Stainless & heat

resisting steels

Stainless steels

Alloys of iron with >11.5% chromium, plus

Ni, Mn, Mo, N etc
Classes of stainless steel
Ferritic stainless steels (cheap, resistant to Cl -)
Martensitic stainless steels (strong, resistant
to Cl-)
Austenitic stainless steels (ductile, wide
applications)
Duplex (strong, ductile, resistant to Cl-)
Precipitation hardening (very strong)

Effects of chromium on steel

Wt
loss

Corrosion rate

above 12% no
austenite at any
temperature

10 12 14 16 18

Cr percent

Increases oxidation &

corrosion resistance
Increases
hardenability and
hardness
Stabilises ferrite

Forms stable
carbides

Corrosion of stainless steels

General corrosion not significant

Pitting corrosion
Crevice corrosion
Intergranular corrosion
Stress corrosion cracking
Galvanic corrosion

Handling stainless steels

Avoid embedding surface with carbon

steel
Causes local rust spots
Scraping with steel tools or surfaces
Grinding debris
Contamination can be removed by pickling
Done using oxidising acid solutions or pickling
paste
Passivating is necessary to restore oxide film

General welding precautions

Avoid surface oxides (excessive heat

tint) which can lead to corrosion in
aggressive environments
Argon gas backing for pipe welds
Acid pickling to remove scale
Glass bead blasting

Ensure slag is removed

Joint designs should avoid crevices

Iron-chromium phase diagram

Liquid

1500C
Temperature

910C

Fe

12%

Cr

Compositions with
over 12% Cr never
become austenitic
Addition of austenite
stabilising elements
widens gamma loop
Carbon, nickel,
nitrogen
Sigma stable at high
Cr levels
Slow
transformation

Effect of nickel additions

Fe-Cr-Ni equilibrium diagram
(schematic)

1000C

Austenite

400C

200C
0

Ferrite or
martensite
2

% nickel

Stabilises austenite
More than 8% in
austenitic stainless
steels
4 to 7% in duplex
austenite-ferrite
steels

Iron-Chromium-Nickel
Cr
90

90

80

80
70

At 1100C

60

60

50

50

Austenitic
Ferritic
Duplex

70

40

40

30

30
20

10

Fe

10

20

20

30

40

50

60

70

10
80

90

Ni

Unwanted secondary phases

Impair corrosion performance and/or

embrittle
Carbides if carbon content is high
(>0.03%)
Intermetallic phases at higher levels of
Cr or Mo
sigma, chi, laves, alpha prime, R and tau

Nitrides

Secondary phase formation

Depends on alloy composition, temperature

and time at temperature
High temperatures tend to dissolve
unwanted phases
May occur during hot fabrication processes
or in high temperature service
High temperature short times during
welding causes sigma in 254SMO and
2205
Extended heating during heat treatment,
hot work or in service causes sigma and
chi in 316L

Weld decay
Heating between 480 and 820C
causes carbide precipitation at grain
boundaries which lowers Cr level in
adjacent matrix. Corrosion occurs at
the denuded areas of sensitised
steels if they are in aggressive
environments.

Time-temperature sensitisation curve

900C

0.06% C

800C

Increasing carbon

700C

600C

0.019% C
500C

400C
10 sec

1 min

10 min

1h

10 h

100 h

1,000 h

10,000 h

Avoiding weld decay

Use low carbon content steels

(maximum 0.03%)
The L grades of stainless eg 304L

Stabilise carbon with Ti or Nb (Cb)

which form carbides that are stable
at high temperature
Grades 347 or 321 are stabilised
versions of 304

Solution treat after welding

Heat to 1100C and water quench
rapidly through the sensitisation range

Avoiding intermetallic phases

Avoid temperatures for the timescale

at which they form
Solution treat
Typically 1100C for 1 hour and rapidly
cool
Temperature and cooling depends on
alloy

In some cases, removal may be

almost impossible

Ferritic stainless

10.5 to 30% chromium

Low carbon, nickel, nitrogen
Very resistant to chlorides, but tends
to be brittle
Grain growth during fabrication
Alpha prime () at 475C
Sigma at higher Cr levels

Ferritic stainless overview

High Cr types solidify as ferrite and

never become austenitic
Grain growth during fabrication
causes loss of toughness
Low Cr types can become austenitic,
and may transform to martensite
(cracking likely during welding)

Fabrication of ferritic grades

Reasonable hot workability

Limited amount of cold work before
annealing
High yield strength and work hardening
rate

