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11/14/2014

Pulp and Paper Corrosion Symposium


Georgia Tech Renewable Bioproducts Institute
November 2014

Duplex Stainless Steels

Margaret Gorog
Federal Way, WA

Duplex Stainless Steel

2205 stainless steel


Microstructure:
f austenite + ferrite
a

304L stainless steel


Microstructure: austenite

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Duplex Stainless Steel

• First 2 digits: nominal chromium


• Last 2 digits: nominal nickel

2205 → 22% Chromium, 5% Nickel

• Family of Grades
• Lean
• Standard
• Super
• Hyper

• 329 one of the oldest grades


• 3RE60, Alloy 86 for suction rolls

Duplex Stainless Steel - Benefits

• Improved corrosion and more importantly, stress


corrosion cracking resistance
• Higher strength and hardness. This provides improved
fatigue and wear resistance
• Higher tensile and yield strength compared to the
austenitics translates into thinner walls and less weight
which can offset the cost to some extent.

Austenitic Tensile Yield Duplex Tensile Yield


304/304L 75 30 Lean DSS 94 65
316/316L 75 30 2304 87 58
317L 75 30 ATI 2003 95 65
6% Mo SS 95 45 LDX2404 99 70
2205 95 65
2507 116 80

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Duplex Stainless Steel - Limitations

• Limitations
• More difficult to weld, especially the grades
containing molybdenum
• Temperature limit of 600 °F
• Availability particularly non plate forms
• Cost not always advantageous even though alloying
cost is less
Lean DSS
304L plate cost

2205
316L
317L
2507
6% Mo

Duplex Stainless Steel – Welding

• Welding is seen as a disadvantage but is probably no


more difficult to weld than the austenitics
– Make sure material starts out in the right condition
through composition and heat treatment
– Use ASTM A923 Standard and ASTM A1084 Lean for
detecting detrimental intermetallic phases in DSS
• Maintain ferrite-austenite phase balance
– Apply a low range of heat input
• Use appropriate weld filler
– 2209 with additional nickel for 2205
• There is a limit as to how many times a duplex can be
welded (lean DSS more forgiving)

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Duplex Stainless Steel - Embrittlement

Lean DSS – Corrosion Resistance

UR2202  Similar to 304L


ATI2102  Similar to 304L
NSSC2120  Similar to 304L
LDX2101  Equivalent to 304L, not always equivalent to 316L
2304  Equivalent to 304L and 316L

Lean duplexes contains little or no molybdenum


Lower corrosion resistance than 2205
Ideal for alkaline liquor service

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Coupon Testing Results


White Liquor Surge Tank 3rd Effect Evap 45% BL Solids
Alloy Corrosion Alloy Corrosion
Rate (mpy) Rate (mpy)
304L 0.001 304L 0.001
316L 0.004 316L 0.017
Alloy 20 0.002 Alloy 20 0.002
600 0.000 600 0.029
2101 0.003 2101 0.003
2304 0.001 2304 0.000
2003 0.003 2003 0.000
2205 0.001 2205 0.000

Green Liquor Clarifier

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Duplex Stainless Steel – Corrosion Resistance

ATI2003  Contains Mo
 More resistant than 304L or 316L. Substitute for 317L
LDX2404  Does not have the corrosion resistance of 2205

2205  Is the standard DSS grade and can be considered a


commodity item. It comes in most forms.
 Contains Mo
 Superior to 316L and 304L
 More resistant than 317L, resistant to low residual
chlorine dioxide solutions

Pre – Bleach Tank

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Super, Hyper – Corrosion Resistance

Ferralium 255
2507 Contains Mo, more difficult to weld, substituted for
Zeron 100 6% mo SS in bleach plant

2707, 3207 Hyper DSS, Offshore oil applications

Duplex Stainless Steel Linings

• The thermal expansion coefficient is close to carbon


steel. With increased strength, they are less likely to
crack than austenitic stainless steel linings.
• NACE SP0292 provides a specification for installing
corrosion resistant sheet linings
• Less welding for larger sheets (10’ x 5’)
• Quicker to install vs overlay in a digester
• Less maintenance than tile lined towers

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Nominal Alloying
UNS Other
Alloy number %Cr %Ni %Mo Elements PREN
304L S30403 18 8 N 18
316L S31603 16 10 2 N 24
317L S31703 18 11 3 N 30
254SMO S31254 20 18 6.1 Cu, N 43
AL-6XN N08367 20.5 24 6.3 Cu, N 45

19D S32001 20 1.7 0.3 N, 5Mn, Cu 23


UR2202 S32202 23 2.5 0.3 N 26
ATI2102 S82011 21 1.5 0.3 N, Mn 26
NSSC2120 S82122 21 1.5 0.3 N, Mn, Cu 26
LDX2101 S32101 21.5 1.5 0.3 N,5Mn, Cu 26
2304 S32304 23 4.5 0.3 N, Cu 26
ATI 2003 S32003 21 3.5 1.6 N 30
LDX2404 S82441 24 3.5 1.6 N, Mn, Cu 33
2205 S32205 22 5 3 N 35
Ferralium 255 S32550 25.5 5.5 3.5 N,2Cu,W 38
2507 S32750 25 6.5 3.5 N,Cu,W 41
Zeron 100 S32760 25 7 3.5 N, Cu, W 41

