Martensitic Stainless Steels

Basic Metallurgy. At high temperatures, the equilibrium microstructure of martensitic

stainless steels is either entirely or
almost entirely austenite. At room temperature, the equilibrium microstructure of these steels is
a mixture of ferrite and
carbides. The reformation of austenite upon heating occurs very rapidly, but the transformation
back to ferrite upon
cooling is extremely slow. As a result, these steels have a very high tendency to transform to
martensite upon cooling
from temperatures at which austenite is the stable phase. In fact, it is very difficult to avoid
martensite in these steels.
They are air hardening, which means that even upon slow cooling in heavy sections, they form
martensite.
The binary iron-chromium phase diagram shown in Fig. 5 indicates that above a level of
approximately 12% Cr, binary
alloys will not form austenite at any temperature, so they cannot be hardened by heating and
cooling. However, the
addition of carbon to iron-chromium alloys increases the range of chromium contents over
which austenite can be formed
at elevated temperatures (Fig. 6). It should be noted that nitrogen, nickel, copper, and, possibly,
manganese, also expand
this range. Even with 17% Cr, a fully austenitic microstructure can be achieved with about 0.4%
C at 1250 C (2280 F).
It can then be fully hardened. When the corrosion-resisting properties of iron-chromium alloys
were first discovered early
in the 20th century, it was extremely difficult to remove carbon from melts of iron-chromium
alloys. Thus, the first
stainless steels, which were discovered more or less simultaneously in Germany and England,
were martensitic.
FIG. 6 CONCENTRATION PROFILE IN TERNARY IRON-CHROMIUM-CARBON
CONSTITUTION DIAGRAM. (A) 13%
CR. (B) 17% CR. SOURCE: REF 1

Carbon content almost entirely determines the hardness of martensite. If virtually 100%
martensite can be achieved in a
steel, then Fig. 7 shows several relationships that have been found experimentally between
carbon and hardness. In
particular, it shows that as little as 0.10% C in martensite will result in a hardness value of
approximately 35 HRC. The
hardness of martensite increases to over 60 HRC at approximately 0.5% C, and it does not
change significantly at higher
levels of carbon, at least on a macroscale.

FIG. 7 HARDNESS VALUES OF FULLY HARDENED STEELS WITH A RANGE OF CARBON

CONTENTS. SOURCE:
REF 13

Figure 7 presents the situation if essentially all martensite is obtained. In carbon and low-alloy
steels, rapid cooling is
usually necessary to avoid the formation of ferrite. However, as more alloy is added, the
avoidance of ferrite becomes
easier. At a 12% Cr level, nearly any cooling rate will result in virtually 100% martensite. The
prototype of all martensitic
stainless steels is type 410 (approximately 12% Cr and 0.10% C). The isothermal transformation
diagram for type 410
stainless steel (Fig. 8) indicates that, after cooling from high temperatures and being held at
approximately 700 C (1290
F), it will take approximately 2 min before any ferrite forms, and several hours will be required
before the transformation
to ferrite with carbides is complete. Cooling to a holding temperature of 400 C (750 F) will
require more than 1 week
before any ferrite forms.

FIG. 8 ISOTHERMAL TRANSFORMATION DIAGRAM FOR TYPE 410 STAINLESS STEEL

(12CR-0.1C)
AUSTENITIZED AT 980 C (1800 F), WITH GRAIN SIZE OF 6 TO 7. A, AUSTENITE; F,
FERRITE; C, CARBIDE;
M, MARTENSITE; B, BAINITE; P, PEARLITE. SOURCE: REF 14

