Chapter 8

Stainless Steels
Stainless steels are iron base alloys that contain a minimum of approximately
11% chromium (Cr); this is an important number that is needed to create a
passivating layer of chromium-rich oxide to prevent rusting on the surface.
Several stainless steel grades are produced to address specific demands of the
environment that they are expected to protect the material. For this purpose,
other elements are also added to the steel. Nickel, copper, titanium, aluminum,
silicon, molybdenum, niobium, nitrogen sulfur, and selenium are some of the
commonly used elements that are alloyed to impart the required properties to
the specific steel grade. The corrosion resistance and corrosion properties of
stainless steel are briefly discussed in this chapter. Readers desirous of more in
depth knowledge about these topics are guided to the book Corrosion and
Corrosion Prevention by the same author.

STAINLESS STEEL PRODUCTION

The process of stainless steel production involves a series of processes. First,
in an electric arc furnace the steel is melted, and alloying elements such as
chromium, silicon, nickel, and so on are added and melted in intense heat.
Usually this process continues for about 8 to 12 hours. This is followed by
casting the molten metal into one of several shapes. These shapes may include
blooms (rectangular shapes), billets (round or square shapes of 1.5 inches),
slabs, rods, and tubes.

Forming
The semi-finished steel goes through forming operations, beginning with hot
rolling, in which the steel is heated and passed through a series of rolls where
the blooms and billets are formed into bar and wire.
l Bars are available in all grades and come in rounds, squares, octagons, or
hexagons of 0.25 inch (6 mm) in size.
l Wire is usually available up to 0.5 inch (13 mm) in diameter or size.
l The slabs are formed into plates, strips, and sheets.
l Plate is defined as rectangular shapes of more than 0.1875 inch (5 mm)
thick and more than 10 inches (250 mm) wide.

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84 SECTION j 1 Introduction to Basic Metallurgy

l Strip are defined as rectangular shapes of less than 0.185 inch (5 mm) thick
and less than 24 inches (610 mm) wide.
l Sheets are defined as rectangular shapes of less than 0.1875 (5 mm) thick
and more than 24 (610 mm) wide.

Heat Treatment
After the final shape is formed, most types of stainless steel must go through
an annealing process. Annealing is a heat treatment in which the steel is heated
and cooled under controlled conditions to relieve internal stresses and soften
the metal. Some steels are heat treated for higher strength. However, such a
heat treatment, known as age hardening, requires careful control because even
small changes from the recommended temperature, time, or cooling rate can
seriously affect the end properties. Whereas Lower aging temperatures pro-
duce high strength with low fracture toughness, higher temperature aging
produces a lower strength, tougher material.
Although the rate of heating to reach the aging temperature of 900
to
1000
F (482
to 537
C) does not affect the properties, the control on cooling
rate is very important because it does affect the properties, if not controlled.
A post-aging quenching treatment is often carried out to increase the tough-
ness of the steel. One such process involves water quenching, in which the
material is quenched in an ice water bath at about 1.6
C (35
F) for 2 hours.
Different type of steels, such as austenitic, ferritic, and martensitic, receive
different heat treatment. Austenitic steels are heated to above 1037
C (1900
F)
for a time depending on the thickness. Thick sections are quenched in water,
and thinner sections are either cooled by air cooling or air blasting. The rate of
cooling is of importance; if cooled too slowly, carbide precipitation can occur.
The carbide precipitation can be eliminated by thermal stabilization. In this
method, the steel is held at 815
to 870
C (1500 to 1600
F) for several hours.
Descaling: Heat treatment causes a scale to build up on the surface of the
steel. The scale is removed by several methods.
Pickling is done to remove scale. The material is immersed in a bath of
nitricehydrofluoric acid; the acid leaches out the scale from the surface.
Electrocleaning is also carried out to descale the steel. The process in-
volves application of an electric current to the surface using a cathode and
phosphoric acid.
The annealing and descaling are carried out at different stages depending
on the type of steel being made. For example, bar and wire go through
further forming steps (more hot rolling, forging, or extruding) after the initial
hot rolling before being annealed and descaled. Sheet and strip, on the other
hand, go through an initial annealing and descaling step immediately after
hot rolling. After cold rolling (passing through rolls at a relatively low
 Stainless Steels Chapter j 8 85

temperature), which produces a further reduction in thickness, sheet and strip

are annealed and descaled again. A final cold rolling step prepares the steel
for final processing.

