Stainless Steels: Martensitic
the precipitation of Mo C (Raynor et al. 1966) and
Martensitic stainless steels are used when corrosion
resistance and\or oxidation resistance are required in
combination with either high strength at low tem-
peratures or creep resistance at elevated temperatures.
There are essentially three types of martensitic stain-
less steels. The first type comprises those which contain
carbon and which are strengthened by iron carbide
precipitation when tempered at low temperatures or
by alloy carbide precipitation on tempering at higher
temperatures (secondary hardening). The second type
is the steels which contain low amounts of carbon but
which are strengthened by the precipitation of particles
of copper or intermetallics on tempering. The third
type is those which are strengthened by the pre-
cipitation of both alloy carbides and intermetallics. All
three types have in common a high chromium content
and alloying combinations that allow austenitization
at some elevated temperature, and martensite start
and finish temperatures which permit quenching from
the austenitizing temperature to obtain an almost
completely martensitic structure with small amounts
of retained austenite. Several review articles discuss
the history and physical metallurgy of these steels
(Irvine et al. 1960, Irvine and Pickering 1964, Pickering
1976). Pickering’s Physical Metallurgy and the Design
of Steels provides an excellent beginning for reading
about these alloys (Pickering 1978). The Physical
Metallurgy of Steels contains useful information about
all classes of stainless steels, including the martensitic
stainless steels (Leslie 1981).
1. Alloying of Martensitic Stainless Steels
The first requirement is that that the steels contain
sufficient chromium to provide for corrosion resist-
ance, which is achieved by the formation of a chro-
mium oxide film on the surface of the steel. It is
generally believed that about 11 wt.% chromium is
required for a steel to have stainless characteristics.
However, the amounts of chromium required can vary
with the composition of the steel, the microstructure
of the steel, the extent to which the chromium content
of the matrix is reduced owing to the formation of
chromium-rich second phase particles such as chro-
mium carbides, and the nature of the environment.
The second requirement is that the steel can be
austenitized. A binary Fe–Cr alloy containing more
than about 10.5 wt.% chromium cannot be auste-
nitized (Lovejoy 1977). To allow the use of chromium
contents of more than 10.5 wt.% austenite stabilizers
such as carbon, nitrogen, nickel, and manganese are
normally added to these alloys (Lovejoy 1977).
Other elements are normally added to control the
type and volume fractions of strengthening particles
precipitated on tempering. For example, molybdenum
and tungsten are common additions to the carbide
strengthened martensitic stainless steels and result in
W C particles (Davenport # and Honeycombe 1975).
#
Elements such as titanium and aluminum are added to
the low carbon martensitic stainless steels to promote
the precipitation of intermetallics such as NiTi and
NiAl on tempering (Pickering 1976, Perry and Jasper
1977). Molybdenum, tungsten, titanium, and alumi-
num are ferrite stabilizers which reduce the size of the
austenite phase field and austenite stabilizers are
sometimes required to compensate for the additions of
the ferrite stabilizers used to form strengthening
precipitates.
The alloying additions used for corrosion and
oxidation resistance, to achieve high strength and to
achieve austenitization, must also permit a fully
martensitic structure on quenching from the austen-
itizing temperature. This means that the martensite
start and finish temperatures cannot be too low. The
effects of alloying additions on the martensite start
and finish temperatures have been extensively studied
for low alloy and high alloy steels both with and
without carbon and chromium. All elements except
cobalt depress the martensite start temperatures
(Pickering 1978, Magnee et al. 1974). While cobalt
raises the martensite start temperature in some systems
it depresses the martensite start temperature in Fe–Cr
alloys (Hammond 1964) and to an even greater degree
in Fe–Cr–C alloys (Coutsouradis 1961), although the
effect of cobalt on depressing the martensite start
temperature is never as great as that of other substi-
tutional alloying additions such as chromium, nickel,
and molybdenum.
2. Heat Treatment and As-quenched
Microstructures
The martensitic stainless steels are austenitized, cooled
to room temperature, possibly refrigerated at some
temperature below room temperature to minimize
retained austenite content, and then tempered to
achieve the desired strength and toughness.
A critical aspect of the heat treatment of these steels
is the cooling rate employed while quenching from the
austenitizing temperature. First, if the cooling rate is
too rapid there is the possibility of quench cracking of
the carbon steels. Quench cracking is a problem in all
steels containing carbon but it is a particular problem
in steels containing carbon and large amounts of
chromium. This is because the volume expansion
associated with the austenite to martensite transform-
ation increases with increasing carbon and chromium
contents (Kenneford 1958). Therefore, water and oil
quenching of carbon-containing martensitic stainless
steels should be approached with caution. However,
slow cooling of the carbon-containing martensitic
stainless steels can lead to large amounts of retained
austenite in the as-quenched structure, which is also
1
Stainless Steels: Martensitic

