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Corrosion Resistant Cast Steels

for Process Industry Pumps


By Arto Riihimäki
Chief Metallurgist, Sulzer Pumps Finland Oy

Abstract

New duplex stainless cast steels and austenitic high The paper deals briefly with the foundry process
molybdenum steels are used in pumps for severe to make high alloy stainless steel pump castings. The
service. The main modern nitrogen alloyed duplex cast AOD-method (AOD= Argon Oxygen Decarburisation) is
steels are presented in the ASTM standard A-890. an important prerequisite for the melting of low carbon,
Grades 3A and 5A are often used as corrosion resis- high chromium and molybdenum alloyed nitrogen steels.
tant cast steel for pumps. From high molybdenum The properties of these steels are included. The main
austenitic stainless steels there are presented two topic is the corrosion resistance of the above men-
grades in ASTM A-744 (-00) standard i.e. CN-3MN and tioned pump materials in severe service. Results of
CK-3MCuN. The latest and most corrosion resistant short time erosion and corrosion tests are discussed
stainless steel grade is AVESTA 654 SMO™. This and compared with the results of plant tests. The new
new stainless steel as pump material for severe ser- high alloyed cast stainless steel (main elements;
vice has improved properties in the hydrometallurgy- Cr~24%, Ni~22%, Mo~7,3% and N~0,5%) has shown
and electro refining processes in the metal industry improved corrosion and erosion properties as process
compared to duplex stainless steels. The accepted EN pump material in several severe service applications
10283 (-98) standard for corrosion resistant cast steels e.g. in the metal industry.
is mentioned and some inaccurate correspondence
between European and American steel grades are
given.
Introduction Some cast stainless steels EN10283 / ASTM
EN10283 ASTM
The process industries need corrosion resistant pumps. Designation Number Designation Standard
Martensitic grades
The hydraulic parts of pumps, such as casings and GX4CrNi13–4 1.4317 CA–6NM A 743
impellers, are manufactured by casting. Alongside com- GX5CrNiCu16–4 1.4525 CB7Cu–2 A 747
Austenitic grades
monly used high alloy steels, new austenitic and auste- GX5CrNiMo19–11–2 1.4408 CF–8M A 743
nitic-ferritic cast steels have been available during the GX5CrNiMo19–11–3 1.4412 CG–8M A 743
Fully austenitic grades
past few years. When attempting to reach better corro- GX4NiCrCuMo30–20–4 1.4527 CN–7M A 743
sion resistance, for instance the molybdenum content GX2NiCrMoCuN25–20–6 1.4588 CN–3MN A 743
Austenitic–ferritic grades Alternative designation
of these steels has been increased. The use of nitro-
Grade
gen as an alloying element is also characteristic. The GX2CrNiMoN22–5–3 1.4470 CD3MN 4A A 890
GX2CrNiMoN25–6–3 1.4468 CD6MN 3A A 890
following examines the new high alloy cast steels used
GX2CrNiMoCuN25–6–3–3 1.4517 CD4MCuN 1B A 890
by Sulzer Pumps for demanding process pumps. The GXCrNiMoN26–7–4 1.4469 CE3MN 5A A 890
manufacture of these steels and their corrosion proper- Table 1. Some European and American corrosion resistant
ties are also discussed briefly. cast steels. Exact correspondence between the grades does
not exist.
Cast high alloy steels
Chemical composition
Due to the global nature of the pump market, the Grade Cmax. Cr Ni Mo N / Cu

