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Stainless Steels at High Temperatures
Stainless Steels at High Temperatures
Euro Inox
Cedinox
www.cedinox.es
Centro Inox
www.centroinox.it
ConstruirAcier
www.construiracier.fr
Industeel
www.industeel.info
Nickel Institute
www.nickelinstitute.org
SWISS INOX
ISBN 978-2-87997-064-6 www.swissinox.ch
S tain l ess S tee l s at hi g h tem p e r at u r es
Contents
1
STAINLESS STEELS AT HIGH TEMPERATURES
1 Introduction
Stainless steels are mainly used for their re- Depending on the operating conditions, the
sistance to aqueous corrosion but are also requirements on material used at high tem-
widely used at high temperatures when peratures may be as follows:
carbon and low-alloyed steels do not pro- • high creep strength (and/or ductility)
vide adequate corrosion resistance and/or • good resistance to oxidation and high-
strength. They can be found in applications temperature corrosion
in which high-temperature oxidation resist- • stable microstructure
ance or high-temperature strength are re- • good resistance to erosion corrosion
quired [1]. Construction material is exposed
to high temperatures in many industrial, Material selection should be determined by
public and domestic applications, some- the specific application and operating con-
times in connection with an aggressive en- ditions in each case [2].
vironment.
22
Ti 23
Tita
nium
V 24
Zr
40 Van
adiu
Cr 25
Mn
m
41 5
B
Chr
26
Nb
omi
F
um
6
e C 42
con
C
Man
M 27
ium gan
ese
o T
Bor
2 43
o
Nio on
bium
28 Iron
f T 73
c N
13 Car
A
Mol
44
i
ybd bon
R
29
l
eniu
a W 75
Cob
14
Cu 0
m alt
7 4
u R S
Tec
4 5
hne
3
i
tium Nick Alum
Z
el
h
Tan iniu
n
talu Rut m
46
Re 6
m eniu
3
Pd 47
Cop
105 1 m
G
per Silic
7 Tun
Db
on
a
g
O
sten Rho
32 dium
Ag 8
Zinc Ph
s I 77
Ge
Rhe
Sg 107
Pall
nium
4 adiu
C
Gal
r P
Dub m lium
7
d A
nium
B
Osm
8 4 ium Silv
h 9 er Ger
In
Sea man
108
t A
borg ium
79
H
ium Iridi Cad
5 0
um
s
59 miu
S
Ars
109
u H
m
Pr 60
Boh en
80
n
rium Plat
M
inum
51 Indi
t D S
um
Nd 61 110
g
Has
81
b
sium Gol
2 d
s T
Tin
Pm 62 111 Mei
l P
miu tner
82
R
m ium Mer
Neo cury Ant
g
dym imo
S
Dar
b
ny
ium
112 mstad
m 83 Tha
92 tium
U
Pro llium
6
U B
met
3 hium
113
Roe
ntge
nium Lea
9 Sam d
STAINLESS STEELS AT HIGH TEMPERATURES
Alloys for high-temperature applications are Higher nitrogen and carbon content en-
designed to be able to form protective oxide hance creep strength.
scales. The only oxides that meet the cri-
teria for protective scales and can form on Molybdenum increases high-temperature
practical alloys are chromium oxide (Cr2O3), creep-rupture strength. It is usually limited
aluminium oxide (Al2O3) and, possibly, sili- to 3.0 %. Higher molybdenum content can
con dioxide (SiO2). cause serious oxidation problems and pro-
mote sigma-phase formation, unless coun-
The effect of chromium is particularly evi- terbalanced by austenite-forming elements
dent at temperatures above 500 °C. This such as nickel.
element forms a tight, adherent layer of
chromium-rich oxide on the surface of the Titanium added in small amounts of about
metal, retarding the inward diffusion of oxy- 0.3−0.7 % increases strength in austenitic
gen and impeding further reaction [3]. alloys. The same is true for niobium. Both
promote sigma-phase formation.
Other elements besides chromium may
also be added to stainless steel to increase Boron increases creep-rupture strength
oxidation resistance. Silicon and aluminium and is used at rather low concentrations –
act very similarly to chromium. They oxi- typically 0.002 %. This interstitial element
dise selectively and if present in sufficient tends to concentrate at the grain boundary.
amounts can form continuous films of SiO2
and Al2O3. The adherence of the oxide scale
can be greatly improved by small additions
of rare earth metals (REM) such as cerium or
lanthanum [4]. This is particularly beneficial
when the application is subjected to ther-
mal cycling [5].