undesirable. The effects of the rate of quenching on the
microstructure and mechanical properties has not
been investigated to the same extent for the low carbon
precipitation-strengthened stainless steels. Because of
their low carbon contents these materials should not
be as susceptible to quench cracking as the carbon-
containing martensitic stainless steels.
The as-quenched microstructure of most martensitic
stainless steels are similar. They will contain inclu-
sions, as do all steels, fine second-phase particles
inherited from the austenitizing temperature, and will
largely consist of lath or dislocated martensite rather
than plate martensite. There will be thin films of
retained austenite between martensite laths, between
martensite packets and at the former austenite grain
boundaries if lath martensite is formed. Significant
amounts of plate or twinned martensite should be
observed only in the steels containing more than about
0.30 wt.% carbon. There will be regions of retained
austenite between the martensite plates if plate
martensite is formed.
3. Toughness/Strength Relationships
When the room temperature strength and some
measure of toughness, such as the Charpy impact
energy, are plotted as a function of tempering tem-
perature a minimum in toughness is observed which is
usually coincident with the onset of precipitation
hardening, whether the precipitation strengthening is
by particles of intermetallics or by fine alloy carbides.
The minimum toughness is often, but not always,
associated with cleavage or quasi-cleavage fracture,
indicating that the microstructures with the minimum
in the room temperature toughness have ductile-to-
brittle transition temperatures above room tempera-
ture.
The toughness minimum appears to be simply
associated with the precipitation of fine, sharable
precipitates in the low-carbon precipitation strength-
ened steels (Garrison and Brooks 1991). In the carbide-
strengthened steels the embrittlement may be due not
only to the precipitation of very fine alloy carbides but
changes in the mechanical stability of the retained
austenite and the precipitation of interlath carbides
associated with the decomposition of retained aus-
tenite on tempering. The decomposition of retained
austenite occurs at much higher tempering tempera-
tures in the carbon-containing stainless steels than it
does in low alloy steels (Garrison et al. 1983). Thus,
the embrittlement trough observed for the carbide-
strengthened stainless steels may partly be owing to
tempered martensite embrittlement (Horn and Ritchie
1978 ), which has been extensively studied in low-alloy
steels.
4. Embrittlement of Martensitic Stainless Steels
In addition to the embrittlement behavior noted
above, alloys of the Fe–Cr system can be embrittled by
the precipitation of certain phases (Leslie 1981). These
precipitation processes exhibit typical carbon-curve
behavior but are not usually observed in martensitic
stainless steels during normal tempering. Precipitation
of αh, σ, and χ phases are associated with the embrittle-
ment of these alloys. There is a miscibility gap in the
Fe–Cr system which leads to the separation of the
solid solution of chromium in iron into two solutions,
the iron-rich phase α and the chromium-rich phase αh.
Both α and αh are b.c.c. phases. Embrittlement by αh is
favored by additions of aluminum, molybdenum,
titanium, silicon, niobium, and phosphorus. The σ
phase formation is favored by high chromium contents
and additions of molybdenum, silicon, titanium, and
phosphorus. The χ phase formation is also favored
by high chromium contents and by additions of
molybdenum.
5. Corrosion and Stress Corrosion Cracking
Resistance
The corrosion and oxidation resistances of high
chromium steels are owing to the formation of a scale
of chromium oxide on the surface. However, the
effectiveness of a particular grade with respect to
corrosion or oxidation resistance depends very much
on the environment. Oxidation resistance of these
alloys are discussed in the Handbook of Stainless Steels
(Morris 1977) and Damage Mechanisms and Life
Assessment of High Temperature Components

Table 1
Compositions in wt.% of carbide strengthened martensitic stainless steels.
Alloy C Cr Ni Mo V W Mn Si
410 0.10 12 — — — 1.0 1.0
416 0.15 12 — 0.60 — 1.25 1.0
422 0.23 12 0.75 1.0 0.22 1.0 1.0 0.75
440A 0.60\0.75 17 — 0.75 — — 1.0 1.0
440B 0.75\0.95 17 — 0.75 — — 1.0 1.0
440C 0.95\1.20 17 — 0.75 — — 1.0 1.0
D2 1.50 12 — 1.0 1.0 — 0.3 0.25
D7 2.35 12 — 1.0 4.0 — 0.4 0.4

