Corrosion Resistant Cast Steels for Process Industry Pumps

By Arto Riihimki Chief Metallurgist, Sulzer Pumps Finland Oy

Abstract
New duplex stainless cast steels and austenitic high molybdenum steels are used in pumps for severe service. The main modern nitrogen alloyed duplex cast steels are presented in the ASTM standard A-890. Grades 3A and 5A are often used as corrosion resistant cast steel for pumps. From high molybdenum austenitic stainless steels there are presented two grades in ASTM A-744 (-00) standard i.e. CN-3MN and CK-3MCuN. The latest and most corrosion resistant stainless steel grade is AVESTA 654 SMO. This new stainless steel as pump material for severe service has improved properties in the hydrometallurgyand electro refining processes in the metal industry compared to duplex stainless steels. The accepted EN 10283 (-98) standard for corrosion resistant cast steels is mentioned and some inaccurate correspondence between European and American steel grades are given. The paper deals briefly with the foundry process to make high alloy stainless steel pump castings. The AOD-method (AOD= Argon Oxygen Decarburisation) is an important prerequisite for the melting of low carbon, high chromium and molybdenum alloyed nitrogen steels. The properties of these steels are included. The main topic is the corrosion resistance of the above mentioned pump materials in severe service. Results of short time erosion and corrosion tests are discussed and compared with the results of plant tests. The new high alloyed cast stainless steel (main elements; Cr~24%, Ni~22%, Mo~7,3% and N~0,5%) has shown improved corrosion and erosion properties as process pump material in several severe service applications e.g. in the metal industry.

Introduction
The process industries need corrosion resistant pumps. The hydraulic parts of pumps, such as casings and impellers, are manufactured by casting. Alongside commonly used high alloy steels, new austenitic and austenitic-ferritic cast steels have been available during the past few years. When attempting to reach better corrosion resistance, for instance the molybdenum content of these steels has been increased. The use of nitrogen as an alloying element is also characteristic. The following examines the new high alloy cast steels used by Sulzer Pumps for demanding process pumps. The manufacture of these steels and their corrosion properties are also discussed briefly.

Some cast stainless steels EN10283 / ASTM

EN10283 Designation Martensitic grades GX4CrNi134 GX5CrNiCu164 Austenitic grades GX5CrNiMo19112 GX5CrNiMo19113 Fully austenitic grades GX4NiCrCuMo30204 GX2NiCrMoCuN25206 Austeniticferritic grades GX2CrNiMoN2253 GX2CrNiMoN2563 GX2CrNiMoCuN25633 GXCrNiMoN2674 Number 1.4317 1.4525 1.4408 1.4412 1.4527 1.4588 ASTM Designation CA6NM CB7Cu2 CF8M CG8M CN7M CN3MN Standard A 743 A 747 A 743 A 743 A 743 A 743 Alternative designation Grade 4A A 890 3A A 890 1B A 890 5A A 890

