2.

19 HIGH ALLOY CREEP RESISTANT AND HEAT RESISTANT STEELS

2.19.1 High alloy creep and heat resistant materials:
The high alloy creep and heat resistant steels distinguish themselves by displaying excellent resistance to
hot gases, combustion products, salts and molten metal at temperatures higher than approximately 550°C.
Chromium is the major alloying element in the high alloy creep and heat resistant steels, providing
oxidation resistance and corrosion resistance at elevated temperatures. As shown in Figure 2.19.1, high
chromium contents ensure good scaling resistance at high temperatures, as long as temperatures do not
cycle. If the application has repeated heating and cooling cycles, the effect of chromium is not as
consistent, and nickel plays an important role by minimising the tendency of the scale to spall away. Other
alloying elements such as aluminium and silicon can also improve the high temperature scaling resistance
of high chromium alloys.

Figure 2.19.1 Influence of silicon and chromium on high temperature scaling resistance in air.

High chromium heat resistant stainless steel plate grades alloyed with nickel, silicon and aluminium are
highly resistant to scaling and retain strength at high temperatures. They also offer excellent resistance to
corrosion on exposure to high temperatures. These alloys can operate at temperatures up to 1150°C in air,
although the presence of sulphur-containing compounds, water vapour or ash reduces the maximum
allowable service temperature significantly.
The high alloy creep and heat resistant alloys have to display excellent resistance to:
• high temperature corrosion,
• creep,
• embrittlement from phase changes that occur at the high temperatures, and
• expansion effects that can lead to distortion
The typical effects of high temperatures and various service environments on the high temperature
properties of these alloys are briefly considered below:
• Oxidation: The chromium oxide passive film remains effective in reducing high temperature oxidation
and corrosion up to about 1000°C. Above this temperature the chromium oxide film starts to
evaporate and other alloying elements, such as aluminium and silicon, are required to improve the
oxidation resistance by forming a layer of Al2O3 and/or SiO2 under the chromium oxide film (Cr2O3).
Niobium, molybdenum, tungsten and cobalt can have a negative effect on the stability of the chromium

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 oxide at very high temperatures and, although increasing the strength of the alloy at these
temperatures, they decrease its oxidation resistance.
• Carburisation: Carbon generally comes from hydro-carbons, either from partially burnt fuel gases or
process fluids/gases. The carbon diffuses into the metal at high temperatures, lowering its melting
point, removing chromium from solution by forming chromium carbides, and decreasing ductility.
Highly carburising gases can also lead to metal consumption in the form of metal dusting. Carburising
resistance can be improved by forming more stable oxide films or by increasing the nickel content
(nickel does not form carbides and it hinders the diffusion of carbon into the steel).
• Sulphidation: Metal sulphides will form if the high temperature alloy is exposed to sulphur dioxide or
hydrogen sulphide gases (often present in furnace atmospheres). Any sulphur in the atmosphere will
produce the same result. The sulphides, if present as a scale, have a lower density than the oxide layer
and thus tend to crack and spall away, leading to further attack. Chromium, aluminium and silicon help
to resist sulphur attack because of the effect these elements have on improving the stability of the
oxide film.
• Chloridation: Chlorine and fluorine can attack the surface of the alloy and produce a volatile chloride or
fluoride scale. High nickel alloys display the highest resistance because of the higher melting point and
vapour pressure of nickel halides. If chlorides are formed they also tend to react with the oxide film to
give a low melting point surface slag that promotes further oxide/chloride attack. Aluminium gives
better protection than chromium against chloridation.
• Nitridation: Nitrides can form readily in chromium-containing alloys at temperatures of 500°C and
above. The nitrides that form have a higher volume and over time will spall off, exposing a fresh
surface. Ammonia and other atmospheres causing nitriding will cause rapid attack of stainless steels.
• Molten salt corrosion: Molten salts can cause fluxing of the oxide layers. Sodium and potassium
compounds are most active, but calcium and magnesium compounds can also cause problems.
Chlorides and sulphates of these metals react with the surface oxide to give a low melting point
complex that then allows easier oxygen diffusion to the underlying metal. Higher chromium alloys help
resist this type of attack.
• Flue gases and fuel ash: Furnace gases can contain sulphur dioxide, hydrogen sulphide and
hydrocarbons. All of these can be harmful to the high temperature alloy. Residual ash from burning
both solid and liquid fuels can contain solids that will react with the protective surface oxides. Of
particular concern are mixtures of vanadium, sulphates and sodium which can form low melting point
salts that can flux away the protective oxide film at temperatures as low as 650°C.
• Thermal Expansion: When there is uneven heating of a heat resistant alloy, the thermal expansion will
be uneven and this can lead to distortion. Uneven heating at higher temperatures, when the strength
of the alloy is lower, can lead to more distortion.
• Creep Strength: The high nickel alloys can produce higher creep strengths and operate over a higher
temperature range. Diagrams giving the creep strain and strength to rupture are used along with
design codes in designing with these alloys. A range of alloys are available but regardless of the alloy
used, the design stress levels are reduced to only a few MPa once temperatures of 900°C to 1000°C are
reached.
• Embrittlement: One of the problems that can occur when an alloy is held for prolonged periods at high
temperatures is the formation of intermediate phases. These generally give inferior properties
although they may not become apparent until the alloy cools down. Sigma phase can occur in high
chromium alloys in the range 540°C to 840°C and in most high chromium alloys there is also a decrease
in toughness for alloys heated in the 475°C range (α prime formation). Carbides can also form. These
can strengthen the alloy at higher temperatures by improving creep resistance, but reduces the room
temperature toughness.
• Grain growth: High temperature alloys can suffer significant grain growth at elevated temperatures, as
shown in Figure 2.19.2.