2

(Viswanathan 1989). Stress-corrosion cracking (SCC)
can be regarded as ‘‘the brittle or quasi-brittle fracture
of a material under the conjoint actions of a stress and
a corrosive environment, neither of which would cause
fracture acting alone or consecutively’’ (Truman
1981). The scc characteristics of martensitic and
ferritic stainless steels are reviewed by Truman (1981).
In general, the resistance of the martensitic stainless
steels to SCC appears to be outstanding compared to
high-strength martensitic steels of low chromium
content and it appears that martensitic stainless steels
can be used in situations where austenitic stainless
steels would fail.
6. Carbide-strengthened Martensitic Stainless Steels
Broadly speaking the steels in this category can be
divided into three groups (Table 1). The first group is
the low to medium carbon (0.10–0.30 wt.%) alloys
containing about 12 wt.% chromium. The second
group of carbide-strengthened martensitic stainless
steels are those containing much higher levels of
carbon (0.60–1.2 wt.%) and rather large amounts of
chromium (16–18 wt.%). The final group of carbide-
strengthened martensitic stainless steels are the high-
chromium cold work die steels such as D2 and D7.
This first group can be divided further into four
classes. The first class would be alloys of this type
which contain no (or very small amounts) of strong
carbide-forming elements or cobalt. The 410 alloy
would be typical of this class. The second class would
be steels of this type which contain molybdenum but
no other strong carbide-forming elements or cobalt.
The alloy 416 would be typical of this class. The third
class would include steels of this type which contain
molybdenum and other strong carbide-forming ele-
ments but no cobalt. The alloy 422 is an example of
such a material. The final class would be such steels
containing strong carbide-forming elements such as
molybdenum and tungsten and vanadium and cobalt;
these compositions often are strengthened by both
alloy carbide and intermetallic precipitation. A major
driving force for the development of the low to medium
carbon martensitic stainless steels has been the im-
provement of high temperature properties, especially
creep resistance, and high temperature ductility
(Briggs and Parker 1965).
The simplest of the commercially available carbon-
strengthened martensitic stainless steels is the 410
alloy. While there are many modifications of the 410
alloy, the tempering characteristics of the alloys are
similar to that of a 0.1C\12Cr composition. The
tempering curve (a plot of room temperature hardness
as a function of tempering temperature for a fixed
tempering time) of the 0.10C\12Cr alloy is essentially
Stainless Steels: Martensitic
flat for tempering temperatures from 200 mC to 500 mC,
although a small secondary hardening peak might be
observed on tempering at 500 mC (Lovejoy 1977). For
tempering temperatures greater than 500 mC the hard-
ness drops rapidly with increasing tempering tem-
perature. In the as-quenched condition and for low
tempering temperatures the carbides within the laths
are M C, where the M is iron and chromium and the
chromium$ occupies a maximum of about 18% of the
metal sites. As the tempering temperature is increased
the M C particles are replaced by M C . Chromium
occupies$ about 50% of the metal ( sites $ in M C
(Woodhead and Quarrell 1965). M C can either form ( $
( $
by nucleation at defects or it can form by in situ
nucleation at M C particles. For tempering tempera-
tures greater than$ about 500 mC, M C forms at lath
and other boundaries and grows at #$ the'expense of the
M C particles (Irvine et al. 1960).
(Modifications
$ of the simple 0.10C\12Cr alloy,
typified by the alloy 410, include additions of the
strong carbide-forming elements molybdenum, tung-
sten, and vanadium, the addition of silicon and cobalt.
In some materials there are small additions of niobium.
The primary aims of these additions, except for the
niobium, have been to increase the hardness after
tempering at higher temperatures or to introduce
particle distributions on tempering which will resist
coarsening at higher temperatures and thus provide
improved creep performance.
The additions of molybdenum and\or tungsten in
sufficient amounts can result in the precipitation of
M C particles, as molybdenum can form Mo C
#
(Raynor et al. 1966) and tungsten can form W#C
(Davenport and Honeycombe 1975). M C can have #
#
up to at least 30% of the metal sites occupied by
chromium atoms (Woodhead and Quarrell 1965). The
precipitation of M C can lead to a pronounced
secondary hardening# peak and to higher hardness at
tempering temperatures above 500 mC. When vana-
dium is added to a 0.10C\12Cr steel a vanadium
carbide will be formed on tempering and this will have
an effect on tempering response qualitatively similar to
those obtained by adding molybdenum or tungsten
(Raynor et al. 1966). Also, vanadium additions to
steels to which molybdenum has also been added can
have a beneficial effect on tempering response as
vanadium partitions strongly to M C and this par-
titioning has the effect of making the#particles of M C
more resistant to coarsening (Raynor et al. 1966). #
Cobalt (Speich et al. 1973) and silicon (Irvine 1962)
do not form carbides but when added to steels they
have significant effects on carbide precipitation. It has
been suggested that cobalt has this effect because it
increases the activity of carbon in ferrite and this
increased carbon activity would increase the driving
force for the formation of M C, and hence increase the
