MPWT19-14327

Sanicro 35, a New Super Austenitic Stainless Steel for

Demanding Wet Corrosive Applications

Jonas Höwing
Sandvik Materials Technology
Torggatan 112
SE-431 35, Mölndal
Sweden

ABSTRACT

A new super austenitic stainless steel has been developed for use in highly corrosive wet environments.
The new alloy, Alloy 35Mo, has the general chemical composition 27Cr-35Ni-6.5Mo-0.28N and PRE>52,
suggesting high resistance towards chloride induced localized corrosion. The Alloy 35Mo has excellent
corrosion resistance in chloride bearing environments, and has also shown surprising mechanical
properties with a combination of high yield strength, excellent ductility and low hardness. The main
applications for the new grade will initially be heat exchanger tubing, small dimension piping and hydraulic
& instrumentation tubing. Target industries are refineries, chemical and petrochemical plants and off-
shore installations. This paper discusses Alloy35Mo, its properties, and a comparison with existing,
competing grades.

Key words: Stainless, PRE, pitting corrosion, crevice corrosion, ductility

INTRODUCTION

Stainless steel comes in a vast variety of grades, the most common being ferritic, austenitic and duplex.
While all three types of stainless steel have their advantages and drawbacks, for wet corrosive
applications the most commonly used grades are the austenitic 304/304L or 316/316L. While these
grades do solve several corrosion, issues seen with carbon or low alloyed steel grades, they have their
limitations in for example strong acids and chloride containing environments at higher temperatures. In
such cases, higher alloyed grades such as 904L, super duplex 2507 or 6Mo super austenitics need to
be considered. In the extreme cases when even these grades are not enough, there exist a limited
number of high alloyed stainless-steel grades or nickel base alloys. Some of the existing high alloyed
stainless-steel grades show poor structure stability though, making it difficult to produce thicker sections
and making fabrication an issue. Therefore, it concluded that a new, high alloyed, austenitic stainless
steel with enhanced structure stability was needed.

With the above in mind, a new grade (Alloy 35Mo), was developed. The aim when developing Alloy 35
was that it should have good corrosion resistance in chloride bearing environments, better than 6Mo
super austenitic grades, while at the same time exhibit a high structure stability, i.e. not being prone to
formation of intermetallic phases. The general chemical composition of Alloy 35Mo is 27Cr-35Ni-6.5Mo-
0.28N and it has a PRE > 52, where PRE is calculated in accordance with NACE MR0175/ISO 15156-31
using the formula PRE = %Cr + 3.3x%Mo + 16x%N.

In this paper, the mechanical and corrosion properties of Alloy 35Mo are discussed and compared to
similar alloys on the market.

EXPERIMENTAL PROCEDURE

Production of material

Seamless heat exchanger tubes were produced from a full-scale heat of Alloy 35Mo with dimensions
25.4x2.11 mm and 19.05x1.24 mm. The heat had a chemical composition according to Table 1 and was
produced using an electric arc furnace and argon oxygen decarburization (AOD) refining. The tubes were
produced by hot extrusion and cold pilgering followed by solution annealing (bright annealing) and
quenching.

For immersion corrosion testing experiments, a strip with 4 mm thickness was produced from an
experimental heat with chemical composition according to Table 1. A high frequency furnace was used
for the experimental heat and the material was forged, hot rolled, cold rolled, solution annealed and
quenched.

Table 1. Chemical composition of Alloy 35 Mo test material

C Si Mn P S Cr Ni Mo Cu N PRE*
Tube ≤0.020 0.18 0.77 ≤0.030 ≤0.010 26.9 34.8 6.3 0.20 0.29 52.3
Strip ≤0.020 0.22 1.01 ≤0.030 ≤0.010 27.2 34.9 6.4 0.19 0.29 53.0

Mechanical testing and microstructure

Tensile testing was performed according to ASTM A3702 and flattening test according to ASTM A10163.
The microstructure was studied using light optical microscopy (LOM) and the grain size was measured
according to ASTM E1124.

