiefly zing, tin, lead and Al). Galvanized steel is a popular example. Thickness of the
coating is much greater than electroplates.
78
e - Diffusion (or surface alloying)
Involves heat treatment to cause alloy formation by diffusion of one element into the metal. Parts to be
coated are packed in solid materials or exposed to gaseous environments which contain the element
which diffuses.
Sherardizing Zn – Fe
chromizing Cr – Fe

Calorizing Al2 O3 used for resistance to high temperature oxidation
cementation C

Nitruratrion N Surface HARDENING
f - Chemical conversion
Anodizing
Conversion of Al to Al2O3 by making it the anode in an electrolytic cell (sulfuric acid bath). Coatings
are somewhat porous, so it is customary to seal them in boiling sodium dichromate solution, in order to
improve their corrosion resistance. They are used for resistance to corrosion and abrasion, or as a
paint base (good adherence).
Phosphate coatings
Dipping or spraying is used to apply to coating (approximate thickness 0.01 mm), following the
sequence below:
- pickle to remove scale, preclean in alkaline and rinse,

- treat with conversion mixture and rinse with water.
Fe + 3 Zn (H2 PO4)2 Zn3 (PO4)2 + Fe H PO4 + 3 H3 PO4 + H2
Zinc phosphate phosphate coating insoluble in

neutral or alkaline solution
They are almost always used as a base for paint or to absorb corrosion-preventive oils or waxes.
g - Porcelain enamels and glass coatings
They must have a suitable coefficient of expansion fused on metals. The coating is applied by
spreading powdered glass on a sand-blasted or pickled surface. Then, heating the article to a high
temperature (850°C approximately) softens the glass so that it flows and bonds with the metal.
Borosilicate (Ca, Na, K, Co, Ni, etc.) is easier to bond to steel, whereas high silica glass has better acid
resistance.
This coatings can resist a wide variety of chemicals, including strong acids. The glass must completely
isolate the metal (no sacrificial protection or inhibition). The main limitations of these linings are
brittleness, and susceptibility to cracking due to thermal shock.
h - Portland cement coatings
Low cost and a coefficient of expansion (1 10-5/°C) approximating that of steel. Used for protecting
steel from water and soil, also for fireproofing. Like glass, cements suffer from brittleness.

79
i - Flushing compounds
They are a kind of inhibitors used to protect steel surfaces temporarily from rusting during shipment or
storage. They consist of oils, greases or waxes that contain small amounts of organic additives.
The was usually provides a longer time of protection, while oil is easier to wipe or dissolve in solvents.
8- PAINTS - ORGANIC COATINGS

Paints are pigment containing compositions that form a liquid film on a surface and subsequently
harden to a solid coating. Most paints are "barrier" coatings. That is to be effective, they must
completely isolate the metal from the corrodent. Zinc-rich paints are an exception to this.
a - Type and composition
Paints usually consist of:
Pigments
- some for opacity and color (TiO2, FeO, Lead chromate, etc.),
- some for inhibition against corrosion: (red led Pb3O4, zinc chromate ZnCrO4, etc.),
They must be soluble enough to supply the minimum ions necessary to reduce the
corrosion rate. They are incorporated into the prime coat.
- some for sealing: pigments having the shape of flakes oriented parallel (by brushing) to the
metal surface (micaceous hematite).
Drier
May accelerate the oxidation and/or polymerization stages of drying.
Solvent or "Thinner"
It is a volatile liquid that enables adequate coverage and ease of application of the paint, and then
quickly evaporates.
Base or "vehicle": it may be:
- natural oil: such a linseed, that when exposed to air oxidizes and polymerizes to a solid
(they are permeable to moisture and their resistance to acid fumes is not very good).
- Synthetic resin: that dries by evaporation of the solvent in which it was dissolved or by
polymerization (heat may be required).
• alkyd paints: not suitable for chemical services,

• polyvinyl acetates and acrylics: ease of application and clean up,
• urethane: good toughness and abrasion resistance,
• chlorinated-rubber: resistant to water, but not strong oxidizing media and < 65°C,
• neoprene: may be applied over chlorinated rubber to increase resistance to
weathering,
• vinyl: resistant to a variety of aqueous acid and alkaline media, but not above
65°C,

80
• epoxy: 3 paints
Amine hardened epoxy consists of 2 components, the hardener and the resin, that
are mixed just before using. These are the most resistant to chemicals.
Polyamide hardened epoxy ; less resistant to acids but tougher and more moisture
proof. COal-tar epoxy: can be used without a primer (good for water, soil,
inorganic acids),
• silicone paints: are used for high temperature service (up to 650°C),
• coaltars: underground applications,
• zinc paints: consist of metallic zinc dust in an organic or inorganic vehicle. They
use galvanic protection by the zinc to prevent pitting at holes in the coatings.
b - Surface preparation
Involves surfaces roughening to obtain mechanical bounding as well as removal of dirt, rust, mill scale,
oil, grease and other impurities.
- blasting: it is the best method. Scale is removed by high velocity particules projected on to
the surface by an air blast. Blast material usually consists of sand or sometimes steel grit,
- others methods: pickling by SO4 H2 and inhibitor, wire brushing, cleaning by solvents or
alkaline solutions.
c - Application of a paint
Remember the cost for labor equals two to three times the cost of the paint. The final stages of
surface preparation and the application of the primer should be performed on the same day. Weather
conditions are also important. If possible, the coating should not be applied to a metal surface that is
too hot (> 60°C) or too cold (< 5°C). The surface should be dry, relative humidity should be below 85%
and metal temperature should be at least 3°C above the dew point. Fresh paint should be used and
carefully mixed, just prior to application. The commonest methods of painting are: spraying, brushing,
dipping.
Spraying is the most popular. The paint is atomized and driven onto the surface by compressed air or
hydraulically (air less). Paint thickness should be checked with special gages during application. This
ensures adequate thickness and guards against too thick a coating.
A paint system is usually constituted of 3 or more coats.
- primer coats: they contain pigments inhibitor (or zinc) and in addition act as barriers.
Wettability is needed so that crevices and other defects will be filled rather than bridged,
- second coats: paint is applied for sealing, moister proof and adherence,
- top coats: multiple coats are needed so a pinhole in one coat is covered by a complete fim
of another.
Top coats are applied for:
• sealing
• appearance (color)
• resistance to infrared and ultraviolet radiations
• resistance to abrasion and mechanical shocks (hardness)
• anti-fouling (particularly under water)
• resistance to temperature
• resistance to acids, alkalines, and solvents
• ease to clean up and touch up
• resistance to cold
• adherence

81
d - Inspection importance
Inspection of coatings is particularly important because it will generally be possible to touch up the
coating in a problem area, and delay the need for a complete repainting (the underlying metal will often
have poor resistance to the corrodent).
Possible causes of paint defects
Blistering
- painted over wet surface

- undercoat not dry
- metal too hot when painted (more than about 65°C)
- metal too cold when painted (less than about 10°C)
- improper solvent used
- if sprayed-too much air pressure or water in line
Peeling, flaking
- dirty starting surface

- undercoat not dry
- metal too hot or too cold
- coating too thick
Cracking
- not enough thinner

- undercoat too thick
- surface unclean, too hot or too cold
- paint not completely mixed
- if sprayed - oil or water in air line
Wrinkling
- coating too thick

- drying in too hot or too moist an environment
Running
- too much solvent

- solvent vaporizes too slowly
- coating too thick
- if sprayed - air pressure too low
- if dipped - withdrawn too quickly or jerkily

82
IV - HYDROGEN CORROSION
The presence of hydrogen in a metal network can cause considerable damage to the metal associated with a
drastic drop in metal properties.
The hydrogen atom (H) is the only species capable of diffusing through metal. The molecule form (H2) does
not diffuse. Therefore only the atomic form of hydrogen can damage metal.
1- SOURCES OF NASCENT OR ATOMIC HYDROGEN

• Gas phase hydrogen
Penetration occurs through adsorption of the molecules on the surface of the metal. Atoms are then
formed by molecule dissociation through catalytic action of the metal, which the atomic hydrogen then
penetrates. The higher the temperature, the greater the dissociation of H2 molecules into atoms.
• Hydrogen in solution
Penetration from a solution occurs when the metal surface is the seat of an electrochemical reaction
(cathode).
The reduction of the hydrogen ion (H+ ) first produces hydrogen atoms which then form H2 molecules.
Certain substances such as sulfur ions, arsenic and phosphorus compounds and cyanides lower the
reduction reaction of hydrogen ions:
2
2 H+ + 2 e – 2 H H2
The second stage (formation of molecules) would seem to be that mainly concerned. In the presence
of these substances there is greater concentration of hydrogen atoms on the surface of the metal.
There are four types of damage by hydrogen:
1 - Hydrogen blistering Occur in chemical processing units, welding

and pickling operations or as a result of
2 - Hydrogen embrittlement
corrosion or cathodic protection.
3 - Decarburization
Occur only at high temperatures
4 - Hydrogen Attack

83
2- HYDROGEN BLISTERING
H+ H+
H H H2 H H
Certain H atoms diffuse through the metal
and are halted by voids or inclusions (e.g.
manganese sulfides in rolled steels) where H e H e H
they combine in the form of hydrogen
molecules. H/H2 equilibrium pressure is very
high and capable of causing the rupture of H H2 H
D MAC 042 C
any equipment through blister formation.
Void
H H2 H
• Prevention
- use of killed steels (non- porous)
- use of metallic, organic or inorganic cladding and lining
• cladding with 304-316 type steels or Monel. Hydrogen does not diffuse in austenite
or Monel (66 Ni - 30 Cu) when cold.
• porous guniting favoring the transformation of H into H2 by catalysis.
• rubber and plastic;
- removal of poisons such as sulfides, arsenic compounds, cyanides and phosphorous ions
which in the presence of acids, cause blistering (e.g. in refineries light fractions are washed
with water to eliminate and dilute the H2S and cyanides);
- use of inhibitors which reduce corrosion and the H+ ion rate of reduction, but can only be
employed in closed and recycled systems.
3- HYDROGEN EMBRITTLEMENT
This too is caused by the penetration of atomic hydrogen inside defects or dislocations near the
surface of the metal. In plastic zones, dislocations build up at the particle responsible for the plastic
deformation blocking their progress. The atomic H fixed onto this accumulation of dislocations acts as
a wedge on the metal, which at the same time is subjected to tensile stress, and a fissure may then
form. Once initiated, the fissure will grow, preceded by a plastic zone (which will also fix the H atoms)
at its tip.
The time taken by the hydrogen to initiate a fissure is called ´†incubation time†ª.
Here it can be seen that this is a stress type corrosion, caused by the release of hydrogen (reduction
of H+). Steels with high mechanical properties are more sensitive to hydrogen embrittlement, and the
higher the stresses they undergo, the more sensitive they become.

02947_A_A
MECHANISMS OF HYDROGEN EMBRITTLEMENT
IN THE PRESENTS OF DEFECTS
Elongated plastic
strain zone
No hydrogen
Elongated plastic strain zones

Grain TT° = Sum of applied and residual stresses
boundaries
Oxide at the grain boundary
Existing TC° = Cohesive forces

Cracked or uncracked carbides defect
84
Surface With hydrogen

Cracks (e.g corrosion pits)

Absorbed
opened on the surface TTH = Sum of applied and residual stresses +
hydrogen
hydrogen induced stresses (e.g pressure)
Hydrogen absorbed or trapped + aggregates

Grain Voids betwen grains HH and dislocation stacking
HH HH H
HH H H
Grain H Crack
Grain H
Dislocations pile-ups TCH = Cohesive force reduced in the prescence of
Molecular absorbed or trapped hydogen
hydrogen
(pressure)
D MAC 1382 A
Exemples of existing defects Effects of hydrogen

85
A tendency to embrittlement is strengthened by the concentration of hydrogen on the metal, but the
phenomenon is reversible. This means that it is almost possible to recover the initial mechanical
properties by displacing the hydrogen.
The figure, on the following page, shows that after a given, length of time, cracking occurs at
successively higher stresses as hydrogen concentration in the metal decreases.
2100 300
+ Uncharged
+ + +
1850 +
Bake 24 h 250
1600 Also, the alloys are most
Bake 18 h
susceptible to cracking in
Applied stress (MPa)
Applied stress (ksl)

1350
200 their highest strength level.
Bake 12 h
1100
150
Bake 7 h
850
Bake 3 h 100
600
Bake 0.5 h
D MAC 1370 A
350 50
0.01 0.1 1 10 100 1000
Facture time (hr)
Fracture of AISI 4340 steel baked at 150°C

after initial cathodic hydrogen charging
• Prevention
- reduction of the corrosion rate. During pickling operations an inhibitor should be used to
protect the parent metal from the large quantities of hydrogen released.
- avoid hydrogen release during plating operations
- baking at 150°C to displace the hydrogen
- avoid steels having high mechanical strength. Rule of thumb recommends not exceeding
22 Rockwell C hardness (HRC < 22). Nickel and molybdenum reduce embrittlement
sensitivity
- welding should be done using low-hydrogen electrodes. It is also most important to weld in
dry conditions (dried electrodes) as water and steam are sources of hydrogen (dissociation
at high temperatures).
4- DECARBURIZATION AND HYDROGEN ATTACK

In conversion units using hydrogen at high pressures and temperatures, the steel structures coming
into contact with the gas phase can show signs of hot hydrogen embrittlement (>200°C).
The main effect of hydrogen at high temperatures is decarburization of the alloy:
Fe3C + 2 H2 3 Fe + CH4.
a - Incubation phase
The oxides segregated at the grain boundaries play an important role in the first, or incubation, period,
which precedes actual embrittlement.

86
The H2 reduces the oxides with the formation of water vapor which retards the methane embrittlement
action.
The following reactions are involved:
Fe2O3 + 3 H2 3 H2O + 2 Fe
Fe3O4 + 4 H2 4 H2O + 3 Fe
H2O + CH4 CO + 3 H2
The carbon monoxide formed during the incubation period, diffuses into the steel along the grain
boundaries, avoiding phenomena of fragilization by overpressure.
b - Attack
When all the oxides have been reduced, the final phase of carbide attack (cementite) followed by
embrittlement, begins. The methane cannot diffuse and generates intergranular cracking (methane will
have accumulated preferentially at the grain boundaries).
The zones surrounding the crack contain a partially decarbonized pearlite (the cementite plates vary in
density and discontinuity).
c - Prevention
• Replacement of cementite with stable carbide
Stable carbide steels are produced by adding stabilizing elements which, in increasing order of
efficiency are: Mn, Mo, Cr, W, Va, Ti, Nb.
Ni, Si, and Cu which do not produce carbides, have no effect.
Ti steels are difficult to forge and Cr-Mo steels are preferred. Nelson curves will provide information on
the limits of Cr-Mo steels.
For very severe conditions of temperature and pressure 18/8, 18/8/3 stainless steel with very low
carbon content or stabilized, will be used.
But the danger of intergranular corrosion must be eliminated.
• Use of homogeneous structure, fine grain steels
Spheroid cementite is more stable than plate cementite.
• Weld relaxation
Welds are coarse grained, have a wide range of harnesses, high residual stresses, and are therefore
prone to hydrogen embrittlement.
• Avoid local or accidental overheating
Even for fairly short periods (2 or 3 hours), the penetration of decarburization is considerably
accelerated by an increase in temperature (this has been observed between 500°C and 650°C).