#
nucleation rate of M C particles. Also, because cobalt
#
reduces the rate of dislocation recovery and the greater
dislocation density will result in more and finer M C
#
3
Stainless Steels: Martensitic
particles, since the particles of M C are believed to
nucleate at dislocations (Speich et #al. 1973).
Niobium additions are sometimes made in small
amounts to these steels and these additions have the
effects of refining the prior austenite grain size and of
lowering the ductile-to-brittle transition temperature.
The second group of carbide-strengthened marten-
sitic stainless steels are those containing much higher
levels of carbon (0.60–1.2 wt.%) and rather large
amounts of chromium (16–18 wt.%). Examples of
these steels are 440A, 440B, and 440C (Roberts and
Cary 1980). These steels have a higher carbon content
in order to achieve more hardness and to ensure the
existence of primary carbides after austenitizing. Both
the greater hardness and the primary carbides in the
structure promote wear resistance. Higher chromium
is required for these steels because much of the
chromium is consumed by the formation of the
primary carbides.
The final group of carbide-strengthened martensitic
stainless steels are the high-chromium cold work die
steels such as D2 and D7 (Roberts and Cary 1980).
They combine both high hardness with large volume
fractions of primary carbides to promote wear re-
sistance. Given the amounts of chromium in the steels
and the amounts of chromium which should be in the
primary carbides it is doubtful if these steels have the
corrosion resistance one would expect from a stainless
steel. Both the amounts of primary carbides and
amounts of retained austenite present in D2, D7, and
the alloys 440A, 440B, and 440C are very sensitive to
the austenitizing temperature used and the cooling
rate from the austenitizing temperature.
7. Precipitation-strengthened Martensitic Stainless
Steels
Martensitic precipitation-strengthened stainless steels
are low-carbon martensitic stainless steels which are
strengthened by the precipitation of second-phase
particles, other than alloy carbides, during tempering
of the steel. A number of different approaches to
strengthening such steels have been investigated
(Pickering 1978, Perry and Jasper 1977). Such steels
can be strengthened by the precipitation of pure
copper; the steel PH15-5 is an example of a martensitic
stainless steel strengthened by the precipitation of
copper particles. Precipitation of the compound NiAl
is used to strengthen the steel PH13-8 (Taillard et al.
1982). Such steels can be strengthened by the pre-
cipitation of NiTi and Ni Ti. The precipitation of
$
Ni Be has been reported in steels modified by additions
$
of beryllium (Smolinski 1966, Crawford and Con-
tractor 1969). Japanese workers have reported the
precipitation of a G phase having the composition
4
Ni Ti Si in martensitic stainless steels (Hoshino and
"' ' (
Utsunomiya 1966). The final strengthening system
reported in the literature is strengthening by the R-
phase. R-phase is a complex compound which is
precipitated in martensitic steels containing chrom-
ium, molybdenum and cobalt (Komura et al. 1960,
Dyson and Keown 1969).
While there has been no attempt to exploit strength-
ening by G-phase or Ni Be precipitation in com-
$ by copper precipitation,
mercial alloys, strengthening
NiAl precipitation, NiTi or Ni Ti precipitation, and R-
phase precipitation have been $used in alloys which are
currently being made or which have had at least a brief
commercial existence (Magnee et al. 1974). The com-
positions of some examples of these alloys are given in
Table 1 and mechanical properties of these alloys after
conventional heat treatment are given in Table 2.
Commercial alloys which have employed copper
precipitation include PH15-5, PH17-4, and Custom
450 (Table 3). These three alloys reach a peak yield
strength of about 1250 MPa. The steel PH13-8,
strengthened by precipitation of NiAl, reaches a peak
yield strength of about 1450 MPa. Custom 465,
strengthened by precipitation of Ni Ti, achieves a
peak yield strength of about 1600 MPa $ (Carpenter
Specialty Alloys). There have been a number of steels
which have employed R-phase strengthening (Magnee
et al. 1974). These steels include Pyromet X-15,
Pyromet X-23, and the British steel D-70. All of these
steels, with the exception of Custom 465, were de-
veloped in the 1960s and early 1970s. None of the
alloys using R-phase strengthening are currently pro-
duced. Asayama has investigated the effects of com-
position on the toughness of R-phase strengthened
steels (Asayama 1976, 1978). Custom 450, Custom
465, Pyromet X-15, and Pyromet X-23 are trade-
marks of Carpenter Technology.
8. Steels Combining Carbide and Intermetallic
Strengthening
There have been attempts to combine secondary
hardening with strengthening by other particle types
(Tables 4 and 5). This work was pioneered in the UK
(Pickering 1963) and involved the combined precipi-
tation of NiAl and alloy carbides (secondary hard-
ening). Crucible developed the alloys AFC77 and
AFC260 (Kasak et al. 1963, Webster 1971), which
take advantage of secondary hardening and the
precipitation hardening obtained when large amounts
of chromium, molybdenum, and cobalt are simul-
taneously present (R-phase strengthening). The steels
AFC77 and AFC260 were developed in the 1970s and
are not produced today. However, two steels which
would appear to combine secondary hardening and R-
phase strengthening have recently been introduced.
 Stainless Steels: Martensitic