Corrosion testing

Pitting and crevice corrosion testing

Critical pitting temperature (CPT) testing was performed according to a modified ASTM G150 (ASTM
2018) method using 3 M MgCl2 as test solution instead of 1 M NaCl. This increases the chloride
concentration of the test solution as well as slightly lowering the pH, making it more aggressive and
enabling ranking of pitting corrosion for stainless steels with PRE>50 (Iverson et al. 2018). A starting
temperature of 20°C with a temperature increase of 1°C/min was used with an applied potential of +700
mVSCE. Duplicate specimens were exposed. The test procedure has been described by Iversen et al
(2018) .

CPT was also determined using ASTM G48 method E (ASTM 2015). In this test the sample is immersed
in an acidified 6% FeCl3 solution for 24 h. If no corrosion is observed after the test period, the temperature
is increased by 5°C and the test is repeated.
Critical crevice corrosion (CCT) testing was performed according to ASTM G150 using the standard 1 M
NaCl test solution. The crevice assembly described in ISO 18070 (2015) was used and the crevice
formers were made of poly vinylidene fluoride (PVDF). The titanium screws used to apply torque were
insulated from the sample using PTFE-tape. A torque of 1.58 Nm was applied with torque wrenches, pre-
set and calibrated to the specified values.

RESULTS

Below follow the results from the individual tests done on Alloy 35Mo. A comparison between these
results and the performance of competing alloys are given under Discussions

Mechanical properties and microstructure

In Figure 1, the microstructure of a 19.05x1.24 mm heat exchanger tube of Alloy 35Mo is shown. A fully
austenitic microstructure free from intermetallic phases and precipitates can be observed. The grain size
according to ASTM E112 was 7.5 for the 19.05x1.24 mm tube and 5.5 for the 25.4x2.11 mm tube.

Figure 1. Microstructure of 19.05x1.24 mm tube in Alloy 35Mo. The structure is fully austenitic.

The mechanical properties of the heat exchanger tubes in Alloy 35Mo show a high yield strength in
combination with very high ductility and low hardness (Table 2). In the flattening test no cracking was
observed which is consistent with the excellent ductility of the material.

Table 2. Mechanical properties for the Alloy 35Mo tubes

Dimensions / mm Rp0.2 / MPa Rm / MPa A/% Hardness / HRB
19.05x1.24 473 870 63 90
25.4x2.11 516 872 51 93

Corrosion testing

Pitting and crevice corrosion testing

Pitting corrosion testing according to ASTM G150 in 3 M MgCl2 test solution gave a CPT = 110°C which
is very high. For the ASTM G48 testing, no pitting was observed at up to 95°C (the ASTM G 48 is only
approved for T≤ 85°C). Crevice corrosion testing according to ASMT G150 using 1 M NaCl test
solution gave a CCT > 100°C which is extremely high. The results are summarized in Fig. 2.

Figure 2: Test results for pitting and crevice corrosion testing of Alloy35Mo.

DISCUSSIONS

The testing of Alloy 35Mo has shown that the new grade has very good performance in pitting and crevice
corrosion testing. Testing has illustrated that the mechanical properties of the grade are very good,
especially the ductility being very high for such a high strength stainless steel. Below is a comparison
between Alloy 35Mo and other similar grades on the market.

Mechanical properties

In Table 3, a comparison of the mechanical properties of Alloy 35Mo and some competing grades is
made. As can be seen, the mechanical properties of Alloy 35Mo are superior to that of the other grades,
with both higher strength and better ductility. This will lead to decisive design advantages regardless of
which norm is used for a construction, ASME or the European pressure equipment directive (PED).

Table 3. Mechanical properties for Alloy 35Mo and competing alloys.

Grade UNS Rp0.2 / MPa Rm / MPa A/%
Alloy G30 N06030 241 586 30
Alloy G35 N06035 241 586 30
Alloy 31 N08031 280 650 40
®*
Alloy 31 Plus N08034 280 650-850 40
NEXAGE™ 845** N06845 276 690 30
Alloy35Mo N/A*** ≥425*** ≥850*** ≥45***
*
Alloy 31 Plus is a registered trade mark by VDM metals.
**
NEXAGE is a registered trademark by the Nippon Steel Corporation.
***
All values are preliminary awaiting standardisation.
Corrosion properties

The corrosion properties of Alloy 35Mo in chloride containing environments is extremely good. There are
several other high alloyed stainless-steel grades and nickel base alloys that do not pit in ASTM G48
method C or E though, so this is not a good method to compare the performance of this grade.