production of pumps steels has conventionally been ASTM % % % % %


CA-6NM 0.06 11.5-14.0 3.5-4.5 0.40-1.00
based on the grades of the American ASTM standard CB7Cu-2 0.07 14.0-15.5 4.5-5.5 Nb 0.15-0.35 /2.50-3.20
because this standard is generally known within indus- CF-8M 0.08 18.0-21.0 9.0-12.0 2.0-3.0
CG-8M 0.08 18.0-21.0 9.0-13.0 3.0-4.0
try. The European standard EN 10283, which was CD-4MCu
accepted in 1998, presents corrosion resistant steel 1A (1B) 0.04 24.5-26.5 4.75-6.00 1.75-2.25 (0.10-0.25) /2.75-3.25
CN-7M 0.07 19.0-22.0 27.5-30.5 2.0-3.0 /3.0-4.0
grades intended for general applications. In this stan- CN-3MN *) 0.03 20.0-22.0 23.5-25.5 6.0-7.0 0.18-0.26 /0.75max
dard, the steel grades have been classified in four 654 SMO **) 0.03 23.0-25.0 21.0-23.0 7.1-7.5 0.45-0.55 /0.3-0.7
1B 0.04 24.5-26.5 4.75-6.0 1.75-2.25 0.10-0.25 /2.75-3.25
categories: martensitic, austenitic, completely austenit- 3A 0.06 24.0-27.0 4.0-6.0 1.75-2.50 0.15-0.25 /
ic, and austenitic-ferritic or duplex steels. When com- 4A 0.03 21.0-23.5 4.5-6.5 2.5-3.5 0.10-0.30 /1.00max
5A 0.03 24.0-26.0 6.0-8.0 4.0-5.0 0.10-0.30 /
paring the cast steels presented in the European *) CK - 3MCuN = AVESTA 254 SMO: C = 0.025 max, Cr = 19.5 - 20.5, Ni = 17.5 - 19.5
Mo = 6.0 - 7.0, Cu = 0.50 - 1.00, N = 0.180 - 0.240
standard and in the ASTM standard, there are some **) Cast steel not in accordance with ASTM
equivalent and almost equivalent steels.
Table 2. Some corrosion resistant cast steels according to
ASTM standard A890 presents the most recent
ASTM standards. Main elements of the chemical composition.
nitrogen alloyed duplex steels. The completely austen-
The 654 SMO is a trade mark owned by Avesta Polarit, which
itic and very corrosion resistant AVESTA 654 SMO™
has granted Sulzer Pumps Finland Oy a licence to produce
steel is also highly nitrogen alloyed. This patented
the material.
steel is not included in the American or in the European
cast steel standard. This steel has turned out to be a Mechanical properties
good pump material in severe corrosive service such
Grade Tensile Strength Yield Strength Elongation
as in base metal solutions. The good properties are the ASTM Mpa Mpa %
result of high alloying. The contents of the main alloy- CA – 6NM 755 550 15
CB7Cu – 2 1205 1035 5
ing elements are at the following levels: Cr~24%, CF – 8M 485 205 30
Ni~22%, Mo~7.3% and N~0.5%. Tables 2 and 3 show CG – 8M 520 240 25
CD – 4MCu 1A 690 485 16
the chemical compositions and mechanical properties CN – 7M 425 170 35
of high alloyed corrosion resistant cast steels. CN – 3MN 550 260 35
654 SMO *) 600 350 40
The chemical composition of highly alloyed cast 1B 690 485 16
steels differs somewhat from the corresponding wrought 3A 655 450 25
4A 620 415 25
steel grades. CF-8M and CG-8M correspond to wrought 5A 690 515 18
grades AISI 316 and 317. The corresponding low *) Cast steel not in accordance with ASTM

