Materials for Steam Superheaters

Jyoti Swaroop Repaka Praveen Jain

07010042 07d10002
February 11, 2010

Department of Mechanical Engineering,

Indian Institute of Technology Bombay.

Abstract
This is a part of the course ME 306 - Applied Thermodynamics
taught by Prof. Uday N. Gaitonde. The topic is Materials for Steam
superheaters.
Properties of superheaters have been discussed briefly at the be-
ginning. Then we went on to discuss the various contraints faced in
the material selection for steam superheaters. A case-study has been
quoted as an example in the end.

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Contents
1 Superheater 1
1.1 Types of superheaters . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Advantages and Disadvantages of using a superheater . . . . . 1

2 Constraints in material selection of superheater 2

3 Coal Ash Corrosion 2

4 Superheater Strength 3

5 Steam Oxidation 4

6 Case study of a 700◦ C power plant 5

List of Figures
1 Superheater viewed from a smokebox . . . . . . . . . . . . . . 1
2 Results from synthetic ash corrosion tests for various alloys . . 3
3 Stress requirements for alloys . . . . . . . . . . . . . . . . . . 4
4 Electron Probe analysis of an alloy . . . . . . . . . . . . . . . 5

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1 Superheater
A superheater is a device used to convert saturated steam into dry steam used
for power generation or processes. Figure 1 shows a Superheater viewed from
the smokebox. Top center is the superheater header, with pipes leading to
cylinders. Tubes below feed steam into and out of the superheater elements
within the flues. The stack and the damper have been removed for clarity.

Figure 1: Superheater viewed from a smokebox

1.1 Types of superheaters

There are three types of superheaters namely: radiant, convection, and sep-
arately fired.
A superheater can vary in size from a few tens of feet to several hundred feet
(a few meters or some hundred meters).
1. A radiant superheater is placed directly in the combustion chamber.
2. A convection superheater is located in the path of the hot gases.
3. A separately fired superheater, as its name implies, is totally separated
from the boiler.

1.2 Advantages and Disadvantages of using a super-

heater
The main advantages of using a superheater are reduced fuel and water con-
sumption but there is a price to pay in increased maintenance costs. In

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most cases the benefits outweighed the costs and superheaters were widely
used. An exception was shunting locomotives (switchers). British shunting
locomotives were rarely fitted with superheaters. In locomotives used for
mineral traffic the advantages seem to have been marginal. For example,
the North Eastern Railway fitted superheaters to some of its NER Class P
mineral locomotives but later began to remove them. Without careful main-
tenance superheaters are prone to a particular type of hazardous failure in
the tube bursting at the U-shaped turns in the superheater tube. This is
difficult to both manufacture, and test when installed, and a rupture will
cause the superheated high-pressure steam to escape immediately into the
large flues, then back to the fire and into the cab, to the extreme danger of
the locomotive crew.

2 Constraints in material selection of super-

heater
1. Superheaters strengthSuperheaters operate at high temperatures
and high pressure. (31 to 34.5 MPa; 595◦ C to 650◦ C).[5]

2. Coal Ash Corrosion The attack results form the deposition of the
liquid phase of complex alkali iron sulfates.[2]

3. Steam Oxidation The primary problem caused by steam oxidation

of the internal surfaces of superheater[2] tubes, headers, and piping
components is solid particle turbine erosion.[3]

4. Cost

3 Coal Ash Corrosion

The phenomenon of coal ash corrosion of superheater components has been
well known for some time. The attack results form the deposition of the
liquid phase of complex alkali iron sulfates. The severity of attack varies
with temperature. The corrosion rate increases as the complex alkali-iron
sulfates become molten, and then falls off as they begin to vaporize and
become unstable at higher temperatures. Design approaches, such as burying
the tubes containing the hottest steam in the center of outlet banks to shield
them from cavity radiation, and the use of 309 and 310 stainless steel shields,
have been used in existing 565◦ C and 595◦ C units, but these affect efficiency
and are a continuing maintenance item. Different superheater tubing alloys

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vary widely in their resistance to coal ash corrosion. The Figure 3 shows the
effect of coal ash corrosion on various alloys.[2] Bimetallic tubing is the most
likely means of dealing with coal ash corrosion in the advanced plants. An
interesting approach to the liquid ash corrosion problem is to operate the
superheater tubes above the bell-shaped curve

Figure 2: Results from synthetic ash corrosion tests for various alloys

4 Superheater Strength
The superheater tubing in the advanced plant will have to operate at high
pressures of 4500 to 5000 psi (31 to 34.5 MPa), and steam temperatures of
595◦ C to 650◦ C The need to reduce CO2 emission and increase efficiency has

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been high[1]. Thus, steam temperatures of the most efficient fossil power
plants are now in the 600◦ C range, which represents an increase of about
60◦ C in 30 years. It is expected that steam temperatures will rise another
50◦ C to 100◦ C in the next 30 year. The data bases for the potential can-
didates must be reviewed against the allowed stresses by the ASME boiler
code committee, and where insufficient data exist, the gaps must be filled.
Fabrication methods must also be qualified.