87

88
V- CORROSION BY SULFUR DERIVATIVES IN THE ANHYDROUS PHASE

1- CORROSION BY SULFUR COMPOUNDS
The sulfur content of crude oils varies between 1.8 and 2.6% and is tending to increase due to current
market conditions. This sulfur is in the form of more or less complex organic sulfides with thiophene,
mercaptans, disulfide etc. bases, and corrosivity varies according to composition.
These compounds have been the subject of numerous studies by oil companies and each compound
has been rated on a numbered index so that it can be placed on the steel-corrosion scale. It is thus
possible, given the exact composition of the sulfide derivatives of a crude, to have an idea of its
potential agressivity in relation to existing installations.
• Corrosion mechanisms
The major corrosive substance in the oil industry is nascent hydrogen sulfide coming from the crude
but also and mainly from thermal decomposition of sulfide compounds. Thermal cracking occurs
mainly in the pipes of tube-fired heaters in distillation units, and in zones where temperatures reach
380°C to 400°C can cause drastic corrosion of carbon steel, sometimes associated with steel
carburization. This is why 5% Cr steels are used in straight distillation vacuum stills.
In refineries there are two distinct types of corrosion:
- H2S corrosion without hydrogen, which is the case in straight distillation units, thermal and
catalytic cracking and visbreakers
- H2S corrosion with hydrogen, which is the case in desulfurization, reforming and catalytic
hydrocracking units. In this case there is a synergetic effect between H2S and H2 which
increases corrosion
2- ANHYDROUS PHASE H2S CORROSION WITHOUT HYDROGEN

This corrosion is mainly governed by the H2S concentration and temperature; it is independent of
pressure.
To start with attack is very fast and for carbon steel it is high from 285°C. This corrosion then tends to
lessen with time, the layer of iron sulfide formed, preventing penetration of the sulfur ions. This factor
must be taken into consideration when interpreting corrosion results on removable probes or
specimens.
The specialist literature contains many curves giving the corrosion rate of carbon steels and alloys
commonly used in refineries for hydrocarbon fractions and cuts corresponding to given crude.
However, these are only mean results and care should be taken when extrapolating them to specific
cases.
The corrosion rate can be seen to increase rapidly with temperature between about 300°C and 400°C.
At this temperature hydrocarbons start to generate some coke and also the ferrous sulfide becomes
less porous and forms a protective film (< 0.5 mm/year) from 460°C. However, in units treating light
hydrocarbons, the formation of coke is insufficient and corrosion continues to increase - beyond
400°C.
Limits of use of alloys in hydrogen sulfide corrosion.

89
Usually carbon can still be used up to 285°C with a corrosion allowance compatible with the useful life
of the equipment.
For higher temperatures Cr and Cr Mo low alloy steels will be used. The most commonly used for
vacuum tube fired heaters is 5% Cr. For extreme cases of high turbulence, which tends to eliminate
the protective FeS film by abrasion, 9% and 13% Cr should be considered.
Above 460°C, although the FeS formed provides an effective barrier to penetration by S, C steel is not
recommended due to graphitic corrosion phenomena (425°C).
Regarding the use of 304-304L or 316 austenitic steels, which have a good specific resistance to H2S,
secondary problems of corrosion by polythionic acids must be born in mind, as these may occur on
opening the apparatus (presence of water and air). For this reason, if austenitic steels are required
only 321 or 347 niobium stabilized grades should be used whenever it is impossible to neutralize prior
to opening.
Sulfur corrosion is associated with a problem of plugging by scales of ferrous sulfide removed from the
points of corrosion. This problem is thought to appear when the rate of corrosion exceeds 0.3
mm/year. Plugging of tube bundles or certain filters can occur.
3- H2S CORROSION WITH H2

This type of corrosion occurs most on desulfurization units where the sulfur is eliminated by
hydrogenation as H2S, the effluent being a gas loaded with H 2S (high proportion of H2).
The attack threshold temperature is much lower than without H2, and the corrosion rate increases as a
linear function of the temperature without passing through a maximum (here the molecules are
saturated and do not polymerize to produce coke).
Due to the presence of hydrogen and considering its partial pressure, alloy steel would be
recommended (see Nelson curves). The 5% Cr is corroded by H2S just like C steel. Therefore, from
315°C stabilized austenitic steel grades should be used if possible.
Laboratory tests show that the partial H2S pressure has no impact on the corrosion rate of the steel up
to 0.4 bar, above which the corrosion rate will depend solely on temperature.
Apart from the austenitic steel grades, recent studies in the US have shown the excellent resistance of
aluminized Cr Mo steels or 9% Cr 1% Mo spray coated with a 0.1mm layer of aluminum.
Here too corrosion products can cause plugging. This is major problem as the catalyst beds may
become plugged. The corrosion rate must be kept below 0.3 mm/year.

90
RATE OF CORROSION OF SOME ALLOYS BY H2S WITHOUT HYDROGEN

— Versus temperature, with a crude oil containing 1.5% —
Rate of
corrosion
mm/year
3.5
Ordinary steel
3.0
2.5
2.0
4-6 Cr 0.5 Mo steel

1.5
1.0
0.5
12% Cr steel
D MAC 1233 B
18 Cr-8 Ni steel
Temperature (°C)
300 350 400 450 500
(T.S. CLAIREBORNE - A.W. COULTER)

02947_A_A
Corrosion rate Ordinary steel
mm/ year
2.28 2 % Cr 0.5 % Mo steel
5 % Cr 0.5 % Mo steel
2.03
12%Cr steel
18 % Cr 8 % Ni steel xxxx xxxx xxxxxx

1.78
1.52
91
1.27

1.02
0.76
0.51
0.25
D MAC 1234 B
xxxx
xxxx x x x x x x x xx
xxxxxxxxx
150 250 350 450 550 650 750 temp. (°C)
92
RATE OF CORROSION OF SOME STEELS

— Versus temperature, in a hydrogen sulfide environment
without hydrogen, from products containing 0.6 sulfur —
Corrosion rate
mm/year
2.5
l
1.2 s tee
inary
Ord
st eel
Cr
5%
0.25
el
r ste
9 %C
0.12
eel
Cr st
%
12
0.025
l
stee
18-8
0.012
D MAC 1235 B
Temperature (°C)
250 300 350 400

(MC CONNOMY, PROCEEDINGS, API DIVISION OF REFINING VOL. 43 (III). 1963.)

93
CORROSION RATE BY SULFUR WITH HYDROGEN
3.5
H2 S alone
Corrosion rate
mm/year H2 S + H2
3.0
5 Cr 0.5 Mo STEEL
2.5
ORDINARY STEEL
2.0
9 Cr 1 Mo STEEL
1.5
1.0
11 - 13 Cr STEEL
0.5
5 Cr 0.5 Mo STEEL
D MAC 1236 B
18 Cr 8 Ni STEEL
300 400 500

Temperature °C

94
Weight loss
(mg/cm 2) EFFECT OF PRESSURE ON STEEL CORROSION
9 Cr 1Mo. by H2S + H2 (H2S 5% vol. 400°C).
300
200
100
Total pressure (bar)
35 70 105 140 175
Weight loss
(mg/cm 2)
EFFECT OF H2S PARTIAL PRESSURE ON STEEL CORROSION
150 9 Cr 1 M. in a mixture H2S + H2 (36 bar. 400°C).
100
50
H2S partial pressure (bar)

D MAC 1237 B
0.15 0.28 0.56 2.1 2.8 3.5 4.2 4.9 5.6 6.3
From J.D. Mc Coy, Materials Performance - May 1974 p.21

95
CORROSION RATE OF SOME STELLS

in an H2 + H2S environment (H2S content > molecule)
versus temperature
Corrosion rate (mm/year)

2.5 9% Cr 12% Cr
2.0 Carbone steel
5% Cr steel
1.5
1.0
0.5 18 - 8
300 350 400 450 500

Temperature (°C)
CORROSION RATE OF CHROMIUM STEELS AT 371°C

Versus H2S content in an H2 + H2S environment
Corrosion rate (mm/year) 0 - 5% Cr
1.25
0 - 5% Cr
1.00
12% Cr
0.75
0.5 Temperature 371°C

D MAC 1238 B
1 2 3 4 % H2S molecules
Temperature (°C)
From J.D. Mc Coy, Proceeding, API Division of Refining, Vol. 43 (III). 1963 p.20

96
CORROSION RESISTANCE OF SOME STEELS IN THE PRESENCE

OF HYDROGEN SULFIDE AND HYDROGEN
°C
600 STEEL WITH

CORROSION RATE 0 À 5% Cr
Temperature (°C)
500
> 1 mm/year
400
0.5 à 1 mm/year
300
< 0.5 mm/year
0.02 0.04 0.06 0.08 0.1 0.2 0.4
°C
600
12% Cr STEEL
CORROSION RATE
Temperature (°C)
500
> 0.25 mm/year
400
0.12 à 0.25 mm/year

300
< 0.12 mm/year
0.02 0.04 0.06 0.08 0.1 0.2 0.4
°C
600
STAINLESS STEEL
CORROSION RATE 18%Cr 8%Ni
Temperature (°C)
500 -
> 0.12 mm/year
400
0.02 à 0.15 mm/year

300 < 0.02 mm/year
D MAC 1239 B
0.02 0.04 0.06 0.08 0.1 0.2 0.4

97
EFFECT OF TEMPERATURE ON CORROSION BY SOUR CRUDES
Corrosion rate
(mm/year)
3.5
382°C
2.5
338°C
1.5
310°C
0.5 277°C
D MAC 1240 B
0 2 4 6 8 10
(From G.R. PORT Petroleum Refiner,Vol.40, Mai 61, p.154) % Cr

02947_A_A
Corrosion rate
(mm / year)
CARBONE
STEEL
3
98
2
BY SOUR CRUDES

5%Cr
1
EFFECT OF CHROMIUM CONTENT OF CORROSION
7%Cr
9%Cr
D MAC 1241B
0
275 277 300 310 325 338 350 375 382 400
Temperature (°C)
99
VI - CORROSION BY COLD HYDROGEN SULFIDE IN A HUMID ATMOSPHERE

1- GENERALIZED CORROSION
Hydrogen sulfide is a weak bi-acid. Ionization occurs in two stages :
H2S H+ + (HS)– (1) (HS) – H+ + S2– (2)
In a humid environment hydrogen sulfide generates considerable generalized corrosion for pH values
of between 6 and 8 (see dissociation curve for H2S in water). Here, sulfide films provide little
protection, they are dissolved by the pH variations and especially by erosion (high flow velocities of
more than 1m 50 per second, considerably stimulate corrosion).
Protection can be provided against this type of corrosion by SAKAPHEN type coatings, or if
economically feasible, by using metals such as titanium.
2- ATOMIC HYDROGEN CORROSION
A reaction occurs: H2S + Fe S Fe + 2 H+
This corrosion is similar to the phenomenon of hydrogen embrittlement and results in:
- stress corrosion: this appears on steel or welds with a hardness greater than 22 Rockwell C,
on carbon steel pipes or curved austenitic stainless steel which has not had any relaxation
heat treatment, or if the heat treatment has been ineffective
- blistering: this phenomenon has already been mentioned and appears in the formation of
blisters and splitting. As we have seen, this attack is due to the diffusion of the atomic
hydrogen and its transformation into molecular hydrogen which does not diffuse
3- PREVENTION
- the gas should be dried
- coating to prevent the H2S from acting on the metal
- inhibitors (filament amines or ammonium polysulfides which transform into sulfo-cyanides)
- use of special quality steel plates (high inclusion related cleanliness, low sulfur and hydrogen
contents) made to resist splitting.

100
VII - CORROSION BY COMBUSTION GASES IN FURNACES AND BOILERS

The clogging and corrosion of tube bundles disrupts operation of tube fired heaters and boilers and causes
frequent stoppages.
Also, the environment is degraded by corrosive emissions from chimneys. Installations are designed
according to regulations established by the Authorities (fuel quality, chimney height etc.). The fuels used
contain undesirable products such as sulfur, sodium, vanadium which play a major role in the formation of
deposits and corrosion.
1- FORMATION OF SO3
Operating difficulties due to clogging and corrosion at high and low temperatures are the source of So3
forming from the sulfur contained in the fuel.
Heavy LSC fuels with less than 1% S, are becoming rarer, and more and more HSC are being used
with 1 to 5% S.
Combustion of S produces: S + O2 SO2
The presence of excess air then gives the equilibrium:
1
SO2 + 2 O2 SO3
In theory there is no SO3 in the flame over 1000°C. In fact there is at least 5%, and some say that
there is as much as 50% SO3 for the following reasons:
- catalysis of the reaction by Fe2O3 (ferrous oxide) and V2O5 (vanadium pentoxide)
- the atomic oxygen in the flame at high temperatures has a much greater chemical activity
than molecular oxygen
CO + O2 CO2 + O
H2 + O2 H2O + O
SO2 + O SO3
- a substantial excess of air favors the chemical reaction.

101
SO3 FORMATION VERSUS TEMPERATURE
SO2 + 1 O2 SO3
2
N° of SO3 molecules
% = probability
Total n°. of SO2 + SO3 molecules
100
90
At 100 ° almost all the SO2
has been transformated into SO3
80
70
60
At approx.520° there is 50% SO3
50
40
30
20
At approx 1000° there is no SO3
10
D MAC1242 B
°C
0
100 200 300 400 500 600 700 800 900 1000 1100
From EDF document

102
2- CORROSION AT HIGH TEMPERATURES

a - Effect of metal temperature
This corrosion appears above 540°C. Above this temperature corrosion doubles for an increase in
metal temperature of 35°C, the temperature of the fumes remains constant.
This corrosion in fact limits the yield of large boilers which have estimated yields of:
39.5% at 540°C
40% at 593°C
42% at 649°C
b - Influence of the fumes temperature
The temperature of the fumes affects the metal temperature and certain secondary chemical reactions,
which impact the rate of corrosion.
The rate of corrosion doubles when the fumes temperature increases by 150°C.
c - Influence of excess air
This influence is mainly characteristic of very hot fumes > 950°C:
- the higher the temperature, the greater the action of the oxygen
- a high flame temperature gives highly reactive atomic oxygen
- the presence of S and O2 produces SO3 as a function of temperature
- the presence of oxygen increases the probability of transformation of vanadium oxide V2O3
into vanadium pentoxide V2O5 which is more oxidizing and acts as catalyst in the
transformation of SO2 into SO3.
d - Influence of vanadium, sodium and sediments
Sodium and vanadium compounds have different melting temperatures depending on the Na and V
contents.
At combustion chamber temperatures most of the substances are gas phase; they condense at
1500°C.
Some have a very low melting point, about 500°C.
Sediments such as nitrogen, Si, Ca, Hg, K and Al oxidize in the flame and produce other gas, liquid or
solid phases on coming in contact with pipes.
All these liquid compounds dissolve the ferrous oxides protecting the pipes. Disastrous oxidation can
occur. Liquid phase oxidation is much more rapid than oxidation by oxygen in a gas phase. Moreover,
all the pasty substances formed, facilitate metal deposit adhesion and thus increase clogging.

