CHAPTER 3

ALLOYING ELEMENTS AND

CONSTITUTION DIAGRAMS

Stainless steels contain a number of alloying additions (other than chromium,

carbon, and nickel) that are intended to improve mechanical properties and corrosion
resistance or to control the microstructure. This chapter provides an overview of the
various alloying additions in stainless steels and summarizes the development of
constitution diagrams for the prediction of microstructure based on composition.

3.1 ALLOYING ELEMENTS IN STAINLESS STEELS

Stainless steels are iron-base alloys with iron contents ranging from 50 to 88 wt% of
the composition. The principal alloying additions to stainless steel are chromium and
carbon for the ferritic and martensitic grades, with the addition of nickel for the
austenitic and duplex grades. Essentially all of the stainless steels contain man-
ganese and silicon as intentional additions. Other alloying additions include molyb-
denum, niobium, titanium, aluminum, copper, tungsten, nitrogen, and others to
improve fabricability, develop special properties, enhance corrosion resistance, or
influence microstructure. Impurity elements commonly found in stainless steels
include nitrogen, oxygen, sulfur, and phosphorus. All of these alloy and impurity
elements have some effect on weldability and performance. In most cases, the level
of these elements in the base or filler metal is controlled by the material specification
to assure that the steel performs as anticipated. This section provides some insight

Welding Metallurgy and Weldability of Stainless Steels, by John C. Lippold and Damian J. Kotecki
ISBN 0-471-47379-0 Copyright 8 2005 John Wiley & Sons, Inc.

19
20 ALLOYING ELEMENTS AND CONSTITUTION DIAGRAMS

into the influence of these alloying elements on the properties and performance of
stainless steels.

3.1.1 Chromium
Chromium is added primarily to provide corrosion protection to the steel. It is espe-
cially effective in oxidizing environments such as nitric acid. With the addition of
chromium an oxide of stoichiometry (Fe,Cr),O, forms on the steel surface. The pres-
ence of chromium increases the stability of the oxide since it has a much higher affinity
for oxygen than does the iron. When the chromium level exceeds approximately
10.5 wt%, the steel is considered "stainless" under ambient conditions. Higher levels
of chromium may be required for oxide stability in more aggressive environments.
Chromium is also a ferrite promoter. As shown in Chapter 2, iron-chromium
alloys that contain more than 12 wt% chromium will be fully ferritic. In Fe-Cr-C
and Fe-Cr-Ni-C alloys, increasing Cr will promote ferrite formation and retention
in martensitic, austenitic, and duplex grades. In the ferritic alloys, chromium is the
primary alloying element stabilizing the femtic microstructure.
Chromium is also a strong carbide former. The most common Cr-rich carbide is
M,,C,, where the " M is predominantly Cr but may also have some fraction of Fe
and Mo present. In most stainless steel systems, this is normally the case, and the term
M,C, is used with the understanding that chromium is the predominant metallic ele-
ment. This carbide is found in virtually all the stainless steels. It is also possible to
form a Cr,C, carbide, although this carbide type is not common. Other complex car-
bides and carbonitrides [M,,(C,N),] are also possible [I]. Chromium also combines
with nitrogen to fonn a nitride. The most common is Cr,N, which has been observed
in both ferritic and duplex grades.
Chromium is also a key ingredient in the formation of intermetallic compounds,
many of which tend to embrittle the stainless steels. The most common is sigma
phase (o),which in the Fe-Cr system is a (Fe,Cr) compound that forms below
815°C (1500°F). Sigma phase can form in virtually any stainless steel but tends
to be most common in the high-Cr austenitic, ferritic, and duplex alloys. Chromium
is also present in chi (x)and Laves intermetallic phases. These are discussed in
more detail later in the appropriate chapters associated with specific alloy systems.
From a mechanical properties standpoint, chromium will provide some degree
of solid solution strengthening since it is a substitutional atom in both the body-
centered cubic (BCC) and face-centered cubic (FCC) crystal lattices. High chromium
levels in ferritic alloys can result in very poor toughness and ductility, particularly
when carbon and nitrogen are present. High-chromium ferritic grades must be treated
very carefully, or carbon and nitrogen reduced to very low levels, to have acceptable
mechanical properties in welded fabrication. This is discussed in detail in Chapter 5.