1.4470 1.4468 1.4517 1.4469

CD3MN CD6MN CD4MCuN CE3MN

Table 1. Some European and American corrosion resistant 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 production of pumps steels has conventionally been based on the grades of the American ASTM standard because this standard is generally known within industry. The European standard EN 10283, which was accepted in 1998, presents corrosion resistant steel grades intended for general applications. In this standard, the steel grades have been classified in four categories: martensitic, austenitic, completely austenitic, and austenitic-ferritic or duplex steels. When comparing the cast steels presented in the European standard and in the ASTM standard, there are some equivalent and almost equivalent steels. ASTM standard A890 presents the most recent nitrogen alloyed duplex steels. The completely austenitic and very corrosion resistant AVESTA 654 SMO steel is also highly nitrogen alloyed. This patented steel is not included in the American or in the European cast steel standard. This steel has turned out to be a good pump material in severe corrosive service such as in base metal solutions. The good properties are the result of high alloying. The contents of the main alloying elements are at the following levels: Cr~24%, Ni~22%, Mo~7.3% and N~0.5%. Tables 2 and 3 show the chemical compositions and mechanical properties of high alloyed corrosion resistant cast steels. The chemical composition of highly alloyed cast steels differs somewhat from the corresponding wrought steel grades. CF-8M and CG-8M correspond to wrought grades AISI 316 and 317. The corresponding low carbon grades are CF-3M and CG-3M, and in wrought grades AISI 316L and 317L. The above cast steels typically contain ca. 10-20% of delta-ferrite. When the amount of ferrite in the steel grows, it becomes austenGrade ASTM CA-6NM CB7Cu-2 CF-8M CG-8M CD-4MCu 1A (1B) CN-7M CN-3MN *) 654 SMO **) 1B 3A 4A 5A Cmax. % 0.06 0.07 0.08 0.08 0.04 0.07 0.03 0.03 0.04 0.06 0.03 0.03 Cr % 11.5-14.0 14.0-15.5 18.0-21.0 18.0-21.0 24.5-26.5 19.0-22.0 20.0-22.0 23.0-25.0 24.5-26.5 24.0-27.0 21.0-23.5 24.0-26.0 Ni % 3.5-4.5 4.5-5.5 9.0-12.0 9.0-13.0 4.75-6.00 27.5-30.5 23.5-25.5 21.0-23.0 4.75-6.0 4.0-6.0 4.5-6.5 6.0-8.0 Mo N / Cu % % 0.40-1.00 Nb 0.15-0.35 /2.50-3.20 2.0-3.0 3.0-4.0 1.75-2.25 2.0-3.0 6.0-7.0 7.1-7.5 1.75-2.25 1.75-2.50 2.5-3.5 4.0-5.0 (0.10-0.25) 0.18-0.26 0.45-0.55 0.10-0.25 0.15-0.25 0.10-0.30 0.10-0.30 /2.75-3.25 /3.0-4.0 /0.75max /0.3-0.7 /2.75-3.25 / /1.00max /

*) 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 **) Cast steel not in accordance with ASTM

Table 2. Some corrosion resistant cast steels according to ASTM standards. Main elements of the chemical composition. The 654 SMO is a trade mark owned by Avesta Polarit, which has granted Sulzer Pumps Finland Oy a licence to produce the material.

Mechanical properties
Grade ASTM CA 6NM CB7Cu 2 CF 8M CG 8M CD 4MCu 1A CN 7M CN 3MN 654 SMO *) 1B 3A 4A 5A Tensile Strength Mpa 755 1205 485 520 690 425 550 600 690 655 620 690 Yield Strength Mpa 550 1035 205 240 485 170 260 350 485 450 415 515 Elongation % 15 5 30 25 16 35 35 40 16 25 25 18

*) Cast steel not in accordance with ASTM

Table 3. Some corrosion resistant cast steels according to ASTM standards. Mechanical properties. The 654 SMO is a trade mark owned by Avesta Polarit, which has granted 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 stainless steel is AVESTA 654 SMO /1/. The contents of elements which improve corrosion resistance, such as chromium, molybdenum and nitrogen, have been increased further in comparison with the CN-3MN steel. Figures 1 and 2 show the microstructure of grade CF8M and of the duplex grade 3A after solution heat treatment at 1,100C. The structure is balanced to the 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. 250C /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 Shaeffler diagram. When a modern metallurgical production method, such as an AOD converter, is used in melting, the carbon and nitrogen contents in steel can be controlled precisely. Thorough mixing of the charge ensures that sampling is representantive, resulting in improved control over the desired analysis and steel structure.

Figure 1. Microstructure of the CF-3M austenitic stainless steel (x100). CF-3M; C max. =0,03 %, other elements of chemical composition as in CF-8M. Delta ferrite content 12%.

Figure 2. Microstructure of Grade 3A Duplex Steel (x100). Delta ferrite content 50%.
stainless cast steel grades requires an AOD converter or, when melted in an induction furnace, a raw material that has been pretreated in the AOD converter. There are several reasons for this. Highly chromium and molybdenum alloyed steels must have a low carbon content and an increased nitrogen content. Both of these can be achieved easily in the AOD converter. As to corrosion, a low sulphur content is an advantage achieved through this method.