3
STAINLESS STEELS AT HIGH TEMPERATURES
Microstructure is less important for heat re- For most ferritic grades, long-term service
sistance than chemical composition or the temperature is usually limited to 250 °C,
appropriate selection of alloying elements due to 475 °C embrittlement. This does
but affects suitability for high-temperature not seem to be a serious problem in low-
service for other reasons. The grades of chromium steel grades with 10.5−12.5 % Cr,
wrought stainless steels and nickel-based where temperatures can at times exceed
alloys usually used for products where the 575 °C. One reason is that 475 °C embrittle-
main requirement is resistance to the effect ment can be reversed by heat treatment at
of hot gases and combustion products at higher temperatures. The resistance of some
temperatures above 550 °C are specified in ferritic grades to atmospheric corrosion and
European standard EN 10095 – Heat resist- high-temperature oxidation, and their rela-
ant steels and nickel alloys [6]. This stand- tively low cost, explain why these grades
ard comprises 6 ferritic grades (see Table 1), have been extensively used in automotive
14 austenitic heat-resistant grades (Table 2) exhaust systems [7]. Other exceptions to
and 1 duplex heat-resistant grade (Table 3). the maximum service-temperature limit are
high-alloyed chromium steel grades with
With time and temperature, any metal can 23−27 % Cr, which offer outstanding scal-
be expected to undergo changes in metal- ing resistance in air at high temperatures,
lurgical structure. In stainless steel, the due to their high chromium content. More
changes can be softening, carbide precipi- details on structural stability are provided
tation or embrittlement [8]. later in this publication. Minimum operating
temperatures (to avoid embrittlement) may
be valid in some cases.
4
STAINLESS STEELS AT HIGH TEMPERATURES
MPa ksi
Tensile Strength for Rupture in 1000 h
600
Martensitic and
400 Ferritic Grades
Austenitic
50
Grades
200
Low-Carbon
Unalloyable Steel
Temperature
Figure 1: General comparison of the hot-strength characteristics of austenitic, martensitic and ferritic stainless
steels with those of low-carbon unalloyed steel [8]
5
STAINLESS STEELS AT HIGH TEMPERATURES
1.4878 X8CrNiTi18-10 321H max. 0.10 max. 1.00 max. 2.00 17.0−19.00 9.00−12.00 Ti: 5·%C≤Ti≤0.80
1.4835 X9CrNiSiNCe21-11-2 S30815 0.05-0.12 1.40-2.50 max. 1.00 20.00−22.00 10.00−12.00 Ce: 0.03−0.08
1.4833 X12CrNi23-13 309S max. 0.15 max. 1.00 max. 2.00 22.00−24.00 12.00−14.00
1.4845 X8CrNi25-21 310S max. 0.1 max. 1.50 max. 2.00 24.00−26.00 19.00−22.00
1.4841 X15CrNiSi25-21 314 max. 0.20 1.50−2.50 max. 2.00 24.00−26.00 19.00−22.00
Al: 0.15−0.60
1.4876 X10NicrAlTi32-21 - max. 0.12 max. 1.00 max. 2.00 19.00−23.00 30.00−34.00
Ti: 0.15−0.60
Al: max. 0.025
1.4877 X6NiCrNbCe32-27 - 0.04−0.08 max.0.30 max. 1.00 26.00−28.00 31.00−33.00 Ce: 0.05−0.10
Nb: 0.60−1.00
1.4872 X25CrMnNiN25-9-7 - 0.20−0.30 max.1.00 8.00−10.00 24.00−26.00 6.00−8.00 N: 0.20−0.40
1.4818 X6CrNiSiNCe19-10 S30415 0.04−0.08 1.00−2.00 max. 1.00 18.00−20.00 9.00−11.00 Ce: 0.03−0.08
N: 0.12−0.20
1.4854 X6NiCrSiNCe35-25* S35315 0.04−0.08 1.20−2.00 max. 2.00 24.00−26.00 34.00−36.00
Ce: 0.03−0.08
1.4886 X10NiCrSi35-19 N08330 max. 0.15 1.00−2.00 max. 2.00 17.00−20.00 33.00−37.00
1.4887 X10NiCrSiNb35-22 - max. 0.15 1.00−2.00 max. 2.00 20.00−23.00 33.00−37.00 Nb: 1.00−1.50
Duplex stainless steels have a mixed ferrite The latest research confirms that duplex
and austenite structure. Their yield strength grades have somewhat lower strength re-
is in the range of 550 MPa to 690 MPa tention than comparable austenitic grades
in the annealed condition – significantly in the higher-temperature range. However,
higher than that of their austenitic or fer- even in the high-temperature range typical
ritic counterparts. Despite this relatively of fire situations, their absolute strength is
high strength at room temperature, duplex still similar to that of austenitic grades [11].