103
e - Influence of sulfur
The SO3 formed reacts with the parent metal, producing through oxidation-reduction (Redox):
SO3 + 3 Fe Fe2O3 + Fe S
which explains the presence of ferrous sulfide at the metal-deposit interface.
f - Combating high temperature corrosion
- elimination of impurities:
• possible for Na
• costs are very high for V and Ni and fuel viscosity increases
• distillation units all have a desalting installation which eliminates 90% of the salts
obtained in the crude (except for vanadium and Ni).
- limiting excess air
- inhibition with additives
There are 3 types of action:
- raising the melting temperature of ashes by creating the appropriate eutectic mixtures
- reducing the SO3 (by neutralization or adsorption)
- transformation of the physical structures of the ashes to facilitate elimination
• Magnesium additives: (in the form of oxide)
MgO + V2O5 MgOV2O5 melt above 1000°C
The Na content should be as low as possible as first the Na2O, V2O4, 5 V2O5 complex forms which is
pasty and favors the formation of deposits. The reaction with Mg only occurs afterwards.
Some authors advise a Mg/V ratio of 2.5 for a temperature of 700°C.
• Calcium additives
This is a very fine grained CO3Ca powder. Decarbonization of the powder under the action of the flame
forms highly reactive quick lime.
The compounds obtained have high melting points and the ashes are fine, pulverulent and non-
corrosive (they form a protective film).
• Metallurgy
Ferritic steels are more resistant than austenitic steels although the latter have better mechanical
behavior at high temperatures which justifies their use.
For fired heaters tube supports which reach temperatures of 1000°C, 25 Cr, 20 Ni alloys are used or,
for more severe conditions, 50 Cr, 50 Ni or 60 Cr, 40 Ni.

104
CORROSION RATE AGAINST EXCESS AIR

Corrosion rate
D MAC 1383 A
0 1 2 3 4 5 10
Air excess %
EDF document

105
MELTING POINT SODIUM-VANADIUM COMPOUNDS
1000
900 3Na2O, V2O5

850
800
Na2O, V2O4, 5V2O5 Na2O, V2O5

700
5Na2O, V2O4, 11V2O5 2Na2O, V2O5
659
632 632
600 577
500
400
300
200
100
D MAC 1384 A
Na2O
V2O5 + NaO
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

106
3- LOW TEMPERATURE CORROSION

The improved yield of modern equipment has meant that the fumes temperature has been reduced, so
that any item of equipment downstream the acid dew point becomes vulnerable to low temperature
corrosion. The equipment in question may be water heaters, air heaters or ventilation and chimney
ducts.
The sulfuric acid is generated from SO3 and steam produced by the combustion of hydrogen in the
fuel.
1
There are 2 equilibrium: SO2 + 2 O2 SO3
SO3 + H2O SO4H2
The “water-acid†” mixture condenses on cold elements as soon as the temperature reaches the acid
dew point between 100°C and 150°C.
a - Mechanism
- as the sulfuric acid condenses it attacks the steel:
H2SO4 + Fe Fe SO4 + H2 (ferrous sulfide)
- in the presence of oxygen another reaction prevails:
1
2 Fe SO4 + 2 O2 + H2SO4 (SO4)3 Fe2 + H2O
- the ferric sulfate formed may react on the iron and return to a ferrous state:
(SO4)3 Fe2 + Fe 3 SO4 Fe
this is yet another reason for burning without excess air.
b- Influence of water content
The sulfuric acid in vapor phase has a negligible activity.
SO4H2 hydration is practically complete at dew point temperature (see curve attached).
For a certain type of fuel and 10% excess air, the following stages can be identified:
- at 170°C pure acid, which is only slightly active, condenses.
- From 140°C to 100°C water starts to condense and, by diluting it, causes the acid to ionize
and become active
- from 100°C to 60°C the corrosion stabilizes and a certain degree of passivation prevails
- below 60°C corrosion becomes extensive, passivation is no longer maintained

107
CHEMICAL REACTION
SO3 + H2O H2SO4
[ H2SO4 ]
Moles percent = probability
[ H2SO4 ] + [ SO3 ]
100
80 Bellow200°
at the SO3 is
transformed into
H2SO4 (vapor phase)
60
40
Above 500°
20
there is no H2SO4
D MAC 1243 B
Temperature (°C)
0
100 200 300 400 500 600
From EDF document

108
Dew point (°C)
DEW POINT OF FUMES VERSUS SO3 CONTENT
150
100
50
20 40 60 80 100 Teneur en SO3 ppm
Dew point (°C)

DEW POINT OF FUMES VERSUS THE SULFUR
CONTENT OF THE FUEL (% CO2 = 7,5 %)
150
140
130
120
110
D MAC 2122 B
100
1 2 3 Sulfur content (%)

109
ppm vol. SO3CONTENT IN THEV FUMES VERSUS

SO3 content EXCESS AIR (400 T/H ELECTRIC GENERATOR)
02 % in fumes
0.5 1 1.5 2 2.5 3
ACID DEW POINT VERSUS EXCESS

°C AIR (400T/H ELECTRIC GENERATOR)
Acid dew point
120
100
80
D MAC 1244 B
60
02 % in fumes
0.5 1

110
SO3/H2SO4 VERSUS OXYGEN AND SULFUR CONTENTS
SO2 content in fumes

% volume
0.5
0.4
0.3
es
in fum
es
um
es
in f
fum
3
3% O
in
O
0.2
en
%
o
1.5
yg
1.5 t
ox
1 to
1
5 to
0.1 0.
Sulphur content
in fuel (weight)
0 1% 2% 3% 4%
Dew point
temperature
140
il
130 ulphu r fuel-o
3. 6%s
120
110 fuel-oil
1 . 8 % su l p h ur
100
90
80
70
60
50
40
30
20
D MAC 1385 A
O2 content in fumes
10
0
0 0.5 1 1.5 2 2.5 3 3.5 4
111
Film forming rate (μ a/min)
VERY HEAVY MODERATE SLIGHT

100 CORROSION CORROSION HEAVY
CORROSION
CORROSION
50
ACIDE PH
ABUNDANT WATER
CONDENSATION
20 40 60 80 100 120
Temperature (°C)
Corrosion rate
(g/m2.h)
16
14
EXCESS 02 ACID FORMATION AND
STEEL CORROSION RATE
12
10 % - Versus wall temperature and excess
10 oxygen in the flame
6 5%
4
2%
2
D MAC 1245 B
<1%
50 100 150 Temperature (°C)

(HOFFMAN)

CORROSION BY FUEL COMBUSTION
02947_A_A
Fumes 11m3
350°C
281 1.51
COMPOSITION
FeO
Fe2O3 SO2 - SO3 - CO - CO2 Organic matter 2.1%
Fe3O4 silicates (SIO2) + miscellaneous 6.4%
H 2O N2 NOX Sulfates (SO3) 20.6%
0 Lime (O) 0.7%
0 0+ Soot deposits
< 550°C 875°C Magnesia (MgO )0.0%
Melting of Ash deposits Sodium (Na2O) 9.1%
protective Total iron (Fe2O3) 3.2%
oxide and Aluminium (Al2O3) 0.9%
reoxidation Nikel (NIO) 3.5%
Tube of tube metal Vanadium (V2O5) 53.5%
100%
1150°C VANADATES AND

112
2nd stage of oxydation EUTECTIC MIXTURES

70°C 5V2O5 - V2O4 - Na2O MELTING POINT < 550°C
1st stage of oxydation VANADIUM PENTOXIDE

VANADIUM SESQUIOXIDE
SO2 - CO - Na2
VANADIUM BIOXIDE
Fissuring of V2O3 - V2O4 - V2O5
refractory material ALKALINE SULFATES
through shrinkage Cracking of heavy cuts HYDROCARBONS + CARBON
S O AND VARIOUS ELEMENTS
H2SO4 3 + + C - S - V - Na - Ni
H2O
Vaporization of light cuts
Corrosion of [METHANE - BUTANE - PROPANE - …]
steel wall
by sulphuric =
acid
condensation COMPOSITION
1kg C = 85% Na = 38 ppm

10 m3 Fuel-oil n° 2
+ FO H = 10.6% V = 113 ppm
air PCI 9500 kcal/kg
Condensation temperature S = 3.8% Ni = 35 ppm
60°C
D MAC 045 B
of water in fimes N = 0,3%

113
c - Combating low temperature corrosion
- use desulfurized fuels (expensive solution)
- reduce the percentage of O2 contained in the fumes by reducing the excess air which will in
turn reduce:
• formation of SO2, SO3, Nox, V2O5 (all pollutants)

• high temperature V2O5 corrosion
• low temperature SO3 - SO4H2 corrosion
- try to discharge fumes at 160°C in order to have a temperature of at least 140°C on the
inside walls (with very good insulation). Yield will be reduced by substantial heat loss
increase
- install glass air heaters (Pyrex)
- inject pulverulent additives:
• MgO magnesia
• the double Ca - Mg carbonate: CaMg (CO3)2 (dolomite)
These provide protection against the following types of corrosion:
- through formation of salts, which only melt at high temperatures (sulfates)

- low temperature by neutralization of SO4H2 according to:
CO3 Ca + H2SO4 Ca SO4 + CO2 + H2O

Mg O + SO4H2 Mg SO4 + H2O
However, these, like vanadium and sodium oxides and when coming in contact with hot
refractory material, will contribute to the production of low melting point eutectic mixtures.
The gangue thus formed and fluidized, can rapidly degrade refractory linings.
- injection of ammonia (NH3) into the fumes:
NH3 + H2SO4 NH4H SO4 acid sulfate melting at 147°C

2NH3 + H2SO4 (NH4)2 SO4 solid ammonium neutral sulfate
It is also known that NH3 dissociates between 370 and 700°C
2 NH3 N2 + 3 H2. Injection of NH3 at a temperature greater than 300°C should be

avoided.
As can be seen, this process is not simple to implement.

114
VIII - NAPHTHENIC ACIDS CORROSION

This corrosion is caused by the organic acid present in certain crude. These acids have a variable molecular
weight; they have a saturated cyclic type radical containing acid groups.
For example:
CH2
CH2 CH2
D CHI 138 8 A
CH2 CH COOH
Bubble point 60°C at 200 mm Hg
Molecular weight = 114
(This is only an order of magnitude)
Most naphthenic acids in crude are found in the gas oil and light oil fractions.
Ordinary steel attack starts between 220 and 400°C, usually for an acid number greater than 0.5 mgKOH/g.
In fact, acid numbers of up to 10 mgKOH/g may be encountered.
The corrosion product, iron naphthenate is soluble in hydrocarbons, so that attack is not slowed down by the
corrosion product as it is in the case of sulfur corrosion. There is therefore rapid corrosion which is
accentuated in the zones of turbulence and high flow rates. Corrosion pits with sharp edges and perpendicular
to the surface of the metal is characteristic of this type of attack.
Corrosion can also take the form of oriented groove with smooth and deposit-free cavities.
There is no corrosion of ordinary steel below 220 to 230°C; and corrosion only appears above this range.
Corrosion rates will increase rapidly with the temperature until about 400°C, above which, the acids
decompose. The following figure shows the corrosion rate of the various steels and alloys versus temperature.
As can be seen, only 18-8-3 (AISI 316) stainless steel has an acceptable resistance.
The evident difference in corrosion rates between 18-8 and 18-8-3 steels can serve to identify naphthenic
corrosion if needs be. A specimen of each alloy is placed in a liquid phase medium; if corrosion is naphthenic
corrosion, only the 18-8 steel will be attacked, but if corrosion is due to sulfur, neither of the specimens will be
attacked.
Note that, for a given temperature, the corrosion rate is directly proportional to the acid number: corrosion of
ordinary steel and low alloy steels doubles when the acid number doubles, and it is only from type 18-8 steels
that corrosion rate decreases.
Laboratory tests have shown that corrosion by naphthenic acids occur mainly in liquid phase. The result is
that their vaporization of these naphthenic acids, which for some starts at about 230°C, causes a drop in
liquid phase concentration. This can offset the increase in the corrosion rate due to a rise in temperature. By
contrast, local condensation, e.g., on certain trays, enriches the liquid phase in naphthenic acids and can
cause local corrosion.
Paradoxically, corrosion increases, sometimes very severely, in zones of high vaporization. This can only be
explained by the effect of "liquid-vapor" mixture flow rate which is very high at this point and can affect the
corrosion rate.

115
The activity of acids also affects the corrosion rate.
Activity is considered as increasing in the following cases:
- when the molecules become smaller

- when the acid bubble point is approached
- in the liquid phase rather than the vapor phase
It thus appears that naphthenic acid corrosion depends on:
- material quality
- acid concentration (acid number)
- temperature
- flow velocity
- the activity of the naphthenic acids.
• Equipment concerned and remedies
The equipment vulnerable to naphthenic corrosion attack in a distillation unit are the atmospheric column in
the zones having a temperature which reaches 220-230°C; vacuum tube fired heaters (tubes, transfer lines),
the vacuum column and ancillary equipment: trays, pumps, valves and pipe work.
Neutralization by soda or potash can be an acceptable solution in certain cases, for instance light fractions.
Heavy fractions demand highly concentrated solutions (with considerable clogging of the installations), and it
is often preferable to use 18-8-3 (AISI 316) steel which has a good resistance. It is used either solid,
sometimes centrifuged for heater tubes, or in plating for the walls of vessels or certain transfer lines.

02947_A_A
CORROSION IN THE VACUUM COLUMN CORROSION ACID
AVERAGE MOLECULAR FLOW RATE
— Reduced crude — RATE NUMBRES
TEMPERATURE WEIGHT m/sec.
°C mm/yaear mg KOH /g
LIQ. VAP.
67
VACUUM 60
70 mbar
Gas oil circulating reflux
140 0 0.3 0.6 2.8 260 0.11 1.95
50
200 VACUUM
VACUUM GAS OIL
DISTILLATION 220 4.7 340 0.04 1.50
COLUMN Internal reflux
Circulating
reflux 260 4.2 350 0.08 0.71
116
PACKED DISTILLATE
BED
300 280
DISTILLATE 1

Internal reflux
GRILLS 300 4.4 380 0.03 0.58
360
DISTILLAT E2
320 3.1 410 0.03 0.50
395 90
ATMOSPHERIC
mbar
RESIDUE 366 up to 20 3.0 460 0.37
250
Vapor
VACUUM
350 RESIDUE
D PCD 1332 B
342
117
CORROSION RATE OF SOME STEELS

— With a crude containing naphthenic acids
and sulfur compounds versus temperature —
Corrosion rate
(mm /year)
Carbone steel
3.5
5-9 % Cr. steel
3.0
2.5
18 Cr-8 Ni steel
2.0
12 % Cr. steel
1.5
18 Cr-8 Ni -3 Mo
steel at high velocities
1.0
0.5
D MAC 1246 B
18 Cr-8 Ni-3 Mo
steel at low velocities
Temperature (°C)
300 350 400 450

(From G.A.Nelson).