Figure 3: Stress requirements for alloys

5 Steam Oxidation
The primary problem caused by steam oxidation of the internal surfaces
of superheater tubes, headers, and piping components is solid particle tur-
bine erosion. Turbine erosion damage causes a loss in cycle efficiency, is
expensive to repair, increases the length of turbine overhaul outages and,
in at least one instance, has led to the destruction of a turbine. High
Cr content in the tubing alloys, or in the coatings on the tubing, is the
major means of controlling steam oxidation. Refining the grain size is an-
other metallurgical treatment that can improve steam oxidation resistance of
austenitic stainless steel. Coating method that can be used to increase the
surface Cr content is chromating.This process results in a conversion coating,
and can be performed at lower temperatures and on assembled components.
An adherent chromate film is deposited on the metal surface by heating

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the tubes in the presence of a dichromate solution.During subsequent expo-
sure to high temperature, the film is converted to a tightly adherent Fe-Cr
spinel, which extends the time before exfoliation occurs. Another coating
method,Chromizing, a high temperature Cr diffusion process, is already be-
ing used to achieve this.Chromizing produces an outer layer of chromium
carbide containing over 80 pct Cr, and an inner diffusion zone containing 13
to 25 pct Cr. The thickness of the two layers depends on the carbon activity
and other chromizing process parameters. An example of the type of coating
formed on 2.25Cr-lMo steel is shown below. The variation of Cr, C, and Fe
contents as a function of distance from the surface in this sample is shown
in Figure 5. Because chromizing is a very high temperature process, it is
applied to new and replacement tubing, pipes, and other product forms.

Figure 4: Electron Probe analysis of an alloy

6 Case study of a 700◦C power plant

• In the low temperature ranges of the superheater tubes the same ferritic
materials as for the membrane walls can be used.[4]

• Additionally at material temperatures higher than 550◦ C martensitic

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 materials like VM12 and X20CrMoV12-1 will be applied in 600◦ C-
steam generators

• For the final stages of the superheaters, where the material temperature
exceeds the maximum allowable temperature for martensites of 600◦ C,
austenitic materials like Super304H or HR3C need to be used.

• In a 700◦ C-Power Plant the material temperatures at the final stages

of the superheaters of more than 700◦ C are too high for the common
austenitic materials. The newly developed austenitic material Sanicro
25 extends the range of application of these materials to about 680◦ C.

• For the remaining temperature range up to above 700◦ C materials with

higher strength are necessary. Possible new materials for this tempera-
ture range are nickel base alloys like the modified Alloy 617, Alloy 740
and Alloy 263 and the newly developed Japanese austenitic material
HR6W. For these new superheater materials the qualification of the
base material, creep tests across the weld and bending tests have to be
carried out. The qualification of the base material which is a funda-
mental step on the way to a marketable product for most of the above
mentioned new materials is still ongoing. Only the qualification of the
base material of the modified Alloy 617 is completed, which makes it
presently the preferred material.

References
[1] Dobrzanski, J. The classification method and the technical condition
evaluation of the critical elements’ material of power boilers in creep
service made from the 12cr-1mo-v. Journal of Materials Processing Tech-
nology 164-165 (2005), 785 – 794. AMPT/AMME05 Part 2.

[2] Gold, M., and Jaffee, R. Materials for advanced steam cycles. Jour-
nal of Materials for Energy Systems 6, 2 (1984).

[3] Jacklin, C., Anderson, D. R., and Thompson, H. Fireside de-

posits in oil fired boilers-deposit location vs. chemical composition. In-
dustrial and Engineering Chemistry 48, 10 (1956).

[4] Menp, L., Klauke, F., Tigges, K., Matsuda, J., Kukoski, A.,
and Gaffoor, A. Material aspects of a 700◦ c - power plant. 6–7.

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[5] Viswanathan, R., and Bakker, W. Materials for ultrasupercritical
coal power plantsboiler materials: Part 1. Journal of Materials Engineer-
ing and Performance 10, 1 (2001).