grades are subject to embrittlement and The highest temperature therefore depends
loss of mechanical properties, particularly on mechanical properties (e.g. pressure
toughness, through prolonged exposure vessels) and needs to be qualified for the
to high temperatures. As a result, duplex steel concerned.
stainless steels are generally not recom-
mended for high-temperature applications,
their upper temperature limit being gener-
ally not higher than approximately 300 °C.
6
STAINLESS STEELS AT HIGH TEMPERATURES
Precipitation-hardening (PH) stainless steels The temperature range in which the above
are chromium-nickel grades whose strength stainless steel grades are used is somewhat
can be increased by age hardening. Age lower than that of steel grades specifically de-
hardening is provided by an intermediate- signed and listed as heat resistant. It should
temperature ageing treatment. These steels be borne in mind that maximum service tem-
are of limited use for high-temperature ser- perature differs depending on whether ser-
vice in the aged condition, since they lose vice is intermittent or continuous.
strength rapidly at temperatures above
about 425 °C [12]. They will therefore not be The embrittlement mechanisms discussed
discussed further here. under structural stability should be taken
into account, as they also usually set in be-
Grades designed for aqueous-corrosion re- low the maximum service temperature.
sistance may also be used as heat-resistant
steel grades where corrosion resistance is
of high importance. These steel grades are
listed in EN 10088-1 and EN 10028-7 [13] and
shown below in Table 4.
Table 4: Grades from EN 10088-1 and EN 10028-7 which are used in addition to those in EN10095 as heat-resist-
ant steels
Steels from EN 10088-1 Steels from EN 10028-7 Approximate AISI/ASTM
Number Name Number Name designation
1.4512 X2CrTi12 409
1.4000 X6CrTi13 410S
1.4016 X6Cr17 430
1.4510 X3CrTi17 1.4510 X3CrTi17 439
1.4590 X2CrNbZr17
1.4509 X2CrTiNb18 1.4509 X2CrTiNb18
1.4006 X12Cr13 410
1.4301 X5CrNi18-10 1.4301 X5CrNi18-10 304
1.4948 X6CrNi18-10 304H
1.4541 X6CrNiTi18-19 1.4541 X6CrNiTi18-19 321
1.4941 X7CrNiTiB18-10
1.4950 X6CrNi23-13
1.4951 X6CrNi25-20
1.4362 X2CrNiN23-4 1.4362 X2CrNiN23-4 2304
7
STAINLESS STEELS AT HIGH TEMPERATURES
At high temperatures, metals under stress pressed in terms of “creep strength” – its
are subject to slow plastic deformation as ability to resist distortion over long-term ex-
well as elastic deformation. Time therefore posure to a high temperature. Creep occurs
becomes a critical factor and conventional in most applications where metal tempera-
tensile tests do not furnish values that are tures exceed 480 °C. In time, creep may lead
useful in design. The data required is that to excessive deformation and even fracture
indicating the load which will produce at stresses considerably below those de-
no more than an allowable percentage of termined in room-temperature and high-
elongation at a specified temperature over temperature short-term tensile tests. It is
a given period of time. High-temperature usually satisfactory if creep does not exceed
strength properties thus involve factors of 1 % deformation in 10,000 hours. This does
time and deformation as well as stress and not mean that this rate of creep can be ex-
temperature [14]. pected to continue for 10,000 hours without
failure in every instance.
The strength of materials at high tempera-
ture is not measured in the same way as at Creep values obtained under constant load
room temperature. For room-temperature and temperature conditions are applicable
applications – automobile frames, claw to design. However, safety factors should
hammers, etc. – the designer needs to know always be incorporated. The safety factor
tensile strength, yield strength or hardness, will depend on the degree to which the ap-
but when the material is exposed to high plication is critical [14]. Of the various types
temperatures, the most important mechani- of stainless steel, austenitics provide the
cal property is creep or rupture strength [15]. highest creep strength.