118
IX - CORROSION IN DISTILLATION UNITS

The main cause of corrosion at the head of "crude" distillation units is the presence of chlorides which can
hydrolyze when hot, and produce hydrogen chloride.
The chlorides come from drilling water and pollution by sea water during tanker ballasting and deballasting
operations (75% NaCl, 15% MgCl2 and 10% CaCl2).
• Clogging
The solid sediments contained in the crude oil are found partly in the preheat and in the heater tubes, where
they accentuate a tendency to coke. In order to eliminate these deposits, a minimum of 400 hours storage
hold-up time would have to be respected, which is rarely the case.
1- CORROSIVE AGENTS IN THE CRUDE

In a decreasing order of corrosive action:
1- At the head, the chlorides Mg Cl2, CaCl2, NaCl, generate hydrochloric acid, through
hydrolysis in the 120 to 180°C temperature range. Such temperatures are common
during preheating before and after desalting (in fact, NaCl usually only hydrolyses at about
900°C).
2- Sulfur compounds such as H2S, sulfides, mercaptans and by decomposition in the

furnaces produce mainly H2S, which is also found at the head of the column and in the
condenser.
3- Oxygen, although only found in small quantities in crude (1 ppm), acts as a depolarisant of
the cathodic zones and can come from electrolysis in the electrostatic desalter.
4- Naphthenic acids
Desaturated cyclic compounds have no direct action on corrosion of the head of the
tower, but regarding crude, they favor hydrolysis of sodium chloride at temperatures
where this would not otherwise occur. Considering that the ClNa represents 75% of the
crude salt content, the quantity of HCl thus generated is not negligible.
2- STUDY OF THE REACTION MECHANISMS RELATED TO CORROSION OF

ATMOSPHERIC DISTILLATION HEAD EQUIPMENT
a - Hydrochloric corrosion
An average example of the distribution of chlorides in the water contained in the crude is 85% NaCl,
11% Ca Cl2 and 4% Mg Cl2.
The latter (Mg Cl2) hydrolyses when hot according to the following reaction:
MgCl2 + 2 H2O 2 HCl + Mg (OH)2
Dry HCl does not corrode carbon steel. However, in the presence of water, it forms a highly ionized
acid, very aggressive for the steel, which it dissolves, producing FeCl2, FeCl3. This phenomenon is
encountered in the column head equipment, where the dew point of the acid solution is reached. This
acid can reach azeotropic concentration, i.e. 6.6 times the normal value (241 g/liter).

119
b - H2S corrosion
Hydrogen sulfide is produced by the cracking of sulfide molecules at the outlet of the distillation heater.
As regards the temperature of head equipment (104 to 120°C), H2S alone will have a fairly slight
action, the FeS produced, tending to form a protective film against S-- penetration. However, in the
presence of free HCl, this FeS film is dissolved with the formation of FeCl2 and H2S, and as there is
not more protection, corrosion increases with time, and eventually pierces the condenser tubes.
This phenomenon can also occur on the first trays of the topper head if cold reflux is used. In this
case, the trays should be designed, as should the top of the tower, to resist this aggressive
environment (Hastelloy B - Monel - Nichromaz).
3- CORROSION COMBATING METHODS

There are three possible types of action.
• Use of corrosion resistant alloys
This is the method used in the years when the oil industry was expanding, but it is extremely
expensive. The top of the tower was Monel clad. The first 3 trays of the head were in Nichromaz C,
and the head condensers in Cupro Nickel 70 30 or even titanium.
This method was used before modern and effective neutralization methods were developed.
b - Crude desalting and use of a pre-flash drum
The desalter consists, in most cases, of a large capacity horizontal drum fitted with a system of
electrodes which accelerate the decantation of solid water drops suspended in the crude (electric field).
The desalter can be considered as the element which regulates the chloride content at the unit inlet. It
prevents massive influx of salt water, reduces clogging of the preheating train by trapping the muds
and is an indispensable complement to neutralization, which is the next treatment stage.
A recent study shows that the addition of a desalter can economize on average 1 condenser bundle
per year.
• Role of a pre-flash drum
Among other advantages, the pre-flashing of crude eliminates the water from the crude salts which are
in a state of anhydrous crystal suspension in a hydrocarbon phase. This results in a lower rate of
hydrolysis and a decrease in the clogging of the preheating train.
c - Neutralization and inhibition
At present, the practice of simultaneous neutralization in the crude and at the tower head is the most
effective means to combat corrosion in the head equipment.

120
• Neutralization of the crude
* Objective
The purpose of neutralization is to transform Ca and Mg chlorides which have a high hydrolysis
potential into ClNa which is much less likely to hydrolyze.
This practice reduces the chloride content in condensed water at the head to below 20 ppm (almost 1
to 2 ppm - NaCl). Apart from the action of the chlorides, part of the H2S and naphthenic acids are
neutralized.
• Implementation of neutralization
This operation is done by injecting simultaneously soda (< 60 ppm) and ammonia (< 1 ppm) into the
crude after desalting.
• Extra neutralization at the head
Injection in the form of gaseous NH3 into the head vapor line has the purpose of maintaining the pH of
condensed water at between 6 and 7, corresponding to minimum corrosion. This is a complement to
injection of NH4OH in crude limited to 1 ppm NH3, which is not always enough to neutralize HCl in the
head.
H2S is less dissociated in SH- and S ions - about pH5 - but for HCl it is preferable to have pH 7; this is
a compromise which has to be accepted.
The use of neutralizing volatile bases at the distillation head can generate crystal deposits (NH4Cl)
which can form before water condensation. These deposits will be partially entrained by the
hydrocarbons which have already condensed and will cause fouling. Therefore means should be
employed to ensure that the water dew point is higher than the NH4Cl point of crystallization (there is a
connection between the chloride content at the head and the crystallization temperature). Action
should be taken during desalting and on complementary neutralization mainly in order to avoid fouling.
• Role of extra protection by corrosion inhibitors
The role of corrosion inhibitors is to form a protective film between the surface of the equipment and
the surrounding corrosive environment.
They make it possible to eliminate corrosion peaks when there is a momentary failure of neutralization,
but cannot replace this.
Classic inhibitors are long chain film forming amines which have a dipole behavior and are adsorbed
on the metal surfaces on which they lose their charge and have to be replaced by other molecules,
which implies a continuous injection, even for homeopathic doses (2 to 5 ppm).

121
• Criteria for injection of neutralizing agents
* Injection of soda
Soda is injected in a solution of 3 to 6° BeaumÈ in order to obtain a chloride content in the condensed
water at the head of less than 20 ppm. However, this injection is limited to 60 ppm (NaOH) due to
crude train plugging and caustic embrittlement phenomena of the heater tubes and transmission lines.
Although the use of spent soda with a view to saving fresh soda and in order to eliminate residues is
effective, it is not recommended from the point of view of corrosion and plugging of the preheating
train.
• Injection of ammonium hydroxide into the crude
This injection of ammonium hydroxide is implemented in the form of a 10°B solution.
The injection flow rate is adjusted in order to obtain a maximum content of 1 ppm NH3 relative to the
crude. Initially, this injection adjusts the pH at the head of the tower in condensed water at a value of 6
to 7.
• Monitoring neutralization efficiency
The end objective of neutralization is to reduce the corrosion rate of head condensates to 0.2 mm/year
on carbon steel.
A daily check of the various parameters should be made in order to verify the efficiency of the various
injections, with corrosion monitored by corrosion probes.
• Analytical criteria
Desalted water and sometimes water from the tank bottom and head drum condensers are analyzed
daily to determine the pH, chloride content (NaCl ppm), H2S content and dissolved iron.
• Corrosion monitoring
Probes are placed respectively in the condensed water circuits at the outlet of the head drums. The
corrosion rate curves can thus be plotted versus time.
Simultaneous to these in situ controls, the injection parameters of the various products must be
recorded.

122
DISSOCIATION OF HYDROSULFURIC ACID H2S

IN WATER VERSUS pH
% of H2S dissociated
in sulfides HS- et S-- F.C.C.
condensates
75
50
25
Compromise
Condensates of
the atmospheric
D MAC 1247 B
distillation head
drum pH
5 6 7 8
From "Les méthodes de la chimie analytique" G. CHARLOT

123
HYDROLYSIS OF MAGNESIUM CHLORIDE AND

CALCIUM CHLORIDE DURING DISTILLATION
100
Hydrolysis (%)
80
Mg Cl 2
60
40
20
CaCl 2
D MAC 1275 B
Temperature (°C)
100 200 300 400

(From LE PETRECO MANUAL "IMPURITIES IN PETROLEUM" fig.1 p.6).

ATMOSPHERIC DISTILLATION UNITS INHIBITOR
02947_A_A
— Corrosion prevention — Protects metal
from attack
BASE by H2S and HCl
SUBSTANCE
neutralises
HCl pH
monitoring
Inlet crude oil characteristics Desalting conditions

GAS +
Temperature: 100 to 150°C GASOLINE
Mineral salt content: 20 to 300 g/t Water flooding ratio: 3 to 8% volume/crude
Water content: WATER
0.1 to 0.6% volume Residence time: 20 to 30 minutes
Desalting efficiency: about 95%
Steam
124
ATMOSPHERIC KEROSENE
DEEMULSIFIER COLUMN
Prevents stable emulsions
stable due to asphaltenes DESALTER

Steam
GAS OIL
Mixing PREHEAT
valve
PREHEAT
CRUDE WATER
FURNACE
+
SALTS Steam
DESALTER WATER ATMOSPHERIC

CAUSTIC SODA
RESIDUE
Dissolves the mineral salts Transforms part of the
Washes the crude residual salts into NaCl
D PCD 481 B
CORROSION MECHANISM BY HYDROGEN
02947_A_A
SULFIDE IN A BASIC ENVIRONMENT
AND HYDROGEN BLISTERING OF CARBON STEEL IN A FCC UNIT
(Hydrocyanic acid) 3
2 HCN
H2 S
1 H 2S
(Hydrogen sulfide)
(Ammonia) NH 3
FCC gas CN -
+ steam HS -
HS -
pH Droplet
of condensed
basique
water
125
Iron sulfide
CARBON
1
STEEL

3 4
5
H
H
H H
H2
BLISTER 2
In FCC gas there is a gaseous mixture of steam, ammonia, hydrogen sulfide and hydrocyanic acid which will dissolve when steam condenses (alcaline condensate)
The carbon steel is corroded by hydrogen sulfide. Iron sulfide is created and is poreous and does not cling to carbon steel.
D PCD 692 B
(Fe + 2HS- FeS + S2- + 2 H+). The iron sulfide is itself corroded by HCN to create ferrocyanide (blue). (FeS + 6 CN- Fe (CN)4- + S2-)
126
X- CORROSION BY POLYTHIONIC ACIDS

1- INTRODUCTION
Polythionic acids are not naturally present in petroleum products. The general formula is H2S x
O6,and they are produced by oxidation and hydrolysis of sulfides in the presence of water.
This type of corrosion can be considered as a spin off of hydrosulfuric corrosion. It is an intergranular
corrosion phenomenon occurring in austenitic steels under cold conditions. It is found in structures
under load (stress/strain) covered in sulfide deposits when oxygen and water are present (e.g. on
opening apparatus).
2- INITIATING FACTORS OF PSCC (Polythionic Stress Cracking Corrosion)

On all equipment which may carry H2S and having austenitic structure, hydrofiners, catalytic reforming,
cat cracker, etc., sulfide deposits may form during normal operation.
During stoppages, damp air may enter the equipment and the iron sulfide immediately hydrolyses in
the presence of oxygen and water, which produces compounds known as polythionic acids according
to the reaction:
FeS + H2O + O2 H2Sx O6
(x may be equal to 2, 3 or 4),
the pH drops between 3 and 5.
Conditions in which intergranular corrosion by polythionic acid occurs are:
- sensitization of the steel structure by carbide precipitation at grain boundaries. This is

related, as we know, to the steel composition (high carbon) and the temperature exposure
time for carbide migration
- presence of sulfides or polysulfides on the surface of the metal
- presence of oxygen and water;
- presence of residual stress, in particular in the HAZ of welded assemblies or rolled sheets
which have not been quenched (case of certain linings).
Carbon steel is not sensitive to corrosion by polythionic acids.
a - Sensitization of AISI 300 austenitic steels
Prevention of the sensitization of austenitic steels is the most important factor when combating PSCC.
Sensitization of austenitic is due to the precipitation of carbides which accumulate at the grain
boundaries creating preferential passages for any intergranular type of attack in the vicinity of the
chromium depletion zones.
This phenomenon occurs very rapidly at high temperatures, and therefore around welds. This
concerns the construction phase of the plant and during operation when temperatures exceed 400°C
over longer periods. The sensitization temperature is higher than 450°C for so-called stabilized
titanium or type 321 or 347 Nb steels having carbide migration and precipitation kinetics which are
much slower. Among structures insensitive to this type of cracking, are dendritic structure austenitic
weld overlay which can be for lining material in certain hydrofining reactors.

127
b - Presence of sulfide deposits
These deposits result from hydrosulfic corrosion during operation of stainless steel installations or C
steel lines located upstream. If these deposits can be eliminated by oxidation during decoking
operations or by sanding or alkaline chemical cleaning before opening, PSCC can be avoided.
c - Presence of water and oxygen
These two elements are always present when installations are opened. To avoid contact with the
deposits, it is recommended, when stopping without opening, to pressure-up the apparatus with
nitrogen in order to avoid any influx of air and keep the internal temperature above the water vapour
dew point.
d - Presence of stresses in the steel
Generally, prevailing stresses are always above the threshold of the critical level, below which no
cracking will occur in the presence of polythionic acids.
3- PREVENTION OF POLYTHIONIC CRACKING

Use Ti or Niobium stabilized steels, or at least 304 L and 316 L low carbon austenitic steels.
Avoid any influx of air or water during stoppages (keep the apparatus which are not opened under
nitrogen pressure).
Before opening, neutralize existing sulfide deposits and recirculate a 2% sodium carbonate solution
with 0.5% sodium nitrite and a wetting agent, for four hours, to penetrate the hydrofobic surface of the
deposits.

