January 2018

Nippon Steel & Sumitomo Metal Corporation

018F-No7519 AMAGASAKI WORKS

New Metallurgy : Anti-PTASCC Solutions for all petroleum refineries

・ Background
It is known that the conventional stainless steels such as Type 316L, Type 317L, Type 321(H) and Type 347(H)
have higher risk to occur PTASCC (PolyThionic Acid Stress Corrosion 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 SP0170-2012 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 is a source of
Polythionic acid
・Dry air to prevent from liquid water formation
(2) For minimizing sensitization of stainless steel
・Usage of stabilized stainless steel (Type 321, Type 347 etc)
・Stabilization heat treatment after welding (around 900 deg. C for 4 hrs)
Fig. 1 Example of PTASCC
(3) For reduction of residual stresses
・PWHT (Post Weld Heat Treatment)
As new PTASCC mitigation method to save cost, NSSMC proposes AP(Anti-PTASCC) series austenitic stainless
steels as New Metallurgy to PTASCC solution for all petroleum refineries. Table 1 shows the summary of candidate
AP series stainless steels developed by NSSMC. The remarkable characteristic of AP series austenitic stainless
steels 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 Heat
Affected Zone during welding.

Table 1 Target application and properties of AP series austenitic stainless steels.

Conventional Candidate PTASCC NAC Target material of
Application
Stainless AP series steel resistance resistance mechanical property
TM
CDU (Crude Distillation Unit) Type 316L NSSMC
Good Good Type 317L
VDU (Vacuum Distillation Unit) Type 317L 317AP
Hydrotreater Type 321(H)
347AP Good － Type 347
Hydrocracker Type 347(H)
Type 347
Delayed Coker Type 347H 347AP Good － (Lower creep strength
than Type 347H)

In addition to Seamless tubes and pipes with wide available size range, NSSMC can supply the assembly products
of AP series stainless steels such as return bends, flange etc for application in actual plants.

© 2018 NIPPON STEEL & SUMITOMO METAL CORPORATION All Rights Reserved.
 January 2018
Nippon Steel & Sumitomo Metal Corporation
018F-No7519 AMAGASAKI WORKS
・ 347AP
Fig. 2 shows the schematic illustration of relationship between TP347LN and 347AP regarding chemical
composition range. As reported S. A. Bradley and M. W. Mucek of UPO LLC2, 347AP is the proprietary version of
Type 347LN with both fine tuning of chemical compositions such as low extra C content by application of
NSSMC’s sophisticated refining process and strict control of microstructure to achieve further improvement of
sensitization resistance.
Composition range of Type 347LN

347AP

Fig. 2 Relationship of composition range between Type 347LN and 347AP

Fig. 3 shows the PTASCC test results of 347AP welded joint using the matching welding consumable of 347AP
and Type 321 welded joint without PWHT in accordance with ASTM G35 U-bend test3. Although Type 321 shows
higher PTA-SCC susceptibility after short-term aging for 100 hrs, 347AP has no PTASCC even after long-term
aging at 565 deg. C for 10,000 hrs. Fig. 4 shows the longitudinal varestraint test results to evaluate weld cracking
susceptibility. The weld cracking susceptibility of 347AP is much lower than that of Type 347 because of lower Nb
content, and 347AP has much better weldability than Type 347(H). In addition, it is also clarified that SRC (Stress
Relaxation Cracking) susceptibility of 347AP is much lower than Type 347H without PWHT by 3-points bending
tests in TNO. Therefore, PWHT is not required for 347AP to prevent both PTASCC and SRC4.

(b) 347AP (a) Type 321

Fig. 3 Comparison of PTASCC test results between 347AP and Type 321 welded joints according to ASTM G35.

(a) Schematic illustration of varestraint test (b) Varestraint test result

Fig. 4 Weldability of 347AP by varestraint test.

