Beruflich Dokumente
Kultur Dokumente
The corrosion severity in various regions of America can vary greatly depending
on a multitude of factors. While accelerated laboratory testing can be
satisfactory for evaluating the corrosion resistance of new materials and
coatings, the automobile proving grounds are definitively the primary means
for testing completed systems. Proving grounds are, in effect, large
laboratories. But the proving ground test contents and procedures can differ
sharply between manufacturers. Because each test is expressly different, each
brings different results, and in this type of test, proper interpretation of the
test results is the key to successful testing.
For many years, bare steel coupons were attached to different vehicles in the
northeastern U.S. and Canada. Periodically removed and measured for metal
loss, the data from these coupons was used to target the corrosion test
objectives to metal loss and to determine the most severe corrosion localities
for captive fleet testing and future survey evaluations. The following map is a
composite picture of the corrosivity differences observed in that study.
This map shows macroscopic differences between areas, with coastal regions
(especially in humid tropical conditions) and regions under the influence of
corrosive de-icing salts being the most severe. The high corrosion rates in the
Gulf Coast and Florida can be attributed to the corrosive marine environment.
In the North Eastern regions, de-icing salts applied to road surfaces in winter
are primarily responsible for the high corrosion rates.
Direct exposure testing rack
Atmospheric Corrosion Monitoring:
Atmospheric corrosion accounts for the highest overall cost and metal loss
of all the fundamental corrosive environments. A defining feature of
atmospheric corrosion is the thin aqueous layer between the surface of the
corroding material and the atmosphere. Three phases (solid [corroding
substrate], liquid [thin aqueous layer] and gaseous [atmosphere]) and the
interfaces between these phases are therefore important and can be used in
corrosion monitoring principles.
Smart Coatings:
The use of "smart materials" for corrosion sensing purposes relies on a
material undergoing a transformation through its interaction with the
corrosive environment. It is such transformations that can potentially be
used for indicating and detecting corrosion damage. Ideally, in principle, the
sensing function could be integrated with additional actuation and control
functions, designed to control corrosion damage.
• Fiber optics
ASTM B117: Standard Practice for Operating Salt Spray (Fog) Apparatus
ASTM B368: Standard Test Method for Copper-Accelerated Acetic Acid-Salt Spray
(Fog) Testing (CASS Test)
ISO 7253: Paints and varnishes - Determination of resistance to neutral salt spray (fog)
ASTM D5894: Standard Practice for Cyclic Salt Fog/UV Exposure of Painted Metal,
(Alternating Exposures in a Fog/Dry
Cabinet and a UV/Condensation Cabinet)
ASTM G85: Standard Practice for Modified Salt Spray (Fog) Testing - Annex A5, dilute
electrolyte cyclic fog dry test
The stability of materials at high temperature has been traditionally introduced through
plots of the standard free energy of reaction (∆ G0) as a function of temperature,
commonly called Ellingham diagrams. Such diagrams can help to visualize the relative
stability of metals and their oxidized products. The values of ∆ G0 on an Ellingham
diagram are expressed as kJ per mole O2 to normalize the scale and be able to compare
the stability of these oxides directly, i.e. the lower the position of the line on the diagram
the more stable is the oxide.
For a given reaction (M + O2 = MO2) and assuming that the activities of M and
MO2 are taken as unity, the following equations can be used to express the
oxygen partial pressure at which the metal and oxide coexist, i.e. the
dissociation pressure of the oxide:
The table visible here lists the coexistence equations, temperature ranges and
standard energy changes that can be used to construct such diagrams.
Ellingham diagrams may, of course, be constructed for any class of compounds.
Vapor species that form in any given high temperature corrosion situation often
have a strong influence on the rate of attack, the rate generally being
accelerated when volatile corrosion products form. Gulbransen and Jansson
have shown that metal and volatile oxide species are important in the kinetics
of high temperature oxidation of carbon, silicon, molybdenum, and chromium.
Six types of oxidation phenomena were identified:
It is possible to use plots of the free energy of formation of metal oxides vs.
temperature to predict the temperatures at which a metal is stable and the
temperatures at which it will spontaneously oxidize. For temperatures at which
the free energy of formation of the oxide is positive, the reverse reaction is
favored and the oxide will spontaneously decompose to the metal.
From evaluation of the thermodynamic data presented in this figure, it can be seen that at
1100oC, Al will oxidize in an environment that has an oxygen partial pressure of 10-32 atm
or greater, while chromium will oxidize in an oxygen partial pressure of 10-19 atm or
higher. In general, a vacuum environment will be oxidizing to these elements unless a
reducing species such as hydrogen is present. If inadequate oxygen is present, a non-
protective oxide film may be formed which could promote alloy depletion and loss of
strength.
Thermodynamic data for the oxidation of metals
M and D are the molecular weight and density of the metal oxide whose
composition is (Metal)a(oxygen)b; m, and d are the atomic weight and density of
the metal.
Pilling and Bedworth realized that, when R is less than 1, a metal oxide tends
to be porous and non-protective because it cannot cover the whole metal
surface. Later researchers found that, for excessively large R, large
compressive stresses are likely to exist in metal oxide, leading to buckling and
spalling. In addition to R, factors such as the relative coefficients of thermal
expansion and the adherence between metal oxide and metal should also be
favorable in order to produce a protective oxide.