Cutting Stainless Steel

A cutting operation is usually necessary to obtain the desired blank shape or
size. This is done to trim the part to final size. Mechanical cutting is
accomplished by a variety of methods, including straight shearing by guillo-
tine knives, circle shearing by circular knives horizontally and vertically
positioned, or blanking by metal punches and dies to punch out the shape by
shearing. Nibbling is a process used for cutting by blanking out a series of
overlapping holes and is ideally suited for irregular shapes. Only some
stainless steels can be saw cut by high-speed steel blades.
Some stainless steel can also be cut using flame cutting, which involves a
flame-fired torch using oxygen and propane in conjunction with iron powder.
This method is clean and fast.
Another cutting method that is used is plasma jet cutting. To make a cut,
this process uses an ionized gas column in conjunction with an electric arc
passing through a small orifice. The force of the gas and high heat generated
by the gas plasma melt the metal and make the cut.

Finishing
Surface finish is an important requirement for stainless steel products,
depending on the end application. The surface finish is a very important
property to specify.
The main reasons to consider for specifying the surface finish could
include one or all of the following.
1. The appearance
2. Process convenience
3. Corrosion protection
4. To facilitate lubrication (often a rougher surface is specified)
5. Surface condition specific to facilitate further manufacturing steps

FABRICATION OF STAINLESS STEEL

After the stainless steel in its various forms is packed and shipped to the
fabricator or end user, a variety of secondary processes is needed to make it
useful for specific service. Further shaping is accomplished using a variety of
secondary processing that may include rolling forming, press forming, forging,
press drawing, and extrusion, welding cutting, additional heat treating,
machining, and cleaning processes.
86 SECTION j 1 Introduction to Basic Metallurgy

WELDING AND JOINING

The details of welding stainless steel are discussed in the Section 2 of this
book; however, a brief introduction is included here.
A variety of methods are used for joining stainless steel, welding being the
most common. Several variations of the fusion and resistance welding pro-
cesses can be used. In fusion welding, heat is provided by an electric arc struck
between an electrode and the metal to be welded. In resistance welding,
bonding is the result of heat and pressure. Heat is produced by the resistance to
the flow of electric current through the parts to be welded, and pressure is
applied by the electrodes. After parts are welded together, they must be
cleaned around the joined area.

TYPES OF STAINLESS STEELS

Stainless steels are used for both corrosion and high-temperature resistance
applications. A three-number system as listed below is used to identify
stainless steels. In the following list, the three-digit number generally corre-
sponds with the type and group of alloying elements. The first digit is the
group identifier, and the last two digits identify the specific type of alloy.
l 2xx: chromiumenickelemanganese: nonhardenable, austenitic, nonmagnetic
l 3xx: chromiumenickel: nonhardenable, austenitic, nonmagnetic
l 4xx: chromium: hardenable, martensitic, magnetic
l 4xx: chromium: nonhardenable, ferritic, magnetic
l 5xx: chromium: low chromium, heat resisting
The corrosion resistance in stainless steel is obtained by the presence of a
thin, adherent, stable chromium oxide or nickel oxide film, which protects the
steel. A minimum of 10% Cr is required to develop this tenaciously adhering,
uniformly developed oxide film.

CLASSIFICATION OF STAINLESS STEEL

Stainless steels are classified in to five families. Four of these are based on
their crystallographic structures; these are martensitic, ferritic, austenitic, and
austenitic plus ferritic (called duplex). The fifth class is based on the type of
heat treatment used to produce certain properties; these are called
precipitation-hardenable alloys, often called PH steels. Each of these is dis-
cussed further in the text.

Martensitic Stainless Steels

These are essentially Fe-Cr-C alloys that have body-centered tetragonal (bct)
crystalline structure, which is martensite in a hardened condition. These steels
are ferromagnetic; they can be hardened by heat treatment. These steels can
 Stainless Steels Chapter j 8 87

resist corrosion in mild environments. Addition of small amount of nickel

improves the corrosion resistance properties. Typically, these steels contain
steels 11.5% to 18% chromium and up to 1.2% carbon. The chromium-to-
carbon ratio is balanced to maintain the martensitic structure. Examples of
this group of steel are types 403, 410, 420, and 501.
Other elements, such as vanadium, silicon, tungsten, and niobium, are also
added to induce tempering after hardening. The alloying is in very limited
scale to maintain the martensitic structure.