© 2018 NIPPON STEEL & SUMITOMO METAL CORPORATION All Rights Reserved.
 January 2018
Nippon Steel & Sumitomo Metal Corporation
018F-No7519 AMAGASAKI WORKS
・NSSMCTM 317AP
Recently, in CDU (Crude distillation unit) and VDU (Vacuum distillation unit) using the crude containing higher
TAN (Total Acid Number), the resistance to NAC (Naphthenic Acid Corrosion) is required for materials of these
units as well as PTASCC resistance. NSSMC developed NSSMCTM 317AP with higher Mo content to improve
NAC resistance on the basis of 347AP.
Fig. 6 shows PTASCC test results of NSSMCTM 317AP5. Although Type 317L suffers PTASCC after 10, 000 hrs
aging at 540 deg. C, NSSMCTM 317AP base material and NSSMCTM 317AP welded joint using 625 filler show
excellent PTASCC resistance even after long term aging at high temperatures because of extra low Carbon content
and higher Nb/C ratio. Fig. 7 shows NAC test results of NSSMCTM 317AP. NAC resistance of NSSMCTM 317AP is
even or better to that of Type 317L because of higher Mo content compared with 347AP.

Test Immersion Temperature

pH
Solution Time (h) (deg. C)

1% K2S4O6 2.0 100 20 Item SCC No SCC

900 NSSMCTM 317AP ● ○
850 Type 317L ▲ △
NSSMCTM 317AP weld using 625 filler ■ □
800 NSSMCTM 317AP weld using 317 filler ◆ ◇
750
Temperature (℃)

700
650
600
550
500
450
400
0 .1
0.1 0.3 1 3 10
10 30 100 300 11000
100 ,000 3,000 10000
10,000 30,000 100,000
100000
Ti me (h)
Fig. 6 PTASCC test results of NSSMCTM 317AP by alternative method of ASTM G356.

Crude oil Test Pressure relief Wall shear stress

Temperature TAN
fraction duration valve setting by impeller
Process oil + 350℃ 24h. 125 psig 6mg
350 ℃ 135Pa
Cyclohexylacetic acid (662F) X 2 times (N2 purge) KOH/g
25
rate(mm/year)
(mm/y)

20

15
Corrosionrate

10
Corrosion

0
NSSMCTM 317AP NSSMCTM 317AP Type 317L 9Cr
317AP 317AP welded
welded joint with 317L 9Cr
ERNiCrMo-3 (625)
using 625 filler

Fig. 7 NAC test results of NSSMCTM 317AP.

© 2018 NIPPON STEEL & SUMITOMO METAL CORPORATION All Rights Reserved.
 January 2018
Nippon Steel & Sumitomo Metal Corporation
018F-No7519 AMAGASAKI WORKS
・ Benefit
Applying AP series austenitic stainless steels is beneficial to save fabrication and turnaround operation costs.
For benefit of fabrication, PWHT and thermal stabilization heat treatment heating up to 1650ºF (900°C) for
four hours are not required for 347AP. Thus, 347AP can make fabrication duration shorter and fabrication cost
lower compared with conventional austenitic stainless steels such as Type 347, Type 321, Type 316L and Type
317L. 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. Therefore, the loss of
gross margin and maintenance cost for neutralization are saved.

・ Service Experience
347AP has been used for heater tubes of approximately 19 heaters in Japanese refineries since the
mid-1990’s. Thus, only 347AP has operation experience over 20 years without PWHT including thermal
stabilization treatment and neutralization in commercial plants. Some recent applications of 347AP have been
undertaken in North America.
On the other hand, after NSSMCTM 317AP was commercialized in 2016, two applications of NSSMCTM
317AP to CDU/VDU has been determined by North America’s refineries.

・ Contanct
IF ANY QUESTIONS TO THIS DISCRIPTION, PLEASE CONTACT TO FOLLOWING PERSON.
Toshihide ONO, HOUSTON OFFICE IN NIPPON STEEL & SUMITOMO METAL USA
e-mail : ono.5zs.toshihide@us.nssmc.com

・ 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. Bradley, S.A., M.W. Mucek, H. Anada, and T. Osuki, “Alloy Resistance to Polythionic Acid Stress
Corrosion Cracking for Hydroprocessing Applications”, Materials and Design, Vol 110, 296, 2016.

3. ASTM G35-98 (Reapproved 2015) “Standard Practice for Determining the Susceptibility of Stainless
Steels and Related Nickel-Chromium-Iron Alloys to Stress-Corrosion Cracking in Polythionic Acids,”
(West Conshohocken, PA: ASTM)

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

5. M. Seto, M. Sagara, T. Osuki and T. Ono : Corrosion 2017 Conference & Expo, C2017-9057, (New
Orleans, NACE, 2017).

6. 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).

© 2018 NIPPON STEEL & SUMITOMO METAL CORPORATION All Rights Reserved.