Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
By:
Dr. Irannejad
2015-10-12
1.
E.E.
Stansbury
and
R.A.
Buchanan,
Fundamentals
of
3.
L.L.
Shreir,
R.A.
Jarman,
G.T.
Burstein,
Corrosion
5.
6.
2015-10-12
7.
8.
9.
: . . : -12
.
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Introduction
What is Corrosion?
Importance of Corrosion
Examples of Corrosion
Forms of corrosion
Classification of corrosion
Electrochemical potential
Overview of Electrochemical Corrosion
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Corrosion:
Deterioration of materials by interaction with their environment.
construction
of
machines,
process
equipment,
and
other
manufactured products.
These materials include metals, polymers, and ceramics.
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Naturally occurring
copper single crystals.
Naturally occurring
copper sheet
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Aloha Incident
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One-fifth of the iron and steel produced annually in the world is used to
replace rusted metal.
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Before
After
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Railway bridge
Brass sculpture
White marble
Waterline corrosion
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Corrosion at sea
Corrosion of plastics
Corrosion of Aluminium
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Corrosion of Concrete
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1) Based on materials:
Corrosion of metals;
2) Based on Media:
Natural corrosion;
Industrial corrosion (e.g. solution containing acid, base, H2S, etc).
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3) Based on uniformity:
General corrosion;
Local corrosion.
4) Based on mechanism:
Electrochemical corrosion;
Biochemical corrosion.
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1.
2.
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1. Corrosion by O2
or Oxidation corrosion
Dry Corrosion
2. Corrosion by H2
and other gases
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can
contain
ions
and
the
Zn Zn2+ + 2e-
zinc corrosion
Fe Fe2+ + 2e-
iron corrosion
Al Al3+ + 3e-
aluminium corrosion
Fe2+
Fe3+
e-
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2. Cathode
3. Electrolyte
4. Electrical Path
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Corrosion Mechanisms
Particularly under the broad definition of corrosion as the deterioration of
materials by reaction with the environment, the number of mechanisms whereby
deterioration occurs is large.
In general, a mechanism of corrosion is the actual atomic, molecular, or ionic
transport process that takes place at the interface of a material.
These processes usually involve more than one definable step, and the major
interest is directed toward the slowest step that essentially controls the rate of
the overall reaction.
When electrochemical corrosion is occurring, mechanisms may be inferred from
measurements of electrical potential and current.
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In more complicated cases, the metal ions move into solution by forming
complex ions, or they combine with other species in the solution and
precipitate compounds such as hydroxides, oxides, or sulfides.
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The
following
sections
review
several
general
types
of
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Thus, the metal passes from the metallic state to ions of valence m
in solution with the evolution of hydrogen.
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In limiting cases, these processes occur within a few atom diameters on the
surface with the sites constantly changing with time, thus producing
uniform corrosion.
Otherwise, the corrosion is nonuniform.
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When dissolved oxygen is present in the solution, usually from contact with air, the following
reactions apply in addition to those just considered.
Uniform corrosion supported by dissolved oxygen and pH is represented schematically in Fig. 1.2.
Since electrons are now consumed by two reactions, the rate of corrosion of the metal increases.
In the case of iron, dissolved oxygen is more important in supporting corrosion than the presence of
hydrogen ions when the pH is greater than approximately 4.
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The adherence and porosity of these layers change with time and can be
influenced by other chemical species in the environment, such as chloride
and sulfate ions.
In any case, the formation of the corrosion product layer influences the
corrosion rate by introducing a barrier through which ions and oxygen
must diffuse to sustain the corrosion process.
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E = 0 V
(by definition; arbitrarily selected)
2H+ + 2e- H2
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e-
e-
Zn
anode
Cu cathode
Salt
bridge
Zn2+
Cu2+
Zn Zn2+ + 2e-
Cu2+ + 2e- Cu
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Cu
Zn
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more anodic
more cathodic
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metal
Au
Cu
Pb
Sn
Ni
Co
Cd
Fe
Cr
Zn
Al
Mg
Na
K
o
Vmetal
+1.420 V
+0.340
- 0.126
- 0.136
- 0.250
- 0.277
- 0.403
- 0.440
- 0.744
- 0.763
- 1.662
- 2.363
- 2.714
- 2.924
Cd
25C
Ni
1.0 M
1.0 M
Cd 2 + solution Ni 2+ solution
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more anodic
(active)
more cathodic
(inert)
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Base Metals
emf between -0.4V and 0.0 V
Corrodes in neutral aqueous solutions with oxygen
Corrodes in acids to produce hydrogen, even without oxygen
Includes Cd, Co, Ni, Sn, and Pb
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Semi-Noble Metals
emf between 0.0 V and +0.7V
Corrodes in aqueous solutions only with the presence of oxygen
Includes Cu, Hg, Ag
Noble Metals
emf between > +0.7V
Includes Pd, Pt, Au
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Galvanic corrosion
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Polarization
may
occur
either
at
the
cathode
(cathodic
Activation polarization
2.
Concentration polarization
3.
Resistance polarization
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Concentration polarization:
Concentration polarization of an electrode is a result of formation of a Diffusion
layer adjacent to the electrode surface where there is a gradient of the ion
concentration.
Diffusion of the ions through the layers controls the electrochemical reaction
(corrosion, Electroplating).
Resistance polarization:
Resistance polarization refers to the potential drop due to either the high
resistivity of the electrolyte surrounding the electrode or an insulation effect of
the film on the electrode surface formed by the reaction products.
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Types of Tests
ANODIC POLARIZATION CURVE
this curve is usually scanned from 20mV below the Eoc upwards
by scanning at a slow rate (.2mV/s) this curve can be used to identify
several corrosion mechanisms shown below
ip -
Epp -
icrit -
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pitting
cracking
zones
passive
active
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Stress corrosion
Uniform Attack
Oxidation & reduction
occur uniformly over
surface.
Erosion-corrosion
Break down of passivating
layer by erosion (pipe
elbows).
Selective Leaching
Preferred corrosion of
one element/constituent
(e.g., Zn from brass (Cu-Zn)).
Intergranular
Corrosion along
grain boundaries,
often where special
phases exist.
Pitting
Downward propagation
of small pits & holes.
Galvanic
Dissimilar metals are
physically joined. The
more anodic one
Corrodes.
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Underground corrosion
Electronic components
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Galvanic corrosion
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O2
Fe
Cl
Cl OH
Fe2+
Fe2+
Cl
Fe2+
Cl
Fe2+
O2 + 2H2O + 4e 4OH
Impurity
Fe = Fe2+ + 2e
Pitting Corrosion
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Pitting Corrosion
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Crevice Corrosion
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Selective Leaching
Stress Corrosion
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Intergranular Corrosion
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