128
XI - CAUSTIC SODA CORROSION

Soda only attacks iron above approximately 40% weight concentration and as a function of the temperature
and oxygen content of the solution.
This is an electrochemical corrosion which gives the following reactions:
- anodic: (formula)
- cathodic: (formula)
FeO2– combines with soda, and hydrogen is released.
For weaker soda concentrations of between 15 and 40% and temperatures over 80°C, generalized corrosion
gives way to intergranular stress cracking. This type of corrosion only occurs if the metal has previously
strain-hardened. This cracking mechanism appears to be related to the very slow rate at which the
passivation layer forms. Before the formation of this layer, the metallic ions enter solution. This is more
evident along the grain boundaries. When the boundaries are too deeply attacked, the passivation layer
cannot form at the base of the boundaries subjected to increasingly high stresses, and corrosion is all the
more rapid as a potential differential prevails between the base of the grains and the surface (passivated).
Glass, tantalum, aluminum and titanium are not particularly soda resistant. A soda resistant material will also
resist potassium. Sensitivity of the boundaries to corrosion is enhanced by the presence of carbon and
nitrogen accumulated along the boundaries.
• Remedies
— Titanium steel grades to avoid the presence of free nitrogen and carbon in the steel
— Addition of nickel. use of Monel-Inconel-Uranus 50
— Avoid hot spots (tracers, etc.)
— Avoid points where soda can accumulate (low points)
— Relaxation of welds and curves
— Do not exceed HRC 22 hardness
— Use of organic coating (paints)
— Some authors advise raising the potential which could cause cracking corrosion to disappear through
passivation.

129
SELECTION OF MATERIALS
— to carry caustic soda —
Above 300 °C, use a 99 % nickel - low carbon (C ≤ 0.22 %) alloy
250
240
230 Limit of use for
stainless steel
220
(304) (316)
210 due to cracking
corrosion
200
Zone D
190
Nickel 99% C≤ 0.15 %
180 Limit of use for
170 stainless steel
due to cracking
160 corrosion
150
140
Température °C
Zone C
130
Stainless steel
120 Type 304
Zones B and C valve faces
110
In nickel alloy
100 or stellite
Zone B
90
carbon steel
80 Stress relief
necessary
70
Zone A
60
50 carbon steel
Stress relieving
40 unnecessary
Melting point curve
30
20
D MAC 021 C
10
0 10 20 30 40 50 60 70 80
Soda concentration in % weight
From Chenical Engineering-November 12-1962
"Gilby-Fodor" catalogue (Wiggin et Huntington nikels alloys)

130
XII - BIOCHEMICAL CORROSION

This is not actually a type of corrosion, but rather a degradation resulting from the activity of living organisms.
These organisms include micro-organisms such as bacteria and macro-organisms such as mussels, algae,
etc. They can live and reproduce in environments where the pH varies between 0 and 11, temperatures from
- 10°C to + 80°C and under pressures of several hundred bars.
These living organisms contribute to the destruction of materials through:
- depolarization of anodic and cathodic reactions

- production of corrosion deposits through differential aeration
- production of corrosive agents (SO4H2, for example).
1- MACRO-ORGANISMS
These animal and plant species attach themselves to the walls. An accumulation of these organisms
creates the conditions required for crevice corrosion and fouling (the latter effect will limit more
particularly heat transfer in the exchangers).
• Prevention
- fast fluid flow in order to hamper attachment of the organisms
- rough or scaly surfaces hampering the attachment of species
- use of anti-fouling paints (these paints contain toxic substances such as copper
compounds)
- regular cleaning
- in closed systems (recirculated water), products such as chloride can be injected which
destroy the living species
- removal of shellfish.
2- MICRO-ORGANISMS
It is mainly bacteria which are involved in metal corrosion. They are about 1 in size and can
reproduce very fast by simple cellular division. The necessary energy to sustain bacteria is provided
by enzymes and catalyzed metabolic reactions.
Biological corrosion often appears in the form of closely packed tubercles which can generate crevice
corrosion. This laminated tuberculiform accumulation is frequently hollow and sometimes contains a
blackish fluid mass.
The presence of iron sulfide can easily be detected by adding a few drops of hydrochloric acid to the
rust (release of H2S).
Here, we will only review the principal types.

131
a - Sulfate-reducing bacteria (desulfovibrio, desulfuricans)
These are sulfate-reducing anaerobic bacteria, which produce the following sulfites:
2–
SO4 + 4 H2 S2– + 4 H2O (production of sulfides and hydrogen sulfide).
The hydrogen is supplied by the cathodic ranges or organic compounds in the environment.
b - Sulfur oxidizing bacteria (thiobacillus and thiooxydans)
These aerobic bacteria can oxidize the sulfur contained in the following sulfur compounds:
2 S + 3 O2 + 2 H2O 2 H2 SO4.
They are found in oil reservoirs and in sewage systems where they cause rapid attack of the cement.
Here, there is in fact a combined effect of the sulfate-reducing bacteria at the lower part (anaerobic
fermentation of settled muds) and aerobic bacteria in the upper part.
c - Iron bacteria (gallionella) bacterial filaments of ferrous oxide
These live in an aerobic environment and acquire their synthesis energy by consuming ferrous ions
and their oxidation from ferric ions (ferric oxides which form a sheath around the cell).
2 Fe2+ + 2 OH– + H2O + O2 Fe2 O3, 2 H2O + Q kcal
This reaction consumes the ferrous ions and the hydroxyl ions and depolarizes both:
- anodes Fe Fe2+ + 2 e
1
- cathodes 2 e + 2 O2 + H2O 2 OH–
with a resulting increase in corrosion.
The growth of ferrous bacteria also eliminates oxygen and covers the steel with tubercles, thus
favoring crevice corrosion.
d - Prevention
— Coating the buried structures with coal tar, plastic tape, concrete, etc.
However, there are certain moulds which attack plastic coating.
— Cathodic protection; the metal is also protected by a coating.
— Alteration of the environment (compounds containing sulfur can be displaced by airing the sewers).
— Increasing the rate of flow in order to remove deposits.

132
— Injection of bactericides (chlorine, chlorinated compounds, etc.).
Care should be taken regarding the association of different bacteria: sulfate-reducing bacteria are
not the only ones in the water, and other species can degrade the inhibitor (which may have been
very effective in another environment).
Before injection of a bactericide, a list of flora and all micro-organisms present should be made.
Certain laboratories advise only changing the bactericide when the analysis of recirculated water
shows the beginning of habituation (alternation of 2 bactericides should be prohibited).
— In certain cases, the steel pipes can be replaced by asbestos or plastic piping.
Contribution of oxygen
in humid environment
condensation
H2SO4
Release H2S
Deposit with thiobacilus Aerobic

bacteria medium
Muds with desulfovibrio Anaerobic
D MAC 2126 B
bacteria medium
Production of sulphides
Double bacterial attack of a metal pipe conveying waste water

133
PROTISTS
ANIMALS
PLANTS
YEA GI
ST
FUN
ALGAE
AE
O
MOULDS
TOZ
PRO
SUPER PROTISTS
(unicellular)
E BACTE
ALGA n) RIA
g ee
r
(blue-
SUBPROTISTS
(acellular)
BACTERIA
Streptococcus
Staphylococcus COCCI
Fusobacterium
Bacillus Corynebacterium
BACILLT
Vibrio Treponema Spirochaete
SPIRIL
D MAC 1386 A
ACTINOMYCETES From J.D. Millez, 1971

02947_A_A
4Fe (OH)2 + O2 + 2H2O 4Fe (OH)3
6OH-
3Fe (OH)2 8H2O
2OH-
M (OH)2
Fe (OH)2 8H+
4H2O S2- (H+)2

4
(+ O + H2O)
134
3Fe2+ FeS

4Fe2+
S2-
8H
4Fe2+
8 e-
ANODE CATHODE
D MAC 1248 B
From GATTELIER - IFP

135
XIII - CORROSION IN AN AQUEOUS ENVIRONMENT

1- INTRODUCTION
Here, two reactions prevail on the surface of the metal:
- anodic reaction: Fe Fe++ + 2e– (1)
This reaction is fast in most environments, but it is usually controlled by a slower cathodic
reaction.
- cathodic reaction:
• in an acid deaerated environment 2 H+ + 2e H2 (2)
• in an alkaline or neutral deaerated environment 2 H2O + 2e 2 OH– + H2
1
• in an aerated acid environment 2 H+ + 2 O2 + 2e H2O
1
• in an alkaline or neutral aerated environment H2O + 2 O2 + 2e 2 (OH)– (3)
This process is called depolarization. The cathodic reaction is accelerated as long as the oxygen can
reach the surface of the metal.
The reaction balance (1) + (3) gives:
1 1
Fe + H2O + 2 H2O + 4 O2 Fe (OH)3
It is the hydrated ferrous oxide (FeO, nH2O) which forms a barrier against diffusion on the metal
surface. The pure substance is white, but it is usually grey due to oxidation which initiates in the
presence of air. On the outer surface of the oxide film, the dissolved oxygen transforms the ferrous
hydroxide into ferric hydroxide.
1 1
Fe (OH)2 + 2 H2O + 4 O2 Fe (OH)3
The hydrated ferric oxide (brownish-red color) forms most of the "rust".
Depending on the oxidation rate, ferrous oxides with various degrees of hydration and various
crystallographical structures will be found on the surface. The ferrous salts which form initially are not
very adhesive; the rust is easily remove, and metal attack develops.
In brief, the role of the oxygen in the process of rust formation is dual:
- depolarization of the microcathodes

- oxidation of the formed products.

136
2- EFFECT OF OXYGEN CONCENTRATION

In the absence of dissolved oxygen, the corrosion rate of low alloy steel is negligible. However, as
soon as the oxygen concentration increases, corrosion will increase by depolarization. Beyond a
critical concentration, the corrosion rate drops to a very low value.
Air Critical value

satured
Corrosion in mg/dm2 day

This critical value increases with the 60
content of dissolved salts and
temperature, and decreases with the
pH and turbulence. The reduction of 40
corrosion beyond the critical value is
thought to be due to the transformation
of the ferrous oxide film into another 20
film providing greater protection.
D MAC 1249 B
Corrosion of mild steel in slightly stirred
6 10 20 25
distilled water at 25°C (48 hour test).
Dissolved O2 concentration (cm3/L)
With high O2 concentrations, pitting may appear, especially at higher temperatures in the presence of
halogen ions (Cl-, B- and l-). This behavior limits the practical use of high oxygen concentrations as a
means to reduce steel corrosion.
• Temperature effect
When the temperature increases, the solubility of all the dissolved gases, in particular free CO2 and O2
is reduced (up to 110°C for the O2). Beyond this temperature, there is a recovery of this gas, and at
200°C, there may be as much dissolved oxygen as at 30°C.
In particular, if a system is open, the oxygen released by a rise in temperature can escape; the
corrosion rate increases with temperature up to 80°C, and then drops at about 100-110°C.
However, in a closed system, the oxygen cannot escape, and corrosion continues with the increase in
temperature until all the oxygen has been consumed.
70 0,75
Corrosion rate mm/year
Corrosion rate mm/year
em
C
yst
50°
s
50 sed
0,50 Clo
30°
C
tem
sys
D MAC 1250 B
25 0,25 d
10°C e ne
Op
2 4 6 8 10 0 40 80 120 160
PPM 0 2 Temperature (°C)
Effect of oxygen concentration on corrosion at Effect of temperature on corrosion of iron

different temperatures (Betz, Handbook) in water containing dissolved oxygen

137
A rise in temperature also affects:
- the decomposition of carbonates and bicarbonates: formation of carbon dioxide (CO2)

corrosion by carbonic acid (CO3 H2)
- the solubility of alkaline-earth salts (calcium and magnesium salts). Solubility decreases
with the rise in temperature when the various equilibrium established in water are thoroughly
disturbed
3- EFFECT OF THE SOLUTION pH
Corrosion rate
1 (mm/year)
From pH = 4 to 10, ferric oxide is
soluble; it is constantly renewed by the
corrosion rate which is stable. In fact, 0,75
the surface of the metal always remains
in contact with an alkaline solution of
hydrated ferrous oxide saturated at 0,50
pH = 9.5
Iron in soft aerated water at room

0,25
DMAC 1251 B
temperature.
0
14 13 10 9 4 3 2 pH
Corrosion will depend only on the diffusion rate of the oxygen. At about pH = 10, the iron becomes
passive, and the corrosion rate decreases in the presence of oxygen and alkaline. If alkalinity
increases sharply, corrosion will increase slightly with the formation of Na Fe O2 or, in the absence of
dissolved oxygen, the formation of Na Fe O2 and of Na Fe O2 with release of H2. Between pH = 4 and
pH = 10, and for as long as the oxygen controls the reaction, small variations in the composition of the
water, the heat treatment and the carbon percentage have no impact on the corrosion rate.
However, for pH < 4, oxygen diffusion no longer governs the reaction alone. The hydrogen generation
rate is also involved. Impurities or phases present in the steel (e.g. carbon) have a lower hydrogen
over voltage, and therefore a depolarizing role. A high carbon steel corrodes at a higher rate in acids
than a low carbon steel.
A pH increase in water containing a solution of calcium bicarbonate and magnesium sulfate will cause,
precipitation of the calcium carbonate and the magnesium hydroxide, respectively, on the surface of
the metal. Deposition of these salts can form an even, adhesive layer which is actually desirable in
certain cases (cathodic protection of offshore platforms).

138
CORROSION OF STEEL
— Versus pH of boiler water —
8.5 pH
12.7 pH
- Safety zone
D MAC 1252 B
1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH

139
4- EFFECT OF STRONG AND WEAK ACIDS ON THE IRON

As we have seen in strong acids (H2SO4, HCl), the oxide film (diffusion barrier) on the metal surface
dissolves when pH < 4.
For weaker acids (acetic or carbonic), the dissolution of the oxide film appears at a higher pH. Thus,
the corrosion rate of iron will increase and be associated with the appearance of hydrogen at a pH of 5
to 6.
This difference can be explained by the total affinity or the greater neutralizing capacity of a partially
dissociated acid compared with a totally dissociated acid for a given pH. In other terms, for a given pH,
there is more H+ available to react and dissolve the oxide film using a weak acid than a strong acid.
An increase in the corrosion rate of iron when the pH decreases is not only due to an increase in
hydrogen generation. In fact the greater accessibility of the oxygen to the metal surface caused by
dissolution of the surface oxide, favors depolarization by oxygen, and this is often the chief reason.
Oxidizing acids and non-oxidizing acids or the role of dissolved oxygen on the corrosion of
mild steel in acid.
Ratio = corrosion rate with O2/Corrosion rate without O2
PRESENCE OF IN PRESENCE OF
ACIDS RATIO
OXYGEN HYDROGEN
6% acetic 0.55 ipy 0.006 ipy 87
6% H2SO4 0.36 0.03 12
4% HCl 0.48 0.031 16
0.04% HCl 0.39 0.0055 71
1.2% HNO3 1.82 1.57 1.2
As can be seen, the oxidizing acids act independently of the dissolved oxygen; they act as
depolarizers. This is not so for non-oxidizing acids.
In general, the ratios are higher in more dilute acids. In more concentrated acids, the rate of hydrogen
generation is such, that the oxygen has difficulty in reaching the surface of the metal.