For the modified version of ASTM G150 used for the electrochemical pitting corrosion test there are some
results to compare with from the work of Delblanc et.al6. The comparison is shown graphically in Fig. 3.
As can be seen, Alloy 35Mo shows extremely good results compared to super duplex UNS S32750 and
super austenitic grades such as S31254 and S34565. Interesting to note is also that S32654 only shows
marginally better pitting corrosion resistance than Alloy 35Mo, despite having PRE=57 as compared to
Alloy 35Mo with PRE=52.

Figure 3: CPT from pitting corrosion testing according to modified ASTM G150 using
3 M MgCl2 test solution and respective alloys PRE-value.

Sour service

Alloy 35Mo is a Ni-rich alloy that fulfils the requirements on chemical composition to be a Type 4a material
in NACE MR0175/ISO 15156-3. A Type 4a material is listed in NACE MR0175 / ISO 15156-3 without any
environmental restrictions, such as partial pressure H2S in production environments.

Fabrication

Several welding trials have been performed on the test material manufactured. It has been found that the
structure stability of Alloy 35Mo is very good and that the grade is not prone to formation of intermetallic
phases. The recommended filler metal for the grade is Alloy 59 and the shielding gas should contain 2-
3% nitrogen to avoid nitrogen loss of the base metal. Pure argon can also be used as shielding gas if
needed.

Due to its high ductility, cracking when bending or forming Alloy 35 Mo is very unlikely. The high yield
strength will mean a higher force is needed when forming the grade compared to forming for example
316L, 904L or Alloy 825. The forces needed will be similar to that of Alloy 625.
 CONCLUSIONS

A new super austenitic stainless-steel alloy with the work name Alloy 35Mo has been developed. The
new alloy exhibits excellent resistance towards localized corrosion such as pitting and crevice corrosion
in laboratory testing. The mechanical properties are also excellent with a combination of high yield
strength, excellent ductility and low hardness. This gives Alloy 35Mo several design advantages
compared to competing grades such as Alloy 35, Alloy 31 Plus and S32654.

The application areas for Alloy 35Mo will initially be heat exchanger tubes for demanding environments,
such as seawater coolers and high chloride, high temperature processes. Hydraulic and instrumentation
tubing where off-shore installations and areas with high demand on H2S resistance is required are target
applications is also going to be a compelling application of this technology.

REFERENCES

1. NACE MR0175/ISO 15156-3 (2015), “Petroleum, Petrochemical, and Natural Gas Industries -
Materials for Use in H2S-Containing Environments in Oil and Gas Production - Part 3: Cracking-
Resistant CRAs (Corrosion-Resistant Alloys) and Other Alloys” (Houston, TX: NACE)

2. ASTM A 370-17 (2017), “Test Methods and Definitions for Mechanical Testing of Steel Products”
(West Conshohocken, PA: ASTM).

3. ASTM A1016/1016M-18 (2018), “Specification for General Requirements for Ferritic Alloy Steel,
Austenitic Alloy Steel, and Stainless-Steel Tubes” (West Conshohocken, PA: ASTM).

4. ASTM E 112-12 (2013), “Test Methods for Determine Average Grain Size” (West Conshohocken,
PA: ASTM).

5. ASTM G150-18 (2018), “Test Method for Electrochemical Critical Pitting Temperature Testing of
Stainless Steels and Related Alloys” (West Conshohocken, PA: ASTM).

6. A. Delblanc, K. Lund, A. Iversen, “Comparison of critical pitting temperatures of stainless steel in

different salt solutions,” CORROSION 2018, paper no. 51318-10846 (Houston, TX: NACE, 2018).

7. ASTM G 48-11 (2015), “Pitting and Crevice Corrosion Resistance of Stainless Steels and Related
Alloys by Use of Ferric Chloride Solution” (West Conshohocken, PA: ASTM” (West Conshohocken, PA:
ASTM).

8. ISO 18070 (1st ed., 2015), “Corrosion of Metals and Alloys – Crevice Corrosion Formers with Disc
Springs for Flat Specimens or Tubes Made from Stainless Steel”, (Geneva, Switzerland: ISO).