Cast Duplex Stainless Steels

UNS Common ASTM Type Wrought


Number Name A890 Equivalent
J93370 CD4MCu 1A 25Cr-5Ni-Mo-Cu
J93372 CD4MCuN 1B 25Cr-5Ni-Mo-Cu-N
J93373 CD3MCuN 1C 25Cr-6Ni-Mo-Cu-N 255
J93345 CE8MN 2A 24Cr-9Ni-Mo-N
J93371 CD6MN 3A 25Cr-5Ni-Mo-N
J92205 CD3MN 4A 22Cr-5Ni-Mo-N 2205
J93404 CE3MN 5A 25Cr-7Ni-Mo-N 2507
J93380 CD3MWCuN 6A 25Cr-7Ni-Mo-N Zeron 100
J93379 7A 27Cr-7Ni-Mo-Cu-N

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Bleach Plant Material Selection


• O2 Delignification
– Historically 316L
– Switched to 2205 for external stress corrosion
cracking resistance
– Now lean DSS
• E stage
– Alkaline Conditions, less aggressive
– 316L/317L
– Lean DSS may be suitable
– Avoid titanium with peroxide

Bleach Plant Material Selection


• D stage
– Resistance to oxidizing chlorides is necessary to prevent
pitting and crevice corrosion
– Titanium up to the point of injection
– Nickel alloys corrode in neutral (pH>3) ClO2
– Historically 317L, 6% molybdenum stainless steels
depending on chlorine dioxide residual
– “Super Duper” 7% moly stainless steel, 654SMO, for
more corrosion resistance
– 2205 or 2507 and cast equivalents now have wide
applicability
– Substitute duplex solid plate or sheet lining for tile lined
towers, chests or washers

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D2 Filtrate Corrosion

Temperature: 160-200 °F
pH: 3.3-4.0
ClO2 concentration: 0.08 g/l
Test duration: ~345 days in the D2 filtrate tank
Materials: 317L, 2205, 254SMO, Titanium

Corrosion Results
Aloy Corr Rate (mpy) Crevice Pitting Open Pitting
Titanium Gr. 2 0
254SMO (6% Mo) 0.26 X
2205 0.20 X X
317L 1.95 X X

2205 317L

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D1/D2 Filtrate Immersion Testing

Temperature: 140 °F Temperature: 160 °F


pH: 2 - 3 pH: 5 - 6
ClO2 concentration: low ClO2 concentration: low
Test duration: 1 year Test duration: 1 year

Corrosion Rates
Alloys for Corr Rate Alloys for Corr Rate Pitting, %
D2-1 (mpy) D2-2 (mpy) Crevice area
316L 0.001 316L 0.022 55
317L 0.002 317L 0.002 10
2205 0.000 2101 0.008 6
CD4MCu 0.001 2003 0.000
254SMO 0.000 2304 0.000
AL6XN 0.003 2205 0.000
625 0.056 AL6XN 0.004
C276 0.044 C276 0.075
Alloys for Corr Rate Alloys for Corr Rate
D1-1 (mpy) D1-2 (mpy)
316L 0.000 316L 0.001
317L 0.001 317L 0.000
2205 0.001 2101 0.000
CD4MCu 0.001 2003 0.000
254SMO 0.000 2304 0.000
AL6XN 0.001 2205 0.000
625 0.001 AL6XN 0.000
C276 0.010 C276 0.007

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D2 316L results

D2 317L, LDX2101
LDX2101 317L

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Vapor Space Corrosion


D1 Two Years No Pitting D2 Five Years Pitting in crevice and open areas

Coupon ID Corrosion Coupon ID Corrosion Description


Rate (mpy) Rate (mpy)
LDX2101 0.001 LDX2101 0.054 Pitted
316L 0.001 316L 0.035 Pitted
2304 0.001 2304 0.033 Pitted
317L 0.001 317L 0.012 Pitted
ATI2003 0.000 ATI2003 0 Clean
2205 0.001 2205 0 Clean
AL6XN 0.001 AL6XN 0 Clean

Bleach Plant Materials Summary

• The bleach plant is not as corrosive as it once


was
– Improved operations has led to lower chlorine
dioxide residuals
– 2205 can be substituted for 317L
– Know residual, pH, temperature and test materials
– Lower alloys than those used in the past may be
suitable

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Machine Room
• Duplex suction roll shells, excellent corrosion
fatigue resistance
• Duplexes are not widely used for whitewater
service since 304L and 316L are usually
resistant.
• Lean grades are not available as piping
• 2205 is used for starch tanks and piping
because of it’s resistance to stress corrosion
cracking in hot, high chloride solutions.

Starch Piping – What Happened?

2205, installed as a replacement for cracked 316L,


corroded and leaked after 2 years.

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Elbow Pipe

Second phase precipitation in the pipe segment indicates


reduced corrosion resistance. It did not occur in the elbow.

• The pipe, unlike the elbow, had been delivered with an


inadequate solution anneal and quench
• The annealing temperature is about 1900 °F. Precipitation
occurs in 2205 when the metal is slow cooled through 1600°F
for some time.
• If the material is water quenched from the solution annealing
temperature, then there is enough time available for
additional thermal cycles such as hot forming or welding
before second phases begin to form.
• Due to poor heat treatment, second phase precipitation
occurred in the pipe during the welding thermal cycle.
• In this case welding quality was not an issue

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Starch Tank

photo courtesy Gina Aiello

Duplex Stainless Steel Summary


• Benefits compared to common stainless steels:
 Improved corrosion and stress corrosion cracking
resistance
 More resistant to external cracking under insulation
 Higher strength. This provides improved fatigue and wear
resistance
• Welding must maintain the duplex structure, especially the
grades containing molybdenum
• Availability
• More Information - Practical Guidelines for the Fabrication of
Duplex Stainless Steel – published by IMOA

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Questions

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