carbon grades are CF-3M and CG-3M, and in wrought Table 3. Some corrosion resistant cast steels according to
grades AISI 316L and 317L. The above cast steels ASTM standards. Mechanical properties. The 654 SMO is a
typically contain ca. 10-20% of delta-ferrite. When the trade mark owned by Avesta Polarit, which has granted
amount of ferrite in the steel grows, it becomes austen- Sulzer Pumps Finland Oy a licence to produce the material.
itic-ferritic or duplex steel. The oldest duplex steels
have been used in pumps for more than 35 years.
Newcomers in this steel group are the nitrogen alloyed
high molybdenum steels. ASTM has had a separate
standard A890 for duplex steels since 1989.
The group of completely austenitic steels has
contained nitrogen alloyed 6 percent molybdenum steels
for quite some time. The newest austenitic cast stain-
less steel is AVESTA 654 SMO™ /1/. The contents of
elements which improve corrosion resistance, such as
chromium, molybdenum and nitrogen, have been in-
creased further in comparison with the CN-3MN steel.
Figures 1 and 2 show the microstructure of grade CF-
Figure 1. Microstructure of the CF-3M austenitic stainless
8M and of the duplex grade 3A after solution heat
steel (x100). CF-3M; C max. =0,03 %, other elements of
treatment at 1,100°C. The structure is balanced to the
chemical composition as in CF-8M. Delta ferrite content 12%.
desired composition on the basis of the Shaeffler
diagram, which shows the impact of elements which
favor ferrite and austenite on the microstructure. ASTM
A800 gives a standard procedure for defining the ferrite
content of cast steel. The ferrite content in duplex
steels is usually in the region of 40-60%. It is a known
fact that the yield strength of steel improves as the
ferrite content increases, as is the case with corrosion
resistant cast steels CF-8M and CG-8M /2/. This fact
has special importance in pump castings with thick
walls. Because of the increased ferrite content, the use
of duplex steels has been restricted to a temperature of
ca. 250°C /3/. For the above reasons, it is necessary to
balance the structure of each steel to the desired
composition. Both the carbon and nitrogen contents
have a great impact on the nickel equivalent in the Figure 2. Microstructure of Grade 3A Duplex Steel
Shaeffler diagram. When a modern metallurgical pro- (x100). Delta ferrite content 50%.
duction method, such as an AOD converter, is used in
melting, the carbon and nitrogen contents in steel can stainless cast steel grades requires an AOD converter or,
be controlled precisely. Thorough mixing of the charge when melted in an induction furnace, a raw material that has
ensures that sampling is representantive, resulting in been pretreated in the AOD converter. There are several
improved control over the desired analysis and steel reasons for this. Highly chromium and molybdenum alloyed
structure. steels must have a low carbon content and an increased
nitrogen content. Both of these can be achieved easily in the
Benefits in the foundry process AOD converter. As to corrosion, a low sulphur content is an
advantage achieved through this method.
For the foundry, the duplex highly alloyed steels are
usually easier to make than the completely austenitic AOD
corrosion resistant grades. The latter have a large
grain size and some sensitivity to cracks during solidifi- The AOD method (AOD = Argon Oxygen Decarburization)
cation. Ferrite in the structure reduces the grain size was originally developed for the treatment of wrought stain-
and has a favorable effect on solidification. The com- less steels. Melting in the AOD method takes place mainly in
pletely austenitic corrosion resistant cast steels (6- an electric arc furnace, from which the liquid metal is trans-
7.5% Mo) require a high temperature during solution ferred to the AOD converter, to the metallurgical unit. The use
heat treatment, ca. 1,200°C. The duplex steels can be of the AOD method permits raw materials for high alloyed
heat treated at lower temperatures, at 1,040°C-1,150°C steels to be selected from the most economical combinations.
depending on the grade. The production of the new The initial carbon content may be several percents. During
decarburization, the partial pressure of carbon monoxide is Pitting and crevice corrosion
reduced by means of argon or nitrogen. This gives a low
carbon content and enables the production of cast grades CF- Pitting and crevice corrosion consist of local forms of
3M and CG-3M conforming to the ASTM A743 standard corrosion that can occur in stainless steels. This form
(maximum carbon content 0.03%). The oxidized chromium is of corrosion can occur in chloride containing solutions,
reduced back to the liquid metal, and desulphurization is such as sea water, bleaching solutions or oxidizing
carried out at the same time. Because of the good mixing of salts e.g. ferric chloride and cupric chloride. Attempts
the liquid metal and slag, the sulphur content of an AOD steel have been made to estimate the pitting and crevice
decreases down to a few thousandths of a percent. The liquid corrosion resistance of steels by calculating the sum of
metal is flushed with argon, which reduces the slag inclusions the most relevant alloying elements /6/. This sum is
to a minimum. Nitrogen alloying of high alloyed cast steels is called PRE (Pitting Resistance Equivalent), and one
easily done in the converter. common formula is shown below.
Using the formula PRE = Cr% + 3.3xMo% +
Corrosion properties 16xN%, PRE values for steels given in Table 4 have
been calculated. In the table, the duplex steels are
The stainless steels treated in the AOD converter have a low favorably placed due to their high chromium content.
sulphur content. Sulphur and MnS sulphides reduce the Nitrogen has a highly positive effect on PRE. AVESTA
pitting potential thus acting as the starting spots for corrosion. 654 SMO™ has clearly the highest calculated PRE
As to pitting corrosion, those high alloy steels which have a figure. When treating the charge with the AOD convert-
few sulphide inclusions are better than the common stainless er, a high nitrogen addition into this steel causes no
cast steels. Resistance against pitting is improved by chromi- problems. The strength and corrosion properties of the
um, molybdenum and nitrogen, among others. discussed duplex steels and completely austenitic cast
Since a low enough carbon content can be ensured by steels make them applicable to several process equip-
the AOD method, there is no risk of sensitizing or intergranu- ment such as pumps.
lar corrosion. Cast steel is not, however, as liable to sensitiz-
ing as wrought steel with the same carbon content according Uniform corrosion
to Lüling and del Villar /4/.
Uniform or general corrosion represents approximately
Stress corrosion 35% of all cases of corrosion encountered in the
chemical industry according to Audouard /7/. In general
Addition of ferrite into the structure improves the stress corrosion, the entire surface of the steel, which is
corrosion of stainless steels. Flowers, Beck and Fontana /5/ exposed to the electrolyte, is attacked uniformly. When
have investigated at an early stage the effect of ferrite on the this happens, depends entirely on the properties of the
susceptibility to stress corrosion in a chloride environment. electrolyte and stainless steel. In pumping applications,
The duplex steels are not susceptible to stress corrosion. there is more corrosion as the motion and velocity of
the liquid result in an accelerated supply of the corro-
sive agent to the metal surface and removal of the
corrosion products. If the solution contains solid parti-
cles, there is usually even more corrosion.
Pitting Resistance Equivalent High alloy stainless steel possesses very good
PRE = Cr% + 3.3xMo% + 16xN% resistance to erosion-corrosion thanks to the stability of
the passive surface film. In practice, however, stainless
ASTM Cr % Mo % N% PRE
CF – 8M 19 2.2 0.08 27.5 steel can be attacked when the composition and tem-
CG – 8M 19 3.2 0.08 30.8
perature of the electrolyte are such that the passivity of
CD – 4MCu 1A (1B) 25.5 2.0 0.08 (0.20) 33.4 (35.3)
CN – 7M 20.5 2.5 0.08 30.0 the stainless steel is not fully stable. Thus erosion-
CN – 3MN 21 6.5 0.22 46.0
corrosion can occur on pump impellers which are
654 SMO *) 24 7.3 0.50 56.0
1B 25.5 2.0 0.20 35.3 exposed for instance to sulphuric acid. Erosion-corro-
3A 25.5 2.1 0.20 35.6
sion can also occur when the solution pumped contains
4A 22 3.0 0.20 35.1
5A 25 4.5 0.20 43.0 solid particles. This is the case in the production of
*) Cast steel not in accordance with ASTM
phosphoric acid, where gypsum can give rise to ero-
Table 4. Pitting Resistant Equivalent figures of some cast sion-corrosion in pumps. The resistance of stainless
stainless steels. steel to erosion-corrosion is generally increased by the
same alloying elements as those which increase resis- Ferric Chloride Solution Test; ASTM G–48
tance to general corrosion in the electrolyte in ques- 90

