Atmospheric corrosion

Atmospheric Corrosion Mechanism

Atmospheric corrosion is an electrochemical process, requiring the presence of
an electrolyte. Thin film "invisible" electrolytes tend to form on metallic
surfaces under atmospheric corrosion conditions, when a certain critical
humidity level is reached. For Fe, this level is around 60%, in unpolluted
atmospheres. The critical humidity level is not a constant - it depends on the
corroding material, the hygroscopic nature of corrosion products and surface
deposits and the presence of atmospheric pollutants.

In the presence of thin film electrolytes, atmospheric corrosion proceeds by

balancing anodic and cathodic reactions. The anodic oxidation reaction involves
the dissolution of the metal in the electrolyte, while the cathodic reaction is
often assumed to be the oxygen reduction reaction. Oxygen from the
atmosphere is readily supplied to the electrolyte, under thin film corrosion
conditions.

Corrosivity Map of North America

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.
Corrosion monitoring in outdoor and indoor atmospheres poses specific
challenges related to characterizing corrosion damage (generally taking
place at a low rate) in a short (practical) time frame. Three basic approaches
to corrosion monitoring are available:
1. Direct measurement/monitoring of corrosion damage.
(Examples include exposing actual components or coated coupons to
corrosive atmospheres and evaluating these for corrosion damage
periodically)
2. Indirect measurement/monitoring of corrosion damage with
corrosion sensors.
(Examples include thin film electrochemical sensors embedded under
paint coatings and smart coatings)

3. Classification of atmospheric corrosivity by categories and

correlating such classifications to actual in-service performance and
corrosion rates.
The main drawbacks of the direct measurement
approach are the lengthy exposure time period usually
required and that only a "snapshot" of cumulative
damage is obtained when detailed analysis of corrosion
damage is performed periodically.
The approach of atmospheric corrosivity classification is
generally one of a simple, low-cost measurement in a
short time frame. Ultimately, such simplistic
measurements require correlation to actual long term
service performance and therefore need to be linked to
the other measurement methodologies.
Atmospheric corrosion monitoring is generally employed to quantify this
type of damage and corrosion risk, rather than merely resorting to broadly
descriptive atmospheric classifications such as "industrial", "rural", etc.

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.

Some smart coating principles relevant to corrosion sensing, or

potentially relevant, include the following:

Paint systems with color-changing compounds,

responding to pH changes that result from corrosion
processes.
Changes of coating compounds from non-fluorescent to
fluorescent states, upon oxidation or complexing with
metal cations.

Release of color dyes, on coating damage, from

incorporated dye-filled micro-capsules.

Piezo-electric thin film applications.

Fiber optics

Atmospheric Corrosion Tests:

Traditional Salt Fog Tests:
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)

Cyclic Exposure Tests:

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
GM 9540P: Accelerated Corrosion Test
SAE J2334: Cosmetic Corrosion Lab Test

Introduction to High Temperature Corrosion

High temperature corrosion is a form of corrosion that does not require the
presence of a liquid electrolyte. Sometimes, this type of damage is called "dry
corrosion" or "scaling". The term oxidation is ambivalent since it can either
refer to the formation of oxides or to the mechanism of oxidation of a metal,
i.e. its change to a higher valence than the metallic state. Strictly speaking,
high temperature oxidation is only one type of high temperature corrosion. In
fact, oxidation is the most important high temperature corrosion reaction.
In most corrosive high temperature environments, oxidation often participates
in the high temperature corrosion reactions, regardless of the predominant
mode of corrosion. Alloys often rely upon the oxidation reaction to develop a
protective scale to resist corrosion attack such as sulfidation, carburization and
other forms of high temperature attack. In general, the names of the corrosion
mechanisms are determined by the most abundant dominant corrosion
products. For example:
Oxidation implies oxides,
Sulfidation implies sulfides,
Sulfidation/oxidation implies sulfides plus oxides, and
Carburization implies carbides.
High temperature corrosion is a widespread problem in various industries such
as:
power generation (nuclear and fossil fuel)
aerospace and gas turbine
heat treating
mineral and metallurgical processing
chemical processing
refining and petrochemical
automotive
pulp and paper

waste incineration

Thermodynamic Principles
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:

or its logarithm form

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:

At low temperature, diffusion of oxygen and metal species through a compact

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

Ellingham Diagram (Richardson Diagram)

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 nonprotective oxide film may be formed which could promote alloy depletion and loss of
strength.

