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High Temperature

Corrosion
High Temperature Corrosion

TOPICS TO BE DISCUSSED
Introduction
Mechanism & Kinetics
High Temperature
Materials
Other Metal-Gas
Reactions

INTRODUCTION
The term high temperature corrosion refers to material degradation at
temperatures higher than the ambient temperatures, when exposed to
corrosive environments. How high is the temperature, is a relative term,
which varies from metal to metal and also in some cases on the type of
environment.
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.
Ex. Gas turbine engine, Rocket engine, Furnace, etc.

INTRODUCTION

Two areas of interest in high temperature corrosion are:


~
The degradation of materials by molten salts, in which the aim
of the research is to identify the fundamental chemical or
electrochemical reactions and the transport processes that are
involved in the degradation process, and
~ The evolution of stresses that develop in oxide scales as a
result of scale growth processes and of cooling and heating.

Applications include hot corrosion of metals and alloys and


dissolution of oxides in molten carbonate salts. Oxide stresses are
being examined by theoretical and modeling studies, measurements
of stresses with high temperature x-ray diffraction, and in-situ
measurements of scale fracture using acoustic emission.

INTRODUCTION
How does high temperature corrosion differ from the so called low
temperature or room temperature corrosion?
Many metals, when exposed to air, even at room temperature, form surface
compounds, which may be oxides or other compounds, depending upon the
contamination in air. The formation of the compound takes place because
the metal is not stable as such in the environment. It tends to undergo a
reaction to reach a stable form. A piece of iron or mild steel, when exposed
to air forms an oxide layer on the surface. It takes from a few hours to a few
days to form this oxide, depending upon the type of environment. The rate of
the same reaction of oxide formation increases many folds, if the sample is
exposed to the same atmosphere, in an oven at a temperature much higher
than the room temperature. It is because of the increase in the rate of
reaction at higher temperatures, many metals and alloys have a tendency to
form stable products and hence undergo degradation. The material
degradation due to the reaction with environment increases many folds with
increase in temperature.

INTRODUCTION
Why is a there need to study high temperature corrosion?
There is need to study high temperature corrosion to know
how fast metals react with environment at high temperatures;
what is the mechanism of the reaction;
how corrosive is the environment;
how to control the reaction or how to protect the metal from
degradation; and finally,
how to select materials for such high temperature applications.

INTRODUCTION
what way the material degrades at high temperatures, i.e.
what are various forms of high temperature corrosion?
Oxidation is the most important high temperature corrosion
reaction. In most industrial environments, oxidation is often one
of the reactions, irrespective of the predominant mode of
corrosion. In fact, alloys often rely upon the oxidation reaction
to develop a protective oxide layer to resist corrosion attack.
Other forms of corrosion reactions depend upon the
environment, which can be oxidizing or reducing. An oxidizing
environment contains molecular oxygen. A reducing
atmosphere is generally produced by combustion under
stoichiometric or substoichiometric conditions with no excess
oxygen. The oxygen activity is very low in this case and is
controlled by CO/ CO2 or H2/H2O ratio. The reducing
atmosphere is generally more corrosive for many corrosion
modes, such as sulphidation, carburization and nitridation.

INTRODUCTION

what way the material degrades at high temperatures, i.e. what are
various forms of high temperature corrosion?
(continue)

When the environment has high sulphur activity or high sulphur


potential, the reaction is more likely to be dominated by sulphidation.
Hydrogen sulphide gas gives mainly sulphide layers. In a sulphur dioxide
environment, one can get sulphidation, oxidation or both, depending upon
the partial pressure of the SO2 gas.
Carburization and nitridation behave in a similar fashion. The reaction
is controlled both by carbon/nitrogen and oxygen activity. Lowering of
oxygen would lead to carburization/ nitridation while increasing oxygen
would lead to oxidation.
Halogen corrosion takes place by forming volatile metallic chlorides
many industrial environments contain, in addition to some salts. For
example gas turbines in a marine environment contain sodium salts.
Presence of sulphur impurity in fuel forms sulphur dioxide, resulting in the
formation of sodium sulphate. These salts become liquid under temperature
of oxidation and cause catastrophic oxidation. Such corrosion which takes
place in the presence of salts and other deposits is known as hot corrosion