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 Figure 2.19.2. Grain growth in austenitic and ferritic heat resistant steels.

The chemical compositions of austenitic and ferritic high temperature stainless steels are shown in Tables
2.19.1 and 2.19.2, respectively. Applicable temperature ranges are shown in Tables 2.19.3 and 2.19.4.
Table 2.19.1. Austenitic high temperature stainless steels.

International steel
Typical steel composition, % National steel designations, superseded by EN
number
Outokumpu
steel name
ASTM/ C
EN N Cr Ni Si Other BS DIN NF SS
UNS (max)

4948 1.4948 304H 0.05 - 18.1 8.3 - - 304S51 1.4948 Z6 CN 18-09 2333
4878 1.4878 321H 0.05 - 17.3 9.1 - Ti 321S51 1.4878 Z6 CNT 18-10 2337
153 MA 1.4818 S30415 0.05 0.15 18.5 9.5 1.3 Ce - 1.4891 - 2372
4828 1.4828 - 0.04 - 20 12 2 - - 1.4828 Z17 CNS 20-12 -
4833 1.4833 309S 0.06 - 22.3 12.6 - - 309S16 1.4833 Z15 CN 23-13 -
253MA 1.4835 S30815 0.09 0.17 21 11 1.6 Ce - 1.4893 - 2368
4841 1.4841 314 0.07 - 25 20 1.7 - - 1.4841 Z15 CNS 25-20 -
4845 1.4845 310S 0.05 - 25 20 - - 310S24 1.4845 Z8 CN 25-20 2361
353MA 1.4854 S35315 0.05 0.17 25 35 1.3 Ce - - -

2.19.2 Welding of high alloy heat and creep resistant steels:

General guidelines for welding heat and creep resistant steels are shown below:
• The alloys are usually welded in the softened or annealed condition to avoid any stresses resulting from
phase changes.
• In the case of austenitic steels, allowance must be made for their high expansion and low thermal
conductivity compared to carbon steel.
• Gas pick-up must be minimised so all welding must be done under an inert atmosphere.
• Problems relating to precipitate formation must be eliminated by keeping welding times low.
• Impurity control, particularly of sulphur, is important. Contamination from other metals can also give
problems. All joints should be free of scale and degreased prior to welding.
• The weld pool is viscous compared to carbon steel and joint preparation must allow for this by leaving
more room to manipulate the weld.
When considering creep strength it is particularly important to ensure that the weld will have similar or
better creep qualities to the base metal. Experimental evidence suggests that weld deposits will generally
display lower creep strength and there should be a design allowance to accommodate this. One report
suggests that there is about a 20% decrease in the creep rupture strength of the weld metal compared to
the parent plate. Recommended filler materials are shown in Table 2.19.5.

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 Table 2.19.2. Ferritic high temperature stainless steels.

Typical steel composition, %

Outokumpu steel International EN
name steel number
C Mn Cr Si

4713 1.4713 0.08 0.7 6.5 0.8

4724 1.4724 0.08 0.7 13.5 1.0
4742 1.4742 0.08 0.7 18.0 1.3
4762 1.4762 0.08 0.7 24.0 1.4

Table 2.19.3. Applicable temperatures for austenitic high temperature alloys.