Thermodynamic data for the oxidation of metals

Range

Coexistence Equation

Standard Free Energy Change

(K)

(Oxidation Reaction)

(J)

900-1154

Pd + 0.5 O2 = PdO

-114,200 + 100 T (K)

884-1126

2 Mn304 + 0.5 O2 = 3 Mn2O3

-113,360 + 92.0 T

298-1300

3 CoO + 0.5 O2 = Co3O4

-183,200 + 148 T

892-1302

Cu2O + 0.5 O2 = 2 CuO

-130,930 + 94.5 T

1396-1723

1.5 UO2 + 0.5 O2 = 0.5 U3O8

-166,900 + 84 T

878-1393

U4O9 + 0.5 O2 = 4/3 U3O8(-2)

-164,400 + 82 T

967-1373

2 Fe3O4 + 0.5 O2 = 3 Fe2O3

-246,800 + 141.8 T

1489-1593

2 Cu + 0.5 O2 = Cu2O

-166,900 + 43.5T

1356-1489

2 Cu + 0.5 O2 = Cu2O

-190,300 + 89.5 T

924-1328

2 Cu + 0.5 O2 = Cu2O

-166,900 + 71.1 T

992-1393

3 MnO + 0.5 O2 = Mn3O4

-222,540 + 111 T

1160-1371

Pb + 0.5 O2 = PbO

-190,580 + 74.9 T

772-1160

Pb + 0.5 O2 = PbO

-215,000 + 96.0 T

911-1376

Ni + 0.5 O2 = NiO

-233,580 + 84.9 T

1173-1373

Co + 0.5 O2 = CoO

-235,900 + 71.5 T

973-1273

10 WO2.90 + O2 = 10 WO3

-279,400 + 112 T

973-1273

10 WO2.72 + O2 = 10 WO2.90

-284,000 + 101 T

973-1273

1.39 WO2+0.5 O2 = 1.30 W O2.72

-249,310 + 62.7 T

973-1273

0.5 W + 0.5 O2 = 0.5 WO2

-287,400 + 84.9 T

949-1273

3 FeO + 0.5 O2 = Fe3O4

-311,600 + 123 T

770-980

Sn + 0.5 O2 = SnO2

-293,230 + 108 T

903-1540

Fe + 0.5 O2 = FeO

-263,300 + 64.8 T

1025-1325

0.5 Mo + 0.5 O2 = 0.5 MoO2

-287,600 + 83.7 T

1050-1300

2 NbO2 + 0.5 O2 = Nb2O5

-313,520 + 78.2 T

693-1181

Zn + 0.5 O2 = ZnO

-355,890 + 107.5 T

1300-1600

0.66 Cr + 0.5 O2 = 0.33 Cr2O3

-371,870 + 83.7 T

1050-1300

NbO + 0.5 O2 = NbO2

-360,160 + 72.4 T

923-1273

Mn + 0.5 O2 = MnO

-388,770 + 76.3 T

1539-1823

Mn + 0.5 O2 = MnO

-409,500 + 89.5 T

1073-1273

0.4 Ta + 0.5 O2 = 0.2 Ta2O5

-402,400 + 82.4 T

1050-1300

Nb + 0.5 O2 = NbO

-420,000 + 89.5 T

298-1400

0.5 U + 0.5 O2 = 0.5 UO2

-539,600 + 83.7 T

1380-2500

Mg(v) + 0.5 O2 = MgO

-759,600 - 30.83 T log T + 317 T

923-1380

Mg(l) + 0.5 O2 = MgO

-608,200 - 1.00 T log T + 105 T

1124-1760

Ca + 0.5 O2 = CaO

-642,500 + 107 T

1760-2500

Ca(v) + 0.5 O2 = CaO

-795,200 + 195 T

Pilling-Bedworth Ratio
Physical metallurgy relies on a set of guidelines to identify protective oxide
coatings for corrosion protection. Such coatings should be pinhole-free, exactly
as the IC industry requires for high-k metal oxides. Accordingly, guidelines
developed for protective oxide coatings in physical metallurgy can be applied
to the protective metal oxides in integrated circuits.
In their 1923 paper "The oxidation of metals in high temperature" presented to
the Institute of Metals, N. B. Pilling and R. E. Bedworth first correlated the
porosity of a metal oxide with the specific density1. The Pilling-Bedworth ratio,
(P-B ratio) R, of a metal oxide is defined as the ratio of the volume of the
metal oxide, which is produced by the reaction of metal and oxygen, to the
consumed metal volume:

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 "nonprotective" metal oxides. The table lists "protective" and "non-protective"
metal oxides and their P-B ratios.
Protective oxides Non protective oxides
Be 1.59

K 0.45

Cu 1.68

Ag 1.59

Al 1.28

Cd 1.21

Cr 1.99

Ti 1.95

Mn 1.79

Mo 3.40

Fe 1.77

Hf 2.61

Co 1.99

Sb 2.35

Ni 1.52

W 3.40

Pd 1.60

Ta 2.33

Pb 1.40

U 3.05

Ce 1.16

V 3.18

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.
Protective metal oxides can be produced by two classes of methods: growth
and deposition. Growth methods include thermal oxidation, plasma oxidation,
anodization, and implantation. Deposition methods include direct sputtering,
reactive sputtering, and CVD. The IC industry does not have much experience
with production of protective metal oxides. Still, manufacturing experience
with sub-10 nm silicon oxide suggests that it is better to form the protective
metal oxide using a growth method, or to form at least a portion of the
protective metal oxide using a growth method and the remaining portion using
a depositing method. Improved oxide thickness uniformity is one added
advantage of such a composite layer.