INTRODUCTION
Some practical examples of high temperature corrosion are:
1. Furnace and heating elements suffer sudden loss in strength due to
material loss as a result of oxidation. Material requirement in these
applications is such that they can withstand high temperatures in normal
atmosphere without undergoing degradation, for a sufficiently long time.
2. Chemical, petrochemical and refining industries require materials that can
sustain high temperatures, coupled with severe oxidizing, carburizing,
sulphidising and other reducing environments.
3. Aerospace and gas turbine materials suffer degradation due to loss of
strength due to oxidation and sulphidation at very high temperatures.
Special materials are needed, which not only have high strength but are
strongly resistant to corrosive environments.
4. Materials used in fossil fuel power generation, suffer oxidation and
corrosion from boiling water and steam on one side and hot corrosion from
other side due to burning of coal and gas, which generates oxidizing,
sulphidizing and carburizing atmospheres and also deposits, which contain
lots of salts

MECHANISMS & KINETICS


PILLING-BEDWORTH RATIO
ELECTROCHEMICAL & MORPHOLOGICAL
ASPECTS OF OXIDATION
OXIDE DEFECT STRUCTURE
OXIDATION KINETICS
EFFET OF ALLOYING
CATASTROPHIC OXIDATION
INTERNAL OXIDATION

PILLING-BEDWORTH RATIO
It is used to know oxidation resistance.
It is a volume ratio of OXIDE & METAL.
Ratio < 1 : oxides generates, insufficient
oxides take place, creutes, unprotected
oxide layer formed.
Ratio > 1 : compressive stress on oxide
produced, i.e.. Spalling.
This Ratio should always nearer to 1.

ELECTROCHEMICAL & MORPHOLOGICAL


ASPECTS OF OXIDATION
Aqueous electrochemical method
~ Anode : Oxidation
~ cathode : Reduction
High temp. corrosion
+2
~Metal-Slag interface : M M + 2e
~Slag-Gas interface : 02 + 2e MO
~Over All Reaction : M + O2 MO
Sequence of formation of oxides at 560`C
is
Fe FeO Fe3O4 Fe2O3

ELECTROCHEMICAL & MORPHOLOGICAL


ASPECTS OF OXIDATION

ENVIROMENT
METAL

OXIDES

(OR)
AIR

OXIDE DEFECT STRUCTURE


All oxides are nonstoichiometric compunds, ie
their actual compositions are variable ans
deviate from their ideal molecular formulas.
Some oxides have an excess and others a
deficiency of metallic ions, or equivalently a
deficiency or excess of oxygen ions.
As taking example of Zieconium oxidation, pure
5+
2+
ZrO, effect Ca addition & affect of Ta addition.

OXIDATION KINETICS
The most important parameter of metal oxidation from
an engineering view-point is the reaction rate.
The various empirical rate laws sometimes observed
during oxidation for various metals under various
conditions are shown in below figure, in which a plot of
weight gain per unit area versus time is shown
The simplest empirical relationship is the linear law,

W = kLt
where, W = weight gain per unit area
kL = linear rate constant
t = time

OXIDATION KINETICS
R
A
NE
I
L

PAR
( LO G

IC
L
O
AB

CUBIC

ARITH

MIC )

EFFECT OF ALLOYING
Alloys were made by adding alloy elements to a
base material:25mass%Cr-20mass%Ni-Fe, and a high
temperature corrosion test was conducted to evaluate
the effects of alloy elements on corrosion characteristics,
and moreover, mechanical properties were measured.
Results of the test conducted the relationship between
high temperature corrosion characteristics and the
added alloy elements. Compared to a base material :
25mass% Cr 20mass% Ni-Fe, by adding 5mass%Si to
it, its corrosion resistance were improved by 160%, and
its hardness was maintained at an elevated temperature.
The formation of scale structures and the effect of
corrosion-resistant alloying elements can be explained
according to the stability tendencies of metals, chlorides,
and oxides in the M -Cl O equilibrium diagrams.

