Safe Operating Windows

for Martensitic & Duplex Stainless Steels

Dr. Russell D. Kane

Honeywell Process Solutions
Houston, Texas USA
russ@rdkane.com
 Data Survey Procedure (1)
• An extensive literature survey was conducted
covering 1985 thru 2006.
• Survey included:
– SSC data for 13Cr, 13Cr-1Mo and 13Cr-2Mo steels
– SCC data for 22Cr and 25Cr duplex steels
• Tests for 13Cr were at 23 C
• Tests for 22-25 Cr duplex were at 80 to 190 C.
• Data recorded included:
– PH2S
– pH
– Cl- concentration
– specimen failure/no failure.
• Data was tracked separately for OCTG and forged
bar.
 Data Survey Procedure (2)
• Data was obtained from tests at applied stress
levels of
– 80 percent SMYS to 90 percent AYS
– Using tensile or C-ring specimens.
• Serviceability limit plots were developed based
on available data using the MR0175-ISO15156
format.
• A comparison of OCTG and forged bar (for
coupling stock) was made for 13Cr-1Mo, 13Cr-
2Mo and 25Cr duplex steels.
 13Cr-1Mo Stainless Steel OCTG
5.5
Test temperature: 23 C
13Cr-1Mo 95 Fail
13Cr-1Mo 95 Passl
13Cr-1Mo 110 Fail

5 13Cr-1Mo 110 Pass

4.5
In Situ pH

3.5

2.5
0.1 1.0 10.0 100.0

H2S Partial Pressure - kPa

Shows useful range of serviceability for 13Cr-1Mo (Actual: 1-1.5 Mo).

(95-110 ksi Grade; Applied Stress 80% SMYS - 90% AYS)
Moves pH limit down and H2S limit up from regular 13Cr.
 13Cr-1Mo – Influence of Chlorides
100.000
13Cr-1Mo 95 Fail Test temperature: 23 C
13Cr-1Mo 95 Pass
13Cr-1Mo 110 Fail
13Cr-1Mo 110 Pass

10.000
Chloride Ion Concentration (Percent)

1.000

0.100

0.010

0.001
0.1 1.0 10.0 100.0

H2S Partial Pressure - kPa

Shows increased tolerance to H2S as the chloride decrease.

(95-110 ksi Grade; Applied Stress 80% SMYS - 90% AYS)
 13Cr-2Mo Stainless Steel OCTG
5.5
Test temperature: 23 C
13Cr-2Mo 95 Fail
13Cr-2Mo 95 Pass
13Cr-2Mo 110 Fail
13Cr-2Mo 110 Pass
5

4.5
In Situ pH

3.5

2.5
0.1 1.0 10.0 100.0

H2S Partial Pressure - kPa

Shows increase range of serviceability for 13Cr-2Mo (Actual: 2-2.5 Mo).
(95-110 ksi Grade; Applied Stress 80% SMYS - 90% AYS)
Substantially expands “Green Zone” over both 13Cr & 13Cr-1Mo.
 13Cr-2Mo – Influence of Chlorides
100.000
Test temperature: 23 C 13Cr-2Mo 95 Fail
13Cr-2Mo 95 Pass
13Cr-2Mo 110 Fail
13Cr-2Mo 110 Pass

10.000
Chloride Concentration (Percent)

1.000

0.100

0.010

0.001
0.1 1.0 10.0 100.0

H2S Partial Pressure - kPa

Increase in H2S resistance at chloride concentration (<1 percent)
95-110 ksi Grade; Applied Stress 80% SMYS - 90% AYS
 13Cr OCTG Summary
• Regular 13Cr has limited resistance to H2S.
– Limited to low levels of H2S (1 kPa/0.15 psia) in gas wells at low
pH (3.5)
– At higher pH (>4.5), H2S tolerance increases (10kPa/1.5 psia).
• Addition of 1% Mo, increases serviceability limits slightly
to 2 kPa/0.3 psia at pH 3.5.
• Addition of 2% Mo, increases serviceability limits
substantially to:
– 20 kPa/2 psia at pH 4.0
– 3kPa/0.45 psia at 3.2
• Cautionary (yellow) regions should be explored using
testing under simulated service conditions (PH2S, pH and
chlorides) with typical materials.
 22Cr Duplex Stainless Steel OCTG
5
Test temperature: 80 to 200 C
22Cr Duplex 110-125 Fail
22Cr Duplex 110-125 Pass

4.5

4
In Situ pH

3.5

2.5
0.1 1 10 100 1000 10000 100000

H2S Partial Pressure - kPa

Shows higher range of serviceability than 13Cr-2Mo and higher strength;

