MECG1019 Handout: Stainless Steel

2017-II C.G. Helguero

Supplementary Lecture about Stainless Steel

The corrosion resistance is imparted by the formation of a strong adherent chromium oxide
on the surface of metal. On the other hand, existence of carbon will form chromium carbide
which takes away ability for chromium to form the shielding chromium oxide. When the
amount of atomic chromium in solution exceeds 12%, improved corrosion resistance and
outstanding appearance are achieved. This category forms what has been commonly called
the true stainless steels.
Several classification schemes have been devised to categorize the stainless steel alloys. The
American Iron and Steel Institute (AISI) groups the metals by chemistry and assigns a three-
digit number that identifies the basic family and the particular alloy within that family. The
following table presents the AISI designation scheme for stainless steels and correlates it with
the microstructural families.
Series Alloys Structure Magnetic?
200 chromium, nickel, manganese, or nitrogen austenitic No
300 chromium, nickel austenitic No
400 chromium only ferritic or martensitic Yes
500 low chromium (<12%) martensitic Yes

The material can also be grouped by microstructural families. In general, there are five main
types as will be described in the following, although new stainless steel alloys have been
developed to meet special needs.
(1) Austenitic (200 and 300 series): These steels are generally composed of chromium,
nickel, and manganese in iron. Nickel is an austenite stabilizer, and with sufficient
amounts of both chromium and nickel, it is possible to produce a stainless steel in which
austenite is the stable structure at room temperature. Known as austenitic stainless steels,
these alloys may cost twice as much as the ferritic variety, with the added expense being
attributed to the cost of the alloying nickel and chromium. Manganese and nitrogen are
also austenite stabilizers and may be substituted for some of the nickel to produce a
lower-cost, somewhat lower-quality austenitic stainless steel. Austenitic stainless steels
are nonmagnetic and are highly resistant to corrosion in almost all media except
hydrochloric acid and other halide acids and salts. However, they are susceptible to
stress-corrosion cracking. In addition, they may be polished to a mirror finish and thus
combine attractive appearance and corrosion resistance. Formability is outstanding
(characteristic of the FCC crystal structure), and these steel strengthen considerably when
cold worked. The popular 304 alloy, suited for all types of dairy equipment, brewing
industry, citrus and fruit juice industry, dye tanks, pipelines buckets, dippers, and food
processing industry, is also known as the 18-8 because of the composition of 18%
chromium and 8% nickel (18-8 also refers to 302, 303, 305, and 384).
Austenitic stainless steels are hardened by cold-working. They are most ductile of all
stainless steels, so they can be easily formed, although, with increasing cold work, their
formability is reduced. These steels are in a wide variety of applications, such as

1
 kitchenware, fittings, welded construction, lightweight transportation equipment, furnace
and heat-exchanger parts, and components for severe chemical environment.
(2) Ferrite (400 series): These steels have a high chromium contentup to 27%. Chromium
is a ferrite stabilizer, the addition of chromium tending to increase the temperature range
over which ferrite is the stable structure. If sufficient chromium is added to the iron, and
carbon is kept low, an alloy can be produced that is ferrite at all temperatures below
solidification. These alloys are known as ferritic stainless steels. Such ferrite alloys are
also the cheapest type among stainless steels. They are magnetic and have good corrosion
resistance.
Ferrite stainless steels possess rather poor ductility or formability because of the BCC
crystal structure (they have lower ductility than austenitic stainless steels), but they are
readily weldable. They are hardened by cold-working and are not heat-treatable. They
are generally used for nonstructural applications such as kitchen equipment and
automotive trim.
(3) Martensitic (400 and 500 series): Most martensitic stainless steels do not contain nickel
and are hardenable by heat treatment. Their chromium content may be as much as 18%.
If increased strength is needed, the martensitic stainless steels should be considered.
However, caution should be taken to assure more than 12% chromium in solution. Slow
cools may allow the carbon and chromium to react and form chromium carbides. When
this occurs, the chromium is not available to react with oxygen and form the protective
oxide. Thus the martensitic stainless steels may only be stainless when in the
martensitic condition (when the chromium is trapped in atomic solution), and may be
susceptible to red rust when annealed or normalized for machining or fabrication. The
martensitic stainless steel cost about 1.5 times as much as the ferritic alloys, part of being
due to the additional heat treatment, which generally consists of an austenitization,
quench, stress relief, and temper. These stainless steels are magnetic.
Martensitic stainless steels have high strength, hardness, and fatigue resistance, good
ductility, and moderate corrosion resistance. They are typically used for cutlery, surgical
tools, instruments, valves, and springs.
(4) Precipitation-hardening (PH): A fourth and special class of stainless steels is the
precipitation-hardening variety. These steels contain chromium and nickel, along with
copper, aluminum, titanium, or molybdenum. These alloys are basically martensitic or
austenitic types, modified by the addition of alloying elements such as aluminum that
permit age hardening at relatively low temperatures. By adding age hardening to the
existing strengthening mechanisms, these materials are capable of attaining properties
such as a 260-ksi (1790-MPa) yield strength and 265-ksi (1825-MPa) tensile strength
with a 2% elongation.