Benefits in the foundry process

For the foundry, the duplex highly alloyed steels are usually easier to make than the completely austenitic corrosion resistant grades. The latter have a large grain size and some sensitivity to cracks during solidification. Ferrite in the structure reduces the grain size and has a favorable effect on solidification. The completely austenitic corrosion resistant cast steels (67.5% Mo) require a high temperature during solution heat treatment, ca. 1,200C. The duplex steels can be heat treated at lower temperatures, at 1,040C-1,150C depending on the grade. The production of the new

AOD
The AOD method (AOD = Argon Oxygen Decarburization) was originally developed for the treatment of wrought stainless steels. Melting in the AOD method takes place mainly in an electric arc furnace, from which the liquid metal is transferred to the AOD converter, to the metallurgical unit. The use of the AOD method permits raw materials for high alloyed steels to be selected from the most economical combinations. The initial carbon content may be several percents. During

decarburization, the partial pressure of carbon monoxide is reduced by means of argon or nitrogen. This gives a low carbon content and enables the production of cast grades CF3M and CG-3M conforming to the ASTM A743 standard (maximum carbon content 0.03%). The oxidized chromium is reduced back to the liquid metal, and desulphurization is carried out at the same time. Because of the good mixing of the liquid metal and slag, the sulphur content of an AOD steel decreases down to a few thousandths of a percent. The liquid metal is flushed with argon, which reduces the slag inclusions to a minimum. Nitrogen alloying of high alloyed cast steels is easily done in the converter.

Pitting and crevice corrosion

Pitting and crevice corrosion consist of local forms of corrosion that can occur in stainless steels. This form of corrosion can occur in chloride containing solutions, such as sea water, bleaching solutions or oxidizing salts e.g. ferric chloride and cupric chloride. Attempts have been made to estimate the pitting and crevice corrosion resistance of steels by calculating the sum of the most relevant alloying elements /6/. This sum is called PRE (Pitting Resistance Equivalent), and one common formula is shown below. Using the formula PRE = Cr% + 3.3xMo% + 16xN%, PRE values for steels given in Table 4 have been calculated. In the table, the duplex steels are favorably placed due to their high chromium content. Nitrogen has a highly positive effect on PRE. AVESTA 654 SMO has clearly the highest calculated PRE figure. When treating the charge with the AOD converter, a high nitrogen addition into this steel causes no problems. The strength and corrosion properties of the discussed duplex steels and completely austenitic cast steels make them applicable to several process equipment such as pumps.

Corrosion properties
The stainless steels treated in the AOD converter have a low sulphur content. Sulphur and MnS sulphides reduce the pitting potential thus acting as the starting spots for corrosion. As to pitting corrosion, those high alloy steels which have a few sulphide inclusions are better than the common stainless cast steels. Resistance against pitting is improved by chromium, molybdenum and nitrogen, among others. Since a low enough carbon content can be ensured by the AOD method, there is no risk of sensitizing or intergranular corrosion. Cast steel is not, however, as liable to sensitizing as wrought steel with the same carbon content according to Lling and del Villar /4/.

Uniform corrosion
Uniform or general corrosion represents approximately

Stress corrosion
Addition of ferrite into the structure improves the stress corrosion of stainless steels. Flowers, Beck and Fontana /5/ have investigated at an early stage the effect of ferrite on the susceptibility to stress corrosion in a chloride environment. The duplex steels are not susceptible to stress corrosion.

35% of all cases of corrosion encountered in the chemical industry according to Audouard /7/. In general corrosion, the entire surface of the steel, which is exposed to the electrolyte, is attacked uniformly. When this happens, depends entirely on the properties of the electrolyte and stainless steel. In pumping applications, there is more corrosion as the motion and velocity of the liquid result in an accelerated supply of the corrosive agent to the metal surface and removal of the corrosion products. If the solution contains solid parti-

Pitting Resistance Equivalent PRE = Cr% + 3.3xMo% + 16xN%

ASTM CF 8M CG 8M CD 4MCu 1A (1B) CN 7M CN 3MN 654 SMO *) 1B 3A 4A 5A Cr % 19 19 25.5 20.5 21 24 25.5 25.5 22 25 Mo % 2.2 3.2 2.0 2.5 6.5 7.3 2.0 2.1 3.0 4.5 N% 0.08 0.08 0.08 (0.20) 0.08 0.22 0.50 0.20 0.20 0.20 0.20 PRE 27.5 30.8 33.4 (35.3) 30.0 46.0 56.0 35.3 35.6 35.1 43.0