8
STAINLESS STEELS AT HIGH TEMPERATURES
Temperature, °F
900 1.000 1.100 1.200 1.300 1.400 1.500
689 100.000
552 80.000
414 60.000
276 40.000
207 30.000
Stress-rupture strength in 10.000 h, MPa
138 20.000
69 10.000
55 8.000
41 6.000
1.4301 (304)
28 4.000 1.4307 (304L)
1.4401 (316)
21 3.000 1.4404 (316L)
1.4541 (321)
14 2.000 1.4550 (347)
1.4833 (309S)
1.4845 (310S)
Plain carbon steel
7 1.000
482 538 593 649 705 760 816
Temperature, °C
9
STAINLESS STEELS AT HIGH TEMPERATURES
4.3 Short-term tensile strength The values obtained are as much as five or six
times the limiting creep-strength values and
Historically, the method used for studying therefore greatly over-evaluate load-carrying
the high-temperature properties of metals ability over a long period of time. High-tem-
and alloys has been short-term tensile test- perature tensile test results can be helpful in
ing. While these tests have been largely su- evaluating resistance to momentary overloads
perseded for design purposes by long-term and are included in some specifications.
creep and rupture tests, high-temperature
tensile testing nevertheless furnishes use- Over about 550 °C, tensile and yield strength
ful data for preliminary appraisal. cannot be used as a basis for design.
10
STAINLESS STEELS AT HIGH TEMPERATURES
4.4 Ductility
1
The importance of using sections that are as light as possible should often be considered in design, as less mass means
less strained material. A change of dimensions from 12.7 mm to 15.9 mm in diameter for a bar frame basket, for example,
could result in halving the lifetime, rather than making the basket stronger. In this case, with increasing diameter the ther-
mal strains were significantly higher. Thermal stress causes more distortion and cracking in heat-resistant alloy equipment
than do the mechanical loads imposed on the part [14].
11
STAINLESS STEELS AT HIGH TEMPERATURES
Heat-resistant alloys have inherently high In the equation, α stands for coefficient of
coefficients of thermal expansion and low thermal expansion, Lo for original length
heat conductivity – both properties tending and T for change in temperature.
to produce temperature and stress differ-
ences between different areas of a part or Table 5: Coefficient of thermal expansion - average
values [18]
assembly. Coefficient of thermal expansion
Coefficient of
is expressed in units of proportional change thermal expansion
(·10-6·K-1)
of length for each degree increase in tem-
Carbon steel 12
perature, usually as 10-6·K-1. Other units
Austenitic stainless steel 17
sometimes used are 10-6/°C, µm/m/°C and
Duplex stainless steel 14
10-6cm/cm/°C. These are identical but are
Ferritic stainless steel 10
outside the International System of Units2.
Martensitic stainless steel 10
2
abbreviated as “SI system” from the French “Système International d’Unités”
12
STAINLESS STEELS AT HIGH TEMPERATURES
a Temperature, °F c Temperature, °F
0 400 800 1200 1600 0 400 800 1200 1600
1250 80
Elongation in 50 mm (2 in.), %
150
1000 60
Tensile strength, MPa
120
750
40
80
500
20
40
200
0
-20 205 425 650 870
0 0
-20 205 425 650 870 Temperature, °C
Temperature, °C
b Temperature, °F
Annealed
1/4 hard
0 400 800 1200 1600 1/2 hard
0.2 % offset yield strength, MPa
1000
0.2 % offset yield strength, ksi
120
750
80
500
40
200
Figure 3: The effect of short-term high temperature
on the tensile properties of cold-worked steel grade
0 0
-20 205 425 650 870 1.4310 (301). (a) Tensile strength, (b) Yield strength,
Temperature, °C (c) Elongation [25].
13
STAINLESS STEELS AT HIGH TEMPERATURES
5 Microstructure stability
Some materials change after a few hundred are Laves and chi (χ) phases. In the case of
or thousand hours in service. They become Laves phase, such intermetallics can even
brittle instead of remaining tough and ductile. improve high-temperature creep strength.
