019F-No.8406 Rev.

0 Confidential
AMAGASAKI WORKS
Sep, 24, 2019

New Metallurgy: Anti-PTASCC Solutions for High Temperature Application

1. Background
It is known that the conventional stainless steels such as Type 316L, Type 317L, Type 321(H) and
Type 347(H) have susceptibility to PTASCC (PolyThionic Acid Stress Corrosion Cracking) and SRC
(Stress Relaxation Cracking) in Hydrotreating units, Hydrocracking units and Delayed Coker units
etc. of petroleum refineries. PTASCC occurs by the combination of 3 factors; formation of
Polythionic acid due to exposure the metal sulfide scale to oxygen and water in the aqueous phase,
residual tensile stress and sensitized microstructure having the Cr carbide precipitation at the grain
boundary by welding. Therefore, NACE SP0170-2018 provides the following mitigation methods to
protect conventional stainless steels from PTASCC1).

(1) For mitigation of formation of Polythionic acid

・Alkaline washing of equipment surfaces to neutralize Polythionic acid
・Nitrogen purging to exclude oxygen and water which are component elements of Polythionic acid

(2) For minimizing sensitization of stainless steel

・Apply stabilized stainless steel (Type 321, Type 347 etc)
・Stabilization heat treatment after welding (around 900 deg. C for 4 hours)

(3) For reduction of residual stresses

・PWHT (Post Weld Heat Treatment)

NIPPON STEEL proposes AP (Anti-PTASCC) austenitic stainless steels as New Metallurgy to

PTASCC solution for all petroleum refineries. Table 1 shows the summary of AP stainless steels
developed by NIPPON STEEL. The remarkable characteristic of AP material is excellent PTASCC
resistance without PWHT and/or thermal stabilization. These properties are achieved by extra low C
up to 0.02% and higher Nb/C ratio over 15 to prevent M23C6 precipitation at grain boundary of HAZ
(Heat Affected Zone) during welding.

Table 1 Target Application and Properties of AP Austenitic Stainless Steels

Target Material of
Conventional PTASCC SRC NAC
Application AP Material Mechanical
Stainless Resistance Resistance Resistance
Property
CDU* Type 316L
NEXAGETM 317AP 2) Good - Good Type 317L
VDU* Type 317L
Hydrotreater Type 321(H)
347AP 2) Good Good - Type 347
Hydrocracker Type 347(H)
Developed material 3)
Delayed
Type 347H (tentative name: Good Good - Type 347H
Coker
Advanced 347AP)
*CDU; Crude Distillation Unit, VDU; Vacuum Distillation Unit

・Technical information contained in this document describes only some representative properties or performance of products and does not necessarily mean
assured values.
Notes Further, as such information may be subject to change without notice, you are requested to ask the latest information when you order a product.
・We do not take the responsibility for any damage caused by erroneous or inappropriate use of information in this document.
・No part of this document can be reproduced or copied without permission.

1 © 2019 NIPPON STEEL CORPORATION All Rights Reserved.

 019F-No.8406 Rev.0 Confidential
AMAGASAKI WORKS
Sep, 24, 2019

2. Characteristics of Developed material

2-1. Chemical Composition
Table 2 shows the typical composition range of developed material, 347AP, Type 347LN (UNS No.
S34751) and Type 347H (UNS No. S34709).
347AP is the distinctive version of Type 347LN to improve PTASCC resistance by fine tuning of the
chemical composition within the range of Type 347LN. The characteristics of 347AP is extra low C
content and Nb addition under higher Nb/C ratio to prevent the sensitization by precipitation of
M23C6 carbide at grain boundary and higher N content to improve the tensile and creep properties at
elevated temperature.
In order to achieve much higher creep strength, Cu, Mo and B were added to 347AP and fine
chemical tuning was conducted.
As a result, developed material (Low C-18Cr-11Ni-3Cu-Mo-Nb-B-N) was developed.