PROPERTIES OF MARTENSITIC STAINLESS STEEL

In annealed condition, these steels exhibit good tensile properties. Generally,
these steels have a yield strength of approximately 275 MPa (40 ksi). Steel
responds to cold work by a moderate increase in hardness. In annealed con-
dition, these alloys have good toughness and ductility, which decreases as
hardness is increased by heat treatment. Heat treatment hardening and
tempering increase yield strength up to 1900 MPa (275 ksi). Typically, the
hardness values range from 150 HB in annealed condition to 600 HB in fully
hardened condition.
Martensitic stainless steels are magnetic and can be easily cold worked and
machined. In annealed condition, they have good toughness and moderate
corrosion resistance and are easily hot worked. They are most corrosion
resistant when properly heat treated. Because of the high alloy content, these
steels undergo sluggish transformations and result in high hardenability.
Maximum hardness can be achieved by air cooling. Type 416 steels contain a
small amount of sulfur to improve machinability, which also reduces corrosion
resistance.

FERRITIC STAINLESS STEELS

These are straight ironechromium alloys that contain chromium in the rage of
14% to 27%. Examples of this group of steel are Type 405 and Type 430 steel.
This type of steel has bcc structure. To obtain specific properties, some grades
are alloyed with molybdenum, aluminum, silicon, titanium, and niobium.
These steels are ferromagnetic; they possess good ductility and are rela-
tively easy to work with. Carbon percentage for these steels range from 0.02%
to 0.2%. Because of the low carbon content, hardenability cannot be increased
by heat treatment and can be only moderately hardened by cold working. Cold
work also strengthens the material and reduces its ductility. In comparison,
these steels in the annealed condition have about 1.5 times more strength than
that of carbon steel. In annealed condition, they have the best resistance to
corrosion. Prolonged exposure of these steels to the temperature range of
400
C to 510
C (750
F to 950
F) can cause brittleness and loss of notch-
impact strength.
88 SECTION j 1 Introduction to Basic Metallurgy

Properties of Ferritic Stainless Steel

In annealed state, the yield strength of typical ferritic stainless steel is in the
range of 240 to 380 MPa (35e55 ksi), specially alloy grades such as Type 444,
UNS S 44660, and S 44627. These specially alloyed steels also called
superferritic stainless steels; they have good resistance to corrosion and are
especially good for resistance to stress corrosion cracking and pitting.

PITTING RESISTANCE EQUIVALENT

Most of these alloys are developed to serve in a specific type of environment,
and resistance to corrosion is one of them. The resistance to general corrosion
of these steels is addressed by alloying elements that develop passivating
layers of metallic oxide. However, the localized corrosion is not easy to predict
and hence is not easy to control. The ability to assess the resistance to pitting
of an alloy is determined by the calculated value called the pitting resistance
equivalent (PRE) number.
These alloys exhibit some degree of pitting resistance, which is calculated
by a weighted average of key elements such as chromium molybdenum, and
nitrogen as given in the following equation. Higher PRE number is an indi-
cator of better resistance to pitting, and such alloys are preferred when
localized corrosion in the form of pitting may be of specific concern.
PRE ¼ %Cr þ 3:3ð%MoÞ þ 16ð%NÞ
It may be noted that the elements include nitrogen, which is a gas, because
it has a significant influence on pitting resistance property of an alloy.

AUSTENITIC STAINLESS STEELS

We have discussed basics of stainless steel in the chapter dealing with pro-
duction of steel. This group of steel is by far the largest group of stainless steel.
These steels contain chromium (Cr) in the range of 16% to 26%; nickel (Ni) is
in the range of 3.55% (grade 201) to 37% (grade 330); other alloying elements
include, carbon ranging from 0.03% to 0.25%; and molybdenum, niobium,
titanium, and tantalum are specialty additions to improve specific properties
such as stabilizing or for marine services. Other regular alloying elements
include manganese, silicon, sulphur, and phosphorous.
Stainless steels are nonmagnetic and can be hardened by cold working.
However, they cannot be hardened by heat treatment. They have excellent low-
temperature ductility. Some grades such as grade 310 are equally good for
moderate- to high-temperature services.
The chromiumenickel (Type 3xx) and chromiumenickelemanganese
(Type 2xx) stainless steels are the two major groups; they can be hot worked
and cold worked, but they do readily work harden. Austenitic stainless steels
are extremely shock resistant and are not easy to machine.
 Stainless Steels Chapter j 8 89