CATASTROPHIC OXIDATION
catastrophic oxidation refers to metal oxygen
reactions that occur at continuously increasing rates or
that break away from protective behaviour and thereafter
react very rapidly.
Metal with linear oxidation kinetics at a certain
temperature have a tendency to undergo so called
catastrophic oxidation ( also referred as a breakaway
corrosion ).
If the rate of heat transfer to the metal and
surrounding is less than the rate of heat evolution by the
reaction, the surface temperature increases

INTERNAL OXIDATION
The formation of isolated particles of
corrosion products beneath the metal surface.
(This occurs as the result of preferential
oxidation of certain alloy constituents by inward
diffusion of oxygen, nitrogen, sulfur, etc.)
It is the process in which oxygen diffuses into
alloys and causes subsurface precipitation of the
oxides of one or more alloying elements.

HIGH TEMPERATURE
MATERIALS
Criteria for material selection at high temperatures is first to

meet the requirements of the mechanical properties of the material.


These include materials with high melting point, high Youngs
modulus, good creep resistance and high temperature strength, and
microstructure stability at high temperatures.
Once these requirements are fulfilled, additional requirements for
high temperature corrosion resistance are as follows:
1. Choose a metal which either has very low rate of oxidation at the
temperature of interest or forms a scale which is thin, slow
growing and impervious to the atmosphere.
2. Since only a few metals have properties mentioned in (i), the
alternative way is to choose an alloy which contains at least
one such element that forms a protective, thin and slow
growing oxide layer.
3. The last alternative is to apply a coating of another element or
compound which has all those properties mentioned in 1 and 2
above.

OTHER METALGAS
REACTIONS
Decarburization & hydrogen attack
Corrosion of metals by sulfur compounds
at high temperatures
Hot corrosion of alloys

DECARBURIZATION &
HYDROGEN ATTACK

carbon diffusion and hardness changes in Fe-C-Cr-Mn-Si steels initiated by


surface oxidation are reported. The oxidation anneals were carried out in
ambient air. The measurements of carbon concentration and the
metallographic investigation have shown that the steels decarburize
expressively in the course of the oxidation process. The evaluation of the
carbon concentration curves Nc(x, t) yielded diffusion coefficients DC of
carbon in the given steels. The dependence of DC on the concentration Ni
of alloying elements i is expressed by the use of diffusion interaction
coefficients Ci. The decrease of carbon concentration caused the increase
of grain size in subsurface layers and the decrease of hardness HV. The
dependence of HV(x,t) on NC(x, t) is expressed by the general parabolic
relationship y(t) = k tm.

Hydrogen and hydrocarbon gases: if steel is exposed to hydrogen at high


temperatures, the following reaction can occur:
C(Fe) + 4H(Fe) = CH4
Carbides or dissolved carbon, reacts with the dissloved hydrogen [H(Fe)] to
form methane.

EQUILIBRIYM DIAGRAM OF Fe-CH4-H2 SYSTEM


10.0

Fe

2H 2

+2H

te +

3C

= CH

1.1%C

0.5
0.4
0.3

0.2
0.1
400

=Fe

Fe

hi
rap
Cg

1.0

Fe3C

H4
+C

%CH4

H2+CH4= 100%

3Fe

5.0
4.0
3.0
2.0

3Fe +CH4 =Fe3C +2H2

0.7%C
0.3%C

The equilibrium
between carbon &
hydrogen-methane gas
mixtures of 1 atm total
pressure can be
obtained from T/D data
as shown in figure,
which can be used to
estimate the possibility
of decarburization of
carbon steels in
methane-hydrogen
mixtures.

600

800 1000
TEMP.

1200

CORROSION OF METALS BY SULFUR


COMPOUNDS AT HIGH TEMPRATURES
Sulfur forms a wide variety of compounds with halogen
elements. In combination with chlorine it yields sulfur chlorides such
as disulfur dichloride, S2Cl2, a corrosive, golden-yellow liquid used
in the manufacture of chemical products.
It reacts with ethylene to produce mustard gas, and with
unsaturated acids derived from fats it forms oily products that are
basic components of lubricants.
With fluorine, sulfur forms sulfur fluorides, the most useful of
which is sulfur hexafluoride, SF6, a gas employed as an insulator in
various electrical devices.
It has a characteristic rotten egg odor, is extremely toxic, and is
corrosive to metals such as iron, zinc, copper, lead and cadmium.
Hydrogen sulfide is also a precursor to sulfuric acid formation,
which corrodes lead-based paint, concrete, metals and other
materials.