High Temperature Corrosion Kinetics

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 oxidegas 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:
ke is the rate constant

c and b are constants

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:
kL is the rate constant
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 nonprotective oxide layers. Clearly, the linear rate law is highly undesirable.
Metals with linear oxidation kinetics at a certain temperature have a tendency
to undergo so-called catastrophic oxidation (also referred to as breakaway
corrosion) at higher temperatures. In this case, a rapid exothermic reaction
occurs on the surface, which increases the surface temperature and the
reaction rate even further. Metals that may undergo extremely rapid
catastrophic oxidation include molybdenum, tungsten, osmium, rhenium and
vanadium, associated with volatile oxide formation. In the case of magnesium,
ignition of the metal may even occur. The formation of low-melting point
oxidation products (eutectics) on the surface has also been associated with
catastrophic oxidation. The presence of vanadium and lead oxide
contamination in gases deserves special mention, as they pose a risk to
inducing extremely high oxidation rates.

Practical High Temperature Corrosion Problems

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.

High Temperature Intergranular Attack

Metallographic method of measuring hot corrosion attack

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
An accelerated corrosion of metal surfaces that results from the
combined effect of oxidation and reactions with sulfur compounds
and other contaminants, such us chlorides, to form a molten salt on

a metal surface that fluxes, destroys, or disrupts the normal

protective oxide.

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
2 NaCl + SO2 + 0.5 O2 + H2O = Na2SO4 + 2 HCl

However, the effective corrosion action is generally believed not to be by the

sulfate itself. It stems from the activity of Na2O arising from the
decomposition
Na2SO4 = Na2O + SO3
because only the Na2O is attacking the protective scale from SiO2 by
x SiO2 + Na2O = Na2O*(SiO2)x
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.

HOT CORROSION by Vanadium Pentoxide (V2O5)

Ash forming contaminants in fuel: Vanadium, sodium and lead
Vanadium and sodium are the most harmful elements, respectively
forming vanadium pentoxide (V2O5) and sodium sulfate (Na2SO4).
Vanadium appears in fuel in the form of oil-soluble porphyrins.
These organic vanadium compounds decompose in the gas stream
to give mainly V2O5. Vanadium pentoxide is most damaging since
due to its low melting point (690 C) it is in its liquid state at
normal combustion temperatures.
The mechanism of formation of vanadium compounds can be
explained as follows:
In high-temperature (approximately 1,730 C), low-oxygen zones,
the solid, non-volatile vanadium tetroxide (V2O4) is formed.
Vanadium pentoxide is formed from the tetroxide in lowtemperature (approximately 800 C), high-oxygen zones. In fact,
deposits are observed to comprise both oxides, although the
tetroxide oxidises to the pentoxide in excess air.
The extent of the vanadium attack on metal is determined by two
factors :
The amount of corrosive vanadium compounds at the metal/oxide
interface and the diffusion rate of oxygen to the metal oxide
interface. In that respect, the nature of the oxide layer on the metal
surface is very important as it may hinder oxygen diffusion
towards the metal surface. For instance, Ni3(VO4)2 is formed on
nickel-based alloys which forms a stagnant phase on its surface
which stops oxidation

Sodium is normally present in the fuel as NaCl collected by the

fuel either from underground water or transportation facilities. It
can be removed by combined water-washing and subsequent
centrifugation . Sulfidation attack (also known as "hot corrosion")
is corrosion caused by sulfates, mainly Na2SO4, on nickel and
aluminum alloys, by dissolving the carbide network of the metal.
These alloys are commonly used in high metal temperature
applications, in place of stainless steel and cobalt-based alloys.
Gaseous sodium sulfate is almost harmless, unlike its solid or
liquid forms, which are particularly harmful when they exceed the
theoretical Na "dew point", over 60 ppm. This threshold is lowered
by the presence of Mg, which could be introduced as an antivanadium reagent, and also by other alkaline metals such as Ca and
K, which form eutectic mixtures with sodium (eg,
Na2Mg(SO4)24H2O).
As a result, sodium can work to decrease the efficiency of Mg
additives on vanadium corrosion, by forming eutectic mixtures of
low melting point (below 590 C) with liquid vanadium pentoxide.
Sodium vanadyl vanadate (Na2OV2O4V2O5), very corrosive above
647 C, is of particular importance . However, there seems to exist
a threshold of Na2SO4 concentration beyond which the addition of
more sodium sulphate decreases the corrosion activity of vanadium
pentoxide.
Solid carbon deposits increase hot corrosion by reducing Na2SO4 to
the very corrosive Na2S.
The harmful effects of Na are enhanced when Pb is present in the
fuel. However, lead corrosion can also be tackled by Mg by means
of the formation of compounds such as PbO and PbSO4 of high
melting point. However, in the more realistic case of Pb, V and Na
mixtures acting at high temperatures, Mg alone does not suffice
against corrosion, and combinations of magnesium and silica are
efficiently used if the concentration of sodium is reduced below 0.5