140
5- EFFECT OF DISSOLVED SALTS

The effect of sodium chloride on corrosion of iron in aerated water at atmospheric temperature is
indicated in the following diagram.
Corrosion rate
D MAC 1253 B
1
0
3 5 10 15 20 25
NaCl concentration (% weight)
Effect of NaCl concentration on iron

in an aerated solution at room temperature
At the beginning, corrosion increases with the salt concentration and then decreases; the rate value
drops below that found in distilled water when saturation point is reached (25° NaCl).
When oxygen depolarization governs the rate from one end of the NaCl concentration range to the
other, it is of interest to understand why the rate increases to begin with, reaches a maximum at
approximately 3% NaCl (sea water concentration), and then decreases. The solubility of oxygen in
water decreases steadily with the sodium chloride concentration, thus explaining a drop in the
corrosion rate at high concentrations of sodium chloride.
The initial increase seems to be connected to a change in the nature of the rust film forming a diffusion
barrier which is produced by the iron corrosion.
In distilled water, with low conductivity, the anodes and cathodes have to be fairly close together.
Consequently, the OH- ions which form at the cathodes according to the following process:
1 –
2 O2 + H2O + 2e 2 OH
are always near to the Fe++ ions which form at the anodes. The result is the formation of an Fe (OH2)
film adhering to the metal surface. This produces a film which is an effective barrier against diffusion.
By contrast in sodium chloride solutions, conductivity is greater. Thus the anodes and cathodes can
operate at greater distances from each other. For such cathodes, the NaOH does not react
immediately with the Fe Cl2 formed at the anodes. Instead, these substances diffuse in solution and
react to form Fe (OH)2 far from the surface of the metal. Consequently, all the Fe (OH)2 thus formed
does not generate a protective film on the surface of the metal. More dissolved oxygen can reach the
cathodic zone in diluted sodium chloride solutions, so the iron will corrode faster.
Above 3% NaCl, the drop in dissolved oxygen is much greater than the modification of the diffusion
barrier layer, so corrosion decreases.

141
The alkaline metal salts (KCl, Li Cl, Na2 SO4, Kl, Na Br, etc.) affect the corrosion rate of iron and
steels in the same way as sodium chloride.
Acid salts which hydrolyze and produce acid solutions, cause corrosion, with the appearance of
hydrogen and depolarization by the oxygen. Examples of such salts are AlCl3, Ni SO4, MnCl2 and
FeCl2.
Ammonium salts (e.g.: NH4Cl, NH4NO3) are also acid and produce a higher corrosion rate. The
increase in corrosion due to the ability of NH4+ ions to transform the iron into a state of Fe++ ions to
form a complex mole. The ammonium nitrate in high concentrations is more corrosive than chlorides
or sulfates, partly because the NO3- ion has a depolarizing capacity. The complex molecule in this
case is (Fe(NH3)6) (NO3)2.
Alkaline salts which hydrolyze to form pH > 10 solutions act as corrosion inhibitors. They passives
the iron in the presence of dissolved oxygen in the same way as NaOH (see the curve representing the
effect of pH on corrosion in aerated water).
Examples of such salts: Na3 PO4 (sodium phosphate), Na2 B2 07 (sodium tetraborate), Na2SiO3
(sodium silicate), Na2CO3 (sodium carbonate), with added dissolved oxygen to enhance iron
passivation, these salts form a layer (corrosion products) of ferrous phosphates or ferric phosphates in
the case of Na3P04 or similar components in the case of Na2SiO3. These layers form more effective
diffusion barriers than FeO.
Oxidizing salts
These salts are: either good depolarizers, and consequently corroding, e.g.:
FeCl3, CuCl2, HgCl2

Fe+++ + e– Fe++ (depolarizing action)
or effective passivators and inhibitors, e.g.:
Na2CrO4, Na2Cr2O7
NaNO2, KMn O4, K FeO4
2–
(passivation) Cr2O7 + 8 H+ + Fe (surface) 2 Cr+++ + 4 H2O + O2 + O (adsorbed on the iron).
Salts contained in natural water
Natural fresh water contains calcium and magnesium salts dissolved in various concentrations.
If the concentration of such salts is high, the water is said to be hard. If the concentration is low, the
water is said to be soft.
Soft water is usually more corrosive than hard water; this will be developed in the following paragraph.

142
6- EFFECT OF CARBON DIOXIDE (CO2 - CARBONIC ACID H2C03)

The presence of carbon dioxide in water in the absence of oxygen results in the formation of carbonic
– 2–
acid H2C03, which partially ionizes to produce the ion H+, HCO3 and CO 3 .
– 2–
CO2 + H 2O H2CO3 H+ + HCO3 2 H+ + CO3 (1)
The appearance of H+ ions contributes to the lowering of the pH: the water becomes more acid.
These H+ ions also act as an electron pump so that corrosion is either initiated or accelerated. In the
– 2–
case of iron and steels, the Fe+2 ions formed during dissolution react with the HCO 3 and CO3 ions
to produce soluble ferrous bicarbonate and ferrous carbonate which, as soon as the solubility product
is reached, precipitate on the surface of the steel.
–
Fe+2 + 2 HCO3 Fe (HCO3)2 (2)
2–
Fe+2 + CO3 FeCO3
It has been demonstrated that attack of the iron by carbonic acid is negligible for concentrations equal
to or less than 10-6 mole/l. This limit concentration is a function of the pH and total CO2:
–
Total CO2 H2CO3 + HCO3 + CO3– –
CO2 + H2O CO2 bonded
excess CO2
For a given total CO2 concentration, the higher the carbonic acid H2CO3 concentration, the lower the
pH will be.
Water with a H2CO3 content greater than this limit value will attack iron and steel, and will be
considered as steel corrosive. It is important to clearly distinguish between this aggressiveness of
water towards steel and the aggressiveness of water towards marble.
Water is aggressive towards marble when the equilibrium:
1
CaCO3 + CO2 + H2O Ca(HCO3)2 (4)
2
H2CO3
is displaced towards 1 (case where there is too little calcium carbonate to balance all the CO2). The
carbonate then dissolves in the form of bicarbonate (limy aggressiveness).
However, if reaction 4 evolves towards 2, calcium carbonate precipitation occurs, and the water
becomes scale-forming.

143
Equilibrium (4) like any other equilibrium depends on many parameters, and in particular on the total
CO2, the pH and temperature.
By combining the theories of limy aggressiveness and corrosivity GIRARD has defined characteristic
zones regarding these two chief properties on a total CO2-pH diagram so that it can be determined
whether the aggressiveness of a given water will be corrosive, aggressive, non-corrosive, calcifying-
corrosive, or calcifying-non-corrosive. The advantage of such a diagram is that it is possible from a
qualitative point of view to forecast the evolution of a given water in the presence of iron.
It should be noted that many authors have compiled indexes for forecasting from the pH, TH, TAC, etc.
whether a water will tend to be aggressive or scaling, corrosive or non-corrosive, among others:
Langelier and Rysnar.
It is useful to use this type of index to determine whether a water is aggressive or scaling, but
precautions should be taken when using them to predict corrosion (non-protective scale, under-scale
corrosion, pitting).
(H2CO3)Ca CaCO3 + H2CO3 H2CO3 = 10-6 mol/l
4
Total CO2 in (mol/l)
Corrosive water
2
1 Aggressive water
0.80
0.60
0.40 Calcifuing water
0.20
D MAC 2123 B
0.1
5 6 7 8 9 10 11
If the carbonic acid is consumed (corrosive action of the water with formation of iron carbonate which
precipitates), equilibrium (4) evolves towards the formation of this acid (2), which generates the
formation of sodium carbonate. The deposit that forms on the surface of the steel will thus be a
mixture of calcium and iron carbonate. This mixed deposit can be adhesive and provide protection
against corrosion; this is known as scale inhibition.

144
• Appearance of carbonic acid corrosion in the presence of oxygen - role of oxygen
Although no tubercles can be seen when oxygen is not involved in the corrosion process, the presence
of dissolved oxygen causes local attack with the formation of pits below the tubercles (products of
reaction between the oxygen and the iron carbonates or bicarbonates). The corrosiveness of the water
is increased by the presence of oxygen.
1
2 Fe (HCO3)2 + 2 O2 Fe2O3 + 4 CO2 + 2 H2O
1
3 Fe (HCO3)2 + 2 O2 Fe3O4 + 6 CO2 + 3 H2O
Likewise, the reactions:
Fe ( HCO3)2 FeO + 2 CO2 + H2O (high temperature)

and
Fe (HCO3)2 Fe (CO3) + CO2 + H2O
are also possible. Carbonic acid corrosion in the presence of oxygen gives corrosion products
containing FeO, Fe2O3, Fe3O4, and Fe (CO3) in more or less hydrated forms.
7- PREVENTION OF CORROSION BY WATER

1 - Choice of suitable materials or coating the material with paint, resins or galvanization.
2 - Reducing the temperature
3 - Treatment of water to remove corrosive species (02, CO2, etc.).
Deactivation: consisting in passing the water slowly over steel bars in a closed vessel. The
oxygen will corrode this steel and be consumed. In order to eliminate CO2, the water is
neutralized by running it through a neutralizing product (marble).
Dearation: this generally consists in thermal degassing by flowing the water counter-current the
vapor: O2 and CO2 are entrained.
4 - Corrosion inhibitors.
5 - Cathodic protection.
6 - Ensure cleanliness and homogeneity of the surfaces.

145
XIV - ATMOSPHERIC CORROSION

Steel does not corrode without humidity. For corrosion to occur, an electrolyte must be present.
Corrosion depends on humidity, dust and gaseous impurities which favor condensation of the humidity on the
metal.
1- FILMS FORMED BY CORROSION PRODUCTS
Weight loss
in g/dm 2
6
Rust becomes a protection with time. The
corrosion rate drops with time. The oxide 4
film of low alloy steels is compact and Low alloy steel
adhesive.
D MAC 1254 B
2
0 2 3 4
Years
2- ATMOSPHERIC CORROSION FACTORS

The rates of atmospheric corrosion of metals are generally lower than those encountered in water or
soil.
• Dust
Industrial atmosphere contains particles of carbon, metallic oxides, H2SO4, (NH4)2, NaCl and other
salts which, when combined with humidity, can form galvanic cells, or through differential aeration or
due to their hygroscopic properties, form an electrolyte on the surface of the metal.
• Gases
CO2 does not accelerate corrosion, in fact it forms a protective film. The most corrosive component is
SO2 (which converts into SO4H2). Stainless steel, aluminum and lead have a better resistance than
zinc, iron, nickel or cadmium.
Copper forms a protective film of base sulphate. A green patina of CuSO4, 3 CU (OH)2 forms. In a
coastal environment, this products a base chloride.
• Humidity
In an uncontaminated atmosphere at constant temperature, no corrosion should be found for a

humidity of less than 100%. In practice, however, due to temperature fluctuations and to the presence
of hygroscopic impurities in the atmosphere or on the metal itself, the relative humidity will be above a
critical value (approximately 60%) and will create water condensation on the metal surface so that
corrosion starts rapidly.

146
3- REMEDIES FOR ATMOSPHERIC CORROSION

Organic, inorganic or metal coating.
Vapor phase inhibitors for storing manufactured products.
Use of low alloy steels (addition of small quantities of Cu, P, Ni, Cr are most effective against
atmospheric corrosion).
Corten steel (0.09% C, 0.4% Cu, 0.8% Cr, 0.3% Ni, 0.09% P) produces a highly protective rust in an
atmosphere which is alternately dry and humid (constant plunging in water, the rust film is not more
protective than the rust on ordinary steel).
Stainless steel and aluminum are also highly resistant.
In a marine atmosphere, the following can be used: C Hastelloy (54% Ni, 17% Mo, 5% Fe, 15% Cr, 4%
W) or low alloy steels: Corten and Mariner by U.S. Steel, IN 787 by Inco or Marine 50 by Nippon
Kokan.
In certain special cases, it is possible to reduce the relative humidity in the air to below 50% by heating.
XV - SEA WATER CORROSION
1- CHARACTERISTICS OF SEA WATER

• Salinity
This is the total quantity (in grams) of solid matter contained in 1 kg of sea water. It is in the order of
35 g/litre.
The principal ions present in sea water are in decreasing order of content:
Cl-, Na+, SO4--, Ca++, K+ , HCO3-, Br-, Sr++ , F -
NaCl represents 77.8% weight of the dissolved salts.
MgCl2 10.9%
MgSO4 4.7%
CaSO4 3.6%
K2SO4 2.5%
• Dissolved gas
The gases contained in air dissolve in the surface layers of the sea water. Regarding oxygen, the O2
produced by photosynthesis must be included (algae and bacteria assimilate CO2 and sunlight to
produce O2).
At 20°C and for a normal salinity of 3.5%, we have:
Oxygen 5.25 ml/l

Nitrogen 9.60 ml/l
Argon 0.25 m/
CO2 0.23 ml/l

147
• pH
The pH is between 7.8 and 8.3. It can drop to 7 in the presence of H2S.
• Resistivity
In the range of 20 to 30 cm (perfect electrolyte).
Sea water also contains dissolved organic compounds (< 2 ppm), suspended solids (5 mg/l), colloidal
mineral and living organism compounds, etc. (their average size varies from 10 to 50 ).
2- CARBON STEEL CORROSION

This is an electrolytic type corrosion
Anodic: Fe Fe2+ + 2e-
1 - -
Cathodic: 2 O2 + H2O + 2e 2 OH
2 H+ + 2 e- H2 ou 2 H2O + 2 e - H2 + 2 OH-
Secondary reactions persist and the ferrous hydroxide formed is oxidized by the dissolved oxygen into
hydrated magnetite and ferric hydroxide.
Cl- is also involved.
This corrosion can be uniform, but heterogeneities on the surface of the metal or in the electrolytic
layer tend to localize the anodes (differential aeration under deposit).
The exact composition of the steel is of little importance; however, the condition of the surface (in
particular calamine) has an important role. The layer of calamine, which is very protective, is
unfortunately not unbroken and pits will form. Calamine has a higher potential than steel (0.3 V). The
presence of galvanic couples is particularly harmful. The general expression of uniform corrosion rate
is:
O2 diffusion coeff. . O2 concentration . actual diffusion area

Corrosion rate = thickness of the diffusion layer
• Temperature
The corrosion rate doubles every 10°C.
The use of steel is limited to 43°C. Moreover, for higher temperatures, the precipitation of:
carbonate for t > 65°C

sulfates for t > 143°C
should be taken into consideration.

148
• Circulating velocity
The thickness of the diffusion layer will depend on the flow regime (laminar or turbulent). The corrosion
rate increases with an increase in circulation velocity.
The turbulence maintains high concentration of oxygen by stirring up the water.
• Suspended solids
These have an abrasive effect which lowers the protective capacity of corrosion products.
• Fouling
Fauna (barnacles, mussels, bacteria, etc.) and flora (algae) can accumulate on the surface of the steel
and form cells. Flowing at rates greater than 1 m/s will usually remove them.
Remedies
- suppression of living organisms in the case of exchangers by intermittent chlorination

- medium and steady circulating velocity
- cathodic protection (soluble anodes for the exchangers)
- previous descaling (tank bottoms - exchangers)
- Brai-epoxy + anti-fouling type coating (for offshore structures)
3- CORROSION OF STAINLESS STEELS

These are sensitive to:
- pitting corrosion (absorption of Cl- through the passive film)

- crevice corrosion (differential aeration + acidization)
- intergranular corrosion
- stress corrosion and fatigue corrosion.
• Austenitic steels
Grade 316 L has a good resistance to pitting, but like all austenitics, it is sensitive to crevice corrosion.
Impurities such as sulfur have a disastrous effect. Integration of at least 2.5% Mo is highly
recommended.
• Ferritic and austeno-ferritic steels
Uranus 50 by Creusot Loire has a better resistance than 316, but has still not adequate resistance to
crevice corrosion.
4- CORROSION OF NON-FERROUS METALS

• Nickel alloy
Monel: overall corrosion is proportional to the O2 content and this alloy has no anti-fouling capacity, as
the Cu content is not high enough (avoid aerated water).
Ni - Cr - Mo alloys: Incoloy 825, Hastelloy C and Inconel 625, together with Titanium are almost
exempt from sea water corrosion (the Inconel 625 also has good weldability and can be used for
surfacing steels).