They have good corrosion resistance and ductility, and they have high strength at elevated
temperatures. Their main application is in aircraft and aerospace structural components.

(5) Duplex structure: Duplex stainless steels contain between 21 to 25% chromium and 5 to
7% nickel and are water quenched from a hot-working temperature that is between 1830
and 1920F to produce a microstructure that is approximately half ferrite and half
austenite. The structure offers a higher yield strength and greater resistance to stress
corrosion cracking than either then austenitic or ferritic grades. These steels have a
mixture of austenite and ferrite.

2
 They have good strength, and they have higher resistance to both corrosion and stress-
corrosion cracking than do the 300 series of austenite steels. Typical applications are in
water-treatment plants and in heat-exchanger components.

(6) Other stainless steels: Still other stainless alloys have been developed to meet special
needs. Ordinary stainless steels are difficult to machine because of their work-hardening
properties and their tendency to seize during cutting. Special free-machining alloys have
been produced within each family, with addition of sulfur or selenium raising the
machinability to approximately that of a medium-carbon steel.

The following tables shows typical alloy compositions, structure, and usage for the first three
families of stainless steels.

TABLE: Typical Composition (in wt. %) of the ferritic, martensitic, and austenitic Stainless
Steels
Element Ferritic Martensitic Austenitic
Carbon 0.08-0.20 0.15-1.2 0.03-0.25
Chromium 11-27 11.5-18 16-26
Manganese 1-1.5 1 2 (5.5-10)
Molybdenum some cases
Nickel 3.5-22
Phosphorus and sulfur Normal (0)
Silicon 1 1 1-2 (0)
Titanium Some cases

TABLE: Popular alloys structures and AISI designation for three primary types of stainless
steel
AISI Type
Martensitic 410, 420, 440C
(Hardenable by heat treatment )
Ferritic 405, 430, 446
(More corrosion resistant than martensitic,
but not hardenable by heat treatment)
Austenitic 201, 202, 301, 302,
(best corrosion resistance, but hardenable 302B, 304L, 310,
only by cold working) 316, 321

TABLE: Key purpose and usage for different stainless steel alloys
Purpose and Usage AISI Types
General purpose 410, 430, 202, 302
Automobile parts 301, 409, 430, 434
Hardenable by heat treatment 410, 420, 440C
Hardenable by cold working 201, 301
For elevated-temperature service 446, 302B, 310
Modified for welding 405, 304L, 321
Superior corrosion resistance 316
Catalytic converters 409

3
Remarks:
(1) Sensitization: Problems with stainless steels are often due to the loss of corrosion
resistance (sensitization) when the amount of chromium in solution drops below 12%.
Since chromium depletion is usually caused by the formation of chromium carbides along
grain boundaries, and these carbides form at elevated temperatures, various means have
been developed to prevent their formation. One approach is to keep the carbon content of
stainless steels as low as possible, usually less than 0.10%. Another method is to tie up
the carbon with small amounts of stabilizing elements, such as titanium or niobium,
that have a stronger affinity for carbon than does chromium. Rapidly cooling of these
metals through the carbide-forming range of 900 to 1500F (480 to 820C) also works to
prevent carbide formation.
(2) Embrittlement: Another problem with high-chromium stainless steels is an embrittlement
that occurs after long times at elevated temperatures. This is attributed to the formation
of sigma phase, a brittle compound that forms at elevated temperatures and coats grain
boundaries, thereby producing a brittle crack path through the metal. Stainless steels used
in high-temperature service should be checked periodically to detect sigma-phase
formation.
(3) Passivation & surface treatment: According to ASTM A380, passivation is the removal
of exogenous iron or iron compounds from the surface of stainless steel by means of a
chemical dissolution, most typically by a treatment with an acid solution that will remove
the surface contamination, it will not significantly affect the stainless itself. In addition,
it also describes passivation as the chemical treatment of stainless steel with a mild
oxidant, such as a nitric acid solution, for the purpose of enhancing the spontaneous
formation of the protective passive film. Passivation is recommended where the surface
must be free of iron. Passivation can also aid in the rapid development of the passive
surface layer on the steel, but usually does not result in a marked change in appearance of
the steel surface.
Passivation is performed with acid solutions (or pastes) to remove contaminants and
promote the formation of the passive film on a freshly created surface (for example, via
grinding, machining or mechanical damage). Common passivation treatments include
nitric acid (HNO3) solutions or pastes which will clean the steel surface of free iron
contaminants. Since dangerous acids are involved, only trained personnel can perform
such process. In addition, stainless steel pickling acids are highly corrosive to carbon
steel, and should be thoroughly removed by rinsing the component after completing the
process, and/or neutralize with alkali before the rising. Residual hydrofluoric acid will
initiate pitting corrosion.