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Overview9

Stainless steels constitute a group of high alloy steels based on the Fe-Cr, Fe-Cr-C, and
Fe-Cr-Ni systems. These steels contain a minimum of 11 - 12 wt% chromium. This level of
chromium forms a passive surface oxide that prevents oxidation and corrosion of the underlying
metal under ambient conditions. Corrosive media that can remove the passive oxide will result
in corrosive attack of the stainless steels. Stainless steels have good resistance to oxidation,
even at high temperatures which makes them useful in steam environments, such as power
generation applications.
Stainless steels are used in a wide variety of applications such as power generation,
chemical and paper processing, and many commercial products such as kitchen equipment, and
automobiles. Stainless steels also find extensive usage for purity and sanitary applications in
areas such as pharmaceutical, dairy, and food processing.
Most types of stainless steels are weldable, however some require special procedures.
Since chromium oxidizes readily, the back side of open root joints and thin materials must be
protected from the ambient environment during welding. If this is not done, the metal will
oxidize exhibiting what is commonly known as sugaring. This term comes from the fact that
the chromium oxide looks like burned sugar with a characteristic black, lumpy appearance.
Protection can be in the form of non-metallic backing, permanent backing, chill bars or inert
backing gas. Fluxes and slags may also be used to protect the molten metal from oxidation with
certain welding processes.

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The first reported stainless steel alloys are attributed to Harry Brearly who
was a metallurgist at Thomas Firth and Sons in Sheffield, England. Brearly came
from a poor working class family and started at Firth at the age of 12 as a bottle
washer in the chemical laboratory. In 1907, at the age of 36, he was named head of
the research laboratories.
In May 1912, Brearly visited the Royal Small Arms factory in Enfield to
investigate the failure of rifle barrels made of 5% chromium steel due to internal
corrosion. He concluded that higher chromium contents could possibly be a
solution to the corrosion problem. He initially cast two steels with 10% and 15% Cr
and nominally 0.30% C. Both these were unsuccessful because of excessively high
carbon contents. In August 1913, however, an acceptable ingot was cast of
composition 12.86% Cr, 0.24% C, 0.20% Si, and 0.44% Mn. This material was
used to make twelve experimental gun barrels, but the new barrels did not show the
expected improvement. Some of this material was also made into cutlery blades
and the age of stainless steel had begun.
The first stainless steel ingot was cast in the United States by Firth Sterling
Ltd. in Pittsburgh on March 3, 1915. This eventually led to U.S. Patent No.
1,197,256 that was assigned to Brearly for cutlery grade steel. It covered the
composition range from 9 to 16 wt% chromium and less than 0.7 wt% carbon.
Steels made under this patent son came to be called Firth Stainless.
Reference: Materials Performance, March 1990, pages 64-68.

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Stainless steels are an important class of engineering materials. Since stainless steels are
so widely used, considerable research has been conducted to define their microstructure and
properties. Because so many varieties of stainless steel are available, a wide range of desirable
properties are achievable and they can be used in a number of different applications.
In the United States, wrought grades of stainless steels are generally designated by the
American Iron and Steel Institute (AISI) numbering system, the Unified Numbering System
(UNS), or the proprietary name of the alloy. In addition, designation systems have been
established by most of the major industrial nations. Of the two institutional numbering systems
used in the U.S., AISI is the older and more widely used. Most of the grades have a three-digit
designation; the 200 and 300 series are generally austenitic stainless steels, whereas the 400 series
are either ferritic or martensitic. Some of the grades have a one- or two-letter suffix that indicates
a particular modification of the composition.
Stainless steels are categorized based on the the metallurgical phase (or phases) which is
predominant. The three phases possible in stainless steels are martensite, ferrite and austenite.
Duplex stainless steels contain approximately 50% austenite and 50% ferrite, taking advantage of
the desirable properties of each phase. Precipitation hardenable (PH) grades are termed such
because they form strengthening precipitates and are hardenable by aging. PH stainless steels are
further grouped by the phase of matrix in which the precipitates are formed: martensitic, semiaustenitic, or austenitic types. The American Iron and Steel Institute (AISI) has a system that uses
three numbers, sometimes followed by a letter, to designate stainless steels. Examples are 304,
304L, 410, 430, etc.
Magnetic properties can be used to identify some of the stainless steels. The austenitic
types are essentially non - magnetic. A small amount of residual ferrite or cold working may
introduce a slightly magnetic condition, but it is notably weaker than a magnetic material. The
ferritic and martensitic types are ferromagnetic.
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Physical properties, such as thermal conductivity and thermal expansion, and


mechanical properties vary widely for the different types and influence their welding
characteristics. For example, austenitic stainless steels possess low thermal conductivity and
high thermal expansion resulting in higher distortion than other grades.

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Overview15

Production of stainless steels is a two-stage process involving the melting of scrap


and ferro-alloys in an electric-arc furnace followed by refining by oxygen-inert gas
injection (argon oxygen decarburization) or oxygen injection under vacuum
(vacuum oxygen decarburization) to adjust carbon content and remove impurities.
(Both of these processes are described in the Section "Iron and Steelmaking
Practices" in this Handbook.) The refined molten metal is then poured into molds to
form ingots, followed later by blooming or slabbing, or is poured directly into a
continuous casting machine to form slabs, blooms, or billets. Cast ingots can be
rolled or forged; and flat products (sheet, strip, and plate) can be produced from
continuously cast slabs. The rolled product can be drawn, bent, extruded, or spun.
Stainless steels can be further shaped by machining, and they can be joined by
welding, brazing, soldering, and adhesive bonding. Stainless steels can also be used
as an integral cladding on plain carbon or low-alloy steels, as well as some
nonferrous metals and alloys.
Reference: ASM Metals Reference Book, 3rd Ed., 1993.

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Overview18

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Overview21

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Overview23

Stainless steels are used in a wide variety of applications. Most of the structural
applications occur in the chemical and power engineering industries, which account
for more than a third of the market for stainless steel products (see the table). These
applications include an extremely diversified range of uses, including nuclear
reactor vessels, heat exchangers, oil industry tubulars, components for chemical
processing and pulp and paper industries, furnace parts, and boilers used in fossil
fuel electric power plants.
Reference: ASM Metals Reference Book, 3rd Ed., 1993.
Catherine M. Houska of TMR Consulting from Pittsburgh, USA lately reported in
the Stainless Steel World magazine (July/August edition) on the state of St. Louis
Gateway Arch. Whilst it appears that the original metal chemical certifications of
the type 304 stainless plates and weld filler used for constructing the arch can no
longer be traced (the mills that produced the plate are now part of the corporate
history of ATI Allegheny Ludlum and Outokumpu), these companies were able to
provide information on the testing capabilities of the time period of the build though
type 304 stainless plates would have been prepared in the 1960s according to
ASTM A167. Likewise, information about the source of the filler metal used in the
welds also no longer exists. However, welding procedures qualifications, and
records for the horizontal and vertical butt joints show us that MIG welding was
used with different argoncarbon dioxide helium cover mixtures for each joint
orientation at the time of construction. Similarly, the welds were cleaned up with a

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wire brush and two weld passes and a grooved back up root treatment were used. Further, a
PittsburgDes Moines Steel Company letter from December 1963 informs us that weld haloes
were removed using electrolytic methods. Electrolytic cleaning wands were used fifty years
ago. Although it is an old technology, it is still in use today, techniques not having changed
very much. It was most likely used in combination with brushing to restore corrosion
resistance. Moreover, the cleaner used, Oakite 33 which is a phosphoric acid-based, is also
still used. In connection with the St. Louis Arch, the technique was used to clean and degrease
the surface of the plates prior to welding. Additionally , both AWS and ASME code Section
IX were referenced in the weld procedures.
Ref: http://www.stainless-steel-world.net/articles/89/st.-louis-gateway-arch-reaches-thegrand-old-age-of-fifty-a-historical-quantifying-assessment.html

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Overview24

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Overview26

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The physical properties of stainless steels are quite different from those of commonly used
nonferrous alloys such as aluminum and copper alloys. However, when comparing the various
stainless families with carbon steels, many similarities in properties exist, although there are some
key differences. Like carbon steels, the density of stainless steels is 8.0 g/cm3, which is
approximately three times greater than that of aluminum alloys (2.7 g/cm3). Like carbon steels,
stainless steels have a high modulus of elasticity (200 GPa, or 30 106 psi) that is nearly twice that
of copper alloys (115 GPa, or 17 106 psi) and nearly three times that of aluminum alloys (70 GPa,
or 10 106 psi).
Differences among these materials are evident in thermal conductivity, thermal expansion, and
electrical resistivity, as well. The figure shows the large variation in thermal conductivity between
various types of materials; 6061 aluminum alloy (Al-1Mg-0.6Si-0.3Cu-0.2Cr) has a very high
thermal conductivity, followed by aluminum bronze (Cu-5Al), 1080 carbon steel, and then stainless
steels. For stainless steels, alloying additions, especially nickel, copper, and chromium, greatly
decrease thermal conductivity.
Thermal expansion is greatest for type 6061 aluminum alloy, followed by aluminum bronze and
austenitic stainless alloys, and then ferritic and martensitic alloys. For austenitic stainless alloys,
additions of nickel and copper can decrease thermal expansion. Stainless steels have high electrical
resistivity. Alloying additions tend to increase electrical resistivity. Therefore, the ferritic and
martensitic stainless steels have lower electrical resistivity than the austenitic, duplex, and PH alloys,
but higher electrical resistivity than 1080 carbon steel. Electrical resistivity of stainless steels is 7.5
times greater than aluminum bronze and nearly 20 times greater than type 6061 aluminum alloy.
Reference: ASM Metals Reference Book, 3rd Ed., 1993.

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Reference:
RAMIREZ, A.J. Sigma Phase and Chromium Nitride Precipitation Study by
Thermal Simulation of Duplex Stainless Steels Multipass Welding HAZ. So
Paulo-Brazil, 1997. 151p. Dissertation (Master) Metallurgical Engineering
Department, Polytechnic School of So Paulo University.
ASM Metals Reference Book, 3rd Ed., 1993.

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Many stainless steels--particularly the austenitic types 304, 309, 310, 316, 321, 330, and 347; certain
precipitation-hardening types such as PH 15-7 Mo, 15-5 PH, 17-4 PH, 17-7 PH, AM-350 and AM355; and certain martensitic types such as the so-called "Super 12 Chrome" steels that contain
molybdenum (up to 3%), tungsten (up to 3.5%), and/or vanadium--are used extensively for elevatedtemperature applications. As shown in the figure, the austenitic types retain their strength at higher
temperatures (up to 815 C, or 1500 F) than do the other types of stainless steels. For the best creep
strength and creep-rupture strength, the H grades of austenitic stainless steels are specified. These
steels have carbon contents of 0.04 to 0.10% and are solution annealed at temperatures high enough
to produce improved creep properties.
Valve steels are austenitic nitrogen-strengthened steels that have been used extensively in
automotive/internal combustion engine valve applications. Examples of such alloys include 21-2N
(21Cr, 8Mn, 2Ni + N), 21-4N (21Cr, 9Mn, 4Ni + N), 21-12N (21Cr, 12Ni, 1.25Mn + N), and 23-8N
(21Cr, 8Ni, 3.5Mn + N) (see Table 3 ). The nitrogen contents in these alloys range from 0.20 to
0.50%. These engine valve grades are used at temperatures up to 760 C (1400 F), but they provide
fairly low strength at the upper end of their temperature capability.
Extended service at elevated temperature can result in embrittlement (sensitization) of austenitic
stainless steels, which degrades the ability of the material to withstand corrosion and induces
embrittlement. Most often, such degradation is caused by the precipitation of secondary phases such
as carbides and sigma phase. Precipitation depends on both time and temperature: longer times at
temperature and higher temperatures both promote more extensive precipitation.
Reference: ASM Metals Reference Book, 3rd Ed., 1993.

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The selection of stainless steels can be based on corrosion resistance, fabrication


characteristics, availability, mechanical properties in specific temperature ranges,
and product cost. However, corrosion resistance and mechanical properties are
usually the most important factors in selecting a grade for a given application.
Corrosion resistance is frequently the most important characteristic of a stainless
steel but often is also the most difficult to assess for a specific application. General
corrosion resistance to pure chemical solutions is comparatively easy to determine,
but actual environments are usually much more complex.
General corrosion is often much less serious than localized forms such as SCC,
crevice corrosion in tight spaces or under deposits, pitting attack, and intergranular
attack in sensitized material such as weld heat-affected zones. Such localized
corrosion can cause unexpected and sometimes catastrophic failure while most of
the structure remains unaffected, and therefore it must be considered carefully in the
design and selection of the proper grade of stainless steel. Corrosive attack can also
be increased dramatically by seemingly minor impurities in the medium that may be
difficult to anticipate but that can have major effects, even when present in only
parts-per-million concentrations: heat transfer through the steel to or from the
corrosive medium, contact with dissimilar metallic materials, stray electrical
currents, and many other subtle factors. At elevated temperatures, attack can be
accelerated significantly by seemingly minor changes in atmosphere that affect
scaling, sulfidation, or carburization.
Reference: ASM Metals Reference Book, 3rd Ed., 1993.

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