ppm by water-washing. Silica does not inhibit corrosion on its

own, but enhances the efficiency of Mg additives and increases the
friability (capacity of deposits to break into small pieces) of the ash
deposits . Finally, greater amounts of Mg are to be used if the
metal surface is exposed to higher temperatures.
Preventing or reducing ash deposition and corrosion
Several different methods have been devised in order to either
diminish, avoid or remove corrosive deposits:
1. Coatings : Oxide scales build up a protective layer on the
metal surface, separating the substrate from the corrosion
environment. Coatings provide active elements for buildingup this protective oxide scale .

2. Cooling of metal surfaces , intended to solidify deposits

before their attack is initiated. Corrosion is increased
exponentially by the metal surface temperature.

3. Additives: Additives combine with fuel constituents and

combustion products to form solid, innocuous products that
pass harmlessly through the combustion equipment.
Additives may contain metals such as Mg, Al, Si, Mn or Ba ,
or combinations like Mg-Si, Mg-Al-Si, Al-Si. Data indicate
that at certain temperatures and with sufficient additive the
corrosion rates can be reduced to zero. Additives also help to
decrease corrosion by preventing the catalytic formation of
SO3). However, large concentrations of additives may
increase particulate output.

4. Surface cleaning procedures in gas turbines: These can be

split in three categories:
a. On-line techniques: Injection of an abrasive material
such as crushed nutshells or coke. These techniques are
effective on low temperature (under 970 C) deposits.
b. Off-line techniques: Usually a sequence of successive
water-wash, soak and re-start is used to soften the
MgSO4 deposits, then followed by the breakage of other
deposits. Off-line techniques are efficient on deposits
formed at any temperature, although at the cost of
efficiency loss as the engine must be switched off.
c. Thermal excursions: Deposits suffer spallation if a
sudden momentary increase of the turbine inlet gas
temperature is caused.

Hot corrosion of ceramics

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
2 NaCl + SO2 + 0.5 O2 + H2O = Na2SO4 + 2 HCl {1}
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 884C does not vary much, the dewpoint depends on pressure, Scontent 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 11001200C from eq. {1}.
However, the effective corrosion action is generally believed not to be by the
sulfate itself. It stems from the activity of Na2O arising from the decomposition
Na2SO4 = Na2O + SO3 {2}
because only the Na2O is attacking the protective scale from SiO2 by
x SiO2 + Na2O = Na2O*(SiO2)x {3}
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 lowS fuels (<0.5 %, a condition met by many modern fuels) and at comparatively
high temperatures ( > 1000C).
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.
As a result of new investigations of the hot corrosion of SiO2, Si3N4, and Si by
Na2SO4-melts at temperatures up to 1150C, a new model for the hot corrosion
attack of Na-sulfate on Si-containing materials was developed. In current models

it is proposed that the Na2O-activity of the sulfate melt, and, hence, the corrosive
attack is controlled by the partial pressures of gas species like O2 and SO3 in the
ambient. In contrast to that it could be shown, that the oxygen partial pressure at
the interface between substrate and sulfate melt is the controlling factor. Due to an
extremely low oxygen partial pressure at the interface between Si-containing nonoxides and the sulfate melt, these materials act as reducing agents and promote the
decomposition of the sulfate and the formation of Na2O. As a result a rather
violent corrosion reaction is observed. In the case of SiO2 a much less violent
reaction takes place which is related to a higher oxygen partial pressure at the
interface.
During the hot corrosion of Si-containing materials by Na2SO4, SiO2-rich Nasilicate melts are formed which are immiscible with the overlying sulfate melt.
Different surface tensions and dynamic processes at the interfaces between both
melts lead to the formation of isolated melt areas at least in the beginning of the
hot corrosion attack. Between these melt areas direct contact between substrate
and sulfate melt exists allowing a local corrosive attack which may be responsible
for pit formation.
To protect non-oxides against hot corrosion by Na2SO4 a direct contact between
the substrate and the sulfate melt must be avoided. Preoxidation of the non-oxide
materials to form thick and dense oxide scales or for example the deposition of
mullite scales could be a suited means.