The most common problem is that the alloy
forms a hard, brittle, non-magnetic phase, Intermetallic phase embrittlement is primar-
called sigma. Sigma phase forms in the tem- ily a service problem involving long exposure
perature range of 500–980 °C [15]. This micro- to high temperatures. These phases can be
structural change can occur in austenitic, ferri- dissolved by heating to above 1000 °C [12].
tic or duplex stainless steel, the process being
dependent on both time and temperature. At temperatures between 400 °C and 500 °C,
Some lower-chromium ferritic grades can ferritic stainless steels tend to split into two
form sigma phase at temperatures as low as separate phases, with respectively high and
480 °C, albeit over extended periods of time. low chromium contents. The rate of the re-
In addition to temperature, the time required action reaches its maximum at 475 °C and is
to form sigma phase varies considerably de- therefore called 475 °C embrittlement. The
pending on composition and processing (the 11 % Cr ferritic grades are the least sensitive
amount of cold working, for example). Embrit- to this phenomenon, which occurs only to a
tlement due to sigma phase starts rapidly if limited extent in 17 % Cr alloys, whereas 25 %
the material has been cold worked. Cr materials, including duplex stainless
steels, are highly prone to it [23].
With a sufficiently high level of nickel, sig-
ma-phase formation can be completely sup- At high temperatures, grain growth may also
pressed. If a material is to be used in the occur, possibly increasing creep strength
sigma-phase-formation range, it is impor- somewhat but simultaneously substantially
tant to evaluate how much embrittlement reducing ductility. Even if these microstructur-
is likely to occur over the service life of the al changes lead to impaired material proper-
component and what effect this will have on ties, they can be acceptable as long as one is
the component’s performance. aware of them and considers them during ser-
vice as well as at maintenance shutdowns [2].
Embrittlement is not normally a problem
when material is at operating temperature
Some austenitic stainless steels can
(except when thermal fatigue is involved)
suffer significant ductility loss or em-
but can become serious at ambient tem-
brittlement upon long-term exposure to
peratures [19]. Generally, such phases are
intermediate temperatures (500−900 °C),
of the most concern when affected parts are
due to sigma phase formation [25]. Use
cooled down to room temperature. At high
of iron-chromium-nickel types should
temperatures, from a ductility or toughness
be limited to applications in which tem-
standpoint, the phases do not appear to be
peratures are steady and not within the
a major problem. Other intermetallic phas-
sigma-forming temperature range [24].
es very often present besides sigma phase
14
STAINLESS STEELS AT HIGH TEMPERATURES
YES
(long
1.4742 X10CrAl18 - 550−1000 1000 - Medium YES - YES - -
expo-
sure)
Medium
but YES σ-phase after long exposure,
1.4762 X10CrAl24 - 550−1150 1150 - higher YES - (long ex- YES - but faster than 1.4742
than posure) grain growth
1.4742
15
STAINLESS STEELS AT HIGH TEMPERATURES
16
STAINLESS STEELS AT HIGH TEMPERATURES
Water vapour has a specific effect on oxida- Historically, the oxidation resistance of an
tion. Thus, while oxidation rates in air are alloy has been specified as the “scaling
generally slightly lower than in pure oxygen, temperature”, i.e. the temperature at which
water vapour significantly increases the cor- the oxidation rate becomes unacceptably
rosion rate, particularly in iron-rich alloys. The high. Since this temperature is of little tech-
oxide layer formed tends to be porous and nical importance, the concept of “scaling
less protective. This is generally attributed to temperature” has been abandoned.
the formation of volatile chromium-oxide and
hydroxide species. A cold-worked surface The maximum application temperatures for
leads to improved behaviour in water vapour air are given in EN 10095.
compared to an annealed structure, since it
promotes the formation of a compact layer of
Cr2O3 [4]. If elevated water vapour content is
present, the maximum recommended service
temperature can be reduced by 50−150 °C,
depending on steam content [27].
Table 7: Maximum application temperature in air for some heat-resistant stainless steel grades (for guidance only) [6]
Steel designation Maximum application
Approximate AISI/ASTM temperature
Number Name °C
designation
17
STAINLESS STEELS AT HIGH TEMPERATURES
Table 8: Generally accepted maximum service temperatures in air for some standard stainless steel grades (for guidance only) [12]
Steel designation Maximum service temperature
Approximate AISI/ASTM Intermittent service Continuous service
Number Name
designation °C °C
1600
1400
1200
1000
Weight gain, g/m2
800
600
1.4818
400
1.4833
1.4828
1.4835
200
1.4845
1.4854
Time, h
Figure 4: Long-term oxidation at 1100 °C. The specimens were cooled down to room temperature once a week for weighting, 165 h cycles [28].
