New Advanced materials for extreme corrosion (Cr-Ni-Mo)

Ramesh Venkat, Tubacex Group Global Technical Marketing, Heat Exchanger Product Manager

vramesh@tubacex.com

Brief (50 words):

Corrosion is not avoidable but can be controlled either through process improvement or improving the
material of construction. This article introduces the story of evolution of corrosion resistance alloys
from the past... to future developments, highlighting the materials for high chloride and high
temperatures, acidic dew point corrosion and Metal dusting corrosion.

eNews Copy (300 words)

New Advanced materials for extreme corrosion (Cr-Ni-Mo)

Corrosion is not avoidable but can be controlled either through process improvement or improving the
material of construction. Corrosion has been a menace to many particularly to industries / companies
related to up, mid and downstream. This was an issue even decades back but over the years the
problem has worsened due to several factors such as plants operating under more aggressive
parameters like temperature, pressure etc with core objective of improving performance and efficiency
of plants. The economics and geo political reasons has played a vital role to trying to find a cheaper /
alternative feedstock (crude oil for refinery or some chemicals for petrochemical plant) which led to
possibility of higher corrosion rates in original materials of construction in these plants.

Suppliers of metals and materials for these plants started focussing on developing new materials with
higher corrosion resistance due to needs arising out of above mentioned scenario. In context of
stainless steels, addition or reduction of % of certain alloying elements in steel led to development of
various steel grades and families with varying amount of corrosion resistance based on certain
conditions. These families can be classified in ways such as carbon steel, alloy steels, austenitic
steels, duplex steel, super austenite’s, High nickel alloyed steels which could be further classified into
Ni-Cr, Ni-Cr-Mo etc. This article introduces the story of evolution of corrosion resistance alloys from
the past... to the future.

Article:

Corrosion is not avoidable but can be controlled either through process improvement or improving the
material of construction. Corrosion has been a menace to many particularly to industries / companies
related to up, mid and downstream. This was an issue even decades back but over the years the
problem has worsened due to several factors such as plants operating under more aggressive
parameters like temperature, pressure etc with core objective of improving performance and efficiency
of plants. The economics and geo political reasons has played a vital role to trying to find a cheaper /
alternative feedstock (crude oil for refinery or some chemicals for petrochemical plant) which led to
possibility of higher corrosion rates in original materials of construction in these plants.

Suppliers of metals and materials for these plants started focussing on developing new materials with
higher corrosion resistance due to needs arising out of above mentioned scenario.

In context of stainless steels, addition or reduction of % of certain alloying elements in steel led to
development of various steel grades and families with varying amount of corrosion resistance based
on certain conditions.

These families can be classified in ways such as carbon steel, alloy steels, austenitic steels, duplex
steel, super austenite’s, High nickel alloyed steels which could be further classified into Ni-Cr, Ni-Cr-
Mo etc.

This article introduces the story of evolution of corrosion resistance alloys from the past... to the
future.

Evolution of corrosion resistance steels

The first major evolution of corrosion resistance steels was steel with Min 12% Chromium which was
called stainless steels due to formation passive chrome oxide layer thanks to higher chrome starting
with TP304. The advancements in steel melting such as AOD process led to development of low
carbon grades or L grades such as 304L which was important aspect also for fabrication. Addition of
Molybdenum mainly to improve pitting corrosion resistance led to development of 316L and 317L.
Addition of Niobium or Titanium to form stabilised grades such as 321 and 347 mainly to arrest inter
granular corrosion arising to arrest chrome carbide formation on grain boundaries.

300 Series

300 series of stainless steels were good for general corrosion resistance but not good enough for
more severe corrosion such as pitting, crevice or stress corrosion.
Grade Max
C% Cr% Ni% Mo% Others
TP304L 0.035 18-20 8-12
TP316L 0.035 16-18 10-14 2-3
TP317L 0.035 18-20 11-15 3-4
TP316Ti 0.08 16-18 10-14 2-3 Ti, N
TP321 0.08 17-19 9-12 Ti
TP347 0.08 17-20 9-13 Nb
Table 1: commonly used standard austenitic stainless steels.

Duplex Grades

Duplex grades which have mix of austenitic and ferritic phases and with inclusion of Nitrogen as
alloying element led to materials with good to very good resistance to pitting and crevice corrosion.
Also having good resistance to Chloride and Sulphide stress corrosion cracking. Lean duplex, a
version with low Molybdenum also has good caustic stress corrosion resistance. The PREN number
mainly acts as thumb rule to decide the kind of duplex steel to be used. Due to limits on temperatures
within which duplex steels could be used was major obstacle to expand the use of duplex steels. This
was mainly suitable for low temperature wet corrosion. Also, the max limit to which one can add
molybdenum and nitrogen to duplex steels kind of limits the development of superior duplex steels
which must maintain the fine balance between austenitic and ferritic phases. Also, important to note
that high strength makes duplex grades also suitable for applications involving erosion corrosion.
Grade Max
UNS C% Cr % Ni % Mo% N%
S32101 0.04 21-22 1.35- 1.70 0.10-0.80 0.20-0.25
S32304 0.03 21.5-24.5 3- 5.50 0.05-0.60 0.50-0.20
 S32205 0.03 21-23 4.50- 6.50 2.50-3.50 0.80-0.20
S32750 0.03 24-26 6- 8 3- 5 0.24-0.32
S32906 0.03 28-30 5.80 - 7.80 1.5-2.60 0.30-0.40
Table 2: commonly used duplex stainless steels