tion. 80 654 SMO X

70
Material tests

T, Critical Pitting Temperature oC


60

The properties and usability of the most common cast 50 ASTM-A890


steel materials used in pumps in severe conditions Grade 5A ASTM-A 744
40 X CN-3MN
were tested through the following tests.
30 A890 Grade 1B
A890 Grade 3A X
Critical pitting temperature 20 CG-8M

10 CF-8M
The critical pitting temperature was measured for sev-
eral cast stainless steels according to the ferric chlo- 0
20 30 40 50 60
ride solution test of ASTM G-48. The results are shown PRE =%Cr+3,3%Mo+16%N (Pitting Resistance Equivalent)
in Figure 3.
Figure 3. Critical pitting temperatures of cast stainless steel in
In the ferric chloride test, cast steel 654 SMO™
withstands pitting corrosion well, and the test shows a
ferric chloride solution test according to ASTM G-48.
critical pitting temperature which is almost 40°C higher
than the corresponding temperature with duplex steels.
Immersion test 11 days, Phosphoric acid T ~82oC
Corrosion 25.3
Corrosion test rate mm/a 11.8
5.8
The process for making phosphoric acid is known for
0.5
its aggressive corrosive environment. The raw material 0.5
used, phosphate or apatite, has its own impact de- 0.4
Loss of material

pending on the fluorine and chlorine contents of the


mineral. At one phosphoric acid plant, pump materials 0.3
were tested on site for 11 days. Moreover, a short time