18
STAINLESS STEELS AT HIGH TEMPERATURES
6.2 Sulphidation adherent oxide layer. This requires high Materials may be
chromium content and preferably also addi- exposed to extreme
conditions. Photo: Drever
As with oxidation, resistance to sulphida- tions of silicon, aluminium and REM.
International, Angleur
tion relates to chromium content. Unalloyed (Liège) (B)
iron will be converted rather rapidly to iron- In addition to the usual factors of time, tem-
sulphide scale, but when iron is alloyed perature and concentration, sulphidation
with chromium, sulphidation resistance is depends on the form in which the sulphur
enhanced. Alloying elements that provide exists. Of particular interest are the effects
some protection against sulphidation are of sulphur dioxide, sulphur vapour, hydro-
silicon, aluminium and titanium. gen sulphide and flue gases. Combustion
gases normally contain sulphur compounds.
Various sulphur compounds are often pre- Sulphur dioxide is present as an oxidising
sent in flue gases and other process gases. gas, along with CO, CO2, nitrogen and ex-
They have a highly detrimental effect on the cess oxygen. Protective oxides are generally
useful life of exposed components. Due to formed and, depending on the conditions,
kinetic factors, non-equilibrium sulphides the corrosion rate may be approximately the
can form and grow under (nominally) oxi- same as in air or slightly greater. The resist-
dising conditions. Even if initially formed ance of stainless steels to normal combus-
sulphides are later overgrown by oxide or tion gases goes up as chromium content is
dissolved, their earlier existence has made increased.
the oxide layer less protective. In existing
oxide layers, attacks can occur in pores
and cracks. It is therefore essential that the
material is able to form a thin, tough and
19
STAINLESS STEELS AT HIGH TEMPERATURES
20
STAINLESS STEELS AT HIGH TEMPERATURES
21
STAINLESS STEELS AT HIGH TEMPERATURES
22
STAINLESS STEELS AT HIGH TEMPERATURES
Hot working should be carried out within the (GTAW, also TIG), plasma arc welding (PAW)
temperature ranges given in Table 11. Like and gas metal arc welding (GMAW, also
other austenitic steels, heat-resistant steels MIG), with pure argon used as the shielding
can be formed in cold condition. However, gas, and submerged arc welding (SAW).
due to their relatively high nitrogen content,
the mechanical strength of certain steels is Heat treatment after hot or cold forming or
higher and greater deformation forces are welding is often not needed if the material
consequently required. The relatively high is exposed to high temperature during ser-
hardness of austenitic steels and their abil- vice. However, if that is not sufficient, the
ity to strain-harden must be taken into con- best option is solution annealing for auste-
sideration when machining. nitic stainless steels and soft annealing for
ferritic stainless steels. Suitable tempera-
These steels have good or very good weld- ture ranges are given in Table 11.
ability and can be welded using the follow-
ing methods: shielded metal arc welding
(SMAW) with covered electrodes, gas shield-
ed welding, e.g. gas tungsten arc welding
Table 10: Weldability and welding filler materials for some selected heat-resistant steels [32]
23
STAINLESS STEELS AT HIGH TEMPERATURES
Steel designation
Hot working Soft annealing Solution annealing
Nearest °C °C* °C
Name Number
ASTM/AISI
24
STAINLESS STEELS AT HIGH TEMPERATURES
25
STAINLESS STEELS AT HIGH TEMPERATURES
Alloys intended for use in high-temperature scale thickness. Continuous weight change
environments rely on the formation of a is usually obtained by thermo-gravimetric
continuous, compact, slow-growing oxide analysis (TGA). Weight change data pro-
layer for oxidation and hot-corrosion resist- vides a very useful measure of the amount
ance. To be protective, this oxide layer must of metal converted to oxide and a helpful
be chemically, thermodynamically and me- comparison among alloys. However, the ul-
chanically stable. Successful alloy design timate engineering criterion of the oxidation
for oxidative environments is best achieved resistance of a material is retention of me-
by forming adherent scales of either alumi- chanical properties after exposure. Creep-
na (Al2O3), chromia (Cr2O3) or silica (SiO2). rupture data from inert atmosphere tests
cannot be used for design purposes when
The basic test method for evaluating oxi- the material will be exposed to conditions
dation resistance is to expose the mate- of severe oxidation [25].
