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.

Alloys generally rely upon an oxidation reaction for the formation of a protective scale that will
improve the corrosion resistance to sulfidation, carburization, and the other forms of high-
temperature attack.

The properties of high-temperature oxide films, such as their thermodynamic stability, ionic
defect structure, and detailed morphology, therefore play a crucial role in determining the
oxidation resistance of a metal/alloy in a specific environment.

High-temperature materials are used for many critical components in a wide number of
Industries, including power generation, chemical processing, and gas turbine. With ever-
continuing demands for increased throughput and efficiency, there has been a trend toward
higher service temperatures and pressures.

This has resulted in continued corrosion problems, countered by continued improvements

in material compositions such as minimizing detrimental trace elements, development of coating
procedures, and improved fabrication, notably casting, forging, and welding.
Materials of construction must withstand excessive metal loss by scale formation from oxidation
and from penetration by internal oxidation products that could reduce the remaining cross-
sectional area to a level that cannot sustain the load-bearing requirements.

The component will then yield and may swell or distort. In some cases the internal fluid Pressures
can be sufficient to burst the component releasing hot, possibly toxic or flammable fluids.

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.

Corrosion is best reported in penetration units that reveal the actual loss of sound metal.
environments other than oxygen, water, or CO2 can produce
metallic oxides because of their oxidizing capacity.
Six types of oxidation/corrosion rate-controlling mechanisms have been identified:

1. At low temperature, diffusion of oxygen and metal species through a compact oxide film
2. At moderate and high temperatures, a combination of oxide film formation and oxide volatility
3. 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
4. At moderate and high temperatures, the direct formation of volatile oxide gases
5. At high temperature, the gaseous diffusion of oxygen through a barrier layer of volatilized oxides
6. At high temperature, spalling of metal and oxide particles.

When a metal is oxidized at elevated temperatures, a stable scale of oxides or other compounds
may buildup to cover and protect the exposed metal surface from further corrosion. The corrosion
product layer may therefore act as a barrier between the underlying metal and the corrosive
environment (air, flue gas, molten salt, or any other corrosive agent). The compound may be a solid,
a liquid, or a gas.

For instance, if chromium, vanadium, and molybdenum were exposed to air at 1100C:

1. Chromium would form solid Cr2O3.

2. Vanadium would form liquid V2O5.
3. Molybdenum would form gaseous MoO3.
2D Isothermal stability diagrams
When a metal reacts with a
gas containing more than
one oxidant, a number of
different phases may form
depending on both
thermodynamic and kinetic
considerations.

Isothermal stability
diagrams, usually
constructed with the
logarithmic values of the
activities or partial pressures
of the two nonmetallic
components as the
coordinate axes, are useful
in interpreting the
condensed phases that may
form.
Aqueous galvanic corrosion can be retarded by either by increasing the electrolyte resistance or by
avoiding metal contact.

It is impossible to eliminate electronic contact between metal and oxide .

Cations and anions do not diffuse at the same rate leading to growth of scale at the metal /scale or
the scale /gas interface.

To control oxidation retardation of the flux of ions necessary done either by doping or alloying.
After an initial
period of time,
the rate of scale
growth will
decrease to a
low level, that
is, a
considerable
measure of
oxidation
resistance will
be obtained
and, provided
the scale
remains intact,
will be
maintained for
very long times.
Under special conditions, particularly at intermediate temperatures, the oxidation
process may essentially stop after the initial scale formation.

In such cases, no change in scale thickness or weight would be observed after very long
intervals. Presumably this occurs because, when the scale reaches some minimum
thickness the diffusion rate is so low as to be essentially zero, thus creating a condition
under which the metal should last almost indefinitely without further deterioration.

Some investigators have chosen to call this type of behavior tarnishing and thereby to
distinguish it from the higher temperature phenomenon of scaling.

The parabolic rate law, although obviously an oversimplification of the actual state of
affairs during oxidation, nevertheless provides a relatively accurate approximation of
the behavior of the majority of metals and alloys practically used at high temperatures.
It was assumed that once formed, the oxide scale would remain intact and protective. Scale
thickness may be an important factor. In early stages, the scale is thin and reasonably elastic.
It also will have little intrinsic strength and usually will remain tightly adherent to the base metal.

As it thickens, however, less desirable properties may become manifest. Heavy scales tend to be
brittle and will therefore crack and spall from the surface.
The volume of the oxide formed, relative to
the volume of the metal consumed, is an
important parameter in predicting the degree
of protection provided by the oxide scale.

If the oxide volume is relatively low, tensile

stresses will tend to crack the oxide layers.
Oxides, which are essentially brittle ceramics,
are particularly susceptible to fracture and
cracking under such tensile stresses.

