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Stainless & heat resisting steels

EF402 Lecture 8

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Stainless steels
Alloys of iron with >11.5% chromium, plus Ni, Mn, Mo, N etc Classes of stainless steel
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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)
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Effects of chromium on steel


Wt loss Corrosion rate

Increases oxidation & corrosion resistance Increases hardenability and hardness Stabilises ferrite
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10 12 14 16 18

above 12% no austenite at any temperature

Cr percent

Forms stable carbides

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Corrosion of stainless steels


General corrosion not significant Pitting corrosion Crevice corrosion Intergranular corrosion Stress corrosion cracking Galvanic corrosion

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Handling stainless steels


Avoid embedding surface with carbon steel
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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

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General welding precautions


Avoid surface oxides (excessive heat tint) which can lead to corrosion in aggressive environments
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Argon gas backing for pipe welds Acid pickling to remove scale Glass bead blasting

Ensure slag is removed Joint designs should avoid crevices

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Iron-chromium phase diagram


1500 C Temperature Liquid

910 C

Compositions with over 12% Cr never become austenitic Addition of austenite stabilising elements widens gamma loop
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Carbon, nickel, nitrogen

Sigma stable at high Cr levels


+ +
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Slow transformation

Fe

12%

Cr

Effect of nickel additions


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

400C

Austenite

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

200C 0

Ferrite or martensite
2 4 6 8

% nickel

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Iron-Chromium-Nickel
Cr
90 80 90 80 70 60 50 40 30 20 10 10 Fe Qualmet Services

At 1100 C

70 60 50 40 30

Austenitic Ferritic Duplex

20 30 40 50 60 70 80

20 10

90

Ni
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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
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sigma, chi, laves, alpha prime, R and tau

Nitrides

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Secondary phase formation


Depends on alloy composition, temperature and time at temperature
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High temperatures tend to dissolve unwanted phases

May occur during hot fabrication processes or in high temperature service


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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
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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.

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Time-temperature sensitisation curve


900C 800C 700C 600C

0.06% C

Increasing carbon

0.019% C
500C 400C 10 sec

1 min

10 min

1h

10 h

100 h

1,000 h

10,000 h 13

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Avoiding weld decay


Use low carbon content steels (maximum 0.03%)
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The L grades of stainless eg 304L

Stabilise carbon with Ti or Nb (Cb) which form carbides that are stable at high temperature
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Grades 347 or 321 are stabilised versions of 304 Heat to 1100C and water quench rapidly through the sensitisation range
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Solution treat after welding


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Avoiding intermetallic phases


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

In some cases, removal may be almost impossible

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Ferritic stainless
10.5 to 30% chromium Low carbon, nickel, nitrogen Very resistant to chlorides, but tends to be brittle
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Grain growth during fabrication Alpha prime ( ) at 475 C Sigma at higher Cr levels

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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)

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Fabrication of ferritic grades


Reasonable hot workability Limited amount of cold work before annealing
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High yield strength and work hardening rate Only thin sections welded Cool quickly to avoid embrittlement

Welding is complex
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Austenitic stainless steel


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

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Fabrication of austenitic SS
Good hot ductility over a limited temperature range
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Embrittled by S, O and P

Better cold ductility than ferritic, martensitic or duplex grades, but limited Good weldability when reasonable care is exercised

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Weld solidification cracking


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

Predicted from Schaeffler, DeLong or WRC 1992 diagrams

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Weld metal composition diagrams


First was the Schaeffler diagram - 1949
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Still used because it covers wide range of compositions Nitrogen term added Kotecki and Siewert. Most accurate predictions

Next was the DeLong - 1956


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WRC 1988 & 1992 diagrams


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All cover weld metal only and are NOT equilibrium diagrams!
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Nickel and chromium equivalents


Some elements are similar to nickel & stabilise austenite in steels
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Carbon, manganese (now found to have little effect) and nitrogen Molybdenum, niobium

Some elements stabilise ferrite like chromium


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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 0 0 A+F+M Ferritic alloys Ferrite

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40 Chromium Equivalent = Cr + Mo + 1.5 Si + 0.5 Nb 24

WRC 1992 Diagram


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

2 4

10 8

14

20

AF

24 30

40 50 60

FA
13 12 11 10 9 17 18 19 20 21 22 23 24 25 26 27 28 29

70 80 90

100

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
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Use nickel-based filler metals Solution anneal after welding


1080 C and water quench (impractical)

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

High hardenability - austenite to martensite transformation under almost all cooling rates
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Air hardening steels

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Applications
12 Cr low carbon engineering grades 403, 410, 414, 416, 420
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Well head Christmas trees, valves, pumps Cutlery, tools

High carbon grades 431


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


Tempers martensite

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Low hydrogen practice Austenitic filler beneficial


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Weldable 13 Cr martensitic
Sufficient resistance to corrosion in H2S (sour) & CO2 contaminated petrochemicals Newly applied to pipelines Very low carbon, oxygen and nitrogen
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Typically 0.02% maximum Duplex stainless steel filler used, which may undermatch strength
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Weld preheat and PWHT is not required


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Duplex stainless steels


50/50 mix of ferrite and austenite
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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

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Fabricating duplex stainless


More demanding than austenitic grades
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Avoid secondary phases Balance ferrite and austenite proportions Higher ferrite levels Work hardens rapidly

Hot work at high temperatures


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Cold work limited


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Welding duplex stainless steel


Sensitive to arc energy
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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

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Finishing stainless fabrication


Required for aggressive environments, food or pharmaceutical industries Avoid or remove embedded iron
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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 Qualmet Services
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