Table 2 Chemical composition (mass%)

Item C Si Mn Cr Ni N Nb Cu Mo B
Developed 0.005 Max. Max. 17.0 10.0 0.06 2.50 0.20 0.001
0.20-0.50
material -0.02 0.60 2.00 -19.0 -13.0 -0.12 -3.50 -1.20 -0.005
347AP 0.007 0.36 1.48 17.2 10. 0.08 0.31
Type 347LN 0.005 Max. Max. 17.0 9.0 0.06 0.20-0.50
(S34751) -0.020 1.00 2.00 -19.0 -13.0 -0.10 (Min. 15 x C)

Type 347H 0.04 Max. Max. 17.0 9.0 Min.

-
(S34709) -0.10 0.75 2.00 -19.0 -13.0 10 x C

2-2. Sensitization Resistance

Figure 1 shows microstructure of developed material and Type347H aged at 600 °C for 1,000 hours
(the result of ASTM A262 Practice A)
Dual structures were observed in developed material, on the other hand, Type 347H showed ditch
structure due to the precipitation of M23C6 at grain boundaries. These results suggest that
developed material has higher resistance to sensitization than Type 347H.

Figure 2 shows the EPR (Electrochemical Potentiokinetic Reactivation) test results. Closed symbols
show Degree of Sensitization (DOS, Rm; Measured value of reactivation ratio) exceeded 10%.
DOS of 347H was over 10% after 30-hour aging at 650 °C and 1,000-hour aging at 600 °C. On the
other hand, DOS of developed material was under 10% even after 10,000-hour aging.

(1) developed material (2) Type 347H

Figure 1 Microstructure after 1,000-hour aging at 600 °C (ASTM A262 Practice A)

・Technical information contained in this document describes only some representative properties or performance of products and does not necessarily mean
assured values.
Notes Further, as such information may be subject to change without notice, you are requested to ask the latest information when you order a product.
・We do not take the responsibility for any damage caused by erroneous or inappropriate use of information in this document.
・No part of this document can be reproduced or copied without permission.

2 © 2019 NIPPON STEEL CORPORATION All Rights Reserved.

 019F-No.8406 Rev.0 Confidential
AMAGASAKI WORKS
Sep, 24, 2019

850
(1,562 F)
800
(1,472 F)

750
[Test Condition] (1,382 F)

Temperature ℃
Method Refer to ASTM G108
700
Solution 0.5 mol/l H2SO4 + (1,292 F)
0.01 mol/l KSCN
650
Temp. 30 °C (1,202 F)
600
(1,112 F)
Item Rm<10% Rm≧10%
Developed material ○ ● 550
(1,022 F)
347H △ ▲
500
(932 F) 10 100 1000 10000 100000
Time /h

Figure 2 EPR Test Results

2-3. PTASCC Resistance

PTASCC test results are shown in Figure 3. 347H suffered from PTASCC after 300-hour aging at
600 °C. However, developed material showed good PTASCC resistance even after long-term aging
up to 10,000 hours in the temperature range from 600 to 700 °C

800
(1,472F) Developed material No SCC
347H No SCC
[Test Condition] 750
347H SCC
Tempetature / oC

Method Hosoya, Yamamoto (1,382F)

4)
and Kagawa’s method
Solution 1% K2S4O6, pH=2.0 700
(1,292F)
(acidified by H2SO4)
Temp. Room Temp. 650
Duration 100 hours (1,202F)

600
(1,112F)

550
(1,022F)
100 1000 10000
Aging Time / h

Figure 3 PTASCC Test Results

2-4. Creep Property

The maximum allowable tensile stress of developed material was estimated shown in Figure 4 in
comparison with that of the conventional materials. developed material showed more than 30%
higher maximum allowable tensile stress at the temperatures where creep properties control the
stresses compared to that of ASME SA213 Type 347H and ASME Code Case 2196-4.

Higher allowable tensile stress is achieved by fine precipitates of copper rich phase and Z-phase
(NbCrN) as shown in Figure 5.