They exhibit the best high-temperature strength and scaling resistance and
superior corrosion resistance compared with the ferritic and martensitic
stainless steels. Type 302 is a basic alloy that has been modified to more than
20 basic alloys.

PROPERTIES OF AUSTENITIC STAINLESS STEEL

The strength of austenitic stainless steel is very much comparable to mild carbon
steel; the, typical yield strength is between 200 and 275 MPa (30e40 ksi). The
elongation is measured in the range of 40% to 60%. Grade 200 series of steel have
better yield strength in annealed conditions (345e482 MPa or z50e70 ksi).
The corrosion resistance of these steels is excellent in most of environ-
ments. Of the 3xx series stainless steels, the basic grade 304 is commonly used
in the food, dairy, and beverage industries. They are also good in oxidizing
environments. The stabilized form of basic, Grade 304dand renumbered as
Grade 321 (titanium stabilized) and 347 (niobium stabilized)dcan resist
thermally induced embrittlement.
Grade 310 with higher chromium and carbon levels is suitable for higher
temperature services. Similarly, Grade 316 is alloyed with molybdenum to
impart resistance from marine environments.

DUPLEX STAINLESS STEELS

The Fe-Cr-Ni system alloys have two phases. They typically contain 20% to
30% chromium and 5% to 8% nickel. The alloy system is called duplex
because it typically contains approximately 50/50 austenitic and ferritic phase
in their microstructure. These steels contain low carbon, and molybdenum,
tungsten, copper, and nitrogen are added as alloying elements.

Properties of Duplex Stainless Steel

The yield strength of these steels range from 550 to 690 MPa (80e100 ksi).
The alloy, because of its ferritic structure, is susceptible to loss of me-
chanical strength and lead to embrittlement at elevated temperature. Prolonged
service at and above 300
C (570
F) is not advised.
The greatest advantage of Duplex stainless steel is the resistance to
corrosion, especially to pitting corrosion. The alloys exhibit PRE from 22
(UNS S 32304) to 47 (UNS S 32750).

PRECIPITATION-HARDENING STAINLESS STEELS

Precipitation hardening is defined as caused by the precipitation of a con-
stituent from a supersaturated solid solution. Artificial aging of metal is carried
out in which a constituent precipitates from the supersaturated solid solution.
These chromium nickel grades of steel are hardened by an aging treatment.
90 SECTION j 1 Introduction to Basic Metallurgy

TABLE 1-8-1 Types of Precipitation Hardened Steels

UNS Number Alloy Type

S13800 PH13-8Mo
S15500 15-5 PH
S 17400 17-4 PH
S45500 Custom 455

These grades were developed during World War II. They are usually
supplied in the solution-annealed condition and are aged for strength following
forming. The main grades are 17-4PH and 17-7PH; the classification is based
on their solution-annealed microstructure. In annealed condition, these grades
are semiaustenitic steels. On heat treatment, the microstructure is changed to
martensite. Cold work enhances the aging effect. Certain alloying elements
such as aluminum, niobium, titanium, and copper are added to facilitate aging.
ASTM A 286 is the standard to find various grades of PH steels. Some alloys
in this class are listed in Table 1-8-1 with their UNS numbers.
The 17-4PH is solution treated and air cooled to allow the austenite to
martensite transformation. Reheating is performed to increase the strength and
corrosion resistance.

Properties of Precipitation-Hardening Stainless Steel

Precipitation-hardening alloys can achieve high strength, ranging from 690 to
1700 MPa (100e250 ksi).
Grade PH 15-7 Mo(h) (UNS S 15700) has a yield strength of 1590 MPa
(230 ksi) and corresponding hardness of above 46 HRC, but the elongation,
which is a measure of ductility, ranges from 1% to 15%, seriously low in all
PH alloys. The corrosion resistance of these alloys is at best the moderate.