Martensitic Stainless Steels

Extrait:

Martensitic stainless steels are similar to low alloy or carbon steels, having a
structure similar to the ferritic steels. However, due the addition of carbon, they can
be hardened and strengthened by heat treatment, in a similar way to carbon steels.
The main alloying element is chromium, typically 12 to 15%, molybdenum (0.2-1%),
no nickel, except for two grades, and 0.1-1.2% carbon.
Martensitic stainless steels are similar to low alloy or carbon steels, having a structure similar to
the ferritic steels. However, due the addition of carbon, they can be hardened and strengthened
by heat treatment, in a similar way to carbon steels. The main alloying element is chromium,
typically 12 to 15%, molybdenum (0.2-1%), no nickel, except for two grades, and 0.1-1.2%
carbon.
Their structures are "body-centered tetragonal" (bct). and they are classed as a "hard" ferromagnetic group. In the annealed condition, they have tensile yield strengths of about 275 MPa
and so they are usually machined, cold formed, or cold worked in this condition. The strength
obtained by heat treatment depends on the carbon content of the alloy. Increasing the carbon
content increases the strength and hardness potential but decreases ductility and toughness. The
higher carbon grades are capable of being heat treated to hardnesses of 60 HRC.
Optimum corrosion resistance is attained in the heat-treated i.e. hardened and tempered
condition. In comparison with the austenitic and ferritic grades of stainless steels, martensitic
stainless steels are less resistant to corrosion. Martensitic grades of stainless steels can be
developed with nitrogen and nickel additions but with lower carbon levels than the traditional
grades. These steels have improved toughness, weldability and corrosion resistance. Figure 1
shows the microstructure image of a martensitic stainless steel.

Figure 1: Microstructure image of a martensitic stainless steel.

In order to obtain a useful property profile martensitic stainless steels are normally used in the
hardened and tempered condition. The hardening treatment consists of heating to a high
temperature in order to produce an austenitic structure with carbon in solid solution followed by
quenching. The austenitizing temperature is generally in the range 9251070C. The effect of
austenitizising temperature and time on hardness and strength varies with the composition of the
steel, especially the carbon content.

In general the hardness will increase with austenitizising temperature up to a maximum and then
decrease. The effect of increased time at the austenitizising temperature is normally a slow
reduction in hardness with increased time.
Quenching, after austenitizising, is done in air, oil or water depending on steel grade. On cooling
below the MS-temperature, the starting for the martensite transformation, the austenite
transforms to martensite. The MS-temperature lies in the range 300-700C and the
transformation is finished of about 150-200C below the MS-temperature.
Almost all alloying elements will lower the MS-temperature with carbon having the greatest effect.
This means that in the higher alloyed martensitic grades the microstructure will contain retained
austenite due to the low temperature (below ambient) needed to finish the transformation of the
austenite into martensite.
In the hardened condition the strength and hardness are high but the ductility and toughness are
low. In order to obtain useful engineering properties, martensitic stainless steels are normally
tempered. The tempering temperature used has a large influence on the final properties of the
steel. The effect of tempering temperature on the mechanical properties of a martensitic stainless
steel AISI 431 is shown in Figure 2.

Figure 2: Effect of tempering temperature on the mechanical properties of AISI 431.

Hardening treatment: 1020C/30m/Oil quench
Normally, increasing tempering temperatures below about 400C will lead to a small decrease
tensile strength and an increase in reduction of area while hardness, elongation and yield
strength are more or less unaffected. Above this temperature there will be more or less
pronounced increase in yield strength, tensile strength and hardness due to the secondary
hardening peak, around 450-500C.
In the temperature range around the secondary hardening peak there is generally a dip in the
impact toughness curve. Above about 500C there is a rapid reduction in strength and hardness,
and a corresponding increase in ductility and toughness. Tempering at temperatures above the
780C for the steel in Figure 2, will result in partial austenitizising and the possible presence of
untempered martensite after cooling to room temperature. The Table 1 shows the composition
and typical use of AISI standard martensitic grades:

Table 1: The composition and typical use of martensitic grades

AISI
grade

Mn Si Cr Ni Mo

410

0.15

416

0.15 1.25 1

420

0.151
0.40

431
440A
440B
440C

0.2

1 0.5

0.601
0.75
0.751
0.95
0.951
1.20

1
1
1
1
1

11.513.0
12.014.0
12.014.0
15.017.0
16.018.0
16.018.0
16.018.0

Comments/Applications

The basic composition. Used for cutlery, steam

and gas turbine blades and buckets, bushings.
Addition of sulphur for machinability, used for
0.6 0.04 0.15 screws, gears etc. 416 Se replaces suplhur by
selenium.
-

0.04 0.03

0.04 0.03 Dental and surgical instruments, cutlery.

1.250.04 0.03 Enhanced corrosion resistance, high strength.

2.00
Ball bearings and races, gage blocks, molds
- 0.75 0.04 0.03
and dies, cutlery.
-

- 0.75 0.04 0.03 As 440A, higher hardness.

- 0.75 0.04 0.03 As 440B, higher hardness.

In addition to the standard grades, a large number of alloyed martensitic stainless steels have
been developed for moderately high temperature applications. Most common additions
include Mo, V and Nb. These lead to a complex precipitation sequence. A small amount (up to 2
wt %) of Ni is added which improves the toughness. The 12Cr-Mo-V-Nb steels are used in the
power generation industry, for steam turbine blades operating at temperatures around 600C.
The effect of nitrogen on localized corrosion resistance of martensitic stainless steels showed that
intergranular corrosion effectively takes place in martensitic microstructures exposed to sulphuric
acid solutions, and that nitrogen additions up to 0.2 [wt-%] allow improving resistance to this kind
of localized attack.
Figure 3 shows a much better corrosion resistance of high-temperature nitrided AISI 410S
stainless steels which tested in acid solution containing chloride ions, in comparing with AISI 420.
The superiority of the high nitrogen steel prevailed for all the tempering temperatures studied,
200, 400 and 600C.

Figure 3: Comparison between polarization curves for AISI 420, and high temperature
nitrided AISI 410S steels tested at 25C, tempered at 200C.
Some corrosion-erosion experiments performed with martensitic stainless steels have shown that
corrosion-erosion resistance of the high-nitrogen stainless steels (AISI 410N, 410SN, is higher
than that of the conventional AISI 420 stainless steel for the testing temperatures, in the range
from 0C to 70C, which can be associated to the beneficial effect of nitrogen in solid solution in
martensite.
As mentioned above, the martensitic stainless steel have the highest strength but also the lowest
corrosion resistance of the stainless steels. They are also easily welded. Due to their high
strength in combination with some corrosion resistance, martensitic steels are suitable for
applications where the material is subjected to both corrosion and wear. Martensitic steels with
high carbon content are often used for tool steels.
Typical applications are: aerospace, automotive, hydroelectric engines, cutlery, defense, power
hand tools, pump parts, valve seats, chisels, bushings, ball bearings, sporting equipment
industry, surgical instruments etc.
Date Published: Apr-2007

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