149
• Aluminum alloys
Good resistance of these alloys in oxygenated water (constant replacement of oxide film).
• Copper alloys
These are sensitive to erosion, and also, deposits on the surface can initiate differential aeration
corrosion.
Copper and its alloys do not owe their good resistance only to a passive film, but to an intrinsic
resistance due to the nobility of this metal.

Vitesse
METAL C Cr Ni Mo Cu Ti Mn Zn Al Sn Fe As Mg Eq. Cr
M/sec <
02947_A_A
Naval brass 70 29 1 0.04 1.5 Addition of As inhibits zinc depletion.
The Sn forms a protective compound
Aluminum brass 76 22 2 2 The NH4+ ions and Hg are harmful for

brass
Cupro-Nickel 8.4 90 1.6 2.5 Here, there is a Fe2O3 gamma layer

which provides good resistance to
localized erosion corrosion
28.4 70 1.6 3 The cupro-nickels are not H2S resistant

(< 0.1 ppm)
Monel 400 < 0.3 66.5 31.5 1 1.25 Good resistance in moving sea water
150
316 0.06 17 12 2.5 <2 25.5 20-50 This is the minimum which can be used
317 0.06 17 12 3.5 <2 28 for stainless steels
Uranus 50 < 0.03 22 8 2.5 1.5 <2 30.5 20-50 Austeno-ferritic recommended when
stress cracking is expected

Uranus B6 0.02 20 25 4.5 1.5 1.2 34 20-50 Creusot Loire
904 L ?
Nicrofer ?
NSCD < 0.03 17.5 16 >5 3 34 " Ugine and Vallourec
Sanicro 28 0.02 27.5 31 3.5 1 ? 38 " Sandvick

Sweden
254 SMO 0.02 20 18 6.1 0.7 ? 40 " Avesta
Hastelloy C 0.02 15 Solde 16 <1 5 65
Titane 99.8 > 20 This is sensitive to under-scale

corrosion from 140°C.
But it can withstand high velocities and
provides a weight gain
Alu 5454 Solde < 4.5 Seems valid (results not well known)
151
Brass (Cu - Zn)
Brasses resist erosion better than copper alone. They are sensitive to dezincification and stress
corrosion. Naval brass (60 Cu - 39 Zn - 1 Sn) and manganese bronze have good erosion resistance
but are sensitive to dezincification. Aluminum brasses (76 Cu - 22 Zn - 2 Al - 0.04% As) are used for
condenser tubes (they have a good resistance to erosion and are inhibited with arsenic to avoid)
dezincification.
The presence of magnesium neutralizes the action of arsenic.
Cupro-Nickels: 70 Cu-30 Ni with added iron is used for the exchanger tubes.
Cupro-aluminums: Inoxyda 90, misnamed aluminum bronze (10 Al - 5 Ni - 2 Fe - 85 Cu) is used for
the tubular plates of exchangers (molded).
Titanium is still very expensive, and there is a critical temperature (about 110°C), above which
differential aeration corrosion may occur.
Plastics
The advantage of these materials is that they do not corrode and are light. However, there are limits
related to risk of combustion, low mechanical properties and lower resistance to hydrocarbons and
solvents.
They are also sensitive to UV rays (although this problem seems, at the present time, to have been
reduced by the use of effective pigments) which is a drawback when repairs are necessary.
For the piping, either thermoplastics: polyethylene, polypropylene, PVC are used, or thermo-hardening
plastics: epoxies, fiberglass reinforced polyesters.
There are also plastic coatings:
- epoxy paints or epoxy pitch

- baked formophenolic products
- powdered epoxy and polyamide combination, which have the combined advantages of
thermoplastics (flexibility and resilience) with those of powdered epoxy (high temperatures).
Coatings
Galvanizing in a bath of melted metal or Schoopage. Concrete cladding.

152
XVI - DRY OXIDATION AT HIGH TEMPERATURE

A cross-section of an oxidation film formed on iron at 700°C shows a thick layer of ferrous protoxide FeO in
contact with the iron, overlaid with a layer of magnetite Fe3O4 and a fine layer of sesquioxide Fe2O3.
For temperatures below 570°C, FeO is unstable, and the film contains mainly Fe3O4 overlaid with Fe2O3.
The FeO formed at high temperatures partially decomposes when cooled according to the equilibrium:
4 FeO Fe3O4 + Fe
1- MECHANISM
Pilling and Bedworth scale:
where W = molecular weight of the oxide

Wd
R = Dw w = molecular weight of the metal
D and d = respective densities of oxide and metal
R represents the volume of oxide formed for a unit of metal volume.
For R < 1, the volume of oxide formed is insufficient to cover all the metal.
For R > 1, compressional stresses enter the oxide, which tends to crack.
A protective oxide should have the following properties:
- 1 < R < 2 (R should be near to 1)

- expansion coefficient close to that of the metal
- good adhesive properties
- high melting point
- low vapour pressure
- low diffusion coefficient (low electrical conductivity)
- high temperature plasticity (to resist cracking)
TABLE R for some oxides
Protective
Non-protective
Cu 1.68 Na 0.57
Al 1.28 Mo 3.4
Cr 1.99 W 3.4
Ni 1.52 Ti 3.4
Pb 1.4 Li 0.57
Si 2.27 V 3.18
Fe (FeO) 2.06
Mg 0.84
• Electrochemical aspects of oxidation
Metal oxides are semi-conductors. The ions can also move through the oxides via vacancies, but the
electronic conductivity is much greater than the ionic conductivity, and it is this which governs
oxidation.

153
There is oxidation of the metal Fe Fe2+ + 2 e and

1
reduction of the oxygen 2 O2 + 2 e O2-
Fe ++
1
Global reaction Fe + 2 O2 FeO. O 2- O2
Oxidation is mainly retarded by reduction of the diffusion

of ions through the oxide film. This diffusion is reduced
e-
in certain cases by doping, i.e., the addition of elements
which reduce the vacancies in the oxide itself. These
D MAC 1255 A
vacancies are a result of the stoichiometric difference.
In fact, the oxide is not stoichiometric; there is an excess

of oxygen or a lack of iron due the ferrous ions
becoming ferric.
O- - Fe++ O- - Fe++
Fe++ O- - Fe++ O- -
O- - Vacancy O- - Fe+++
Fe+++ O- - Fe++ O- -
O- - Fe++ O- - Fe++
Fe++ O- - Fe++ O- -
On the following figure, it can be seen that the presence of 2 Fe+++ ions compensates for the absence
of Fe++ regarding the electrical charge. There are therefore vacancies in the oxide through which the
ions migrate.

154
• Prevention of iron oxidation
Ferrous oxidation can only be limited by reducing the vacancies. This is difficult for FeO, as part of the
Fe++ ferrous ions oxidise to Fe+++ and stoichiometry is not achieved. Nickel is not suitable either, as
it also lacks cations, nor is the addition of chromium advised, as it transforms to Cr+++ (up to 5% Cr,
this is observed with Fe-Ni alloys). In fact, a very adhesive and protective binary or ternary compound
Ni Cr2O4 type is obtained, which prevents any diffusion. It has been noted that, for high pressure and
high temperature services, it is the 18-20 Cr and 8-10 Ni alloy steels which resist oxidation best.
Fe2O3
Fe3O4
FeO
D MAC 2172 A
Fe

155
2- OXIDATION KINETICS
For iron, the layers formed flake off, and oxidation occurs almost only by diffusion of Fe++ cations
through the FeO oxide. The law of oxide growth is linear to begin with, before the film has formed, and
then becomes parabolic.
Weight gain
mg/cm2
100 Weight gain Linear (catastrophic oxydation
t mg/cm2 Na,K, Nb, Ta)
2 =K
x Parabolic
(Fe,Co,Cu)
10 Logarithmic (observed in oxide films

Kt
at low temperatures Al, Cu,Fe

x=
D MAC 1256 B
at ambient for films < 1000 Å)
D MAC 1257 B
1
10 100 Time (min) Time
3- HIGH TEMPERATURE MATERIALS

Alloy steels and refractory alloys developed for use at high temperatures must have:
- good creep resistance (deformation when hot under permanent load)

- good atmospheric resistance (mainly oxidizing environments)
- resistance to thermal shocks (fast cooling from 900°C to ambient temperature)
For very high temperatures, Mo, W, Nb and Ta should be added to improve mechanical
properties.
4- ATMOSPHERES ENCOUNTERED AT HIGH TEMPERATURES

• Carburizing atmospheres and carburization
Atmospheres with a high CO content (burning of fuel or hydrocarbons) generate chromium carbides
which precipitate at the grain boundaries and cause chromium depletion of the matrix; this then
oxidizes more easily.
The increase in the Ni content slows carburization.
In general, carburization alternates with oxidation, giving:
- formation of carbide and Cr depletion in certain zones

- oxidization of depleted zones
- appearance of cracks in the oxidized zones under the action of stresses

02947_A_A
Magnetite Hematite
1200 (Fe3 O4) (Fe2 O3)
Feγ + Wustite +
wustite (FeO)
1000
Wustite + Wustite + Hematite +
magnetite hematite oxygen
156
800
DIAGRAM
IRON/OXYGEN
Feα +
wustite

600
Feα + magnetite
Temperature (°C)
D MAC 1258 B
400
20 22 24 26 28 30 32
Weight % oxygen
157
Maximum
temperature for
Atmosphere constant service use Steels to use Observations
(°C)
650 5-6% Cr Steel Delicate welding
850 17% Cr Ferrite Delicate welding, low creep resistance
900 18-8 Austenite and derivatures Avoid welding, low creep resistance
28% Cr Ferrite
25-12 Austenite
Oxidising 1100 25-20 Austenite
35% Ni Austenite
and 20% Cr
60% Ni and 15-20% Cr Alloys
1150
80% Ni and 15-20% Cr Alloys
900 25-12 Austenite

25-20 Austenite
Carburization 1000 35% Ni and 20% Cr Austenite
Reducing 60% and 15-20% Cr Alloy

1100
80% and 15-20% Cr Alloy
700 18-8 Austenite
750 17% Cr Ferrite To avoid welding
Sulphidation 25-12 Austenite

900
reducing 25-20 Austenite
1000 28% Cr Ferrite To avoid welding, low creep resistance

02947_A_A
OXYDATION OF STEEL VERSUS TEMPERATURE
1 Cr-0,5 Mo
mm/year
2 Cr-0,5 Mo
2,00
steel
mg/cm2
350
mm/year
158
300 1,5
Carbone
1 Mo
1,0
12 C
5 Cr-
Cr
200 1,00
o

2,
1,5
,5M
r-Al
o;
r-0
5 Cr-0,5 Mo
5M
,5M
3C
12 C
-0,
0
r
r-
0,5
5C
100 0,5
5M
2C
r
1 Mo
-r 0,
o;
1 7C ,25 Si
C
M 1 i
5 18-8 ,5 Mo-
9 Cr - o
el 0,5 3 Cr-0 Mo-1,25 S
te 18-8 Nb 5
D MAC 1259 C
ne s 5 Cr-0,5 Mo-1,25 Si 3 Cr-0,

Carbo 18-8 Mo 9 Cr-1 Mo
0 18-8 Ti
500 600 700 800 900 °C 530 600 650 700 °C 550 600 650 700 °C
Comparaison of corrosion rates for ≠ steels Oxydation rate versus T° Oxydation at high
at T° of 595 at 925°C for 1000 h temperature effect of silicium
From document ELF
159
Carburization can also occur by diffusion of the carbon through the steel and from the circulating
product.
There is a risk of hardening (when cooling during a stoppage) with a sharp drop in ductility.
• Reducing atmospheres
The alternation between carburizing and oxidizing atmospheres is dangerous. The protective oxide
film will be destroyed with gradual chromium depletion of the metal.
XVII - CORROSION BY LIQUID AMMONIUM

The presence of oxygen (in the form of impurities) in a tank containing liquid ammonium favors stress
corrosion cracking. The ammonium fixes the oxygen during transfer. A content of 2.5 ppm (weight) in the
liquid phase is considered the upper safety threshold in the presence of 100 ppm water. Larger oxygen
contents can be accepted for greater water contents, but it is always best to keep the oxygen content as low
as possible.
If an item of equipment is empty over a long period, it is essential to maintain a nitrogen atmosphere
throughout the duration, or a small amount of ammonium.
Regarding vessels which have not been relaxed or only partially, the following must be respected:
- the oxygen content should be kept as low as possible

- whenever possible, keep a water content > 0.2% weight
- otherwise, refer to the following figure and perform regular analysis of the oxygen content
Liquid water
in ppm (weight)
10000
1000 A Low risk of stress corrosion cracking
100 High risk of stress corrosion cracking

D MAC 1260 B
10 Do not put the equipment on stream in conditions delimited

1 10 100 1000 by this zone. The oxygen must either be reduced or water
Liquid O2 in ppm (weight) added* for A or B services conditions.
* If water is added intentionally, it should be distilled

water or an equivalent quality condensate.
(Source: APAVE technical publication)

160
XIX - REINFORCED CONCRETE CORROSION

(Reference Document SIKA - Martine MASSON)
1- CORROSION OF STEEL STRUCTURES IN A HUMID ENVIRONMENT
The corrosion of steel embedded in reinforced concrete is one of the major causes of degradation.
The formation of expansive rust (rust expansion: 800%) causes cracks to appear and then splitting and
scaling, with the metal structure being laid bare.
Corrosion of the embedded irons is an electrochemical phenomenon, the principle of which is the
formation of microcells on the surface of the metal in an aqueous medium containing dissolved salts
(chloride, carbonate, nitrates, etc.). Water, with a high salt content (marine environment, for example),
can reach the steel structures via the pore network of the concrete.
The metal which, in a natural state, is oxidized, tends to recover this stable form by emitting positive
ions. The presence of microscopic heterogeneities (impurities, oxides, etc.) favors the formation of a
microcell or electrolytic couple.
2- NATURAL PROTECTION OF STEELS BY CEMENT