rial, monitor the kinetics and subsequently
characterise the oxidation products and
substrate material. Exposures are most of-
ten performed in air, but can be done in any
controlled mix of corrosive gases, such as
H2/H2S, CO/CO2 or O2/SO2. Oxidation kinet-
ics are usually recorded as weight changes
but may also be followed as changes in
Austenitic stainless
steels are used in
environments in which
a combination of high-
temperature corrosion
resistance and mechani-
cal strength is required.
Photo: Stappert Spezial-
Stahl Handel,
Düsseldorf (D)
26
STAINLESS STEELS AT HIGH TEMPERATURES
Technical data illustrating the properties of Air – Those alloys useful in plain hot air are
heat-resistant alloys is a very helpful guide in also suitable for the oxidising combustion
selecting a suitable alloy for an application. products of natural gas and even coal. Gen-
However, long-term exposure to different erally, oxidation and strength are the only
environments and temperatures can neither issues. “Oxidation” usually refers to metal
be completely documented nor described by wastage, but concern about product contam-
laboratory tests. Experiences obtained from ination from scale is an occasional issue [15].
many actual installations are most helpful.
One must develop the judgement needed The combustion of fossil fuels, biofuels or
to determine which of the many factors in- waste produces combustion gases contain-
volved are the most important. ing various aggressive impurities. The least
contaminated fuel is natural gas, the com-
10.1 Temperature bustion products of which are mainly car-
bon monoxide, carbon dioxide and water. It
Temperature is often the first and sometimes may contain minor amounts of sulphur. The
the only data point given in alloy selection, reduction in maximum service temperature
but a successful material selection cannot compared to pure-air exposure is modest,
be based on temperature alone. A simple at around 50−100 °C. Sulphur is more abun-
first guide to alloy selection, however, is to dant in coal and oil. In addition, coal contains
know the maximum temperature at which a chlorine, while rather high levels of vanadi-
given alloy may have useful long-term engi- um can be found in oil. Impurity levels vary
neering properties. Thin sheet material will according to the grade and origin of the fuel
have a lower limiting temperature, due to and can lead to more than 500 °C of reduc-
proportionally greater losses to oxidation. tion in maximum service temperature com-
pared to service in air (see also Table 7 and
10.2 Atmosphere and combustion Table 8). High-nickel alloys are preferred in
gases high-chlorine or fluorine atmospheres [26].
27
STAINLESS STEELS AT HIGH TEMPERATURES
11 Applications
28
STAINLESS STEELS AT HIGH TEMPERATURES
boxes; and for grade 1.4941, pres- 1.4841 is a variant of 1.4845 with in-
sure vessels and steam boilers. creased silicon content for increased
resistance to oxidation. More suscep-
1.4828 is used for service at temper- tible to embrittlement than 1.4845, it
atures up to 950−1000 °C in dry air. is often used for superheater suspen-
Utilisation in the 600−900 °C tem- sions, annealing pots and enamel-
perature range can lead to embrit- ling grates.
tlement of the material. This grade is
used for parts exposed to both high 1.4845 is used at temperatures up to
temperatures and high mechanical 1100 °C in dry air. This steel is also
loads. Typical examples include sup- prone to embrittlement when used in
porting elements and pipes in furnac- the 600−900 °C temperature range.
es, annealing bells, cementation and There is also a creep-resistant vari-
hardening boxes and annealing pots. ant of 1.4845, i.e. 1.4951, which is
included in EN 10028-7 and in ASTM
1.4833 (309S) and 1.4845 (310S) A 240. Applications can be found in
rank higher because of their higher industrial furnaces, seam boilers and
nickel and chromium content. Steel petroleum processing plants.
grade 1.4845 (310S) is useful where
intermittent heating and cooling 1.4854. The maximum service tem-
are encountered, because it forms perature in air is 1150 °C, but after
a more adherent scale than type service at temperatures below ap-
1.4833 (309 S). Both grades are used proximately 950 °C, there is a risk of
for parts such a firebox sheets, fur- reduced room-temperature impact
nace linings, boiler baffles, thermo- toughness.
couple wells, aircraft-cabin heaters
and jet-engine burner liners.