Of these base metals, the lower carbon content alloys, especially type 410 and CA-6NM
(410NiMo), are often used for
turbines in hydroelectric and similar types of facilities. They provide resistance to mild
corrosion, cavitation, and
moderate abrasion, and they possess relatively high strength. CA-6NM is also used in fittings,
valves, and pumps for sour
(H2S-containing) oil and gas service. In this application, the alloy usually must be heat treated to
a hardness value that
does not exceed 22 HRC. This usually requires a double temper treatment consisting of 2 h at
675 C (1250 F)
(intercritical temperature range), an air cool to room temperature, and then 4 h at 615 C (1140
F) (below lower critical
temperature).
Type 420 and similar alloys are used in cutlery, valve parts, gears, shafts, and rollers. One
extensive application is a weld
overlay on rolls for steel mill continuous casters. This type of alloy is quite brittle in the freshly
hardened condition and
usually must be tempered to obtain useful toughness properties.
The higher carbon content martensitic stainless steels, such as types 440A, 440B, and 440C, can
be hardened to values
near 60 HRC. Then, they can be tempered at temperatures up to 480 C (900 F) to toughen
without experiencing much
loss of hardness. In this condition, they serve well as cutting edges and as bearings.
Martensitic stainless steels generally develop full hardness upon air cooling from about 1000 C
(1830 F). They can be
softened by tempering at temperatures ranging from approximately 500 to 750 C (930 to 1380
F), unless they contain
significant amounts of nickel, in which case the maximum temperature for tempering is
reduced. After tempering at 650
to 750 C (1200 to 1380 F), their hardness values generally drop to about 30 HRC or lower.
This can be useful if it is
necessary to soften a martensitic stainless steel before welding to allow enough ductility in the
bulk of the material to
accommodate shrinkage stresses associated with welding. However, such high-temperature
tempering produces rather
coarse chromium carbides, which damage the corrosion resistance of the metal. Then, it may be
necessary after welding
to austenitize, air cool to room temperature, and temper at a low temperature (less than 450 C,
or 840 F) to restore
corrosion resistance.
Engineering for Use in the As-Welded Condition. Except for very small weldments or
very low carbon base metals,
martensitic stainless steels are not usually used in the as-welded condition. This is due to the
very brittle weld area that
normally results. This area includes the weld metal itself, if it has a matching or near-matching
composition to that of the
base metal, and the heat-affected zone. However, repair situations can necessitate that the
engineer work with these
circumstances.
If a weldment of martensitic stainless steel must be used in the as-welded condition, then it is
usually best to avoid both
autogenous welds (no filler metal) and welds with matching filler metals. Small parts that are
welded by laser-beam
welding (LBW), electron-beam welding (EBW), or GTAW processes are an exception, because
residual stresses can be
very low and the welding processes generate almost no diffusible hydrogen.
If at all possible, an austenitic filler metal, such as type 309 or 309L stainless, or a duplex
ferritic-austenitic stainless filler
metal, such as type 312 stainless, should be chosen, depending on the base metal. The filler-
metal choice should provide
for a small amount of ferrite in the weld metal, in order to avoid hot cracking. This can be
anticipated by using the
extended WRC-1992 diagram (Fig. 4). If the weld metal is austenite with a little ferrite, then the
weld metal itself will
have appreciable ductility, and only the HAZ will be at risk for cold cracking. This possibility
can be minimized by using
high preheat temperatures (200 C, or 390 F, minimum for type 410 base metal and 350 C, or
660 F, minimum for
types 440A, 440B, and 440C base metals) and slow cooling after welding.

Example 1: Type 410 base metal (0.10C-12.5Cr-0.04N), Creq = 12.5

and Nieq = 4.3; to
be welded with E309-16 manual electrode (0.05C-23.5Cr-13.0Ni-
0.06N all-weld metal
composition), Creq = 23.5 and Nieq = 15.95.
If the type 410 base metal is plotted in Fig. 9 (point A), along with the all-weld metal
composition of the E309-16
electrode (point B), then all possible mixtures of these two metals must lie along the line
connecting these two points. If
the root pass is diluted with 30% base metal (a typical result to expect), then the actual root pass
composition will lie
along the tie line, 30% of the distance from point B to point A. This composition is shown as
point C in Fig. 9. It would
correspond to slightly over 8 FN, which is quite safe in terms of the likelihood of hot cracking.
Furthermore, because the
tie line is nearly parallel to the isoferrite lines in the diagram, major changes in dilution would
have practically no effect
on weld-metal ferrite content. Additional weld passes on top of the root pass would have
compositions that are also along
the tie line, but closer to the E309-16 all-weld metal composition. Therefore, E309-16 would be
a very good filler metal

