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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

0 2 4 6 8 10 12 14 16 18

Increases oxidation & corrosion resistance Increases hardenability and hardness Stabilises ferrite
above 12% no austenite at any temperature

Cr percent

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

1500C

Liquid

g 910C

a+s

s a+s

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

Temperature

Fe

12%

Cr

Effect of nickel additions


Fe-Cr-Ni equilibrium diagram (schematic)
1000C

400C

Austenite

200C 0

Ferrite or martensite
2 4 6 8

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

% nickel

Iron-Chromium-Nickel
Cr
90
80 90 80

At 1100C
60 50 40 30 20 10

70

70 60

a+g

50
40 30

Austenitic Ferritic Duplex

g
20 30 40 50 60 70 80

20 10

Fe

10

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

700C

Increasing carbon

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 (a) 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
0 0

Ferrite

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

WRC 1992 Diagram


18 17 Nickel Equivalent = Ni + 35C + 20N + 0.25Cu 16 15 14
0

4 8

10

14

20

24 30 40 50 60 70

AF A

FA
13 12

80 90

F
11
10 9 17

100

18

19

20

21

22

23

24

25

26

27

28

29

30

31

Chromium equivalent = Cr + Mo + 0.7 Nb

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

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