HOT CORROSION

Hot corrosion is a mechanism of "high


temperature corrosion", others include
high temperature oxidation, sulfidation
and carbonization.
Hot corrosion can be done by three
different types..
1) Hot corrosion by sulfates
2) Hot corrosion by vanadium
3) Hot corrosion by lead

Hot corrosion by sulfates


Two types of sulfate-induced hot corrosion are generally distinguished:
Type I takes place above the melting point of sodium sulfate and Type II
occurs below the melting point of sodium sulfate but in the presence of small
amounts of SO3.
In Type I the protective oxide scale is dissolved by the molten salt.
Sulfur is released from the salt and diffuses into the metal substrate forming
discrete grey/blue colored aluminum or chromium sulfides so that, after the
salt layer has been removed, the steel cannot rebuilt a new protective oxide
layer. Alkali sulfates are formed from sulfur trioxide and sodium-containing
compounds. As the formation of vanadates is preferred, sulfates are formed
only if the amount of alkali metals is higher than the corresponding amount
of vanadium.
The same kind of attack has been observed for potassium and
magnesium sulfate.

Hot corrosion by lead


Lead can form a low melting slag capable of fluxing protective
oxide scales.

Hot corrosion by vanadium


Vanadium is present in petroleum, especially from Canada, western
United States, Venezuela and the Caribbean region, in the form of
porphyrine complexes. These complexes get concentrated on the higherboiling fractions, which are the base of heavy residual fuel oils. Residues of
sodium, primarily from sodiumchloride and spent oil treatment chemicals,
are also present. More than 100 ppm of sodium and vanadium will yield ash
capable of causing fuel ash corrosion.
Most fuels contain small traces of vanadium. The vanadium is oxidized
to different vanadates. Molten vanadates present as deposits on metal can
flux oxide scales and passivation layers. Furthermore, the presence of
vanadium accelerates the diffusion of oxygen through the fused salt layer to
the metal substrate; vanadates can be present in semi conducting or ionic
form, where the semi conducting form has significantly higher corrosivity as
the oxygen is transported via oxygen vacancies. Ionic form in contrast
transports oxygen by diffusion of the vanadates, which is significantly
slower. The semi conducting form is rich on vanadium pentoxide.
At high temperatures or lower availability of oxygen, refractory oxides vanadium dioxide and vanadium trioxide - form. These do not promote
corrosion. However, at conditions most common for burning, vanadium
pentoxide gets formed. Together with sodium oxide, vanadates of various
composition ratios are formed.

Hot corrosion by vanadium


Vanadates of composition approximating Na2O.6 V2O5 have the highest
corrosion rates at the temperatures between 593 C and 816 C; at lower
temperatures the vanadate is in solid state, at higher temperatures vanadates
with higher proportion of vanadium provide higher corrosion rates.
The solubility of the passivation layer oxides in the molten vanadates
depends on the composition of the oxide layer. Iron(III) oxide is readily soluble
in vanadates between Na2O.6 V2O5 and 6 Na2O.V2O5, at temperatures below
705 C in amounts up to equal to the mass of the vanadate. This composition
range is common for ashes, which aggravates the problem. Chromium(III)
oxide, nickel(II) oxide, and cobalt(II) oxide are less soluble in vanadates; they
convert the vanadates to less corrosive ionic form and their vanadates are
tightly adherent, refractory, and acting as oxygen barriers.
The corrosion rate by vanadates can be lowered by lowering the amount
of excess air for combustion (thus forming preferentially the refractory oxides),
refractory coatings of the exposed surfaces, or use of high-chromium alloys,
e.g. 50% Ni/50% Cr or 40% Ni/60% Cr.
The presence of sodium in a ratio of 1:3 gives the lowest melting point
and most be avoided. This melting point of 535 C can cause problems on the
hot spots of the engine like piston crowns, valve seats, and turbochargers.

Over.