Table 2
Compositions in wt.% of martensitic precipitation strengthened stainless steels.
Alloy C Cr Ni Mo Co Cu Al Ti
PH15-5 0.04 15 4.7 — — 3.0 — 0.20 Nb
Custom 450 0.04 11.5 8.5 — — 1.5 — 0.7 Nb
PH17-4 0.07 16.5 4.0 — — 3.5 — 0.3 NbjTa
PH13-8 0.03 12.6 7.9 1.7 — — 1.0 —
Custom 465 0.02 11.8 11 1 — — — 1.7
Custom 455 0.05 11.5 8.5 0.5 — 2.0 — 1.1
Pyromet X-15 0.01 15 — 2.9 20 — — —
Pyromet X-23 0.03 10 7 5.5 10 — — —

Table 3
Properties of selected martensitic precipitation strengthened stainless steels.
Tempering Yield strength UTS Fracture toughness Charpy
Alloy temperature (mC) (MPa) (MPa) (MPa m"/#) (J)
PH15-5 496 1213 1317 — 79
Custom 450 510 1269 1289 — 55
PH17-4 550 1117 1158 — 54
PH13-8 510 1448 1551 — 41
Custom 465 510 1603 1738 93 —
Custom 455 510 1516 1585 — 19
Pyromet X-15 550 1482 1620 — 20
Pyromet X-23 510 1634 1779 77 24

Table 4
Compositiions in wt.% of martensitic stainless steels combining intermetallic and alloy carbide strengthening.
Alloy C Cr Ni Mo Co V Nb
AFC77 0.15 14.5 — 5 13.5 — —
AFC260 0.08 15.5 2.0 4.3 13.0 — —
HSL 180 0.20 12.5 1.0 2.0 15.5 — —
CSS-42L 0.13 13.8 2.1 4.7 12.5 0.60 0.04

Table 5
Properties of martensitic stainless steels combining intermetallic and alloy carbide strengthening.
Tempering Yield strength UTS Fracture toughness Charpy
Alloy temperature (mC) (MPa) (MPa) (MPa m"/#) (J)
AFC77 371 1379 1758 68 24
593 1476 2000 25 12
AFC260 427 1296 1544 101 —
538 1572 1751 67 —
HSL 180 385 1340 1800 121 43
CSS-42L 496 1200 1764 — 65

HSL 180 was developed by Sumitomo Precision 9. Summary

Products and Hitachi Metals and CSS-42L was
There are three types of martensitic stainless steels.
developed by Timken Latrobe Steel for bearing
The first type consists of alloys containing carbon
applications.

5
Stainless Steels: Martensitic
which are strengthened by the precipitation of alloy
carbides. Alloys of this type fall into two main
groups. The first are alloys with carbon levels of
0.10–0.30 wt.%, which were primarily designed for
creep resistance in addition to oxidation and corrosion
resistance. The second group consists of alloys with
high carbon contents; these alloys were developed
primarily for wear resistance. The second type of mar-
tensitic stainless steel is low carbon alloys strength-
ened by the precipitation of intermetallics. The
most widely used alloys of this type are PH13-8 and
PH15-5. However, none of the alloys of these two
types have sufficient toughness at high strength levels
to be used in critical applications requiring both high
strength and high toughness. The alloy development
leading to the third type of martensitic stainless steels,
those alloys combining strengthening by alloy carbide
and intermetallic strengthening, was motivated by a
need for stainless steels with reasonable toughness at
high strength levels.
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 Stainless Steels: Martensitic

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Encyclopedia of Materials : Science and Technology
ISBN: 0-08-0431526
pp. 8804–8810