3.1.2 Nickel
The primary function of nickel is to promote the austenite phase such that predomi-
nantly austenitic or austenitic-ferritic alloys can be produced. By adding sufficient
 ALLOYING ELEMENTS IN STAINLESS STEELS 21

nickel, the austenite phase field can be greatly expanded such that austenite is stable
to room temperature and below. Nickel is not a strong carbide former and does
not generally promote the formation of intermetallic compounds, although there is
evidence that its presence in the alloy may influence precipitation kinetics [I]. There
is some evidence that the presence of nickel in femtic alloys improves general cor-
rosion resistance, particularly in reducing environments such as those containing
sulfuric acid. However, nickel has been associated with a decrease in stress corro-
sion cracking (SCC) resistance. The work of Copson [2] clearly showed a decrease
in SCC resistance in an aggressive C1-containing environment when nickel w&
added to a Fe-20Cr alloy. The famous Copson curve shows that the lowest SCC
resistance occurs in the range 8 to 12wt% Ni and increases with either an increase
or decrease in nickel outside this range. Nickel is a good solid solution strengthener
but is most beneficial in terms of improving toughness in both the martensitic and
ferritic grades. Additions of up to 2 wt% Ni to high-Cr femtic stainl~s.stee1 can dra-
matically reduce the ductile-to-brittle fracture transition temperature (DBTT) [3].

3.1-3 Manganese
Manganese is added to virtually every steel. In austenitic stainless steels, it is nor-
mally present in the range 1 to 2 wt%. In femtic and martensitic stainless steels, it is
more commonly present at less than 1wt%. Historically, it was added to prevent hot
shortness during casting. This is a form of solidification cracking that is associated
with the formation of low melting point iron-sul6de eutectic constituents. Since
manganese combines much more readily with sulfur than does iron, the addition of
sufficient manganese and the formation of stable manganese sulfide (MnS) effectively
eliminated the hot shortness problem.
Manganese is generally considered to be an austenite-promoting element, although
the degree of promotion is dependent on the amount present and the level of nickel,
as discussed later in this chapter. It is very effective in stabilizing austenite at low
temperature to prevent transformation to martensite. Its potency in promoting austen-
ite at elevated temperature is dependent on the overall composition of the alloy. In
austenitic stainless steels, such as Type 304, it appears to have little effect on pro-
moting austenite versus femte.
Manganese is sometimes added to specialty alloys to increase the solubility
of nitrogen in the austenite phase. For example, the addition of 15 wt% man-
ganese to a Fe-20Cr alloy raises the nitrogen solubility from 0.25 to approxi-
mately 0.4 wt% [4]. The manganese effect on mechanical properties is minimal. It
provides some solid solution strengthening and appears to have little effect on
embrittlement.

3.1.4 Silicon
Silicon is also present in virtually all stainless steels and is added primarily for deox-
idation during melting. In most alloys it is present in the range 0.3 to 0.6 wt%. In
some cases aluminum may be substituted as a deoxidizer, but this is rarely the case
22 ALLOYING ELEMENTS AND CONSTITUTION DIAGRAMS

in stainless steels. It has been found to improve corrosion resistance when present at
levels of 4 to 5 wt% and is added to some heat-resisting alloys in the range 1 to
3 wt% to improve oxide scaling resistance at elevated temperature. The role of sili-
con in promoting ferrite or austenite is not entirely clear. In austenitic stainless
steels, up to 1wt% seems to have no effect on the phase balance, but higher levels
appear to promote ferrite. In ferritic and martensitic stainless steels, silicon appears
to help promote ferrite.
Silicon forms a number of iron silicides (FeSi, Fe,Si, Fe3Si, Fe,Si3) and a Cr3Si
intermetallic, all of which tend to embrittle the structure. It also expands the compo-
sition range over which sigma phase forms [ S ] . Silicon is known to segregate during
solidification, resulting in the formation of low melting eutectic constituents, particu-
larly in combination with nickel [6].For these reasons, it is usually held below 1wt%.
Silicon is well known to improve the fluidity of molten steel. For this reason, it
may be added in somewhat higher than normal amounts to weld filler metals. Some
stainless steels, particularly the austenitic grades, tend to be quite sluggish in the
molten state, and the addition of silicon can greatly improve the fluidity.