Welding is complex
Only thin sections welded
Cool quickly to avoid embrittlement

Austenitic stainless steel

Widespread uses, piping, process

vessels
Minimum Ni or Ni + Mn to ensure
structure is completely austenitic
Some quenched from ~1100C to
retain 100% austenite

Fabrication of austenitic SS

Good hot ductility over a limited

temperature range
Embrittled by S, O and P

Better cold ductility than ferritic,

martensitic or duplex grades, but
limited
Good weldability when reasonable
care is exercised

Weld solidification cracking

Depending on composition
Low susceptibility if there is some
ferrite during solidification
Weld metal with 5% ferrite at room
temperature (coincidence)

Predicted from Schaeffler, DeLong or

WRC 1992 diagrams

Weld metal composition diagrams

First was the Schaeffler diagram 1949

Still used because it covers wide range of
compositions

Next was the DeLong - 1956

Nitrogen term added

WRC 1988 & 1992 diagrams

Kotecki and Siewert. Most accurate
predictions

All cover weld metal only and are NOT

equilibrium diagrams!

Nickel and chromium equivalents

Some elements are similar to nickel

& stabilise austenite in steels
Carbon, manganese (now found to have
little effect) and nitrogen

Some elements stabilise ferrite like

chromium
Molybdenum, niobium

Schaeffler diagram

30

Nickel equivalent = Ni + 30 C + 0.5 Mn

Austenite
Austenitic alloys

A+M

A+F

Duplex alloys
Martensitic alloys
Martensite
M+F

A+F+M
Ferritic alloys

Ferrite

0
0

40
Chromium Equivalent = Cr + Mo + 1.5 Si + 0.5 Nb

WRC 1992 Diagram

Nickel Equivalent = Ni + 35C + 20N + 0.25Cu

18
17
16

10

14

20

24

AF

15

30

40
50
60

14

FA

13

70
80
90

12

100

11
10
9
17

18

19

20

21

22

23

24

25

26

Chromium equivalent = Cr + Mo + 0.7 Nb

27

28

29

30

31

Super austenitic 6Mo stainless

Excellent resistance to pitting in

chlorides (sea water)
Serious segregation on solidification
Sigma phases form in weld metal
Use nickel-based filler metals
Solution anneal after welding

1080C and water quench (impractical)

Martensitic stainless

Fe-Cr-C alloys
Chromium and carbon balanced so that
transformation to austenite occurs on
heating
More than 18Cr always ferritic

High hardenability - austenite to

martensite transformation under
almost all cooling rates
Air hardening steels

Applications

12 Cr low carbon engineering grades

403, 410, 414, 416, 420
Well head Christmas trees, valves,
pumps

High carbon grades 431

Cutlery, tools

Fabrication

Hot worked only

Cold work limited applicability
High risk of hydrogen cracking on
welding
Preheat 200 to 320C
Subcritical PWHT (700C) often applied

Tempers martensite

Low hydrogen practice

Austenitic filler beneficial

Weldable 13 Cr martensitic

Sufficient resistance to corrosion in

H2S (sour) & CO2 contaminated
petrochemicals
Newly applied to pipelines
Very low carbon, oxygen and nitrogen
Typically 0.02% maximum

Weld preheat and PWHT is not

required
Duplex stainless steel filler used, which
may undermatch strength

Duplex stainless steels

50/50 mix of ferrite and austenite

Low Ni with 22-26Cr

High strength with good ductility and

toughness
More economical than austenitic
stainless steel
Better resistance to chlorides than
austenitic stainless steel

Fabricating duplex stainless

More demanding than austenitic

grades
Avoid secondary phases
Balance ferrite and austenite proportions

Hot work at high temperatures

Higher ferrite levels

Cold work limited

Work hardens rapidly

Welding duplex stainless steel

Sensitive to arc energy

Solidify as ferrite, austenite forms during
cooling
Low arc energy causes high ferrite levels
Embrittlement & loss of corrosion
performance
High arc energy causes sigma phase to form
Embrittlement & loss of corrosion
performance
Arc energy ranges
0.5 to 2.0 kJ/mm for 2205
0.5 to 1.5 kJ/mm for 2507

Finishing stainless fabrication

Required for aggressive environments, food

or pharmaceutical industries
Avoid or remove embedded iron
Test surface for contamination

Ferroxyl test is immediate, alternatively wet surface &

leave for 24 hours

Pickling with acid or paste

Remove heat tint by pickling

Remove surface contaminants such as slag,
dirt and paint, which are a crevice corrosion
risk