Using the P-B ratio, Bruce Chalmers, Gordon McKay professor at Harvard
University (Cambridge, MA), separated "protective" metal oxides from "non-
protective" metal oxides. The table lists "protective" and "non-protective"
metal oxides and their P-B ratios.
The list can be readily applied to the protective metal oxides used in
integrated circuits. The intrinsic protective metal oxides, including the oxides
of Be, Cu, Al, Cr, Mn, Fe, Co, Ni, Pd, Pb, and Ce, may be able to replace silicon
oxide. On the other hand, a few popular metal oxides, e.g. Ti oxide and Ta
oxide, are non-protective, suggesting a possible reason why these oxides have
not been successfully used in commercial products after years of research.
Besides oxides of elemental metal, the P-B ratio can be applied to oxides of
metal alloy, metal nitrides and other metal ceramic systems.
Three basic kinetic laws have been used to characterize the oxidation rates of
pure metals. It is important to bear in mind that these laws are based on
relatively simple oxidation models. Practical oxidation problems usually involve
alloys and considerably more complicated oxidation mechanisms and scale
properties than considered in these simple analyses.
The parabolic rate law assumes that the diffusion of metal cations or oxygen
anions is the rate controlling step and is derived from Fick's first law of
diffusion. The concentrations of diffusing species at the oxide-metal and oxide-
gas interfaces are assumed to be constant. The diffusivity of the oxide layer is
also assumed to be invariant. This assumption implies that the oxide layer has
to be uniform, continuous and of the single phase type. Strictly speaking, even
for pure metals, this assumption is rarely valid. The rate constant, kp, changes
with temperature according to an Arrhenius type relationship:
where:
x is the oxide film thickness (or the mass gain due to oxidation, which is
proportional to the oxide film thickness)
t is time
kp is the rate constant, directly proportional to the diffusivity of the ionic
species that is rate controlling
x0 is a constant
The logarithmic rate law is an empirical relationship with no fundamental
underlying mechanism. This law is mainly applicable to thin oxide layers
formed at relatively low temperatures, and therefore rarely applicable to high
temperature engineering problems:
where:
The linear rate law is also an empirical relationship that is applicable to the
formation and build-up of a non-protective oxide layer.
where:
It is usually to be expected that the oxidation rate will decrease with time
(parabolic behavior), due to an increasing oxide thickness acting as a stronger
diffusion barrier with time. In the linear rate law, this effect is not applicable,
due to the formation of a highly porous, poorly adherent or cracked non-
protective oxide layers. Clearly, the linear rate law is highly undesirable.
The oxidation rate laws described above are simple models derived on the
behavior of pure metals. In contrast, practical high temperature corrosion
problems are much more complex and involve the use of alloys. For practical
problems, both the corrosive environment and the high temperature corrosion
mechanism(s) have to be understood. In the introduction, it was pointed out
that several high temperature corrosion mechanisms exist. While considerable
data is available from the literature for high temperature corrosion in air and
low sulfur flue gases and for some other common refinery and petrochemical
environments, small variations in the composition of a process stream or in
operating conditions can cause markedly different corrosion rates. Therefore,
the most reliable basis for material selection is operating experience from
similar plants and environments or from pilot plant evaluation.
There are several ways of measuring the extent of high temperature corrosion
attack. Measurement of weight change per unit area in a given time has been a
popular procedure. However the weight change/area information is not
directly related to the thickness (penetration) of corroded metal, which is
often needed in assessing the strength of equipment components.
D = original diameter
D1 = diameter of apparently useful metal
D2 = diameter of sound metal
The parameters shown in this figure relate to cylindrical specimens and provide
information about the load bearing section (metal loss) and on the extent of
grain boundary attack that can also affect structural integrity.
Hot Corrosion
because only the Na2O is attacking the protective scale from SiO2 by
Hot corrosion is an attack via a salt melt. A representative member of the hot
corrosion agents is Na2SO4. Its generation is explained in combustion
environments by
Since the action in the liquid state is regarded most effective, the first condition
for the window of hot corrosion is given by melting and dewpoint of Na2SO4. The
melting point of 884°C does not vary much, the dewpoint depends on pressure, S-
content of the fuel and NaCl-concentration in the atmosphere. For conditions with
NaCl > 1ppm and combustion pressures of 100 bar it is calculated to run to 1100-
1200°C from eq. {1}.
because only the Na2O is attacking the protective scale from SiO2 by
This is the reason why other compounds releasing alkali oxide on decomposition,
e.g. Na2CO3, have similar hot corrosion effects. It should be noted that complex
salts, in particular those containing vanadium, can have an even stronger hot
corrosion effect, as is well known from metals and oxides
From eq. {2} it can be calculated that only for conditions with a low P(SO3) we
will have a dissociation sufficient to drive reaction {3} to the right side.
Consequently the window of hot corrosion has a third axis, the P(SO3) of the
combustion, and it has been computed that the window should only open for low-
S fuels (<0.5 %, a condition met by many modern fuels) and at comparatively
high temperatures (» > 1000°C).
In reality the attack starts already at the melting point of Na2SO4. This is attributed
to internal controlling factors. Many SiC-based materials contain free carbon,
which promotes the dissociation of Na2SO4 and makes the silicate melt more
basic. The dramatic attack of Na2SO4 on SiC with free carbon has experimentally
been confirmed.