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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
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)
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
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.
ENVIROMENT
METAL
OXIDES
(OR)
AIR
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
OTHER METALGAS
REACTIONS
Decarburization & hydrogen attack
Corrosion of metals by sulfur compounds
at high temperatures
Hot corrosion of alloys
DECARBURIZATION &
HYDROGEN ATTACK
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
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
HOT CORROSION
Over.