29
STAINLESS STEELS AT HIGH TEMPERATURES
30
STAINLESS STEELS AT HIGH TEMPERATURES
12 Cost considerations
Some of the factors affecting the service life, From a competitive standpoint, alloy selec-
not necessarily in order of importance, are tion must be based on expected cost-ef-
alloy selection, design, maintenance proce- fectiveness. The best choice is usually the
dures, furnace and temperature control, at- lowest-cost material able to meet design
mosphere, contamination of atmosphere or criteria. However, a higher-cost material of-
workload, accidents, number of shifts oper- fering greater reliability may be justified for
ated, thermal cycles and overloading. High- certain components in a system that is criti-
alloyed parts may last from a few months to cal and/or expensive to shut down for main-
many years, depending on operating condi- tenance. Knowledge of alloy capabilities can
tions. In selecting a heat-resistant steel for be helpful in making a wise decision [25].
a given application, all properties should
be considered in relation to the operating Heat-resistant alloys are supplied in either
requirements, to obtain the most economi- wrought or cast forms. In some situations,
cal life. they may be a combination of the two. The
properties and costs of the two forms vary,
Life expectancy is best measured in cycles even though their chemical compositions
rather than hours, particularly if the parts are similar.
are quenched. It may be cheaper to replace
all trays after a certain number of cycles,
to avoid expensive shutdowns caused by
wrecks in the furnace. Chains or belts that
cycle from room temperature to operating
temperature several times a shift will not
last as long as stationary parts that do not
fluctuate in temperature. Parts for carburis-
ing furnaces will not last as long as those
used for straight annealing [16].
31
STAINLESS STEELS AT HIGH TEMPERATURES
13 Summary
It should be apparent that the intelligent and repair must be carefully planned and
selection of an alloy for high-temperature can only be performed during annual or
service is a complex business and should semi-annual shutdowns. Obviously, a more
not be lightly or inexpertly undertaken. It careful choice of material must be made in
should also be evident that choice will never those cases.
be easy, since the ideal alloy that satisfacto-
rily fills all of every designer’s requirements Choosing material for high-temperature ap-
will never be discovered [3]. plications requires an extensive knowledge
of existing or expected service conditions,
The very complex nature of high-tempera- such as gas temperature and composition
ture corrosion and the lack of standardised and material temperature. Knowledge of
testing practices make it virtually impossi- previously used materials, their service per-
ble or at least not meaningful to present cor- formance and the cause(s) of previous fail-
rosion data in tables. ures is usually of great help when trying to
identify an optimum grade [26].
Corrosion-resistance requirements de-
pend on the processes and constructions
involved. In some plants, components can
be maintained, repaired, or replaced with
little if any interference to normal service
while in other applications maintenance
32
STAINLESS STEELS AT HIGH TEMPERATURES
14 Appendix
The values in the tables are given for guidance only [6].
Table 12: Creep properties. Estimated average value of strength for rupture at high temperature(1)
Creep-rupture strength Rm (N/mm2) Creep-rupture strength Rm (N/mm2) Creep-rupture strength Rm (N/mm2)
1,000 h 10,000 h 100,000 h
Nearest
Number AISI/ Temperature Temperature Temperature
ASTM °C °C °C
500 600 700 800 900 1000 500 600 700 800 900 1000 500 600 700 800 900 1000
(1)
Values in parentheses involve time and/or stress extrapolation
33
STAINLESS STEELS AT HIGH TEMPERATURES
Table 13: Creep properties. Estimated average value of strength for 1 % elongation at high temperature(1)
Elongation 1 % in 1,000 h Elongation 1 % in 10,000 h Elongation 1 % in 100,000 h
(Strength in N/mm2) (Strength in N/mm2) (Strength in N/mm2)
Nearest
Number AISI/ Temperature Temperature Temperature
ASTM °C °C °C
500 600 700 800 900 1000 500 600 700 800 900 1000 500 600 700 800 900 1000
(1)
Values in parentheses involve time and/or stress extrapolation
34
STAINLESS STEELS AT HIGH TEMPERATURES
(1)
slightly magnetic when cold worked
35
STAINLESS STEELS AT HIGH TEMPERATURES
15 References
36
STAINLESS STEELS AT HIGH TEMPERATURES
37
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