Super Austenitic steels

Super Austenitic steels were another development airing out of standard austenitic steels which may
have higher % of Molybdenum, Higher Nickel and in some cases additional alloying elements such as
nitrogen, copper etc which make these alloys also suitable for use in acidic conditions part from
having much better pitting, crevice and general corrosion resistance compared to standard austenitic
steels. These again have limitations with regards to process involving acids & salts at high
concentration, high temperature. They basically fill the gap between standard austenite’s and high
nickel alloyed grades.
Grade Max
C% Cr% Ni% Mo% Cu% N%
N 08904 0.02 19-23 23-28 4-5 1-2
S 31254 0.02 19.5-20.5 17.5-18.5 6-6.50 0.5-1 0.18-0.22
N 08925 0.02 19-21 24-26 6-7 0.8-1.50 0.10-0.20
N 08926 0.02 19-21 24-26 6-7 0.5-1.50 0.15-0.25
Table 3: commonly used super austenitic stainless steels.

Nickel rich stainless steels

For extremely challenging environments involving chlorides, sulphides, acids etc where standard
austenitic, super austenitic or duplex steels have limitations several Nickel rich steels were developed
which together with higher chromium sometimes or in combination with several other alloying
elements such as copper, Aluminium, Silicon, Niobium, Titanium etc would give better corrosion
resistance behaviour. These could be further classified into Pure Nickel alloys such as N02200 and
N02201, Nickel Chromium alloys (Ni % is much higher than Chromium), Nickel chrome molybdenum
alloys which have substantially high Mo % to be able to give a strong passive layer, Nickel copper
alloys where copper helps mainly in resistance to acidic solutions, Nickel Molybdenum alloys etc.
Some of the Nickel rich steels are suitable for high temperature applications where additional
elements such as Aluminium helps in formation of extra string passive layer of chrome aluminium
oxide.

While development of new alloys continues to find better solutions like for metal dusting corrosion.
The challenge right now is to be able to get a steel which also has better formability and weldability
along with being a good corrosion resistance. This means there is a limit to which alloying elements
can be introduced in steels without compromising on mechanical and physical properties beyond a
certain limit.

Major areas for new improved alloys

The four major areas of applications where search for new improved alloys is still ongoing are:

1) Materials for high chloride and high temperatures such as hot tropical sea waters
2) Materials for acidic dew point corrosion
3) Materials for Metal dusting corrosion.

High chloride and temperatures

Duplex steels have good corrosion resistance to chlorides but have a temperature limitation. Standard
duplex steels have critical pitting temperature of 45 degree centigrade which limits the applications
such as coolers or condensers. Here cooling media inside heat exchanger tubes is generally water
and inlet temperature are ambient temperature. It is important to note that ambient temperature varies
a lot across world. This point is often missing in engineering which lead to failure of duplex steels in
some parts of the world also aggravated by higher chloride % and salts in water. Another factor which
may work against duplex steels is concentrated salts which can cause corrosion at rapid rate. There
was a need to find materials with much higher critical pitting temperatures and which could work over
a wider temperature range than duplex steels.

Some of the austenitic steels with rich alloying elements such as higher % of Nickel along with
chromium were able to work over higher temperature range over duplex but were no better in
resistance to super duplex. Some examples of such grades are Alloy 28 and 6 Moly steels.

Here comes further development of Ni-Cr-Mo steels with some even alloyed with Molybdenum. One
example is Alloy 59 which has Molybdenum % of 15 to 16.5. High Nickle also provides for strength at
higher temperatures. Further development is happening like for example is VDM Alloy 2120 Mo N
which has Molybdenum % of 18.5 to 21 along with being alloyed with Nitrogen apart from High Ni and
Cr. It has pitting resistance equivalent number of 86 (Cr + 3.3 Mo + 30 N).

Acidic dew point corrosion:

Often an issue in condensing vapours where there is a limit set for outlet temperature of tube side.
Example of such application could be over head condensers in crude distillation units where crude
flows inside tube and light hydrocarbons condense on shell side. Under certain conditions for example
hydrochloric acid can condense on to tubes leading to rapid and severe corrosion. The acid is high in
concentration and most metals are not able to withstand the corrosion. VDM Alloy 2120 MoN
discussed above with high PREN and which is also good in strong reducing acids right up to oxidizing
conditions.

However, in extreme cases a ceramic coating on Tube outside can be a good solution. Once such
example could be TUBACOAT which has shown good results under lab conditions and is also being
now tried on field.

Metal Dusting:

VDM Alloy 699XA, an alloy developed by VDM and TUBACEX in partnership, can produce seamless
tubes and pipes. Three key requirements for steels in this application besides resistance to metal
dusting corrosion are creep strength, weldability and workability.