3.1.5 Molybdenum
Molybdenum is added to a number of stainless steels and has dierent functions
depending on the particular grade. For the ferritic, austenitic, and duplex grades, Mo is
added in amounts up to 6 % or more in super austenitics in order to improve corrosion
resistance, particularly with respect to pitting and crevice corrosion. In austenitic stain-
less steels, Mo also improves elevated temperature strength. For example, the addition
of 2 wt% Mo to a standard 18Cr-8Ni alloy results in a 40% increases in tensile strength
at 760°C (1400°F) 111. This can also have a negative effect, since alloys containing Mo
will be more difficult to hot work. Some of the martensitic stainless steels contain Mo
as a carbide former. The addition of as little as 0.5 wt% Mo increases the secondary
hardening characteristics of the steel, resulting in higher room-temperature yield and
tensile strength and improved elevated-temperature properties. Molybdenum is a
femte-promoting element, and its presence will promote femte formation and reten-
tion in the microstructure. This can be a potential problem in the martensitic grades,
where residual room-temperature ferrite can reduce toughness and ductility.

3.1.6 Carbide-Forming Elements

In addition to Cr and Mo, a number of other elements added to stainless steels also
promote carbide formation. These include niobium, titanium, tungsten, tantalum, and
vanadium. Niobium and titanium are added to austenitic stainless steels to provide
stabilization of the carbon to avoid intergranular corrosion. Both elements form an
MC-type carbide that resists dissolution during welding and heat treatment, thereby
preventing the formation of Cr-rich M,C, carbides that are associated with the
onset of intergranular corrosion. This phenomenon is discussed in greater detail in
Chapter 6. Tungsten, tantalum, and vanadium are added to some specialty stainless
steels, primarily to provide elevated temperature strength by the formation of a fine
 ALLOYING ELEMENTS IN STAINLESS STEELS 23

dispersion of carbides. These elements tend to promote ferrite in the microstructure

since they tie up carbon and effectively neutralize this powerful austenite promoter.
In addition, these elements in solid solution promote ferrite formation in their own
right.

3.1.7 Precipitation-Hardening Elements

Aluminum, titanium, copper, and molybdenum can be added to stainless steels to pro-
mote a precipitation reaction that hardens the alloy. The precipitation-hardenable(PH)
martensitic alloys contain Cu, Al, and Mo and can be heat-treated to produce room-
temperature yield strengths in excess of 1375MPa (200ksi). Austenitic PH stainless
steels usually contain titanium and aluminum and form Ni3Ti and Ni,Al [garnma-
prime (y')] precipitates that are similar to the hardening precipitates in Ni-base super-
alloys. Aluminum in solid solution is a potent ferrite-promoting eledEnt. Copper, on
the other hand, is a weak austenite-promoting element. Nearly pure copper precipitates
can be used for hardening in martensitic stainless steels such as 17-4PH.