choice if a nonhardenable weld deposit is acceptable. By similar reasoning, type 309 (or 309L)
would be an excellent
choice for gas-metal arc weld wire, flux-cored wire, or submerged arc wire.
FIG. 9 WRC-1992 DIAGRAM WITH EXPANDED SCALE FOR DILUTION CALCULATIONS,
IN WHICH FERRITE IS
CALCULATED FOR TYPE 410 STAINLESS STEEL WELDED WITH E309-16 (REFER TO
EXAMPLE 1)

Example 2: Type 440A base metal (0.7C-17.0Cr-0.04N), Creq = 17.0

and Nieq = 25.3; to
be welded with E309-16 manual electrode (0.05C-23.5Cr-13.0Ni-
0.06 N all-weld metal
composition), Creq = 23.5 and Nieq = 15.95.
Because the type 440A base metal cannot be plotted on the WRC-1992 diagram, it is necessary
to calculate the weld Creq
and Nieq. Assuming a 30% dilution, the weld Creq = 0.7 (E309-16 Creq) + 0.3(440A Creq) =
0.7(23.5) + 0.3(17.0) = 21.55;
and the weld Nieq = 0.7(E309-16 Nieq) + 0.3(440A Nieq) = 0.7(15.95) + 0.3(25.3) = 18.8.
Because the weld-metal
composition would clearly lie above and to the left of the 0 FN line in Fig. 4, there would be no
ferrite in such a weld
deposit. Therefore, E309-16 would not be a good choice for welding type 440A base metal.
Example 3: Type 440A base metal (0.7C-17.0Cr-0.04N), Creq = 17.0
and Nieq = 25.3; to
be welded with E312-16 manual electrode (0.10C-29.0Cr-8.8Ni-
0.06N), Creq = 29.0
and Nieq = 13.3.
Because the type 440A base metal cannot be plotted on the WRC-1992 diagram, it is necessary
to calculate the weld Creq
and Nieq. Assuming a 30% dilution, the weld Creq = 0.7(E312-16 Creq) + 0.3(440A Creq) =
0.7(29.0) + 0.3(17) = 25.4; and
the weld Nieq = 0.7(E312-16 Nieq) + 0.3(440A Nieq) = 0.7(13.3) + 0.3(25.3) = 16.9. Plotting the
weld Creq and Nieq on the
WRC-1992 diagram shows this composition corresponds to about 12 FN. Therefore, E312-16
would be a good choice for
welding type 440A base metal, if a nonhardenable weld is acceptable.
However, unlike the situation in Example 1, the tie line from the E312-16 electrode all-weld
metal composition on the
WRC-1992 diagram to the type 440A base-metal composition is nearly perpendicular to the
isoferrite lines. This means
that large changes in dilution would have a strong effect on weld-metal ferrite content. In
particular, it can be calculated
that an increase in dilution to just over 35% would put the weld composition into the primary
austenite solidification
mode and, therefore, at risk of hot cracking. Because higher dilution is normal in submerged arc
welding (SAW) and
spray-transfer GMAW processes, the avoidance of these processes would be suggested by this
example. However, the
GMAW process using short-circuiting transfer with type 312 filler wire should be acceptable.

Although the welding filler metals of Examples 1 and 3 seem appropriate choices for avoiding
hot cracking in joints in
the martensitic stainless steels used in these examples, the weld metals would considerably
undermatch the strengths of
the base metals, unless the base metals were annealed. The base metals could easily have tensile
strength values that
exceed 1000 MPa (145 ksi), depending on their condition of heat treatment before welding,
whereas the weld metals are
likely to have tensile strengths on the order of 550 to 600 MPa (80 to 90 ksi). Furthermore, the
austenitic weld metals
cannot be hardened by heat treatment. If higher-strength weld metal is essential, then a
martensitic filler metal is
necessary, which almost always requires a PWHT to obtain reasonable ductility in the weld
metal.