The pH of water contained in the pores has an decisive impact on the corrosive potential of a metal.
In PORTLAND cements, which are likely to be used in reinforced concrete, the alkalis (soda
potassium) dissolve in the water at the time of hydration. Similarly, as the silicates hydrate, they
produce free lime and the pH becomes clearly basic (11 to 12).
The pH then remains at this value due to the steady generation of lime by the silicates. The lime
causes the formation of a ferrite Fe2O3CaO which forms deposits on the surface of the metal: the steel
structure is passivated by this protective film. As long as the metal is surrounded by this basic solution
there is no corrosion risk.
Also, in the case of aluminous cements, hydration of the monocalcic aluminates liberates alumina,
which forms deposits on the steel structure and protects it.
3- WEAKENING OF THE NATURAL PROTECTION OF THE EMBEDDED METAL

STRUCTURE: ALTERATION OF THE CONCRETE
Several agents can attack this natural protection and favor corrosion of the steel. They are:
- carbon dioxide
- oxygen
- sea water
- aggressive agents
- pure water
- frost

161
a - Action of carbon dioxide: carbonation
Air contains 0.03% carbon dioxide; this content can vary with temperature, pressure, the environment
(towns, industrial areas) and reach 0.10%.
The lime liberated by hydration of the silicates can carbonize according to:
Ca (OH)2 + CO2 CaCO3 + H2O
This reaction, catalyzed by the atmospheric humidity, progresses from the outside inwards and causes
gradual neutralization of the cement alkalinity: the basic medium (pH = 11 to 12) loses its alkalinity and
the pH drops to below 9. Natural protection of the embedded metal is no longer ensured.
Moreover, water containing carbon dioxide generates weak acid (H2CO3: carbonic acid) and attacks
the lime and lime carbonate according to the following reactions:
Ca (OH)2 + CO2 Ca (HCO3)2
Ca CO3 + CO2 + H2O Ca (HCO3)2
The lime bicarbonate thus formed is soluble in water and the concrete is destroyed by gradual watering
down of the binder (photos 2 and 4) and sometimes stalactites form.
Rate of carbonation: the layer of carbonate hampers the diffusion of carbon dioxide. However, for
concrete in an ordinary atmosphere at 65% R.H., carbonation progresses as follows:
1 year .......... 5 mm Dept at which natural

4 years .......... 10 mm } protection is eliminated
25 years .......... 25 mm
This is why the metal structures are covered with 2 cm concrete.
• Factors affecting carbonation:
- type of cement: the more lime contained in the cement, the slower carbonation
- dosage of water and cement: when the cement content is increased, the carbonation rate
will decrease fast as the quantity of lime for carbonation will be greater (figure 3).
If a large quantity of water is used for making up the cement, it can leave voids or porosity which favor
penetration and diffusion of carbon dioxide:
- implementation: strong binding increases the density of the concrete and makes it more
waterproof; this will slow down carbonation.
- environment: in a water saturated atmosphere, the fixing of carbon dioxide is weak; water
only dissolves its own volume of gas.
In a dry atmosphere, the carbon dioxide hardly reacts at all and the water acts as a catalyst.
In practice, the carbonation rate is maximum for a mean relative humidity (approximately 50%)
(figure 2).

162
b - Action of the oxygen
When the carbon dioxide has removed the passivating lime film, the oxygen can reach the metal
structures: ferrous hydroxide, and then ferric hydroxide form. This chemical attack, unlike electrolytic
corrosion, is found at all points of the metal structure and does not require an electrolytic environment.
c - Action of sea water or gritting salt
The mechanism of salt water action on cement is highly complex, and here we will only give an
overview.
Salt water contains mainly:
- sodium chloride NaCl

- magnesium chloride MgCl2
- magnesium sulfate MgSO4
- calcium sulfate CaSO4
- potassium carbonate acid KHCO3
Magnesium sulfate is the most harmful of these salts. It reacts with the hydrated lime to produce
gypsum CaSO4, 2 H2O and brucite Mg (O)2. Also, its action on the aluminates in the cement result in
the formation of ettringite (Ca3Al2O6, 3 CaSO4, 31 H2O). Expansion due to crystallization of the
ettringite (approximately 300%) causes cracking and the sea water penetrates through to the metal.
The ettringite or CANDLOT salt can also form when the water has a high concentration of selenite.
Corrosion in the splash zone:
In this zone, the concrete undergoes desiccation-rehydration cycles which have various effects:
- the aggressive environment allows anhydrous salts to crystallize. These are rehydrated
when coming in contact with the water and cause swelling, which can eventually cause the
concrete to burst (e.g., reaction):
Na2SO4 + 10 H2O Na2SO4 , 10 H2O
(corresponds to a volume increase of 320%!).
- in addition, there is an incremented effect of oxygen and carbon dioxide in these zones,
thawing phenomena, effect of light and temperature.
d - Action of aggressive agents
In an industrial atmosphere, the highly aggressive environment contains acids, alkalis or oxidizers
which can seep into the concrete and attack the metal directly.
Rainwater can entrain certain aggressive agents such as sulfur dioxide, SO2, coming from the burning
of petroleum and coal wastes or nitrogen oxides from engine exhausts. The rain is acidized, and a pH
in the range of 2.5 in certain large industrial centers (North of France, Ruhr, England, etc.) can be
observed. This aggressive water can dissolve the salts in the cements and depassivate the metal
structure.
In some zones (marshes, forests), the humid acids can, by capillarity, rise in the concrete and
considerably reduce the pH. In this type of environment, corrosion can also occur through the
development of bacteria.

163
e - Action of pure water
The purity of rainwater or condensation water makes it a remarkable solvent which entrains the soluble
salts and waters down the binder.
Gradual deterioration of concrete exposed to rain
• Rainwater penetrating the concrete by capillarity reduces compactness.
• Carbonation, accelerated by the fact that the structure is in a zone polluted by CO/CO2 (centre of
Paris), will have penetrated in depth and reached the irons. Protection by the lime in the cement is
thus eliminated.
• Steel structures will oxidize and exert a pressure strain on the layer of concrete, the resistance of
which (cohesion) will be weakened and will burst.
f - Frost effect
When the water in the capillary network of the concrete freezes, the pressure of the ice causes micro-
cracking (expansion rate of ice: 9%). Successive freezing-defreezing cycles will enlarge the cracks
gradually until the concrete bursts.

164
- Figure 1 -
Sodium ion Chloride ion
Na + Na Cl Cl -
Sodium chloride
Hydrated
ferrous ion
water water
water
+ Na OH Fe Cl3 Fe Cl2 Fe 2+
water
Hydroxide ion Na
soda Ferrous Ferrous water wate
r
O 2 oxygène chloride chloride
O2 + H2O + 2 ( e - ) Ferrous ion
Fe 2 O3 Fe 2+
Fe (OH) 3 Redish-yellow rust
- Cathode (precipitate) +
Electrical charges
Impurities e- e- e-
(electrons)
EMBEDDED METAL STRUCTURE

(external cell circuit)
1,0
3
g/m
0k
0,8 20 3
DEGREE OF CARBONATION
4 g/ m
30 0k
3
0,6 3 kg/m
350 /m3
kg
400 /m3
2 g
0,4 500 k
1
0,2
Scale time
3 month 1 year 5 year
0 20 40 60 80 100% Influence on cement dosage on carbonation rate
RELATIVE HUMIDITY (CERILH document)
Influence on relative humidity on - Figure 3 -
- Figure 2 - carbonation (CERILH document)
+2
pH easily monitored using
I III Fe3 O4
phenol-phtaleine
+1
POTENTIEL (VOLT)
pH < 9 → concrete does not change Passivation

colors
Carbonation occurs +
0 Fe2 Alkaline
corrosion
pH > 9 → concrete turns pinkish Acid corrosion
+
Immunity II Fe2
D MAC 1261 B
Carbonation not yet initiated -1 IV Fe
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
- Figure 4 - pH
POURBAIX diagram for iron

165
PROGRESSIVE DEGRADATION OF CONCRETE
Atmosphéric
pollution
Rain Marine environment
Condensation and highways
CO2 SO2,NO2...
Mécanical Pure carbonate Aggressive Sea water or

action water water water defrosting
O2
(oxygen)
Pore Expansive
Network Cracks Opening of cracks
salts Bursting metal structure
(ettringite.…)
Laid bare
Solution Depassivation Oxydation Expansive

of salts of metal of metal rust
structures structures
Watering down
Efflorescence Widening
of cracks
Frost
1st step 2nd step 3rd step
Fine crack Widening of crack Bursting between cracks
D MAC 2124 B
Efflorescence Grumbling of corners Bursting along steels

Traces of rust Swelling of concrete Deep corrosion of steel
Gravity of damages

166
4- PREVENTION
All failures are due to compactness or density. The penetration of water into the pore network is the
responsible vector.
The water can rise through capillarity over a height of:
15 m in a 1 diameter tube
7.5 m in a 2 diameter tube
3.25 m in a 4 diameter tube.
For outside structures, dry climates will therefore favor long life for the concrete more than climates
which have frequent changes of rain and wind, causing an influx of water and rapid evaporation.
It is necessary to take preventive measures against corrosion by installing barriers between the outside
environment and the embedded metal. Care should be taken to choose concrete of the right quality
and to ensure direct protection of the steel.
a - Concrete quality
The concrete provides the main protection of the metal and must prevent the water from filtering
through to the metal. The two main factors are therefore high compactness and low cracking potential:
- high compactness: in order to reduce the porosity of the concrete, it is necessary to

reduce the quantity of water used in making up the cement to a minimum. Plastifiers should
be used, as these make it possible to reduce the water by 10 to 15%.
Integrated water repellents can provide good protection, but by a different means, as they
leave crystals in the pores which hamper the progress of the water.
- low cracking potential: the metal structure must be sufficiently covered and the steel
properly configured.
b - Protection of the concrete
Penetration of water into the concrete can be avoided either by taking protective measures (projecting
cornice, etc.) which prevent rainwater washing over the structure, and also by waterproofing the
surface with paints.
Structures can also be protected without changing the surface appearance, by using a silicone water
repellent. Water repellent mortar cladding provides a very effective protection against water infiltration.
c - Protection of the metal
Apart from natural protection of the steel by cement, there are many possible solutions.
A cement coating made up with a resin and applied by brush or dipping. Thanks to the sealing
properties and alkalinity of the film, this method provides long lasting protection.

167
Other processes used more rarely:
• Metallization: it is possible to spray a layer of metal onto the iron:
- if the metal is more noble than iron, the protection will only be provided if the layer is smooth
and thick
- if the metal is less noble, this protection is ´†sacrificial†ª. This is the case of galvanization in
which zinc acts as anode and iron acts as cathode. Protection is thus provided by the
activity of the iron-zinc cell at the expense of the zinc. The activity of the protective cell
ceases with the removal of the last traces of zinc.
There are other methods for protecting prestressed cables: protection using oil, plastic coating, paints,
etc.
d - Concrete of the future
Fluidizers are integrated (liquefaction of concrete without water, which is added at the site) and silica
smoke. (The diameter of the particles is 0.1 micron, whereas a grain of cement represents 10 .) The
density obtained is much greater. Porosity is reduced, impermeability increases and so does
resistance to freezing and degradation in general; bubbles are fewer and smaller. The cladding of the
metal structure is improved.
It is easy to achieve a resistance to compression of 800 bars which corresponds approximately to the
resistance of the granular material.
The best formula corresponds to 2.5% fluidizer and 6% silica smoke.
Carbonation does not exceed one millimeter.
Any crack which may appear would have catastrophic effects, as here, pH is low.
Moreover, for a compressive strength of 1,000 bars, the concrete will be fragilized due to a sort of
vitrification (which is why it is limited to 800 bars).

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Refining-Petrochemicals-Chemicals-Engineering

I - DEFINITIONS AND MECHANISMS ..............................................................................................1

II - THE MANY FORMS OF CORROSION .......................................................................................35

MX DCA - 02947_A_A - Rev. 2 15/06/2009

III - CORROSION PREVENTION .......................................................................................................53

V - CORROSION BY SULFUR DERIVATIVES IN THE ANHYDROUS PHASE.............................88

VI - CORROSION BY COLD HYDROGEN SULFIDE IN A HUMID ATMOSPHERE.......................99

VII - CORROSION BY COMBUSTION GASES IN FURNACES AND BOILERS............................100

VIII - NAPHTHENIC ACIDS CORROSION.........................................................................................114

IX - CORROSION IN DISTILLATION UNITS ...................................................................................118

X - CORROSION BY POLYTHIONIC ACIDS..................................................................................126

XI - CAUSTIC SODA CORROSION .................................................................................................128

02947_A_A © 2009 - IFP Training

XII - BIOCHEMICAL CORROSION....................................................................................................130

XIII - CORROSION IN AN AQUEOUS ENVIRONMENT ...................................................................135

XIV - ATMOSPHERIC CORROSION..................................................................................................145

XV - SEA WATER CORROSION .......................................................................................................146

XVI - DRY OXIDATION AT HIGH TEMPERATURE...........................................................................152

XVII - CORROSION BY LIQUID AMMONIUM.....................................................................................159

XIX - REINFORCED CONCRETE CORROSION...............................................................................160

02947_A_A © 2009 - IFP Training

I- DEFINITIONS AND MECHANISMS

It is the cause of most failures and malfunctions of pressure vessels.

- transformation of steel into rust

2- ECONOMIC ASPECT OF CORROSION

- cost of the parts to be replaced, the repairs to be made

02947_A_A © 2009 - IFP Training

Food processing Chemical

Annual cost of corrosion in the production and manufacturing category

3- REVIEW OF CHEMISTRY AND ELECTROCHEMISTRY

Schematic representation of the Bohr model

02947_A_A © 2009 - IFP Training

• Ions, anions, and cations

Water is partially dissociated into ions according to the following equilibrium:

[H+] = [OH–] = 10–7 moles per liter

Definition of pH: pH = Log 1/[H+] = - log [H+ ]

For neutral water, pH = - log [10-7] = 7

• Crystals and ionic solutions

Diameter of Na+ = 0.196 nm

02947_A_A © 2009 - IFP Training

If a sodium chloride crystal is put in water, it dissolves.

• Solid state metal structure

02947_A_A © 2009 - IFP Training

A system is said to be an oxidant when it may capture electrons.

A system is said to be a reducer when it may release electrons.

• Behavior of a metal plate in pure water (deaerated or without oxygen)

The “metal plate + water” system constitutes an electrode.

Layer of dipolar water molecules

02947_A_A © 2009 - IFP Training

Cu2+ Cu2+ Cu2+ Cu2+ Cu2+

Cu2+ Cu2+ Cu2+ Cu2+ Cu2+

Schematic representation of a reversible copper electrode plunged in a copper

R: perfect gas constant

02947_A_A © 2009 - IFP Training

Standard equilibrium potential E0

4 OH– O2 + 2 H2O + 4 e + 0.40

• Electrode potential measurement

02947_A_A © 2009 - IFP Training

Electrode Electrolyte Reactions E/V

Calomel KCl, saturated Hg2Cl2 + 2e– = 2 Hg + 2 Cl– 0.241

Mercury sulfate K2SO4 saturated 2– 0.658

Silver chloride KCl, saturated AgCl + e– = Ag + Cl– 0.195

Hydrogen H2SO4 2 H+ + 2e– = H2 0.000

Nernst law applies and specifies the potential’s value: