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Heat-resisting steels

Abstract: Steels are now used for a wide variety of conditions entailing heat and corrosion under both
static and dynamic stresses, such as aero engine valves, furnace conveyers, retorts, oil cracking units and
gas turbines. Three important properties are necessary in material used at elevated temperatures:
1. Resistance to oxidation and to scaling.
2. Retention of strength at the working temperature.
3. Structural stability as regards carbide precipitation, spheroidisation, sigma formation and temper
embrittlement.
Steels are now used for a wide variety of conditions entailing heat and corrosion under both static and
dynamic stresses, such as aero engine valves, furnace conveyers, retorts, oil cracking units and gas
turbines. Three important properties are necessary in material used at elevated temperatures:
1. Resistance to oxidation and to scaling.
2. Retention of strength at the working temperature.
3. Structural stability as regards carbide precipitation, spheroidisation, sigma formation and temper
embrittlement.
Other properties may also be important in particular applications, such as specific resistance and
temperature coefficient for electrical purposes, coefficient of expansion for constructional units and
resistance to penetration by products of combustion in many furnace applications. In the case of gas
turbine steels additional characteristics have to be considered; internal damping capacity and fatigue
strength, notch sensitivity and impact strength (hot and cold), machining and welding characteristics,
especially as large rotors may have to be built of small sections welded together.
The scale which forms on iron is porous and loosely adherent, but it is rendered adherent and protective
by the addition of certain elements to the steel. These are usually chromium, silicon and aluminium, and
they are characterised by their great affinity for combining with oxygen, but the reaction is rapidly stifled
by the formation of the inert oxide films.
The resistance of mild steel to oxidation is vastly improved by forming an aluminium-iron alloy on the
surface. This is done by heating at 1000C in contact with powdered aluminium (calorising) or by metalSpraying the steel surface with aluminium, coating with bitumastic paint to prevent oxidation and heating
to 780C (aluminising).
Improved creep strength may be attained by

raising the softening temperature by the solution of alloying elements;


judicious use of precipitation hardening at the working temperature without readily over-ageing.
Second phase hardening is critically dependent on the degree and uniformity of the dispersion
achieved and creep rate is related to a critical range of particle spacing;
controlled degree of work-hardening in the appropriate temperature ranges which often reduces
the extent of the primary creep stage;
variations in the process of manufacture; deoxidisers and particles in the crystal boundary can
have a marked effect on creep properties;
vacuum melting permits the use of advantageous compositions which cannot be melted by
conventional methods. lt also improves ductility in the transverse direction.

Mechanical properties, are improved by the addition of various elements.


Cobalt, tungsten and molybdenum cause the steels to withstand the action of tempering. High alloy
austenitic steels have no change points and therefore do not harden by air cooling, but their resistance to
wear resistance is not great. A sufficiency of elements such as silicon and chromium raise the Ac, point to
temperatures above those reached in service and prevent the steel from air hardening on cooling.

Steels with high nickel content should not be used at high temperatures in contact with gases containing
sulphur dioxide or other sulphur compounds, since intercrystalline films of nickel sulphide are formed.
In high chromium steels the carbides coalesce into large particles which have less obstructive action on
grain growth of the ferrite at temperatures above 700C. The excessive grain growth reduces still further
the toughness which these steels possess.
Grain growth also occurs in the austenitic steels above 1000C, but no trouble arises since they remain
tough and ductile even in the coarse grained condition. When heated in the range 500-900C austenitic
steels precipitate carbides along the boundaries of the austenite and as a result intercrystalline cracks are
liable to develop if the steel is stressed continuously in tension in this temperature range. With certain
compositions both ferritic and austenitic steels are embrittled by the formation of sigma phase.

Stainless steel
Abstract: The stainless steels owe their resistance to corrosion to the presence of chromium. Brearley
discovered this fact more or less accidentally in 1913. Today, there is a range of steels from the plain
chromium variety to those containing up to six alloying elements in addition to the usual impurities.
The stainless steels owe their resistance to corrosion to the presence of chromium. Brearley discovered
this fact more or less accidentally in 1913. Today, there is a range of steels from the plain chromium
variety to those containing up to six alloying elements in addition to the usual impurities. A simple
classification of the steels follow:
Hardenable alloys
1. 12-14 % chromium, iron and steels, whose mechanical properties are largely dependent on the
carbon content. High strength is combined with considerable corrosion resistance:
a) Stainless iron,
b) Stainless steel, (mild, medium and hard)
2. Secondary hardening ,10-12% chromium, 0.12% C, with small additions Mo, V, Nb, Ni; a steel with
ultimate stress of 927 MPa is used for gas turbine blades.
3. High chromium steel 17% Cr, 0.15% C, 2.5% Ni (431 S29). It has a higher resistance to corrosion
than iron, due to higher chromium content. It is used for pump shafts, valves and fittings subjected to high
temperature and high-pressure steam, but is unsuitable for acid conditions.
High carbon, 0.8 C, 16.5 Cr, 0.5 Mo steel (oil quenched at 1025C and tempered at 100aC to give
hardness of 700 HB) is used for stainless ball bearings and instruments such as scalpels.
Ferritic iron
- 16/18% chromium rustless iron with low carbon content (430 S15). It has high resistance to corrosion
but low impact and cannot be refined by heat-treatment alone. Prolonged service at 480C can cause
embrittlement. It is used for motor car trim.
- 25/30% chromium iron for furnace parts, resistant to sulphur compounds. Forms sigma phase additions
of Nb and Mo prevent excessive grain growth.
Austenitic steels
1. Plain 18/8 Austenitic Steels,
2. Soft Austenitic,
3. Decay-proof Steel,

4. Special Purpose Austenitic Steels,


5. High Manganese Steel,
6. Heat-resisting Steels,
7. Precipitation-hardening high tensile steels.
(a) martensitic,
(b) Semi Austenitic
(c) Austenitic,
Heat-treatment
The hardening alloys possess critical ranges comparable with ordinary carbon steels, and can, therefore,
be hardened, tempered and refined by heat-treatment which does not depend on recrystallisation after cold
working.
The ferritic and normal austenitic steels, on the other hand, are not amenable to such treatment. Only cold
work with subsequent heat-treatment involving recrystallisation can be employed to refine large grained
material.
Effects of chromium and nickel
It will be readily appreciated that chromium is the chief alloying element in iron and steel for inhibiting
corrosion. This resistance is not due to the inertness of the chromium, for it combines with oxygen with
extreme rapidity, but the oxide so formed is very thin and stable, continuous and impervious to further
attack.This property is, fortunately, conferred upon its solid solution in iron, becoming very marked as the
amount exceeds 12 % in low carbon steels.
Thus, in oxidising environments, such as nitric acid, the high chromium steel is initially attacked at the
same rate as ordinary plain steel, but it rapidly builds up an oxide film, known as a self-healing passivefilm, which efficiently protects the underlying metal. This film has actually been isolated by U. R. Evans.
The thickness of the film and its Cr2O3 content increases with the degree of polish.
In oxidising media any defect in the film which may arise through abrasion will be quickly repaired and
such steel is quite satisfactory in the atmosphere, but the film does not offer sufficient permanent
resistance to the less oxidising action of hydrochloric and sulphuric acids, except in very dilute solutions.
Nickel has a low solubility in these acids and thus, with 8 to 10 % of nickel in addition to chromium, the
steel is immune from attack by nitric acid and the resistance to the other acids is markedly increased.
Hence it is very evident why the 18/8 steels have such extensive uses. Their resistance to particular acids
have been further improved by additions of elements such as molybdenum and copper.

Corrosion Resistance of Ferritic Stainless Steels


Abstract: Ferritic stainless steels have certain useful corrosion properties, such as resistance to chloride
stress-corrosion cracking, corrosion in oxidizing aqueous media, oxidation at high temperatures and
pitting and crevice corrosion in chloride media. These steels contain above approximately 13% Cr and
precipitate a prime phase in 350C to 540C range, and the maximum effect is at about 470C. Because
precipitation hardening lowers temperature ductility, it must be taken into account in both processing and
usage of ferritic stainless steels, especially those with higher chromium content.
Ferritic stainless steels have certain useful corrosion properties, such as resistance to chloride stresscorrosion cracking, corrosion in oxidizing aqueous media, oxidation at high temperatures and pitting and
crevice corrosion in chloride media.
These steels contain above approximately 13% Cr and precipitate a prime phase in 350oC to 540oC range,
and the maximum effect is at about 470oC. Because precipitation hardening lowers temperature ductility,
it must be taken into account in both processing and usage of ferritic stainless steels, especially those with
higher chromium content.

Structures of these steels are kept completely ferritic at room and high temperature by adding titanium or
columbium, or by melting to very low levels of carbon and nitrogen, or both. Such microstructures
provide ductility and corrosion resistance in weldments. Molybdenum improves pitting corrosion
resistance, while silicon and aluminum increase resistance to high temperature oxidation.
The newer ferritic steels with high content of chromium have become possible through vacuum and
argon-oxygen decarburization, electron-beam melting, and large-volume vacuum induction melting. The
representatives of this group include ASTM designations 409 and 439.
Type 409 with 12% Cr is relatively low-cost and has good formability and weldability. Recommended
thickness is limited to approximately 3,8 mm maximum if ductile-to-brittle transition temperature
(DBTT) at room temperature or lower is needed (Figure 1). Its atmospheric corrosion resistance is
adequate for functional uses, so applications of this type of steel include automobile exhaust equipment,
radiator tanks, catalytic reactors, containerization and dry fertilizer trunks.
Type 439 with 18-20% Cr resists chloride stress-corrosion cracking. Resistance to general and pitting
corrosion is approximately equivalent to that of austenitic types 304 and 316. This grade is suitable for
equipment exposed to the aqueous chloride environments, heat transfer applications, condenser tubing for
fresh water power plants, food-handling uses and water tubing for domestic and industrial buildings.
Sheet thickness cannot exceed approximately 3,2 mm if DBTT (Figure 1) at room temperature or lower is
needed.

Figure 1. Ductile-to-brittle transition temperatures (DBTT) for ferritic stainless steel rise with section
thickness. Bands for 409 and 439 indicate data scatter
Resistance to stress-corrosion cracking is the most obvious advantage of the ferritic stainless steels.
Ferritic steels resist chloride and caustic stress corrosion cracking very well. Nickel and copper residuals
lower resistance of these steels to stress corosion.
Susceptibility of the ferritic steels to intergranular corrosion is due to chromium depletion, caused by
precipitation of chromium carbides and nitrides at grain boundaries. Because of the lower solubility for
carbon and nitrogen and higher diffusion rates in ferrite, the synthesized zones of welds in ferritic steels
are in the weld and adjacent to the weld. To eliminate the intergranular corrosion, it is necessary either to
reduce carbon to very low levels, or to add titanium and columbium to tie up the carbon and nitrogen.
Pitting, an insidious localized type of corrosion occurring in halide media, can put complete installations
out of operation in relatively short time. Resistance to this type of corrosion depends on chloride
concentration, exposure time, temperature and oxygen content. In general, resistance to pitting increases
with chromium content. Molybdenum also plays an important role and it is equivalent to several
percentages of chromium.
General corrosion resistance: The atmospheric corrosion resistance of the ferritic steels is excellent.
These steels have good corrosion resistance in strongly oxidizing environments, such as nitric acid. In

organic acids, all ferritic steels are superior to austenitic, but in reducing media general corrosion
resistance of ferritic steels is worst than austenitic.
High-chromium ferritic stainless steels

High-chromium ferritic stainless steels - such as types 442 and 446 - have excellent resistance to
corrosion and to oxidation in many industrial environments. These alloys are included in ASTM
specifications A176-74 (Chromium stainless flat products), A 511 (Seamless stainless steel mechanical
tubing), A268-74 (Ferritic stainless steel tubing for general service) and also in ASME code and AISI and
SAE specifications.
High-chromium ferritic steels have 18-30% Cr and low content of carbon and nitrogen. Titanium in these
alloys prevents intergranular chromium-carbide and nitride precipitation during welding or processing.
Because of the ferritic structure and controlled composition, the alloys exhibit good resistance to general,
intergranular and pitting corrosion, and stress corrosion cracking. Similar to other high chromium
stainless steels, types 442 and 446 have excellent oxidation resistance at elevated temperatures. They also
have high thermal conductivity, higher yield strength than austenitic stainless steels, and lower tensile
ductility.
The excellent resistance to chlorides, organic acids and chloride stress-corrosion indicates that these
alloys should be suitable for a wide range of applications in which conventional stainless steels or other
materials are either inadequate or uneconomical. High-chromium ferritic stainless steels are useful in heat
exchanger tubing, feed-water tubing and in equipment that operate with chloride-bearing or brackish
cooling waters.
Available in sheet, strip, tubing and welding wire, alloys are finding substantial application in replacing
brass and cupronickel, corrosion-resistant high-nickel alloys, and other materials in the food processing,
power, chemical, petrochemical, marine and pulp and paper industries.

Steels for Cryogenic and Low-Temperature


Service
Abstract: Carbon and alloy grades for low-temperature service are required to provide the high strength,
ductility, and toughness in vehicles, vessels, and structures that must serve at 45C and lower. Because a
number of steels are engineered specifically for service at low temperature (about 100C), selecting the
optimum material calls for thorough understanding of the application and knowledge of the mechanical
properties that each grade provides.
Carbon and alloy grades for low-temperature service are required to provide the high strength, ductility,
and toughness in vehicles, vessels, and structures that must serve at -45C and lower. Because a number
of steels are engineered specifically for service at low temperature (about -100C), selecting the optimum
material calls for thorough understanding of the application and knowledge of the mechanical properties
that each grade provides.
At temperature below ambient, a metals behavior is characterized somewhat by crystalline structure. The
yield and tensile strengths of metals that crystallize in the body-centered cubic from iron, molybdenum,
vanadium and chromium depend greatly on temperature. These metals display a loss of ductility in a
narrow temperature region below room temperature.
The tensile strength of metals with face-centered cubic structures - aluminum, copper, nickel and
austenitic stainless steel - is more temperature dependent than their yield strength, and the metals often
increase in ductility as temperature decrease.
Transformation occurring in compositions that are normally stable at room temperature, but metastable at
cryogenic temperatures, can greatly alter their behavior. For example, the combination of gross plastic
deformation and cryogenic temperatures can cause a normally ductile and tough stainless steel, such as

301, 302, 304, 321, to partially transform to bcc structure, resulting in an impairment of ductility and
toughness. A fully stable stainless steel 310 cannot be transformed at cryogenic temperatures.
The 300 series steels offer a fine combination of toughness and weldability for service to the lowest
temperatures. In the annealed condition, their strength properties are adequate for ground-based
equipment but inadequate for lightweight structures. For aerospace applications, fabricators can take
advantage of the alloys strain-hardening characteristics and use them in highly cold-worked condition.
The principal shortcomings of cold-worked materials are: low weld-joint efficiencies caused by annealing
during welding and the transformation to martensite that occurs during cryogenic exposure. Selection of
fully stable grade type 310, overcomes the transformation problem. Precipitation-hardening A286
stainless has even higher strength when cold worked before aging.
The only alloy steel recommended for cryogenic service is 9% nickel steel. It is satisfactory for service
down to -195C and is used for transport and storage of cryogenics because of its low cost and ease of
fabrication. Other alloy steels are suitable for service in the low-temperature range. The steels A201 and
T-1 can suffice to -45C, nickel steels with 2.25% Ni can suffice to -59C, and nickel steels with 3.5% Ni
to -101C.

Steel for Cryogenic Service: An Example


Designers of cryogenic assemblies base their stress calculations on the room-temperature properties of the
material. The reason is that it is the highest temperature the material will encounter. And it stands that if a
higher-strength material that stands up to super cold conditions were available, designers might specify it.
At 26C austenitic stainless steel has tensile and yield strengths that are 172 MPa greater than the
corresponding strengths for type 304 stainless. At -100C its tensile and yield strength exceed those of
type 304 by 550 MPa and 276 MPa respectively.
A grade with following chemical composition shows good mechanical properties at cryogenic
temperatures:
C - 0.072%
Mn - 16%
P - 0.02%
S - 0.008%
Si - 0.41%
Ni - 5.85%
Cr - 17.8%
N - 0.36%
Fe - Remainder
(The composition is given for plates with 12.7mm thickness)
The material combination of high strength, good toughness, and weldability should prompt designers to
specify it for welded pressure vessels for the storage of cryogens.

Steels for Low-Temperature


When designing low-temperature systems or equipment, the engineer finds that notch toughness ranks
high in importance, because a part or structure will generally fail due to a notch or other stress
concentration. Test results measure the steels capacity to absorb energy, and thus signify its ability to
resist failure at points of local stress concentration.
Fatigue limit of steel also must be considered. At low temperatures, systems are usually subjected to
dynamic loads, and structural members to cycle stresses. Examples include vessels that frequently
undergo pressure changes and large structures and mobile equipment that experience extreme stress
imposed by packed snow or high winds. Other considerations include heat conductivity and thermal
expansion.

Carbon steels have a better weldability, greater toughness, and higher strenght with low coefficients of
termal conductivity than alloy steels. The A 516, one of the most frequently used group of carbon steels,
have tensile strengths ranging from 379 MPa to 586 MPa minimum. The big advantage of A 516 steels is
their low initial cost.
Compared with A 516, A 442 class have higher carbon and manganese in plates less than 25.4 mm
thickness, and lower manganese beyond 25.4 mm. However, applications for A 516 Grades 55 and 60
duplicate those of A 442. They are easier to fabricate than A 442 grades because carbon content is lower.
Higher strength with good notch toughness is available in carbon steels A 537 Grade A and A 537 grade
B. Their can be earlier normalized or quenched and tempered to raise yield and tensile strength and
impact toughness beyond those of the A 516`s. Table 1 shows mechanical properties at low temperatures
for some typical ASTM carbon steels.
Table 1. Specifications for Low-temperature Steels

Designation

Lowest usual
Min Yield
service
Strength
temperature,
(MPa)
(C)

Tensile
Strength
(MPa)

Min
Elongation,
L0= 50 mm
(%)

Uses

A442 Gr. 55

-45

221

379 - 448

26

A442 Gr. 60

-45

221

414 - 496

23

A516 Gr. 55

-45

207

379 - 448

27

A516 Gr. 60

-45

221

414 - 496

25

A516 Gr. 65

-45

241

448 - 531

23

A516 Gr. 70

-45

262

483 - 586

21

A517 Gr. F

-45

690

792 - 931

16

Highly stressed vessels

A537 Gr. A

-60

345

483 - 620

22

A537 Gr. B

-60

414

551 - 690

22

Offshore drilling platforms,


storage tanks, earthmoving
equipment

A203 Gr. A

-60

255

448 - 531

23

A203 Gr. B

-60

276

482 - 586

21

A203 Gr. D

-101

255

448 - 531

23

A203 Gr. E

-101

276

482 - 586

21

A533 Gr. 1

-73

345

552 - 690

18

A533 Gr. 2

-73

482

620 - 793

16

A533 Gr. 3

-73

569

690 - 862

16

A543 Gr. 1

-107

586

724 - 862

14

A543 Gr. 2

-107

690

793 - 931

14

Welded pressure vessels and


storage tanks; refrigeration;
transport equipment

Piping for liquid propane, vessels,


tanks
Land-based storage for liquid
propane, carbon dioxide,
acetylene, ethane and ethylene
Nuclear reactor vessels where low
ambient toughness required for
hydrostatic testing; some
chemical and petroleum
equipment
Candidate material with high
notch toughness for heavy-wall
pressure vessels

Since a variety of low-temperature steels are available, the engineer must consider the advantages each
has to offer according to the application. The cost-strength ratio is but one factor; others, such as welding
and fabrication costs, have equal or greater bearing on final costs. However, heat-treated carbon grades
are often used for low-temperature services. Besides offering excellent low-temperature toughness plus
fabricability, these grades are lower in initial cost.

Pipeline Steels for Low Temperature Uses


Steels for natural gas pipelines must meet more demanding requirements than that used for oil. For
example they carry compressed gas at -25C to -4C, making crack growth and brittleness a problem in
the severe artic environment. Achieving low-temperature notch toughness, grain size control, and low
sulfur content were among major problems in developing the steel, particularly since economic feasibility
had to be considered.
Hot-rolled steels present a good opportunity to cut both cost and weight if the cost per unit strength could
be reduced. As strength of high-strength, low-alloy steels rise, toughness usually drops.
In steel alloyed with molybdenum, manganese and columbium, which is use for these pipe-lines,
molybdenum raises both strength and toughness. Carbon is reduced to make columbium more soluble,
and to improve weldability and impact strength. Steels with small and large amount of columbium have
similar precipitation kinetics; higher strengths are produced by larger quantities of columbium.
Columbium also promotes hardenability, which is needed to develop an acicular-ferrite microstructure.
Manganese, along with molybdenum, helps to inhibit transformation to polygonal ferrite on the steel.
Where sulphur cannot be kept low, however, rare earth additions will control the shape of the sulfide
inclusions. During hot working, grain refinement is enhanced because columbium has a grain-boundary
pinning effect. This effect makes it possible to produce a highly substructured austenite prior
transformation, which helps in assuring transformation to fine grained acicular ferrite.
Contributing to high strength and good impact resistance is the transformation mechanism - austenite
changes to fine-grained acicular ferrite, which is further strengthened by the precipitation of columbium
carbonitride. Other advantages include good formability and most important, excellent weldability.
Aside from pipeline, this steel can be used in the automotive, railroad, heavy equipment, construction and
shipbuilding industries, application areas which the keynote is low cost per unit strength. Because of their
inherently good strength-toughness relationship, the manganese-molybdenum-columbium steels may well
satisfy this requirement.

Cast Stainless Steels


Abstract: Stainless steel castings are usually classified as either corrosion-resistant castings or heatresistant. The usual distinction between heat-resistant and corrosion-resistant cast steels is based on
carbon content.
Cast stainless steels are most often specified on the basis of composition using the designation system of
the High Alloy Product Group of the Steel Founders Society of America (the Alloy Casting Institute).
Stainless steels are a class of chromium-containing steels widely used for their corrosion resistance in
aqueous environments and for service at elevated temperatures. Stainless steels are distinguished from
other steels by the enhanced corrosion and oxidation resistance created by chromium additions.
Chromium imparts passivity of ferrous alloys when present in amounts of more than about 11%
particularly if conditions are strongly oxidizing. Consequently, steels with more than 10 or 12% Cr are
sometimes defined as stainless steels.
Stainless steel castings are usually classified as either corrosion-resistant castings or heat-resistant.
However this line of demarcation in terms of application is not always distinct, particularly for steel
castings used in the range from 450 to 650oC. The usual distinction between heat-resistant and corrosionresistant cast steels is based on carbon content.
In general, the cast and wrought stainless steels possess equivalent resistance to corrosive media and they
are frequently used in conjunction with each other. One significant difference between the cast and
wrought stainless steels is in the microstructure of cast austenitic stainless steels. There is usually small

amount of ferrite present in austenitic stainless steel castings, in contrast to the single-phase austenitic
structure of the wrought alloys.
The presence of ferrite in the castings is desirable for facilitating weld repair, but ferrite also increases
resistance to stress-corrosion cracking. The principal reasons for this resistance are apparently:

Silicon added for fluidity gives added benefit from the standpoint of stress-corrosion cracking.
Sand castings are usually tumbled or sandblasted to remove molding sand and scale, this probably
tends to put the surface in compression

Wrought and cast stainless steels may also differ in mechanical properties, magnetic properties, and
chemical content. Because of the possible existence of large dendritic grains, intergranular phases, and
alloy segregation, typical mechanical properties of cast stainless steels may vary more and generally are
inferior to those of any wrought structure.
Cast stainless steels are most of ten specified on the basis of composition using the designation system of
the High Alloy Product Group of the Steel Founders Society of America (the Alloy Casting Institute). The
first letter of the designation indicates whether the alloy is intended primarily for liquid corrosion service
(C) or high temperature service (H). The second letter denotes the nominal chromium-nickel type of the
alloy. As nickel content increases, the second letter of the designation is changed from A to Z. The
numeral or numerals following the first two letters indicate maximum carbon content (percentage x 100)
of the alloy. Finally, if further alloying elements are present, these are indicated by the addition of one or
more letters as a suffix.
Corrosion-Resistant Steel Castings. These steel castings for liquid corrosion service are often classified
on the basis of composition, although it should be recognized that classification by composition often
involves microstructural distinction.
Alloys are grouped as:

Chromium steels
Chromium-nickel steels, in which chromium is the predominant alloying element
Nickel-chromium steels, in which nickel is the predominant alloying element.

The service ability of cast corrosion-resistant steels depends greatly on the absence of carbon, and
especially precipitated carbides, in the alloy microstructure. Therefore, cast corrosion resistant alloys are
generally low in carbon (usually lower than 0,20% and sometimes lower than 0,03%).
All cast corrosion-resistant steels contain more than 11% chromium, and most contain from 1 to 30%
nickel (a few have less than 1% Ni).
In general, the addition of nickel to iron-chromium alloys improves ductility and imparts strength. An
increase in nickel content increases resistance to corrosion by neutral chloride solutions and weakly
oxidizing acids.
The addition of molybdenum increases resistance to pitting attack by chloride solutions. It also extends
the range of passivity in solutions of low oxidizing characteristics.
The addition of copper to duplex (ferrite in austenite) nickel-chromium alloys produces alloys that can be
precipitation hardened to higher strength and hardness. The addition of copper to single-phase austenitic
alloys greatly improves their resistance to corrosion by sulfuric acid. In all iron-chromium-nickel stainless
alloys, resistance to corrosion by environments that cause intergranular attack can be improved by
lowering the carbon content.
Compositions of Heat-Resistant Steel Castings. Castings are classified as heat resistant if they are
capable of sustained operation while exposed, either continuously or intermittently, to operating
temperatures that result in metal temperatures in excess of 650oC. Heat-resistant steel castings resemble

high-alloy corrosion-resistant steels except for their higher carbon content, which imparts greater strength
at elevated temperature.
The three principal categories of this type cast steels, based on composition are:

Iron-chromium alloys
Iron-chromium-nickel alloys
Iron-nickel-chromium alloys

In the cast stainless steels structures may be austenitic, ferritic, martensitic, or ferric-austenitic (duplex).
The structure of a particular grade is primarily determined by composition. Chromium, molybdenum, and
silicon promote the formation of ferrite (magnetic), while carbon, nickel, nitrogen, and manganese favor
the formation of austenite (non-magnetic).
Chromium (a ferrite and martensite promoter), nickel, and carbon (austenite promoters) are particularly
important in determining microstructure. In general, straight chromium grades of high-alloy cast steel are
either martensitic or ferritic, the chromium-nickel grades are either duplex or austenitic, and the nickelchromium steels are fully austenitic.
Cast austenitic alloys usually have from 5 to 20% ferrite distributed in discontinuous pools throughout the
matrix, the percent of ferrite depending on the nickel, chromium, and carbon contents. The presence of
ferrite in austenite may be beneficial or detrimental, depending on the application.
Ferrite can be beneficial in terms of weldability because fully austenitic stainless steels are susceptible to
a weldability problem known as hot cracking, or microfissuring. The intergranular cracking occurs in the
weld deposit and/or in the weld heat-affected zone and can be avoided if the composition of the filler
metal is controlled to produce about 4% ferrite in the austenitic weld deposit. Duplex CF grade alloy
castings are immune to this problem.
The presence of ferrite in duplex CF alloys improves the resistance to stress-corrosion cracking (SCC)
and generally to intergranular attack. In the case of SCC, the presence of ferrite pools in the austenite
matrix is thought to block or make more difficult the propagation of cracks. In the case of intergranular
corrosion, ferrite is helpful in sensitized castings because it promotes the preferential precipitation of
carbides in the ferrite phase rather than at the austenite grain boundaries, where they would increase
susceptibility to intergranular attack.
The presence of ferrite also places additional grain boundaries in the austenite matrix, and there is
evidence that intergranular attack is arrested at austenite-ferrite boundaries. It is important to note,
however, that not all studies have shown ferrite to be unconditionally beneficial to the general corrosion
resistance of cast stainless steels. Some solutions attack the austenite phase in heat-treated alloys, whereas
others attack the ferrite.
Ferrite can be detrimental in some applications. One concern may be the reduced toughness from ferrite,
although this is not a major concern, given the extremely high toughness of the austenite matrix. A much
greater concern is for applications that require exposure to elevated temperatures, usually 315oC and
higher, where the metallurgical changes associated with the ferrite can be severe and detrimental. In
application requiring that these steels be heated in the range from 425 to 650oC, carbide precipitation
occurs at the edges of the ferrite pools in preference to the austenite grain boundaries.

Heat-Resisting Alloys
Abstract: Heat-resisting alloys useful at temperatures above 1200oF are based on iron, on nickel and on
cobalt and contain elements that form precipitates that harden the matrix after solution treating and aging.
Structural stability and resistance to oxidation and corrosion at elevated temperatures are required of these
alloys.

Heat-resisting alloys useful at temperatures above 1200oF are based on iron, on nickel and on cobalt and
contain elements that form precipitates that harden the matrix after solution treating and aging. Structural
stability and resistance to oxidation and corrosion at elevated temperatures are required of these alloys.
Iron-base (actually, iron-chromium-nickel-base) alloys are the least costly and are applied in the lower
temperature range, 1200 to 1500oF. Nickel-base and cobalt-base alloys are both applicable within the
range of 1500 to 2000oF, and at temperatures below 1500oF as well. The hardening phase in nickel-base
alloys is a nickel-aluminum-titanium phase called gamma prime. The hardening phase in cobalt-base
alloys is complex carbide.
Vacuum melting permits accurate adjustment of composition and deoxidation with carbon, thus
permitting oxygen removal in gaseous combination with carbon and inhibiting the formation of solid
oxides in the bath. Under vacuum, gaseous hydrogen and nitrogen are removed to trace residuals. Vacuum
melting also removes volatile metals, such as lead and zinc. Final additions of reactive metals are
facilitated by the absence of any reaction of the bath with either air or slag.
For the most complex alloy systems, powder metallurgy is employed to prevent gross segregation. The
alloy is melted in a conventional way and atomized while still in the liquid state, to form spheres, which
are ground to fine powders of homogeneous chemical composition. The powders are compacted into
preforms, sintered and then forged in the conventional way to produce segregation-free forgings.
A great many cast and wrought heat-resisting alloys are available. Iron-base heat-resisting alloys are only
slightly more alloyed than stainless steels. They maintain useful strength within the lower range of
temperatures, up to 1200oF; some are used at up to 1500oF. Figures 1 show rupture strengths for about 40
different compositions as a function of temperature. Ascoloy, with the curve shown at the extreme left in
Fig. 1 over a temperature range of 900 to 1200oF, is a martensitic chromium stainless steel.

Figure 1.
The curves shown on diagrams are typical and reflect neither statistical distribution nor specified
minimums. Variations in composition, melting, forging and heat treatment are not reflected by these
smoothed, typical curves. The curves therefore provide only a first approximation for material selection.
Creep characteristics, microstructural stability, and resistance to corrosion by sulfur-containing gas at high
temperature must also be taken into consideration.
Although developed originally for use at high temperature, some heat-resisting alloys have also been used
at cryogenic temperatures, as forged components for handling liquid oxygen and liquid hydrogen.
Mechanical-test results for Inconel 718 at room and cryogenic temperatures are shown in Fig. 2 for
specimens cut from forged components of over-all dimensions 4x9x15 in. The forgings were produced
from 6-in.-diameter billets broken down from an 18-in.-diameter ingot.
Test results shown in Fig. 2 include tensile, notch-tensile and Charpy impact values. Each plotted point is
an average of four tests. Testing was at room temperature, at -110oF in gaseous nitrogen, at -320oF in

liquid nitrogen, and at -423oF in liquid hydrogen. The test values that concern ductility (elongation, notchtensile / smooth-tensile ratio, and impact toughness) are shown for both longitudinal and transverse
directions. Longitudinal bars were machined parallel to the 15-in. dimension of the forging; longtransverse direction bars were machined parallel to the 9-in. dimension; and the short-transverse direction
bars, parallel to the 4-in. dimension.

High-Alloy Cast Steels


Abstract: Cast high alloy steels are widely used for their corrosion resistance in aqueous media at or near
room temperature and for service in hot gases and liquids at elevated and high temperatures (> 650C).
High-alloy cast steels are most often specified on the basis of composition using the designation system,
which has been replaced by the Alloy Casting Institute (ACI), which formerly administered these
designations.

Cast high alloy steels are widely used for their corrosion resistance in aqueous media at or near room
temperature and for service in hot gases and liquids at elevated and high temperatures (> 650C). Highalloy cast steels are most often specified on the basis of composition using the designation system, which
has been replaced by the Alloy Casting Institute (ACI), which formerly administered these designations.
Mechanical properties of these grades (for example, hardness and tensile strength) can be altered by
suitable heat treatment. The cast high-alloy grades that contain more than 20 to 30% Cr+Ni, however, do
not show the phase changes observed in plain carbon and low-alloy steels during heating or cooling
between room temperature and the melting point. These materials are therefore non hardenable, and their
properties depend on composition rather than heat treatment. Therefore, special consideration must be
given to each grade of high-alloy cast steel with regard to casting design, foundry practice, and
subsequent thermal processing.
Corrosion-resistant high-alloy cast steels, more commonly referred to as cast stainless steels, have
grown steadily in technological and commercial importance during the past 40 years. The principal
applications for these steels are for chemical-processing and power-generating equipment involving
corrosion service in aqueous or liquid-vapor environments at temperatures normally below 315C. These
alloys are also used for special services at temperatures up to 650C.
Cast stainless steels are defined as ferrous alloys that contain a minimum of 17% Cr for corrosion
resistance. Most cast stainless steels are of course considerably more complex compositionally than this
simple definition implies. Stainless steels typically contain one or more alloying elements in addition to
chromium (for example, nickel, molybdenum, copper, niobium, and nitrogen) to produce a specific
microstructure, corrosion resistance, or mechanical properties for particular service requirements.
Corrosion-resistant high-alloy cast steels are usually classified on the basis of composition or
microstructure. It should be recognized that these bases for classification are not completely independent
in most cases; that is, classification by composition also often involves microstructural distinctions.
Alloys are grouped as chromium steels, chromium-nickel steels in which chromium is the predominant
alloying element, and nickel-chromium steels in which nickel is the predominant alloying element. The
serviceability of cast corrosion-resistant steels depends greatly on the absence of carbon, and especially
precipitated carbides, in the alloy microstructure.
The high-alloy cast steels can also be classified on the basis of microstructure. Structures may be
austenitic, ferritic, martensitic, or duplex; the structure of a particular grade is primarily determined by
composition. Chromium, nickel, and carbon contents are particularly important in this regard. In general,
straight chromium grades of high-alloy cast steel are either martensitic or ferritic, the chromium-nickel
grades are either duplex or austenitic, and the nickel-chromium steels are fully austenitic.
Martensitic grades include alloys CA-15, CA-40, CA-I5M, and CA-6NM. The CA-15 alloy contains the
minimum amount of chromium necessary to make it essentially rustproof. It has good resistance to
atmospheric corrosion as well as to many organic media in relatively mild service. A higher-carbon
modification of CA-15, CA-40 can be heat treated to higher strength and hardness levels. Alloy CA-15M
is a molybdenum-containing modification of CA-15 that provides improved elevated-temperature
strength. Alloy CA-6NM is an iron-chromium-nickel-molybdenum alloy of low carbon content.
Austenitic grades include CH-20, CK-20, and CN-7M. The CH-20 and CK-20 alloys are highchromium, high-carbon, wholly austenitic compositions in which the chromium exceeds the nickel
content. The more highly alloyed CN-7M has excellent corrosion resistance in many environments and is
often used in sulfuric acid service.
Ferritic grades are designated CB-30 and CC-50. Alloy CB-30 is practically nonhardenable by heat
treatment. As this alloy is normally made, the balance among the elements in the composition results in a
wholly ferritic structure similar to wrought AISI type 442 stainless steel. Alloy CC-50 has substantially
more chromium than CB-30 and has relatively high resistance to localized corrosion in many
environments.

Austenitic-ferritic alloys include CE-30, CF-3, CF-3A, CF-8, CF-SA, CF-20, CF-3M, CF-3MA, CF-8M,
CF-8C, CF-16F, and CG-8M. The microstructures of these alloys usually contain 5 to 40% ferrite,
depending on the particular grade and the balance among the ferrite-promoting and austenite-promoting
elements in the chemical composition.
Duplex Alloys. Two duplex alloys CD-4MCu and Ferralium are currently of interest. Alloy CD-4MCu is
the most highly alloyed duplex alloy. Ferralium was developed by Langley Alloys and is essentially CD4MCu with about 0.15% N added. With high levels of ferrite (about 40 to 50%) and low nickel, the
duplex alloys have better resistance to stress-corrosion cracking (SCC) than CF-3M. Alloy CD-4MCu,
which contains no nitrogen and has relatively low molybdenum content, has only slightly better resistance
to localized corrosion than CF-3M. Ferralium, which has nitrogen and slightly higher molybdenum than
CD-4MCu, exhibits better-localized corrosion resistance than either CF-3M or CD-4MCu.
Improvements in stainless steel production practices (for example, electron beam refining, vacuum and
argon-oxygen decarburization, and vacuum induction melting) have created a second generation of
duplex stainless steels. These steels offer excellent resistance to pitting and crevice corrosion,
significantly better resistance to chloride SCC than the austenitic stainless steels, good toughness, and
yield strengths two to three times higher than those of type 304 or 316 stainless steels.
First generation duplex stainless steels, for example, AISI type 329 and CD-4MCu, have been in use for
many years. The need for improvement in the weldability and corrosion resistance of these alloys resulted
in the second-generation alloys, which are characterized by the addition of nitrogen as an alloying
element.
Second generation duplex stainless steels are usually about a 50-50 blend of ferrite and austenite. The
new duplex alloys combine the near immunity to chloride SCC of the ferritic grades with the toughness
and ease of fabrication of the austenitics. Among the second-generation duplexes, Alloy 2205 seems to
have become the general-purpose stainless.
Precipitation-Hardening Grades. The alloys in this group are CB-7Cu and CD-4MCu. Alloy CB-7Cu is
a low-carbon martensitic alloy that may contain minor amounts of retained austenite or ferrite. The copper
precipitates in the martensite when the alloy is heat treated to the hardened (aged) condition.
Heat-resistant high-alloy steel castings are extensively used for applications involving service
temperatures in excess of 650C. Strength at these elevated temperatures is only one of the criteria by
which these materials are selected, because applications often involve aggressive environments to which
the steel must be resistant. The atmospheres most commonly encountered are air, flue gases, or process
gases; such atmospheres may be either oxidizing or reducing and may be sulfidizing or carburizing if
sulfur or carbon are present.
Carbon and low-alloy steels seldom have adequate strength and corrosion resistance at elevated
temperatures in the environments for which heat-resistant cast steels are normally selected. Only heatresistant steels exhibit the required mechanical properties and corrosion resistance over long periods of
time without excessive or unpredictable degradation. In addition to long-term strength and corrosion
resistance, some cast heat-resistant steels exhibit special resistance to the effects of cyclic temperatures
and changes in the nature of the operating environment.
These alloy types resemble high-alloy corrosion-resistant steels except for their higher carbon contents,
which impart greater strength at elevated temperature. The higher carbon content and, to a lesser extent,
alloy composition ranges distinguish cast heat-resistant steel grades from their wrought counterparts.
Iron-chromium alloys contain 8 to 30% Cr and little or no nickel. They are ferritic in structure and exhibit
low ductility at ambient temperatures. Iron-chromium alloys are primarily used where resistance to
gaseous corrosion is the predominant consideration because they possess relatively low strength at
elevated temperatures.

Iron-chromium-nickel alloys contain more than 18% Cr and more than 8% Ni, with the chromium
content always exceeding that of nickel. They exhibit an austenitic matrix, although several grades also
contain some ferrite. These alloys exhibit greater strength and ductility at elevated temperatures than
those in the iron-chromium group and withstand moderate thermal cycling. Examples of these alloys are
the HE, HF, HH, HI, HK, and HL grades.
Iron-nickel-chromium alloys contain more than 10% Cr and more than 23% Ni, with the nickel content
always exceeding that of chromium. These alloys are wholly austenitic and exhibit high strength at
elevated temperatures. They can withstand considerable temperature cycling and severe thermal gradients
and are well suited to many reducing, as well as oxidizing, environments. Examples of iron-nickelchromium alloys are the HN, HP, HT, HU, HW, and HX grades. Even though nickel is the major element
in the HW and HX grades, these grades are ordinarily referred to as high-alloy steels rather than nickelbase alloys.

Austenitic Steels
Abstract: Some elements extend the -loop in the iron-carbon equilibrium diagram, e.g. nickel and
manganese. When sufficient alloying element is added, it is possible to preserve the face-centered cubic
austenite at room temperature, either in a stable or metastable condition.
The presence of chromium greatly improves the corrosion resistance of the steel by forming a very thin
stable oxide film on the surface, so that chromium-nickel stainless steels are now the most widely used
materials in a wide range of corrosive environments both at room and elevated temperatures.
Some elements extend the -loop in the iron-carbon equilibrium diagram, e.g. nickel and manganese.
When sufficient alloying element is added, it is possible to preserve the face-centered cubic austenite at
room temperature, either in a stable or metastable condition.
Chromium added alone to plain carbon steel tends to close the -loop and favor the formation of ferrite.
However, when chromium is added to a steel containing nickel it retards the kinetics of the
transformation, thus making it easier to retain austenite at room temperature.
The presence of chromium greatly improves the corrosion resistance of the steel by forming a very thin
stable oxide film on the surface, so that chromium-nickel stainless steels are now the most widely used
materials in a wide range of corrosive environments both at room and elevated temperatures.
Added to this, austenitic steels are readily fabricated and do not undergo a ductile/brittle transition which
causes so many problems in ferritic steels. This has ensured that they have become a most important
group of construction steels, often in very demanding environments.
Simple austenitic steels usually contain between 18 and 30% Cr, 8 to 20% Ni, and between 0.03 and
0.1% carbon. The binary iron-chromium equilibrium diagram (Fig. 1) shows that chromium restricts the
occurrence of the -loop to the extent that above 13% Cr the binary alloys are ferritic over the whole
temperature range, while there is a narrow ( + ) range between 12% and 13% Cr. The ferrite is
normally referred to as delta ferrite, because in these steels the phase can have a continuous existence
from the melting point to room temperature.

Fig.1: The Fe-Cr equilibrium diagram


The addition of carbon to the binary alloy extends the -loop to higher chromium contents (Fig. 2), and
also widens the ( + ) phase field up to 0.3% C. When carbon is progressively added to an 18% Cr steel,
in the range up to about 0.04% C, the steel is fully ferritic (Fig. 2) and cannot be transformed. Between
0.08 and 0.22% C, partial transformation is possible leading to ( + ) structures, while above 0.40% C
the steel can be made fully austenitic if cooled rapidly from the - loop region.

Fig.2: Effect of carbon on the Fe-Cr diagram


In austenitic steels, M23C6 is the most significant carbide formed and it can have a substantial influence on
corrosion resistance.
If nickel is added to a low carbon iron-18% Cr alloy, the -phase field is expanded until at about 8% Ni
the -phase persists to room temperature leading to the familiar group of austenitic steels based on 18%
Cr 8% Ni. This particular composition arises because a minimum nickel content is required to retain at

room temperature. With both lower and higher Cr contents more nickel is needed. For example, with
more corrosion resistant, higher Cr steels, e.g. 25% Cr, about 15% Ni is needed to retain the austenite at
room temperature.
Lack of complete retention is indicated by the formation of martensite. A stable austenite can be defined
as one in which the Ms is lower than room temperature. The 18Cr8Ni steel, in fact, has an Ms just below
room temperature and, on cooling, e.g. in liquid air, it will transform very substantially to martensite.
Manganese expands the -loop and can, therefore, be used instead of nickel. However, it is not as strong
a -former but about half as effective, so higher concentrations are required. In the absence of chromium,
around 12% Mn is required to stabilize even higher carbon (1-1.2%) austenite, achieved in Hadfields
steel which approximates to this composition. Typically Cr-Mn steels require 12-15% Cr and 12-15% Mn
to remain austenitic at room temperature if the carbon content is low.
Like carbon, nitrogen is a very strong austenite former. Both elements, being interstitial solutes in
austenite, are the most effective solid solution strengtheners available. Nitrogen is more useful in this
respect as it has less tendency to cause intergranular corrosion. Concentrations of nitrogen up to 0.25
%are used, which can nearly double the proof stress of Cr-Ni austenitic steel.
One of the most convenient ways of representing the effect of various elements on the basic structure of
chromium-nickel stainless steels is the Schaeffler diagram, often used in welding. It plots the
compositional limits at room temperature of austenite, ferrite and martensite, in terms of nickel and
chromium equivalents (Fig. 3).
At its simplest level, the diagram shows the regions of existence of the three phases for iron-chromiumnickel alloys. However, the diagram becomes of much wider application when the equivalents of
chromium and of nickel are used for the other alloying elements. The chromium equivalent has been
empirically determined using the most common ferrite-forming elements:
Cr equivalent = (Cr) + 2(Si) + 1.5(Mo) + 5(V) + 5.5(Al) + 1.75(Nb) + 1.5(Ti) + 0.75(W)
while the nickel equivalent has likewise been determined with the familiar austenite-forming elements:
Ni equivalent = (Ni) + (Co) + 0.5(Mn) + 0.3(Cu) + 25(N) + 30(C)
All concentrations being expressed in weight percentages.

Fig.3: Schaeffler diagram. Effect of alloying elements on the basic structure of Cr- Ni stainless steels.

The large influence of C and N relative to that of the metallic elements should be particularly noted. The
diagram is very useful in determining whether particular steel is likely to be fully austenitic at room
temperature. This is relevant to bulk steels, particularly to weld metal where it is frequently important to
predict the structure in order to avoid weld defects and excessive localized corrosive attack.

Galvanic Corrosion
Abstract: Galvanic processes occur between different metals and between different areas of the same
metal in the water environment. Water is an electrolyte, a poorly conductive one at the low dissolved
solids content of fresh waters, and a highly conductive one at the high dissolved solids content of sea
water.
When two different metals are immersed in an electrolyte and connected through a metallic path, current
will flow. Oxidation occurs at the anode and reduction (normally oxygen reduction) occurs at the cathode.
Galvanic processes occur between different metals and between different areas of the same metal in the
water environment. Water is an electrolyte, a poorly conductive one at the low dissolved solids content of
fresh waters, and a highly conductive one at the high dissolved solids content of sea water.
When two different metals are immersed in an electrolyte and connected through a metallic path, current
will flow. Oxidation occurs at the anode and reduction (normally oxygen reduction) occurs at the cathode.
These reactions and the hydrogen reduction reaction that occurs in deaerated waters are represented in the
usual form below.
Oxidation (corrosion)
Reduction (deaerated waters)
Reduction (deaerated waters)

M M+ + 2e
O2 (dissolved) + 2H2O + 4e 4(OH-)
2H+ + 2e 2e

The electrons flow through the metal path from the anode to the cathode. The circuit is completed by
transport (migration) of the ionic species (OH) from the vicinity of the cathode to the vicinity of the
anode. In the absence of other species, the rate at which these reactions occur, and consequently the rate
at which the anode corrodes, is controlled by the rate at which oxygen can be reduced at the cathode.
The rate of reduction of oxygen at the cathode in turn is determined primarily by the resistance to electron
flow in the circuit, the cathodic surface area available for oxygen reduction and the amount of oxygen
available at the cathodic area. The galvanic current (corrosion) is directly proportional to the cathodic area
when the cell is under cathodic control as it normally is in water.
Conductivity plays a major role by limiting galvanic corrosion to the immediate area of contact in low
conductivity fresh water and by spreading the galvanic effect over rather large areas in highly conductive
waters such as seawater.
Painting the anode requires all of the anodic corrosion to occur in the very small areas where coating
breakdown at scratches, welds, etc. occurs and exposes the steel. Painting the cathode reduces the area
available for the rate-controlling oxygen reduction reaction and the amount of oxidation (corrosion) that
can occur at the anode. Stainless steels are positioned towards the cathodic end of the galvanic series in
seawater.
The potential range shown for each alloy should be interpreted as the range within which the metal to sea
water potential is likely to vary for each alloy, not as an indication that alloys close to each other in the
series are likely to change position. This rarely happens. The second more anodic potential band for
stainless steels should be interpreted as the potential that develops in a shielded area where crevice
corrosion has initiated.
Lee and Tuthill have developed quantitative guidelines for the amount of carbon steel or Ni-Resist
required suppressing crevice corrosion of types 304 and 316 stainless steels in seawater.

These data indicate that carbon steel is very effective in suppressing crevice corrosion of 304 and 316
stainless steel in up to 100:1 SS to CS area ratios at 14C (57F) in seawater. At 28C there is complete
protection at 10:1 and a tenfold reduction in the percentage of sites where initiation occurs at 50:1 SS:CS
area ratios. Ni-Resist (NR) is found to provide full protection for 316 and substantial protection for 304 at
50:1 SS: NR area ratios at temperatures up to 28C.
The position of the copper alloys in the galvanic series suggests that copper alloys will not suppress
crevice corrosion in stainless steels and, in fact, may accelerate crevice attack once it has started.
Experience indicates copper alloys provide no useful galvanic protection for stainless steels.
Type 304 is the least noble of the nickel stainless steels and alloy 825 the most noble, being separated by
about 0.05 volt. The various nickel stainless steels are generally coupled mechanically to each other and
to nickel-base alloys without serious galvanic effects. There are two major qualifications:

Should type 316L inadvertently be welded with type 308L filler metal instead of 316L, the weld
metal will suffer severe localized corrosion. Hard facing overlays for rotating seal faces and weld
overlay of tail shafts are other applications where close attention must be given to the position of
individual alloys with respect to each other in the galvanic series in order to avoid costly failures.
Both type 303 and 303Se suffer extraordinarily severe corrosion in seawater. The high density of
manganese sulfide or selenide inclusion in these free-machining alloys create a surface with
numerous built in austenite-to-inclusion galvanic cells.

Carbon is 0.2-0.3 volts or more positive than the nickel stainless steels. Carbon in the form of graphite;
containing gaskets, packing and lubricants has been responsible for serious galvanic corrosion of stainless
steels in seawater. Graphite in any form should never be used in contact with stainless steels in brackish
or seawater.
Carbon filled rubber O-rings and gaskets are widely used in contact with stainless steels in seawater. The
corrosion that occurs under O-rings and black rubber gaskets is normally crevice corrosion. However, in
some instances acids used for chemical cleaning have softened these carbon-filled rubbers sufficiently to
release carbon and set up adverse galvanic cell action, greatly accelerating the crevice attack that occurs
in these rubber-to-stainless crevices.
Galvanic corrosion is a two way street and the effect on the other material coupled to stainless steels must
always be considered. Investigating why copper alloy tube sheets were being so severely corroded when
copper alloy condensers were retubed with stainless steel and titanium tubes, Gehring, Kuester and
Maurer found that the whole inside surface area of the tube of the more noble alloys became effective as a
cathode in copper alloy to stainless steel or titanium couples.
The more noble materials are so easily polarized that the cathodic area available for the reduction reaction
(the rate controlling process) is multiplied far beyond the old two or four diameters rule of thumb, which
was based on copper alloy behavior. Later work by Gehring and Kyle indicated that the intensity of the
galvanic effect decreased with salinity. The increasing resistance of the lower salinity waters limits the
effective cathodic area.
Galvanic corrosion can occur between different constituents of the same metal as well as between
different metals. Iron embedded in the surface of stainless steel, manganese sulfide stringers and less
highly alloyed weld metal are common examples.

Summary of galvanic corrosion of nickel stainless steels

Galvanic corrosion occurs between weld metal and base metal, between different areas of the
same metal and between different metals in water.
The intensity of galvanic corrosion is determined by the conductivity, oxygen content and the
effective anode-to-cathode area ratio.
Galvanic effects are spread over a large area in brackish and seawater; are confined to the
immediate area of the junction in fresh water; and are often negligible in deaerated brines.

Steel, Ni-Resist, zinc and aluminum are very effective in suppressing crevice corrosion on
stainless steels except types 303 and 303Se.
Carbon, graphite-lubricated gaskets, packing, greases etc. are very effective in initiating severe
corrosion of stainless steels.
Galvanic effects can be significantly reduced by removing coatings from the anode and by coating
the more noble (cathodic) material.
Stainless steel (or titanium) tubing increases copper alloy tube sheet attack to the point where
impressed current cathodic protection is normally required to control tube sheet corrosion.
Galvanic corrosion between different grades of nickel stainless steels mechanically joined is rare,
but can be severe when welded. Caution and exposure tests are suggested.
Avoid use of types 303 and 303Se.

Martensitic Stainless Steels


Abstract: 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" ferro-magnetic
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
1 0.5

Cr

Ni Mo

11.513.0

0.04 0.03

Comments/Applications
The basic composition. Used for cutlery, steam and
gas turbine blades and buckets, bushings.

410

0.15

416

0.15 1.25 1

12.014.0

420

0.150.40

12.014.0

431

0.2

15.01.250.04 0.03 Enhanced corrosion resistance, high strength.


17.0
2.00

440A

0.600.75

16.018.0

0.75 0.04 0.03

440B

0.750.95

16.018.0

0.75 0.04 0.03 As 440A, higher hardness.

440C

0.951.20

16.018.0

0.75 0.04 0.03 As 440B, higher hardness.

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 Dental and surgical instruments, cutlery.

Ball bearings and races, gage blocks, molds and dies,


cutlery.

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.

Duplex Stainless Steels: Part One


Abstract: Stainless steel is the name given to a family of corrosion and heat resistant steels containing a
minimum of 10.5% chromium. Just as there is a range of structural and engineering carbon steels meeting
different requirements of strength, weldability and toughness, so there is a wide range of stainless steels
with progressively higher levels of corrosion resistance and strength.
Duplex stainless steels have a mixture of austenitic and ferritic grains in their microstructure; hence they
have a "duplex" structure. This effect is achieved by adding less nickel than would be necessary for
making a fully austenitic stainless steel.

Microstructure
Stainless steel is the name given to a family of corrosion and heat resistant steels containing a minimum
of 10.5% chromium. Just as there is a range of structural and engineering carbon steels meeting different
requirements of strength, weldability and toughness, so there is a wide range of stainless steels with
progressively higher levels of corrosion resistance and strength. This results from the controlled addition
of alloying elements, each offering specific attributes in respect of strength and ability to resist different
environments. The available grades of stainless steel can be classified into five basic families: ferritic,
martensitic, austenitic, duplex and precipitation hardenable.
The division based on microstructure is useful because the members within one family tend to have
similar physical and mechanical properties. However, the properties for one family can be very different
from the properties for another family. For example, austenitic stainless steels are non-magnetic, while
ferritic and duplex stainless steels are magnetic.
The difference between the families is fundamental on the atomic level. The arrangement of atoms in the
ferrite crystal is different from the one in the austenite crystal:

Figure 1: The ferritic stainless steel on the left has a body centered cubic (bcc) crystal structure. By
adding nickel to this stainless steel the structure changes from bcc to face centered cubic (fcc), which is
called austenitic.
In the ferritic stainless steel, the iron and chromium atoms are arranged on the corners of a cube and in the
center of that cube. In the austenitic stainless steels the atoms, here iron, chromium and nickel, are
arranged on the corners of the cube and in the center of each of the faces of the cube. This seemingly
small difference profoundly affects the properties of these steels.
Table 1: Select properties of austenitic and ferritic stainless steels
Properties
Austenitic
Ferritic
Toughness

Very high

Moderate

Ductility

Very high

Moderate

Weldability

Good

Limited

Thermal expansion

High

Moderate

Stress corrosion cracking resistance

Low

Very high

Magnetic properties

Non-magnetic

Ferro magnetic

Because of their good mechanical properties and the ease of fabrication, austenitic stainless steels are
much more widely used than ferritic stainless steels. About 75% of all stainless steel used worldwide is
austenitic and about 25% is ferritic. The other families, martensitic, duplex and precipitation hardenable
stainless steels each represent less than 1% of the total market.
Besides nickel there are other elements that tend to make the structure austenitic. These elements are
called austenite formers. Alloying elements that tend to make the structure ferritic are called ferrite
formers.
Table 2: Alloying elements formers for stainless steel microstructure
Ferrite formers
Austenite formers
Iron

Nickel

Chromium

Nitrogen

Molybdenum

Carbon

Silicon

Manganese
Copper

Duplex stainless steels have a mixture of austenitic and ferritic grains in their microstructure; hence they
have a "duplex" structure. This effect is achieved by adding less nickel than would be necessary for
making a fully austenitic stainless steel.

Figure 2: Adding 8% nickel to a ferritic chromium stainless steel makes an austenitic chromium-nickel
stainless steel, for example Type 304 stainless steel. If less nickel is added to a chromium steel, about four
or five percent, a duplex structure, a mixture of austenite and ferrite, is created as in 2205 duplex stainless
steel.
Austenitic-ferritic (Duplex) stainless steels contain increased amount of chromium (18% -28%) and
decreased (as compared to austenitic steels) amount of nickel (4.5% - 8%) as major alloying elements. As
additional alloying element molybdenum is used in some of Duplex steels. Since the quantity of nickel is
insufficient for formation of fully austenitic structure, the structure of Duplex steels is mixed: austeniticferritic.
The properties of Duplex steels are somewhere between the properties of austenitic and ferritic steels.
Duplex steels have high resistance to the stress corrosion cracking and to chloride ions attack. These
steels are weldable and formable and possess high strength
In the annealed condition, most wrought duplex stainless steels contain about 40-50% austenite in a
ferrite matrix. When these materials solidify, ferrite forms first. Depending upon the composition, a
varying amount of austenite is expected to form as the last material solidifies.
Additional austenite forms by a solid-phase transformation during subsequent annealing. Accordingly, an
annealed product is expected to contain more austenite than as-cast or as-welded material. A sufficient
amount of austenite must be maintained to provide satisfactory corrosion resistance and mechanical
properties. This amount of austenite may vary with the service application and with alloy composition
and thermal history.
Additional phases found in duplex stainless steels can include , , R, ', carbides and nitrides. These
phases have generally been studied using isothermal heat treatments in the laboratory.

Sigma Phase
Sigma is a hard, brittle intermetallic phase which is expected to contain iron, chromium and molybdenum
in most duplex stainless steels. In these alloys, generally can be formed between about 600 and 950C,
with the most rapid formation occurring between 700 and 900C.
Sigma typically nucleates in the austenite-ferrite grain boundaries and grows into the adjacent ferrite.
Often, additional austenite forms in the areas of chromium depletion adjacent to the phase. Elements
which stabilize ferrite such as chromium, molybdenum and silicon increase the tendency to form the
phase. On a weight percent basis, molybdenum can promote phase formation much more effectively
than chromium, particularly at higher temperatures (e.g. about 900C). Austenite forming elements such
as nickel or nitrogen can also accelerate the nucleation and growth of the phase, although these
elements may reduce the total amount formed.

The alloy elements are portioned, and increased levels of each element tend to be present in the phases
they stabilize. As nickel or nitrogen stabilize additional austenite, the reduced amount of ferrite becomes
enriched in chromium and molybdenum. As a result, phase formed may be reduced by nickel or
nitrogen, however, because of the smaller volume fraction of ferrite.
The phase can deplete chromium and molybdenum in surrounding areas and reduce resistance to
corrosion. As little as about 1% phase may reduce impact toughness, while about 10% can cause
"complete embrittlement" of duplex stainless steels.

Duplex Stainless Steels: Part Two


Abstract: Duplex stainless steels (DSS) are widely used in chemical, petrochemical, cellulose and
nuclear plants around the world. Because of their fine austenitic-ferritic microstructure they offer an
excellent combination of mechanical and corrosion resistance properties.
Duplex stainless steels (DSS) are widely used in chemical, petrochemical, cellulose and nuclear plants
around the world. Because of their fine austenitic-ferritic microstructure they offer an excellent
combination of mechanical and corrosion resistance properties.
Many researchers have studied and developed methods of detection and quantification of thermal
embrittlement in DSS. Tsuchiya et al. and Evanson et al. employed magnetic measurements and found
that the hysteresis loss, residual induction and coercive force increased with ageing time in cast DSS.
Controversially, Maeda et al. have found experimentally that there is a decrease in the coercive force
during the ageing of cast duplex stainless steels in the range of 350-450C. Kim et al. found an increase
of the Curie temperature in ferritic stainless steels aged at 370C and 400C.

475C Embrittlement
The susceptibility of a duplex stainless steel UNS S31803 to thermal embrittlement at 475C was
evaluated by means of mechanical tests (impact energy and hardness), magnetic measurements (hysteresis
and thermomagnetic analysis) and scanning electron microscopy.
Results show that the material undergoes severe embrittlement and hardening in the first 100 h. The
corrosion resistance of the ferrite phases in a 10%HNO3 + 0.05%HF solution deteriorated after 500 h of
ageing. The Curie temperature (Tc) was the most sensitive magnetic property to the microstructural
changes that promote embrittlement. Tc increases with ageing time due to the progressive reduction of
chromium in the Fe-rich matrix during spinodal decomposition.
The best performance of wrought Duplex Stainless Steel (DSS) is obtained in the solution treated
condition. Nevertheless, two hardening and embrittlement processes may occur when these materials are
heated: (a) sigma phase () precipitation in the range of 700C to 900C and (b) precipitation of a Cr-rich
phase (') in the range of 300C to 600C.
The (') precipitation leads to a progressive hardening and reduction of the material toughness. This
precipitation occurs by spinodal decomposition, a mechanism by which the ferrite phase decomposes into
a Cr-rich phase (') and a Fe-rich phase. Because this reaction occurs more rapidly at 475C, this process
is also known as "475C embrittlement". However this phase separation may also occur in temperatures
as low as 300C in exposures after thousands of hours or at 600C in exposures for few minutes,
depending on the chemical composition of the steel.

Alloy Designations
Due to excellent corrosion resistance and high strength, the most widely used duplex stainless steel is
2205. The name 2205 comes from a typical composition of 22% chromium and 5% nickel. Alloy 2205
provides a stainless steel with twice the yield strength of the standard austenitic alloys and an upgrade in
general corrosion resistance without any reduction of corrosion resistance in parts that are welded.

Alloy 2205 is known as second generation duplex stainless steels. This alloy offers excellent pitting and
crevice corrosion resistance and significantly better chloride stress-corrosion cracking resistance than 300
series austenitic stainless steels. In addition alloy 2205 has yield strengths two to three times higher than
those of 304, 316, or 317 stainless steels.
First generation duplexes, e.g. 329, have existed for many years. Duplex stainless steels have a
microstructure that is a mixture of austenite and ferrite. This blend produces alloys that exhibit the best
features of both types of stainless steels. One problem with the first generation duplexes is they tend to
lose some of their corrosion resistance when welded, which can only be restored by a postweld heat
treatment.
Second generation duplex alloys like 2205 were developed by adding 0.15 to 0.25% nitrogen, which
reduces the chromium partitioning between the austenitic and ferritic phases of the alloys. This change
enhances the pitting and crevice corrosion resistance and, when properly welded, retains the full corrosion
resistance of the alloy. The mixture of austenite and ferrite is usually 50-50 in the second generation
duplex alloys.
The austenitic stainless steel alloys are generally excellent alloys for corrosion resistance. The most
significant corrosion problem found when using these alloys is the tendency to exhibit pitting and stresscorrosion cracking in halide environments, such as chlorides. The 254SMO alloy was designed primarily
to reduce this problem. By adding extra molybdenum and nickel, the resistance to pitting and stresscorrosion cracking was greatly enhanced.

Corrosion Resistance
Duplex stainless steels are extremely corrosion resistant. They have high resistance to intergranular
corrosion. Even in chloride and sulfide environments, duplex stainless steels exhibit very high resistance
to stress corrosion cracking. The super duplex grades are even more resistant to corrosion.

Heat Resistance
The high chromium content of duplex stainless steels that protects against corrosion causes embrittlement
at temperatures over about 300C. At low temperatures duplex stainless steels have better ductility than
the ferritic and martensitic grades. Duplex grades can readily be used down to at least -50C.

Fabrication
Fabrication of all stainless steels should be done only with tools dedicated to stainless steel materials.
Tooling and work surfaces must be thoroughly cleaned before use. These precautions are necessary to
avoid cross contamination of stainless steel by easily corroded metals that may discolour the surface of
the fabricated product.

Heat Treatment
Duplex stainless steels cannot be hardened by heat treatment. They can however be work hardened.
Solution treatment or annealing can be done by rapid cooling after heating to around 1100C.

Machinability
Although machinable, the high strengths of duplex stainless steels make machining difficult. As an
example, machining of 2205 is around 20% slower than for 304. Machining can be enhanced by using the
following rules:

Cutting edges must be kept sharp. Dull edges cause excess work hardening.
Cuts should be light but deep enough to prevent work hardening by riding on the surface of the
material.
Chip breakers should be employed to assist in ensuring swarf remains clear of the work.

Low thermal conductivity of austenitic alloys results in heat concentrating at the cutting edges.
This means coolants and lubricants are necessary and must be used in large quantities.

Welding
Duplex stainless steels have good weldability. All standard welding processes can be used. They are not
quite as easily welded as the austenitic grades but low thermal expansion in duplex grades reduces
distortion and residual stresses after welding. The recommended filler material for 2205 stainless steel is
2209.

Applications
Duplex stainless steels are typically used in:

Chemical processing, transport and storage


Oil and gas exploration and offshore rigs
Oil and gas refining
Marine environments
Pollution control equipment
Pulp & paper manufacturing
Chemical process plants.

Historically, the structural use of stainless steels in civil engineering applications, such as road and rail
bridges, has been limited. This is because of the perception by owners and designers that the steels are
disproportionately expensive. Their mechanical properties are poor compared to structural steels and there
is also a lack of awareness of the range of steels available. This knowledge deficit can manifest itself in a
number of ways. Common misconceptions regarding stainless steels include the assumptions that.

It is only available in thin strip and coil, and not as thicker hot rolled plates;
These steels cannot be welded
Stainless steels only consist of the traditional AISI 300 series austenitic alloys
The materials have highly reflective surface finishes
They are complicated and sensitive to work with.

These factors combine to make the increased use of stainless steels in civil engineering a struggle. This is
unfortunate as there is little doubt that selection of an appropriate steel type/grade for a given application
would provide an inherently durable solution over the long life, typically 120 years, of these structures.
Given the desire of infrastructure owners to reduce maintenance costs and disruption to the traveling
public, it is perhaps right time to overcome the common perception.
Duplex stainless steels are excellent structural engineering materials that are largely overlooked in civil
engineering, perhaps understandably given the cost of traditional alloys. However, the newer lean alloys
complete a family of steels that can provide corrosion protection over the full range of environmental
exposure conditions typical of bridge structures.
These materials are not appropriate for all bridge or civil engineering applications, but they offer the
potential to provide maintenance free solutions, at least with respect to corrosion protection. This is cost
effective in both initial investment and lifecycle costing. To achieve this potential, there needs to be a
better awareness of what DSS can offer and how they perform in typical service environments. It is also
essential that the supply chain works together to optimize steel production, structure design and
fabrication to meet the demands of this industrial sector by taking account of the particular properties of
duplex stainless steels. This may well demand novel design solutions to make use of the greater flexibility
in stainless steel production compared to structural steels, and to satisfy customers needs without
creating unnecessary waste.

Figure 1: Examples of structures fabricated in duplex stainless steels. Left: Aparte Bridge, Stockholm,
Sweden; right: Menorca Bridge, Spain.

Production of Stainless Steel: Part One


Abstract: In the history of research and development of stainless steels, most important has been the
decarburization of high chromium molten steel. Efficient decarburization and the prevention of chromium
oxidation losses have been central to the development of steelmaking technology for stainless steels.
Because the strong affinity of chromium for carbon, all pneumatic processes for refining stainless steel
attempt to achieve selective oxidation of carbon in the presence of chromium by raising the reaction
temperature and/or reducing the partial pressure of CO by vacuum or mixed gas (argon-oxygen) refining.
In the history of research and development of stainless steels, most important has been the
decarburization of high chromium molten steel. Efficient decarburization and the prevention of chromium
oxidation losses have been central to the development of steelmaking technology for stainless steels.

Process Development
Prior to the late 1940s, stainless steel was made in the electric arc furnace by melting carbon steel scrap,
iron ore and burnt lime; slagging off; adding burnt lime, ferrosilicon and fluorspar; increasing the
temperature; and adding low carbon ferrochrome to attain the specified chromium. In this process (known
as the "Rustless Process"), most stainless grades were made to an aim carbon specification of 0.08
percent. During this period, the only practical and economic way to use stainless scrap was to remelt it in
induction furnaces. With the introduction of tonnage oxygen in the steel industry in the late 1940s, a new
arc furnace practice evolved in which stainless scrap, high carbon ferrochrome, nickel, and lime were
melted, the bath blown with oxygen to temperatures between 1850-1950C, reduced with silicon and
aluminum, and trimmed with low carbon ferrochrome. Relative to the Rustless Process, this practice
resulted in significant decreases in power consumption, process time, and the use of expensive low carbon
ferrochrome as well as improved quality (decreased hydrogen contents) and increased chromium
recoveries.
In 1954, W. Krivsky of Union Carbide was studying carbon-chrome-temperature relationships in
ferrochromium melting in the laboratory. The experiments involved blowing oxygen onto the surface of
molten chromium alloy baths under isothermal conditions. In order to control temperature, he added
argon and found that he could decarburize the melt to low carbon levels without excessive chromium
oxidation. Krivsky's observation led to plant-scale experiments injecting argon/oxygen mixtures by lance
into the arc furnace between 1958 and 1962. Eventually, it was concluded that a separate refining vessel
(duplex process) was necessary to develop a commercial process, and the first successful AOD (argon
oxygen decarburization) heat was made in October 1967 in a modified 15-ton ladle. These trials resulted
in the first commercial AOD installation at Joslyn (now Slater Steel) in July l968.
During the late 1950s, vacuum degassing processes (DH, RH, ASEA-SKF, Finkl VAD, etc.) were
developed for carbon steel production, and led to the development of vacuum decarburization processes
for stainless steels in the mid-1960s. The VOD (vacuum oxygen decarburization) process was developed
by Witten (now Thyssen) in Germany between 1962 and 1967. Between 1959 and 1962, Witten had

produced stainless steels in their LD converter (decarburization of pig iron, addition of low carbon
ferrochrome, and reduction with silicon and aluminum).
With the installation of their ladle vacuum degassing unit in 1962, they began trials duplexing premelt
from the LD to the vacuum degasser. Initially, iron ore was used for decarburization. Later, premelting
took place in the arc furnace, and oxygen was top blown onto the bath surface in the degassing ladle.
The AVR process, in which oxygen was injected below the surface by top lance in the degassing ladle,
was developed by Allegheny Ludlum in the mid-1960s. In recent years, Allegheny has used their TMBI
(top mixed bottom inert) process metal supplied from their induction furnaces when stainless demand
exceeded AOD capacity. The development of the AOD and VOD processes between 1954 and 1968
revolutionized stainless steelmaking and was the primary impetus for the dramatic growth in production
between 1970 and the present. The use of these or similar processes resulted in significant decreases in
raw material costs, increases in productivity, and improved quality.
The Figure 1 shows some of steelmaking processes for production of stainless steels.

Figure 1: The Steelmaking Processes for Stainless Production (a) AOD (b) RH-OB/KTB (c) VOD (d)
AOD-VCR (e) K-BOP/K-OBM-S (f) CLU (g) ASM/MRP Side or Bottom Blow Plug or Tuyeres

Theory of Iron-Chromium-Carbon Equilibria


Because the strong affinity of chromium for carbon, all pneumatic processes for refining stainless steel
attempt to achieve selective oxidation of carbon in the presence of chromium by raising the reaction
temperature and/or reducing the partial pressure of CO by vacuum or mixed gas (argon-oxygen) refining.
The competing reactions,
[C] + [O] = CO (g)

(1)

[Cr] + [O] = Cr oxide

(2)

can be treated by rigorous thermodynamic calculations only when simplifying assumptions are made in
regard to the chromium oxide activity of the slag.
There has been much controversy in the literature concerning the nature of these pure oxide phases in
equilibrium with iron-chromium alloys. When the metal contains less than 5% chromium, there is little
doubt that the phase is chromite, FeCr2O4, and that at higher chromium levels Cr3O4 separates first. This is
shown in Figure 2.

Figure 2: Oxygen solubility curves for iron-chromium alloys


The first detailed study of iron-chromium-carbon equilibria was conducted by Richardson and Dennis,
who investigated the equilibrium between CO and CO2 mixtures in the presence of carbon dissolved in
pure molten iron and in liquid iron-chromium alloys. Based on their data, Chipman calculated the
interaction parameter eCC i.e., the effect of increased concentration of carbon on its activity coefficient, to
be eCC= 358/T, where T is the absolute temperature in Kelvin. The value of eCC has more recently been
calculated by Sigworth and Elliott to be eCC = 158/T + 0.0581. Similarly, eCrC, the effect of chromium on
carbon activity coefficient, was found to vary between 0.020 and 0.024, depending on temperature.
The equilibrium between chromium and carbon can be described by combining two reactions of (1) and
(2). For all stainless grades where Cr3O4 is the equilibrium phase according to Hilty et. al., this becomes
Cr3O4 + [C] = [Cr] + CO (g)

(3)

At equilibrium,
K = {PCO [aCr]} / {[aC] [aCr3O4]}

(4)

where ai refers to activity of i component and K the equilibrium constant given as


log K = - 11520 /T + 7.64

(5)

Thermodynamic activity, ai, deviates from the Henrys law can be expressed in terms of concentration as
ai = fi [% i]

(6)

For a multi-component system where the effects of each of the other components are significant, the
activity coefficient, fi can be expressed as
log fi = eji [% i]

(7)

where the interaction parameter, eji, represents the effect of the alloying element, j, on the activity
coefficient of i component. The values of the interaction coefficient of the most common alloying
elements as compiled by Elliot are listed in Table 1.
Table 1: The values of the interaction coefficient of the most common alloying elements
Dissolved elements (i)
%

Alloyed Elements (j)


Al

Cr

Co

Cu

Mn

Mo

Nb

Ni

Si

Ti

0.043 0.14 -0.024 0.0076 0.016 -0.012 0.0083 0.06 0.012 0.34 0.08

Cr
O

0.12 0.0003 -0.019 0.016

0.0018

0.0002 0.14 0.0043 0.059

3.9 0.45 -0.04 0.008 -0.013 -0.021 0.0035 0.14 0.006 0.02 -0.131 -0.6

The chromium-carbon-temperature relationship for a metal bath in equilibria with a chromium saturated
slag can be derived by combining equations (4) and (7) with aCr3O4 = 1.0 as follows:
K = {PCO [aCr]} / {[aC] [aCr3O4]}= - 11520/T+7.64+(358/T+0.075) [%C] 0.02 [%Cr]

(8)

If alloy steel grades with less than 5% Cr are to be produced, FeCr2O4 becomes the primary oxide phase.
Hence, the following equilibrium equation can be derived similarly:
K = {PCO [aCr]} / {[aC] [aCr3O4]}= - 10830/T+7.06+(358/T+0.05) [%C] 0.02 [%Cr]

(9)

The effect of additional alloying elements such as nickel and manganese can readily be accounted for by
the use of the interaction coefficients listed in Table 1.
For practical application, Hylty, Rassbach and Crafts simplified the thermodynamic expression for use in
the concentration range of 3 to 30% chromium:
log[%Cr]/[%C] = -13800/T + 8.76

(10)

This equation, which has been widely adopted in evolution of electric furnace practices, is very good
approximation of thermodynamic equilibrium in the temperature range of 17001815C (31003300F)
and for concentrations of from 10% to 17% chromium typical of electric furnace practice. However, over
wider temperature and composition ranges encountered in the steelmaking techniques, the deviations of
this equation become increasingly important. Hilty et al. also pointed out that manganese could be
considered approximately similar in its effect to chromium.
Simkovich and McCoy modified equation (10) to apply to austenitic stainless steel:
log[%Cr]/[%C] = -{13800/(T + 4.21 [%Ni])} + 8.76

(11)

Production of Stainless Steel: Part Two


Abstract: For melting and refining of stainless steel grades there are many different process routes. The
individual choice is influenced by raw material availability, desired final product, existing shop logistics
and capital economics. In general the stainless steelmaking process can be classified as a Duplex or
Triplex type. The Duplex refining process which is composed of electric arc furnace melting, followed by
converter refining, can be extended to a Triplex refining route by installation of a VOD plant. Today,
about 90% of all stainless steel is produced according to the duplex or triplex route.

Slag Metal Reactions


For CaO-MgO-SiO2-(Fe, Cr) oxide slags with lime/silica ratios between 1.2 and 2.0, Pathy and Ward
found the experimental solubility limit of Cr2O3 in the slag to vary from 3% in contact with lowchromium alloys (less than 2% Cr) to about 9% when the alloy was in the range 14-20% Cr. These data
agree with the phase diagram Cr2O3-CaO-SiO2 as determined by Glasser and Osborn. These observations
may have somewhat limited validity since it has been found that the primary oxide phase is not Cr2O3,
but, either chromite FeCr2O4 or Cr3O4.
In any case, it is a fact that commercial slags show substantially higher chromium oxide solubilitys than
indicated by these laboratory findings. The difference may also be due to the solvent effect of alumina,

iron oxide, and other components, the presence of suspended solid oxides, or to the fact that slag and
metal do not reach equilibrium in commercial systems.
In laboratory studies by Pathy and Wird, a linear relation was found between the ratio of chromium in
slag to that in metal and the concentration of FeO in slag. The proportionality constant varied from 0.5 at
2950F (1620C) to 0.3 at 3070F (1688C). In case of BOF and EAF heats, Aukrust et al. obtained a
value 0.28. For commercial operation the equation
(Cr)SLAG / [Cr]METAL = 0.3 (%FeO) .......... (1)
will give close representation of the chromium partition ratio. By measuring the iron oxide concentration
of the slag, the extent of chromium oxidation can be determined. The degree of oxidation of the slag
depends on practice and must be determined experimentally.
There are many different process routes for melting and refining of stainless steel grades. The individual
choice is influenced by raw material availability, desired final product, existing shop logistics and capital
economics. In general the stainless steelmaking process can be classified as a Duplex or Triplex type. The
Duplex refining process which is composed of electric arc furnace melting, followed by converter
refining, can be extended to a Triplex refining route by installation of a VOD plant. This is necessary, if
very low carbon, sulfur or nitrogen contents must be achieved in the final product. Today, about 90% of
all stainless steel is produced according to the duplex or triplex route.
In Duplex process, after melting in primary unit, refining is carried out in different vessel. Duplex process
have certain disadvantages with respect to the ratio of ferro-alloys to scrap in the case of VOD and higher
argon, ferro-silicon consumption and shorter converter life in case of AOD, lengthy process time in
secondary vessel converter. However, in order to overcome these demerits and produce different grades
with grater economy and better quality, triplex process is used.
In Triplex process, after melting in primary unit, refining is carried out in two different vessels. In the first
vessel, decarburization and major refining take place and final stages of desulphurization and degassing
take place in second vessel.
Compare to duplex, triplex process has following merits:

Increase productivity
Increase number of heats per day
Increase scrap to liquid metal yield
Improved quality of metal
High operational flexibility
Comparatively lower cost of production.

Figure 1: The standard process routes for stainless steels

AOD process
The AOD process features the use of mixed gas (O2 + inert gas) top-blowing lances to achieve high
decarburization rates even at low steel bath [C] contents. The AOD (argon-oxygen decarburization) is a
bottom-blown process, which since its introduction in the late 1960s has become the dominant stainless
steelmaking process (Figure 2). The AOD is charged with molten steel. The main task in the AOD is to
refine crude steel high in both carbon and sulfide. The often-high carbon content is oxidized and driven
off as carbon monoxide when oxygen is blown through tuyeres located near the bottom.

Figure 2: Schematic AOD Converter


Chromium oxidation is inevitable in the oxygen blowing decarburization process and chromium oxide
with its high melting point is enriched in the slag at steel-making temperature. Depending on carbon and
sulfur demands in the product, the top slag is reduced with either ferrosilicon or aluminum or a
combination of both.
Ferrosilicon is used when sulfur levels only needs to be lowered slightly or when the sulfur already is low
enough. Whenever possible, ferrosilicon is used because it is less expensive. Low sulfur levels as well as
low carbon are achievable in the AOD converter.

Decarburization in AOD converter


Very low carbon levels are acquired in AOD stainless steels, often down to between 0.01 and 0.04
percent. The concept of the AOD converter is reaching such low carbon content by introducing increasing
amounts of argon into the oxygen blown through the steel bath in the decarburization step. The argon
dilutes the carbon monoxide formed during the decarburization, which lead to a lower the partial pressure
of carbon monoxide PCO.
A low carbon monoxide partial pressure favors the formation of carbon monoxide from carbon and
oxygen according to the oxygen potential diagram and therefore a lower temperature can be implemented
in the AOD converter in making a standard stainless steel with chromium content of 18% and carbon
level at 0.03% (Figure 3). At normal pressure (1 atm) a temperature of 1940C is required to reach such a
low carbon level. When the partial pressure of carbon monoxide PCO is reduced to a tenth of normal
atmospheric pressure the equal low carbon level can be met already at 1600C (Figure 3). Economical
benefits are shorter heating times and lower heating costs combined with less refractory wear, and
perhaps less expensive refractory not needing to withstand extreme temperatures.

Figure 3: Oxygen potential diagrams


The efficiency of carbon removal is described in terms of the percentage of total inserted oxygen that is
consumed in the oxidation of carbon. This Carbon Removal Efficiency (CRE) is described in equation 2.
The rest of the oxygen is occupied in oxidizing metal. Keeping the CRE high is therefore of great
importance.
CRE = O2(carbon oxidation) / O2(total) x 100 (%) .......... (2)
When the CRE decreases it indicates the necessity to decrease the oxygen to argon ratio, i.e. higher argon
content in the blowing gas is needed. The blowing is therefore performed step by step constantly
increasing the argon content in the gas.
Figure 4 shows schematically a decarburization procedure. In the initial step the CRE reaches 90%. The
efficiency of carbon decrease as the available carbon in the melt lessens. Step two with equal amounts of
oxygen and argon in the blowing gas, starts when CRE is approximately 45% and carbon level is 0.44%.
CRE rises to 100%. All oxygen is consumed in forming carbon monoxide. After a few minutes CRE
decreases again along with the carbon level. Step three is acting in the same manner but with even higher
argon content. The blowing is performed until the requested carbon level is met. It may require a fourth
step with 100% pure argon blown through the melt.

Figure 4: Chrome Reduction Efficiency CRE in AOD convertor


Not only carbon will be removed during the decarburization procedure, but also other elements with high
affinity to oxygen such as silicon, manganese, chromium and nickel. Stainless steel is highly alloyed with
chromium and nickel. Chromium and nickel, as well as iron, will inevitable at some extent are oxidized
during the decarburization.
A major loss of valuable chromium to the slag in the form of oxides is not acceptable. Due to the argon
dilution carbon is oxidized prior to chromium. The reaction written:
[C] + [O] (CO) .......... (3)
4[Cr] + 3(O2)(G) 2Cr2O3(S) .......... (4)
Cr2O3S + 3[C]Fe 2Cr + 3CO(G) .......... (5)
With the overall reaction of these two combined
2[Cr] + 3CO(G) Cr2O3(S) + 3[C] .......... (6)
Interestingly enough equation 6 does not reach equilibrium according to laboratory and plant studies. The
studies indicate that chromium oxidation occur at greater extent than expected at a certain carbon level
and a certain oxygen/argon ratio. Fulton and Ramachandran showed that chromium oxidation depends of
blowing procedures. The argon protection against chromium oxidation is diminished if the gas is blown
only shallow into the melt from a lance above. The oxygen is consumed in instant chromium oxidation
equation 7 instead of forming carbon monoxide.
4[Cr] + 3O2(G) 2Cr2O3(S) .......... (7)
If the gas mixture on the other hand is injected through tuyeres placed near the bottom of the converter
the solid chromium oxide particles formed by the instant oxidation come to better use. As the formed
Cr2O3 particles ascend to the surface they perform the actual decarburization. The Cr2O3 particle come in
the contact with carbon on its way up and as a result are freed from one or more of its oxygen, hence
leading to the formation of carbon result are freed from one or more of its oxygen, hence leading to the
formation of carbon monoxide. The reactions can be written as
Cr2O3(S) + 3[Cr]Fe 2[Cr]Fe + 3CO(G) .......... (8)
Chromium oxide particles totally freed from their oxygen molecules re-emerges again as chrome in the
melt. Those Cr2O3 particles not subjected to any carbon on their path ends up in the slag, explaining the
existence of chromium oxide in the slag despite of equation 11. Chromium content in the top-slag is often
referred to as only Cr2O3 even though some extent of it is CrO.

In slag chrome is present both as Cr2O3 and CrO. The formation of CrO is favored by increased
temperature, decreased oxygen potential and decreased basicity. In order to keep the chromium trivalent,
remaining as Cr2O3 the basicity should be held high.
Large amounts of argon purge the steel bath intensely. Nitrogen and Hydrogen follow the argon to the
surface and very low levels remain in the steel at the end of the process.

Corrosion and Corrosion Properties of Stainless


Steels: Part One
This thin, invisible surface layer is an oxide that protects the steel from attack in an aggressive
environment. As chromium is added to steel, a rapid reduction in corrosion rate is observed to around
10% because of the formation of this protective layer or passive film.
Abstract: Stainless steels are stainless because a protective layer spontaneously forms on their surfaces
and reduces the rate of corrosion to almost negligible levels. Under normal conditions, this layer heals
very rapidly if scratched, so that if stainless steels only suffered from uniform corrosion, they could
survive for literally millions of years

Corrosion and Corrosion Properties of Stainless Steels: Part One


Stainless steels represent the most diverse and complex family of all steels. The single most important
property of stainless steels, and the reason for their existence and widespread use, is their corrosion
resistance. Stainless steels are stainless because a protective layer spontaneously forms on their surfaces
and reduces the rate of corrosion to almost negligible levels. Under normal conditions, this layer heals
very rapidly if scratched, so that if stainless steels only suffered from uniform corrosion, they could
survive for literally millions of years.

Passivity
As mentioned above, the reason for the good corrosion resistance of stainless steels is that they form a
very thin, invisible surface film in oxidizing environments. This film is an oxide that protects the steel
from attack in an aggressive environment. As chromium is added to steel, a rapid reduction in corrosion
rate is observed to around 10% because of the formation of this protective layer or passive film. In order
to obtain a compact and continuous passive film, a chromium content of about 17% is needed. This is the
reason why many stainless steels contain 17-18% chromium.

Figure 1: The effect of chromium content on passivity

The most important alloying element is therefore chromium, but a number of other elements such as
molybdenum, nickel and nitrogen also contribute to the corrosion resistance of stainless steels. Other
alloying elements may contribute to corrosion resistance in particular environments, for example copper
in sulfuric acid or silicon, cerium and aluminum in high temperature corrosion in some gases.
A stainless steel must be oxidized in order to form a passive film; the more aggressive the environment
the more oxidizing agents are required. The maintenance of passivity consumes oxidizing species at the
metal surface, so a continuous supply of oxidizing agent to the surface is required. Stainless steels have
such a strong tendency to passivate that only very small amounts of oxidizing species are required for
passivation. Even such weakly oxidizing environments as air and water are sufficient to passivate
stainless steels. The passive film also has the advantage, compared to for example a paint layer, that it is
self-healing. Chemical or mechanical damage to the passive film can heal or repassivate in oxidizing
environments. It is worth noting that stainless steels are most suitable for use in oxidizing neutral or
weakly reducing environments. They are not particularly suitable for strongly reducing environments
such as hydrochloric acid.
Corrosion can nevertheless occur if the passive film breaks down, locally or uniformly. This can happen
by different mechanisms depending on the conditions of use. The most common types of corrosion are the
following.
Uniform corrosion of stainless steels can occur in acidic or hot alkaline solutions. It results in uniform
loss which can easily be predicted and allowed for.
General corrosion resistance is increased with increasing chromium content, but other elements can be
detrimental. In particular, sulfur in solid solution is believed to make passivation more difficult and
therefore is generally undesirable for good corrosion properties.
Unfortunately, sulfur makes welding considerably easier and also improves machinability. In the case of
welding, sulfur appears to modify the surface tension of the weld pool and therefore alters its shape
significantly. Austenitic grade 316 with sulfur content lower than 0.007 wt% tend to have a high width-todepth ratio while higher sulfur contents lead to a narrower, deeper weld pool (specifying the sulfur
content of 316L for welding).
Some of the standard grades contain a quantity of sulfur deliberately greater than the typical 0.003 that
can otherwise routinely be achieved with modern steel-making processes (the free machining grades).
Nickel significantly improves the general corrosion resistance of stainless steels, by promoting
passivation. The austenitic stainless steels series therefore possesses a corrosion resistance superior to that
of martensitic or ferritic stainless steels (no nickel), particularly with mineral acids.
Pitting corrosion is the result of the local destruction of the passive film and subsequent corrosion of the
steel below. It generally occurs in chloride, halide or bromide solutions. If a fault in the passive layer or a
surface defect results in the local destruction of the former, dissolution of the steel underneath leads to a
build-up of positively charged metallic ions, which in turn causes negatively charges (e.g. chloride ions)
to migrate near the defect. Even in a neutral solution, this can cause the pH to drop locally to 2 or 3, and
can prevent regeneration of the passive layer.
In the passive condition, the current density is in the scale of nanoampers/cm2; in the pit, however, it may
be above 1A/cmp2. Similarly, the concentration in chloride ions can be thousands of times greater than
that in the solution.

Figure 2: Schematic illustration of pitting corrosion


The Figure 2 illustrates the process: the anodic dissolution of the steel leads to introduction of M+ in
solution, which causes migration of Cl- ions. In turn, metal chloride reacts with water following:
M + Cl- + H2O MOH + H + ClThis causes the drop of pH. The cathodic reaction, on the surface near the pit follows:
O2 + 2H2O MOH + 4OHWhile the propagation phenomenon is well understood, the mechanism of pit initiation is still debated.
The initiation of pitting has long been associated with the presence of MnS inclusions which are difficult
to avoid in the steel making process. It has recently been shown that these inclusions are surrounded by a
Cr depleted region which is believed to cause the initiation.
The pitting resistance of a stainless steel is affected by its composition. Increasing the Cr content or
adding both the molybdenum and/or the nitrogen enhances the pitting resistance, though they are not
equally potent in this respect. For comparison purposes, an index is often used to represent the combined
effect of these elements:
Pitting index = Cr + 3.3Mo + 16N
where Cr, Mo and N are given in weight percent.
One obvious environment where pitting corrosion is of concern is marine applications. AISI type 316 (an
18Cr-12Ni austenitic stainless steel with 2-3% Mo) is often the material of choice. In this case, although
the severe conditions met in offshore platforms, for example, call for heavily alloyed steels with up to 6%
Mo.
Street furniture is another case where pitting resistance might be relevant, particularly in colder areas
where salt de-icing is common.

Corrosion and Corrosion Properties of Stainless


Steels: Part Two
Abstract: Like all metals and alloys that relay on a passive film for corrosion resistance, stainless steels
are susceptible to localized corrosion, i.e. pitting or crevice corrosion. Both these types of corrosion
usually occur in chloride-containing aqueous solutions such as sea water, but can also take place in
environments containing other halogenides.

Pitting and crevice corrosion


Like all metals and alloys that relay on a passive film for corrosion resistance, stainless steels are
susceptible to localized corrosion. The protective passive film is never completely perfect but always
contains microscopic defects, which usually do not affect the corrosion resistance. However, if there are
halogenides such as chlorides present in the environment, these can break down the passive film locally

and prevent the reformation of a new film. This leads to localized corrosion, i.e. pitting or crevice
corrosion. Both these types of corrosion usually occur in chloride-containing aqueous solutions such as
sea water, but can also take place in environments containing other halogenides.
Pitting is a form of (extremely) localized attack that results in holes in the metal. These holes may be
small or large in diameters, but in most cases they are relatively small. A pit may be described as a hole
with the surface diameter about the same or even much less than the depth.
Pitting is a rather insidious form of corrosion. Pitting usually requires an extended initiation period before
visible pits appear. This period ranges from months to years, depending on both the specific metal and the
corrosive environment. In very aggressive environment like acid media containing ferric chloride serious
pitting of stainless steels like e.g. X2CrNi19-11 (304L) can occur even in a couple of days.
Once started, a pit penetrates the metal at an ever-increasing rate. In addition, pits tend to undermine or
undercut the surface as they grow. Sometimes the diameter of the pit can grow in diameter extensively
below the surface. Pits usually grow in the direction of gravity. Most pits develop and grow downward
from horizontal surfaces. Lesser numbers start in vertical surfaces, and only rarely do pits grow upward
from the bottom of horizontal surfaces.
Pitting is characterized by more or less local points of attack with considerable depth and normally occurs
on free surfaces (See Figure 1).
Crevice corrosion occurs in narrow, solution-containing crevices in which the passive film is more
readily weakened and destroyed. This may be under washers, flanges, deposits or fouling on the steel
surface.
Crevice corrosion can be a result of differences in oxygen or metal ion concentration between the crevice
and its surroundings. Local differences in composition of a solution cause potential differences on an
immersed metal and thus accelerate corrosion. Of particular importance in this respect are differences in
oxygen content, commonly known as differential aeration.
Crevice corrosion is usually attributed to one or more of the following aspects:

Lack of oxygen in the crevice


Build-up of detrimental ions in the crevice
Changes in acidity (decrease of Ph) in the crevice
Depletion of an inhibitor in the crevice.

To avoid crevice corrosion the following preventive measures can be applied:

Application of more resistant construction materials, like high nickel Mo alloys.


Make full penetration welds to avoid crevices
Design vessels for complete drainage
Weld (internal bore weld) instead of rolling in tubes in tube sheets
Inspects vessels and remove deposits frequently
Remove wet packing materials during long shutdowns
Use solid non absorbent gaskets, such as PTFE.

Figure 1: Pitting occurrence depending on Mo content in AISI 304.

Figure 2: Crevice corrosion under a rubber washer in a flat heat exchanger used in brackish water.
Both forms of corrosion occur in neutral environments, although the risk for attack increases in acidic
solutions.
Chromium, molybdenum and nitrogen are the alloying elements that increase the resistance of stainless
steels to both pitting and crevice corrosion. Resistance to localized corrosion in sea water requires 6%
molybdenum or more.
One way of combining the effect of alloying elements is via the so-called Pitting Resistance Equivalent
(PRE) which takes into account the different effects of chromium, molybdenum and nitrogen. There are
several equations for the Pitting Resistance Equivalent, all with slightly different coefficients for
molybdenum and nitrogen. One of the most commonly used formulas is the following:
PRE = %Cr + 3.3 x %Mo + 16 x %N
This formula is almost always used for the duplex steels but it is also sometimes applied to austenitic
steels. However, for the latter category the value of the coefficient for nitrogen is also often set to 30,
while the other coefficients are unchanged. This gives the following formula:
PRE = %Cr + 3.3 x %Mo + 30 x %N
The difference between the formulas is generally small but the higher coefficient for nitrogen will give a
difference in the PRE-value for the nitrogen alloyed grades.
Table 1: Typical PRE-values for various stainless steels
Grade 304L 316L 'SAF 2304' 317L '2205' '904L' 'SAF 2507' '254 SMO' '654 SMO'

PRE16xN 19

26

PRE30xN 20

26

26

30
30

35

36
37

43

43

56

46

63

The effect of composition can be illustrated by plotting the critical pitting temperature (CPT) in a specific
environment against the PRE-values for a number of steel grades. The Figure 3 shows the critical pitting
temperature (CPT) in 1M NaCl as a function of PRE-values. The CPT values are the lowest temperatures
at which pitting corrosion attack occurred during testing.

Figure 3: pitting temperature (CPT) in 1M NaCl as a function of PRE-values.


Since the basic corrosion mechanism is the same for both pitting and for crevice corrosion, the same
elements are beneficial in combating both types of corrosion attack. Due to this, there is often a direct
correlation between the CPT- and CCT-values for a certain steel grade.
Crevice corrosion is more severe of the two types of corrosion attack and the CCT-values are lower than
the CPT-values for any stainless steel grade. This is illustrated in Figure 4 where the critical pitting
temperature (CPT) and the critical crevice corrosion temperature (CCT) in 6% FeCl3 have been plotted
against the PRE-values for a number of stainless steels. Again the CPT and CCT values are the lowest
temperatures at which corrosion attack occurred.

Figure 4: Critical pitting temperature (CPT) and critical crevice corrosion temperature (CCT) in ferric
chloride for various stainless steels.
As can be seen from the diagrams in Figures 3 and 4 there is a relatively good correlation between the
PRE-values and the CPT and CCT. Consequently the PRE-value can be used to group steel grades and
alloys into rough groups of materials with similar resistance to localized corrosion attack, in steps of 10
units in PRE-value or so. However, it cannot be used to compare or separate steel grades or alloys with
almost similar PRE values.

Finally, it must be emphasized that all diagrams of this type show comparisons between steel grades and
are only valid for a given test environment. Note that the steel grades have different CPTs in NaCl
(Figure 3) and FeCl3 (Figure 4). The temperatures in the diagrams cannot therefore be applied to other
environments, unless there is a practical experience that shows the relation between the actual service
conditions and the testing conditions.
The relative ranking of localized corrosion resistance is, however, often the same even in other
environments. The closer the test environment is to the natural environment, i.e. the closer the test
environment simulates the principal factors of the service environment, the more can the data generated in
it be relied on when judging the suitability of a certain steel grade for a specific service environment. A
test in sodium chloride is consequently better than a test in ferric chloride for judging whether or not a
certain grade is suitable for one of the neutral pH, chloride containing water solutions which are common
in many industries.
In order to obtain a good resistance to both pitting and crevice corrosion, it is necessary to choose a
highly alloyed stainless steel with a sufficiently high molybdenum content. However, choosing the right
grades is not the only way to minimize the risk for localized corrosion attack. The risk for these types of
corrosion attack can be reduced at the design stage by avoiding stagnant conditions and narrow crevices.
The designer can thus minimize the risk for pitting and crevice corrosion both by choosing the correct
steel grade and by appropriate design of the equipment.