If the oxide volume is very high, stresses will

tend to lead to a break in the adhesion
Oxidation of stainless steel at various temperatures in between the metal and oxide.
0.1 atm oxygen.
For a high degree of protection, the oxide formed should be similar to that of the metal being
oxidized. This argument is the basis for the Pilling-Bedworth ratio (PB):

PB ratios slightly greater than one are typically expected to indicate optimal protection, with
modest compressive stresses generated in the oxide layer. In practice, it has been found that PB
ratios are generally poor predictors of the actual protective properties of scales. Some of the
reasons advanced for deviations from the PB rule

Some oxides actually grow at the oxide-air interface, as opposed to the metal-oxide interface.

Specimen and component geometries can affect the stress distribution in the oxide films.

Continuous oxide films are observed even when PB < 1.

 Cracks and fissures in oxide layers can be selfhealing as oxidation progresses.

Oxide porosity is not accurately predicted by the PB parameter.

Oxides may be highly volatile at high temperatures, leading to non-protective properties,

even if predicted otherwise by the PB parameter.
If the interface is
planar, it is easy to
conceive of a shear
crack initiating at the
interface and
propagating
rapidly across the
surface.
If, on the other hand, the interface is rough, where incipient grain boundary attack
beneath the scale is occurring, a keying action may prevent rapid crack propagation
and thereby improve scale adherence.

It is believed that the major effect of reactive rare earth additions to heat-resistant
alloys is not to enter the scale and lower diffusion rates, but to accumulate in grain
boundaries and thus ensure a small amount of grain boundary attack to provide
the keying action.
 FUEL ASH AND SALT DEPOSITS
In many industrial applications, the surfaces undergoing high temperature corrosion are
far from clean and mostly covered with surface deposits of ash and/or salt form on the
components.

Chemical reactions between these deposits and the protective surface oxide can lead to
destruction of the oxide and rapid corrosive attack.

In gas turbines, oxidized sulfur contaminants in fuel and chlorides from ingested air
(marine atmospheres) tend to react to form salt deposits.

The presence of sodium sulfate, potassium sulfate, and calcium sulfate together with
magnesium chloride have been reported in such deposits for compressor-stage
components. Sodium sulfate is usually regarded as the dominant component of the salt
deposits.

Testing has indicated that in commercial nickel- and cobalt-based alloys, chromium
additions play an important role in limiting this type of damage. Alloys with less than 15
percent of chromium as alloying addition are considered highly vulnerable to attack.

Ash and salt deposit corrosion is also a problem area in fireside corrosion of waste
incinerators, in calcining operations, and in flue gas streams.
LIQUID METAL CORROSION

To consider destruction of a solid metal by a liquid metal as corrosion, we need to

broaden the definition to allow for the solution or solubility of a solid metal in a
liquid metal wherein no transfer of electrons is involved.

Liquid-metal corrosion simply depends on the solution rate and the extent of
solubility of the solid metal in the liquid metal.

Materials are important from the point of view of their superior heat transfer
characteristics finding use in nuclear power plants.

Liquid metals and fused salts because of their low boiling point and very high
thermal conductivities are much more useful than handling water/water vapour at
high temperature and pressure.

Many complicating factors can influence the solution rate or the attainment of the
solubility limit.
 Liquid metals and fused salts

The formation of surface intermetallic compounds and of oxide or nitride films are good
examples of such factors.

Other factors are: impurities in the liquid metals which can increase the solution rate,
and temperature gradients and multi-metallic systems which can cause an increase in
the amount of attack over that expected t o saturate the liquid metal because of the
mass transfer of material under the driving force of the temperature gradient or the
concentration gradient.

Corrosion in liquid metals is applicable to metals and alloy processing, metals

production, liquid metal coolants in nuclear and solar power generation, other nuclear
breeding applications, heat sinks in automotive and aircraft valves, and brazing (metal
joining) operations.
Several variables affecting liquid-metal corrosion must be considered, and they
are:
(1) temperature (solubility of the solid metal into liquid metal, diffusion
rate)
(2) temperature gradient (difference in solubility of the dissolved metal in
the liquid metal in the hot and cold parts of the system gives rise to
temperature gradient mass transfer)
(3) cyclic temperature fluctuation (dissolution precipitation)
(4) surface area to volume ratio (under static condition as the ratio of
surface area to volume decreases, the amount of corrosion increases)
(5) purity of liquid metal;
(6) flow velocity, or Reynolds number (important in a forced-circulation
pump loop)
(7) surface condition of container material (if films are present it affects
the dissolution rate)
(8) number of materials in contact with the same liquid metal (dissimilar
metal concentration mass transfer)
(9) condition of the container material, such as the presence of a grain-
boundary precipitate, the presence of a second phase, the state
of stress of the metal, and the grain size.
 Practical problems are complicated by the fact that several of these forms can occur
simultaneously. In fact, opposing actions may be required for individual effects that
act in combination.