・Technical information contained in this document describes only some representative properties or performance of products and does not necessarily mean
assured values.
Notes Further, as such information may be subject to change without notice, you are requested to ask the latest information when you order a product.
・We do not take the responsibility for any damage caused by erroneous or inappropriate use of information in this document.
・No part of this document can be reproduced or copied without permission.

3 © 2019 NIPPON STEEL CORPORATION All Rights Reserved.

 019F-No.8406 Rev.0 Confidential
AMAGASAKI WORKS
Sep, 24, 2019

200
Developed Material

Maximum Allowable Stress / MPa

(tentative)
CC2196-4
TP347H
150 S30432(SUPER304H)

100

50

0
0 100 500 600 700 800
(212 F) (1,022F) (1,122F) (1,292F) (1,472F)
Temperature / ℃

Figure 4 Comparison of Maximum Allowable Tensile Stress

Bright Field Electron beam diffraction image

Identification results

Z phase

Figure 5 TEM image of developed material (ruptured specimen at 700 °C/1,292 °F for 2,363 hours)

2-5. SRC Resistance and Weldability

developed material also has better SRC resistance and weldability than type 347H.
Matching filler of developed material has already been developed.

2-6. Standardization
Now developed material is under registration to ASTM and ASME.

・Technical information contained in this document describes only some representative properties or performance of products and does not necessarily mean
assured values.
Notes Further, as such information may be subject to change without notice, you are requested to ask the latest information when you order a product.
・We do not take the responsibility for any damage caused by erroneous or inappropriate use of information in this document.
・No part of this document can be reproduced or copied without permission.

4 © 2019 NIPPON STEEL CORPORATION All Rights Reserved.

 019F-No.8406 Rev.0 Confidential
AMAGASAKI WORKS
Sep, 24, 2019

3. Benefit
Applying AP austenitic stainless steels is beneficial to save fabrication and turnaround operation
costs.
For benefit of fabrication, PWHT and thermal stabilization heat treatment like 1650ºF (900°C) for
four hours is not required for AP materials.
Also, for benefit of turnaround operation, conventional mitigation method for PTASCC such as
neutralization using soda ash and nitrogen sealing can be eliminated during turnaround.
Regarding developed material, wall thickness can be reduced because of higher allowable tensile
stress than Type 347H.
Thus, AP materials can make big benefit for fabrication and operation.

4. Contact
IF ANY QUESTIONS TO THIS DISCRIPTION, PLEASE CONTACT TO FOLLOWING PERSON.
Masaki Ueyama, HOUSTON OFFICE IN NIPPON STEEL NORTH AMERICA
e-mail: ueyama.38y.masaki@us.nipponsteel.com

5. References
1) NACE SP0170, “Protection of Austenitic Stainless Steels and Other Austenitic Alloys from
Polythionic Acid Stress Corrosion Cracking During a Shutdown of Refinery Equipment”, NACE
International, Houston, TX.

2) T. Osuki, M. Seto, H. Okada, M. Sagara, S. Matsumoto and T. Ono : ASME PVP Conference
2017, PVP2017-65536 Proceedings.

3) Y. Suzuki, S. Aota, E. Dan, M. Ueyama, T. Osuki, T. Ono, N. Otaki and H. Okada : ASME PVP
Conference 2019, PVP2019-93187 Proceedings.

4) K. Hosoya etc, “IGSCC Susceptibility of Austenitic Stainless Steels in Acidified K2S4O6 Solution
– New Polythionic Acid SCC Test Solution-”, Boshoku Gijutsu, 34, 568-572 (1985).

// End of this document

・Technical information contained in this document describes only some representative properties or performance of products and does not necessarily mean
assured values.
Notes Further, as such information may be subject to change without notice, you are requested to ask the latest information when you order a product.
・We do not take the responsibility for any damage caused by erroneous or inappropriate use of information in this document.
・No part of this document can be reproduced or copied without permission.

5 © 2019 NIPPON STEEL CORPORATION All Rights Reserved.