A744 CN-3MN
Grade 1B

A743 CN-7M
0.2
A743 CF-8M

abrasion test in the process conditions of the plant was


A890

Grade 5A

Grade 3A
carried out. The results are shown in Figures 4 and 5.
0.1
A 890

A 890

The stainless cast steel samples were kept in the 0.1


reactor tank for 11 days. The corrosive conditions were 0.04
0.0
as follows: P2O5 26-28%, F 5 g/l, H2SO4 40 g/l, solids Average corrosion rate <0,1 mm/a = Practical limit for corrosion

ca. 30%, temperature ca. 82°C. In this test, the com-


Figure 4. Corrosion test. Phosphoric acid plant. Duration 11
pletely austenitic 6% molybdenum steel CN-3MN was
days. The corrosive conditions were as follows: P2O5 26-
the best material; this was more alloyed than the other
28%, F 5g/l, H2SO4 40g/l, solids ~30%, T= ~82 °C.
samples tested. Duplex steel grade 1B was acceptable
and clearly better than the other duplex steels. The
reason for this is most likely the copper, which im-
proves the corrosion resistance of some steels in the same performance as the duplex steels, and probably
phosphoric acid. Copper also improves the resistance better in an immersion test.
of highly alloyed steel against residual sulphuric acid.
When small samples were tested in an abrasion Cavitation erosion test
and corrosion test for a short period of time (5 h), the
corrosive conditions were the same as in the reactor Some common stainless steels used in pumps were tested for
tank. The abrasive effect was boosted by adding 100 g/ cavitation resistance with tap water. The results are shown in
l of fused alumina. Figure 6.
The results in the short time abrasion and corro- In the test, the martensitic cast steel CA-6NM served as
sion test showed that the duplex steels manage these reference material. Duplex steels 3A and 5A had a slightly
conditions well. AVESTA 654 SMO™ appears to have poorer resistance against cavitation erosion than the marten-
sitic CA-6NM steel. The precipitation hardenable stain- Phosphoric acid, reactor solution
less steel CB7Cu-2 withstood cavitation erosion better H3PO4+40 g/l H 2SO4+5 g/l F, 100 g/l Al2O3, T=82°C ±5°C, duration 5 h
than CA-6NM at a hardness level of ca. 400 HB. The 400 o
mg/m2xh +82 ±5 C
corresponding strength values are given in Table 3. 5h
350
The performance of the completely austenitic high
338
alloyed steel 654 SMO™ was clearly superior in this 300
test.
250

Loss of material
260
Summary
200
186

ASTM A743 CN-7M


Modern duplex steels highly alloyed with nitrogen are 148
150

Avesta 654 SMO


commonly used as pump materials. The completely 124 127

A743 CF-8M
100
austenitic 654 SMO™ highly alloyed with molybdenum

Grade 3A
A 890 1B

CN-3MN
and nitrogen has proven to be a very good pump

A 744

A 890
50
material in demanding corrosive applications. This steel
grade also features good abrasive erosion resistance 0
Accuracy in the test ±21 mg/m2xh
in severe service.
Figure 5. Corrosion and abrasion test. Duration five hours.
References Same reactor solution in short time test (5h) on the plant site
as in fig. 4. Additional abrasive 100 g/l fused alumina.
1. B. Wallen, M. Liljas and P. Stenvall, Acom, Avesta
Corrosion Management, Vol 2, 1992.
Average Values
2. A. del Villar, 39. Internationaler Giessereikongress
18
Philadelphia, 1972, Paper 12.
3. K. Röhrig and G. Tither, Proceedings of 1986 Annual 16
A890
Conference, SCRATA, Nottingham, 1986, Paper 4. Grade 3A
14
A743
4. H. Lüling, K.R. Repetzki, F. Schilling, A. del Villar CA-6NM
and H. Zeuner, Giessen für die Kerntechnik, Zentrale 12

für Gussverwendung, Düsseldorf, 1975, 54-55.


Weight loss mg

10
5. J.W. Flowers, F.H. Beck and M.G. Fontana, Corro-
8
sion, Vol 19, 1963, 186-198. A890 A747
6. E. Alfonson and R. Qvarfort, Acom, Avesta Corro- Grade 5A CB7Cu-2
6
sion Management, Vol 1, 1992, 2.
4
7. P. Lacombe, B. Baroux and G. Beranger, Stainless
Steels, Les Editions de Physique Les Ulis, France, 2
1993, 279. 654SMO
0
0 5 10 15 20 25
Test time h

Figure 6. Cavitation Erosion test in tap water. Rotating disc,


D= 300 mm, u= 42,5 m/s

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