Types of liquid metal corrosion usually observed:

18Cr-8Ni, Monel, Hastelloy show good resistance.

Molten salt corrosion is usually applicable to materials retaining the molten salt, as
used in heat treating, solar and nuclear energy systems, batteries, fuel cells, and
extractive metallurgical processes.

Corrosion by fused salt occupy a position between that of liquid metal and aqueous
solutions. Physical solution of many metals in fused salts is possible .

Fused salt can act as a conducting electrolyte sustaining electrochemical reaction.

Mass transport due to thermal gradient has been observed. Sodium hydroxide, fused
carbonates and chlorides are used in heat transfer and high temperature fuel cell
applications.

By acting as fluxes, molten salts destabilize protective oxide layers (on a microscopic
scale, this effect contributes toward fuel ash corrosion described above).

Molten salts are generally good solvents, preventing the precipitation of protective
surface deposits.

Direct chemical reaction between the containment material and the salt.
Ni alloys show good resistance and are most useful and economical in these cases.
When Ni-20Cr alloys and stainless steels are oxidized while submerged in molten
salt (NaCl or NaCl-KCl), readily oxidizable alloy components, such as chromium,
and in some cases iron, migrate to thesurface to form non-adherent, granular and
thus nonprotective oxides.

This loss of alloy constituents causes a counter current flow of vacancies which
condense into an interconnecting pore network filled with salt.

Chromium diffuses down grain boundaries of the grain network to be deposited

at grain boundary pore intersections as chromium ions.

The concentration gradient of chromium ions in the salt phase forces chromium
diffusion out to the bulk salt where the higher effective oxygen pressure forms
Cr2O3 and some chromate ion.

Hot chloride salts, and particularly salt fumes mixed with air, are very corrosive to
heat resistant alloys. In general the higher nickel alloys, such as 600, are
preferred.
The alkali metals in the salt turn the protective chromium oxide scale into an alkali
chromate, which is non-protective and water soluble.

As fast as the scale is removed, more chromium diffusing to the surface reforms
the scale.

Eventually most of the chromium may be removed from the alloy, leaving
primarily iron and nickel.

Fluoride salts are more aggressive than are chloride salts. Molten fluorides are
used to flux metals and alloys for brazing operations.

Along with fluxing the oxide film on the work piece, fluorides also attack the
chromium oxide film on heat resistant alloy.
Examples of cases where noted:

Gas turbines used to power ships or planes near the ocean Na2SO4 +NaCl
caused corrosive degradation of turbine blades. Sulphides were observed in the
microstructure of the corroded alloy.

In fast breeder reactors fission products condense on SS cladding as complex

salts.

In boilers and turbines burning high ash coal or residual fuel oil.

Or Na2CO3

Depending upon the local

acid base chemistry.
Reduction of molecular O2 at
salt-gas interface
Decarburization and hydrogen attack.

At elevated temperature hydrogen can influence mechanical properties.

High temperature gas streams has mixture of gases.
Hydrogen in presence of other gases can react to change material
properties.

Alloys strengthened with interstitial carbon can loose strength due to

decarburization loss of tensile strength, increase in ductility, increase in
creep rate.

Steels tend to loose strength after long term exposure to hydrogen at

elevated temperature.

Carburization also happens in hydrogen-hydrocarbon gas mixture.

Although sometimes less detrimental in low alloy steels it generally leads to

decrease in ductility, loss of solid solution elements due to precipitation.

Hydrogen penetration also causes spalling and fracture of metal.

Thermodynamics provide little information about rate of reaction at ambient
temperature.

But at high temperature local equilibrium at interfaces is quickly achieved.

Thermodynamic data can be used to predict interfacial concentrations accurately .

This serve as boundary condition for diffusion limited reactions.

Cr and Mo addition improves resistance to cracking and decarburization they

form carbides which are more stable than that of iron.

In petrochemical industries steam is used to react with crude petroleum in ethylene

or steam cracking furnace to produce hydrocarbon feedstock.

Alloy pipes get coated with C ------ decoking done by steam air oxidation.

Optimum protection achieved when Cr2O3 layer present over SiO2 layer.

Periodic decoking leads to film rupture ----failure occurs when Cr gets precipitated
as Cr carbide.
However, small additions of Ni to iron based material is beneficial to sulphide
resistance.
In mixed environments like sulphur + oxygen or S + C + O2. Oxide and low sulphides
of chromium are more stable than those for Fe and Ni except in very reducing
atmospheres.