3.1.8 Interstitial Elements: Carbon and Nitrogen

Carbon is present in all steels, but unlike C-Mn and low alloy structural steels, it is
usually desirable to control carbon below 0.1 wt%. The exception is the martensitic
grades, where carbon is critical for the transformation strengthening of these alloys.
In solution, carbon provides an interstitial strengthening effect, particularly at ele-
vated temperatures. In most alloys, carbon combines with other elements to form
carbides, as discussed previously. In the case of Cr-rich M,,C, carbides, a degrada-
tion in corrosion resistance can result, and for this reason low-carbon (C-grade)
alloys are produced where carbon is kept below 0.04 wt%. It should be noted that
M,,C, carbides contain nearly four times as many metal atoms (mostly chromium)
as carbon atoms, and a chromium atom is a bit over four times as heavy as a carbon
atom. So, on a weight percent basis, M,,C, carbide formation can remove as high as
16 times as much chromium as carbon from solid solution.
Nitrogen is usually present as an impurity in many of the stainless steels but is an
intentional addition to some of the austenitic and almost all the duplex grades. Similar
to carbon, nitrogen is a powerful solid solution strengthening agent, and additions of
as little as 0.15 wt% can dramatically increase the strength of austenitic alloys [7].
The strengthening effect of nitrogen in austenite is especially pronounced at cryo-
genic temperatures. For the duplex stainless steels, nitrogen is added to improve
strength, but more important, to increase resistance to pitting and crevice corrosion.
Some duplex grades contain up to 0.3 wt% nitrogen. As noted previously, the solu-
bility of nitrogen in stainless steels is relatively low, particularly in the ferrite phase.
The addition of manganese to the austenitic stainless steels increases nitrogen solu-
bility. In the fenitic and duplex grades, Cr,N will precipitate in the ferrite phase if the
solubility limit is exceeded, as can be observed in the weld metals and HAZs of these
alloys if appreciable austenite fails to form during cooling from temperatures above
about 1100°C (2010°F).
24 ALLOYING ELEMENTS AND CONSTITUTION DIAGRAMS

Carbon and nitrogen are the most potent of the austenite-promotingelements, and
thus the levels of these elements must be controlled carefully if precise microstruc-
ture balance is required. As noted previously, this can be controlled by the level of
each element in the alloy or by the addition of elements that will form carbides (Nb,
Ti) or nitrides (Ti, Al) and effectively neutralize their effect in the matrix. Nitrogen
pickup from the atmosphere can produce a departure from the desired rnicrostruc-
ture if shielding during arc welding is not adequate. In high-nitrogen austenitic and
duplex alloys, nitrogen loss during welding can be a problem. For duplex stainless
steels, nitrogen is sometimes added to the shielding gas to maintain weld metal nitro-
gen levels.

3.1.9 Other Elements

There are a number of other intentional alloying additions made to various stainless
steels for very specific applications. Sulfir; selenium, and lead are added to free-
machining grades to improve machinability by allowing higher machining speeds
and improved tool life. These additions reduce the corrosion resistance and typically
make the alloys unweldable, although control of solidificationbehavior (primary fer-
rite versus primary austenite) may negate the effect of sulfur. This is discussed in
Chapter 6. Tungsten is added to some duplex stainless steels to improve pitting cor-
rosion resistance, and it appears to promote ferrite formation. Aluminum is used in
some of the lower chromiam fenitiigrades to improve general corrosion resistance.
Cobalt is an effective solid-solution strengthener, and in the martensitic stainless
steels it can be added to increase the martensite start (M,)temperature. Cobalt pro-
motes austenite formation.

3.2 FERRITE-PROMOTINGVERSUS AUSTENITE-PROMOTING

ELEMENTS

Stainless steels are iron-based alloys containing from 12 to over 50wt% alloying
additions. Alloying elements affect the equilibrium phase relationships relative to the
stability of the austenite, ferrite, and martensite phases. Elements added to stainless
steels can be divided into those that promote, or stabilize, either the ferrite or the
austenite phase. Remember that martensite is a transformation product that forms
from austenite upon cooling from elevated temperature. If austenite does not form at
high temperatures, martensite cannot form at low temperatures.
Austenitic stainless steels contain high levels of nickel and other austenite-
forming elements which promote the formation of the austenite phase, so it is
stable to room temperature and below. Ferritic stainless steels contain a balance of
elements, such as high chromium contents, such that ferrite is the predominant
metallurgical phase present. Martensitic stainless steels are austenitic at elevated
temperature, but this austenite is unstable and transforms upon cooling. By bal-
ancing austenite- and ferrite-promoting elements, the microstructure of the stain-
less steel can be controlled. This balance has important implications with respect
to mechanical properties, corrosion resistance, and weldability.