110-125 ksi Grade; Applied Stress 80% SMYS - 90% AYS
 22Cr Duplex – Influence of Chlorides
100.00%
Test temperature: 80 to 200 C
22Cr Duplex 110-125 Fail
22Cr Duplex 110-125 Pass
Chloride Ion Concentration (Percent)

10.00%

1.00%

0.10%

0.01%
0.1 1 10 100 1000 10000 100000

H2S Partial Pressure - kPa

Shows lower tolerance to high chlorides than 13Cr-2Mo due to higher temperature.
(110-125 ksi Grade; Applied Stress 80% SMYS - 90% AYS)
 25Cr Duplex Stainless Steel OCTG
5
Test temperature: 80 to 200 C
25Cr Duplex 90-125 Fail
25Cr Duplex 90-125 Pass

4.5

4
In Situ pH

3.5

2.5
0.1 1 10 100 1000 10000 100000

H2S Partial Pressure - kPa

Shows increase in H2S limits over 22Cr; not as much data.

(110-125 ksi Grade; Applied Stress 80% SMYS - 90% AYS)
 25Cr Duplex – Influence of Chlorides
100.00%
Test temperature: 80 to 200 C
22Cr Duplex 110-125 Fail
22Cr Duplex 110-125 Pass
Chloride Ion Concentration (Percent)

10.00%

1.00%

0.10%

0.01%
0.1 1 10 100 1000 10000 100000

H2S Partial Pressure - kPa

Shows improved tolerance to chloride ions over 22Cr, but limited data.
(110-125 ksi Grade; Applied Stress 80% SMYS - 90% AYS)
 22-25Cr Duplex OCTG Summary
• 22 Cr duplex stainless steels have similar
resistance to H2S, pH and chlorides as 13Cr-2Mo
stainless steels.
– 10 kPa/1.5 psia H2S at pH 3.0
– Has higher strength (110 & 125 ksi grades)
– But, has lower tolerance to chlorides in critical
temperature range (80-120 C).
• More data exists for 22Cr at high H2S than for
25Cr stainless steels.
• Limits for 25Cr are:
– 20 kPa/3.0 psia H2S at pH 3.0
– Limits increase to 100 kPa/15 psia H2S at low chlorides
(<1 percent)
 13Cr-1Mo Forged Bar
5.5
13Cr-1Mo 95 Bar Fail
13Cr-1Mo 95 Bar Pass
13Cr-1Mo 110 Bar Fail
5 13Cr-1Mo 110 Bar Pass

4.5
In Situ pH

3.5

2.5
0.1 1 10 100

H2S Partial Pressure - kPa

Serviceability regions from 13Cr-1Mo OCTG overlaid on bar data.

(95-110 ksi Grade; Applied Stress 80% SMYS - 90% AYS)
 13Cr-2Mo Forged Bar
5.5
13Cr-2Mo 95 Bar Fail
13Cr-2Mo 95 Bar Pass
13Cr-2Mo 110 Bar Fail
5 13Cr-2Mo 110 Bar Pass

4.5
In Situ pH

3.5

2.5
0.1 1 10 100

H2S Partial Pressure - kPa

Serviceability regions from 13Cr-2Mo OCTG overlaid on bar data.

(95-110 ksi Grade; Applied Stress 80% SMYS - 90% AYS)
 25Cr Duplex Forged Bar
5
25Cr Duplex Bar Fail
25Cr Duplex Bar Pass

4.5

4
In Situ pH

3.5

2.5
0.1 1 10 100 1000 10000 100000

H2S Partial Pressure - kPa

Shows limited serviceability versus 25Cr OCTG; not as much data.

(110-125 ksi Grade; Applied Stress 80% SMYS - 90% AYS)
 Comparison of Forged Bar to OCTG
• From data obtained from the published
literature:
– There is much less data on bar than tubular products
– Generally, published data show that limits for forged
bar are similar to OCTG (best case scenario).
– However, experience has shown that larger section
sizes can result in reduced SSC/SCC performance.
 Summary
• The performance limits due to SSC and SCC are based on
the interrelationship of the following four parameters:
– PH2S, pH, Cl- concentration, and temperature.
• 13Cr-type steels have limited tolerance to H2S, the H2S
limits of each grade increases with decreasing chloride
(<1%) and higher pH (>4.0).
• 13Cr-2Mo steels were found to be greatly superior to 13Cr
and 13Cr-1Mo steels at higher strength levels (up to 110 ksi
grades)
• Literature shows that OCTG and forged bar can have similar
performance limits. But, experience shows that performance
limits in thick sections depends on processing, and can
decrease for both MSS and DSS steels.
• When evaluating serviceability, need to consider specific
material, composition and processing that dictate
serviceability limits.