Maximum service
Solution Stress annealing
Steel grade Solidification range, °C temperature in dry Hot forming, °C
annealing, °C (min. 0.5 hours)
air, °C

4948 1450-1385 800 1150-850 1050-1110 840-900

4878 1440-1370 800 1150-850 1020-1120
840-900
153 MA 1450-1370 1000 1150-900 1020-1120
900
4828 1420-1350 1000 1150-950 1050-1150
4833 1420-1350 1000 1150-950 1050-1150 1010
253 MA 1430-1350 1100 1150-900 1020-1120 1010
4845 1410-1340 1100 1150-980 1050-1150 900
4841 1400-1330 1125 1150-980 1050-1150 1040
353 MA 1410-1360 1150 1150-980 1100-1150
1040
1010

Table 2.19.4. Applicable temperatures for ferritic high temperature alloys.

Maximum service
Steel grade Hot forming1, °C Annealing2
temperature in dry air, °C

4713 800 1100-750 750-800

4724 850 1100-750 800-850
4742 1000 1100-750 800-850
4762 1150 1100-750 800-850
1
cooling still air
2
cooling forced air or water

2.19.2.1 Welding austenitic high temperature stainless steels:

The austenitic high temperature alloys have good or very good weldability and can be welded using SMAW,
GMAW, GTAW and SAW. To ensure weld metal properties (e.g. strength, corrosion resistance) equivalent
to those of the parent metal, a filler material with an identical or higher alloyed composition should
preferably be used. In some cases, however, a differing composition may improve e.g. weldability or
structural stability.

2.19.2.2 Welding ferritic high temperature steels:

The same precautions as for carbon steels are normally required. Preheating of welded joints to 200°C to
300°C is required for plates thicker than 3 mm. Due to grain growth in the HAZ, the heat input should be
minimised. GTAW, plasma arc welding and GMAW are preferred. Pure argon should be used as the
shielding gas. Matching filler material has detrimental effect on the ductility, hence austenitic welding
consumables, e.g. 307, 309 or 310, are recommended. If the weld will be exposed to a sulphurous
environment, overlay welding with the matching ferritic filler will be necessary.

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 Table 2.19.5. Filler metal selection and post weld heat treatment of various high alloy heat and creep resistant steels.

Type of steel Qualified weld filler metals

Short name of the Welding rods, wire electrodes, welding wires Heat treatment
Material weld deposit of the after welding
Short name Material
number coated stick
Short name
electrode number

Ferritic steels

8CrSi 7 7 1.4700 - X8Cr9 1.4716 In general none; for parts

X10CrAI 7 1.4713 19 9Nb X8Cr9, X5CrNiNb 19 9 1.4716, 1.4551 with highly different cross
X7CrTi 12 1.4720 19 9Nb, 18 8 Mn 6 X2CrNi 19 9, X 15CrNiMn 18 8 1.4316, 1.4370 sections or after heavy cold
X10CrAI 13 1.4724 22 12, 25 4 X12CrNi 22 12, X 12 CrNi 25 4 1.4829, 1.4820 forming, stress relief
X10CrAI 18 1.4742 22 12, 25 X12CrNi 22 12, X 12 CrNi 25 4 1.4829, 1.4820 annealing at temperatures
X10CrAI 24 1.4762 30, 25 4, 25 204 X8Cr 30, C 12 CrNi 25 4, X 1.4773, of 750°C to 800°C for 30 to
12CrNi 2520 1.4820, 1.4842 40 min, followed by air
cooling is recommended
after welding.

Ferritic-austenitic steels

X20CrNiSi 25 4 1.4821 25 4, 25 20 X12CrNi 25 4, X 12CrNi 2520 1.4820, 1.4842 None

Austenitic steels

X12CrNiTi 18 9 1.4878 19 9 Nb, 22 12 X 5CrNiNb 19,9 X 12 CrNi 22 1.4551, 1.4829

X15CrNiSi 20 12 1.4828 22 12 12 1.4829
X7CrNi 23 14 1.4833 25 20 X12CrNi 22 12 1.4842
X12CrNi 25 21 1.4845 25 20 X12CrNi 25 20 1.4842
X15CrNiSi 25 20 1.4841 25 20 X12CrNi 25 20 1.4842
X12 NiCrSi 36 16 1.4864 18 36 X12CrNi 25 20 1.4863
X10NiCrAITi 32 20 1.48763 S-NiCr 15 FeNb X12CrNi 36 18 2.4806
S-NiCr 15 FeMn S-NiCr 20Nb

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