cles, there is usually even more corrosion. High alloy stainless steel possesses very good resistance to erosion-corrosion thanks to the stability of the passive surface film. In practice, however, stainless steel can be attacked when the composition and temperature of the electrolyte are such that the passivity of the stainless steel is not fully stable. Thus erosioncorrosion can occur on pump impellers which are exposed for instance to sulphuric acid. Erosion-corrosion can also occur when the solution pumped contains solid particles. This is the case in the production of phosphoric acid, where gypsum can give rise to erosion-corrosion in pumps. The resistance of stainless steel to erosion-corrosion is generally increased by the

*) Cast steel not in accordance with ASTM

Table 4. Pitting Resistant Equivalent figures of some cast stainless steels.

same alloying elements as those which increase resistance to general corrosion in the electrolyte in question.

Ferric Chloride Solution Test; ASTM G48

90 80 70
T, Critical Pitting Temperature oC

654 SMO X

Material tests
The properties and usability of the most common cast steel materials used in pumps in severe conditions were tested through the following tests.

60 50 40 30 20 10 0 20

ASTM-A890 Grade 5A

X CN-3MN

ASTM-A 744

Critical pitting temperature

The critical pitting temperature was measured for several cast stainless steels according to the ferric chloride solution test of ASTM G-48. The results are shown in Figure 3. In the ferric chloride test, cast steel 654 SMO withstands pitting corrosion well, and the test shows a critical pitting temperature which is almost 40C higher than the corresponding temperature with duplex steels.

A890 Grade 3A X

A890 Grade 1B

CG-8M CF-8M
30 40 50 PRE =%Cr+3,3%Mo+16%N (Pitting Resistance Equivalent) 60

Figure 3. Critical pitting temperatures of cast stainless steel in ferric chloride solution test according to ASTM G-48.

Immersion test 11 days, Phosphoric acid T ~82oC

Corrosion rate mm/a

Corrosion test
The process for making phosphoric acid is known for its aggressive corrosive environment. The raw material used, phosphate or apatite, has its own impact depending on the fluorine and chlorine contents of the mineral. At one phosphoric acid plant, pump materials were tested on site for 11 days. Moreover, a short time abrasion test in the process conditions of the plant was carried out. The results are shown in Figures 4 and 5. The stainless cast steel samples were kept in the reactor tank for 11 days. The corrosive conditions were as follows: P2O5 26-28%, F 5 g/l, H2SO4 40 g/l, solids ca. 30%, temperature ca. 82C. In this test, the completely austenitic 6% molybdenum steel CN-3MN was the best material; this was more alloyed than the other 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 improves the corrosion resistance of some steels in phosphoric acid. Copper also improves the resistance of highly alloyed steel against residual sulphuric acid. When small samples were tested in an abrasion and corrosion test for a short period of time (5 h), the corrosive conditions were the same as in the reactor tank. The abrasive effect was boosted by adding 100 g/ l of fused alumina. The results in the short time abrasion and corrosion test showed that the duplex steels manage these conditions well. AVESTA 654 SMO appears to have

25.3 5.8

11.8

0.5 0.4 0.3

0.5

Loss of material

A744 CN-3MN

A890 Grade 1B

A743 CF-8M

0.2 0.1 0.0

0.1

A 890 Grade 5A

A 890 Grade 3A

0.04

Average corrosion rate <0,1 mm/a = Practical limit for corrosion

Figure 4. Corrosion test. Phosphoric acid plant. Duration 11 days. The corrosive conditions were as follows: P2O5 2628%, F 5g/l, H2SO4 40g/l, solids ~30%, T= ~82 C.

the same performance as the duplex steels, and probably better in an immersion test.

Cavitation erosion test

Some common stainless steels used in pumps were tested for cavitation resistance with tap water. The results are shown in Figure 6. In the test, the martensitic cast steel CA-6NM served as reference material. Duplex steels 3A and 5A had a slightly poorer resistance against cavitation erosion than the marten-

A743 CN-7M

sitic CA-6NM steel. The precipitation hardenable stainless steel CB7Cu-2 withstood cavitation erosion better than CA-6NM at a hardness level of ca. 400 HB. The corresponding strength values are given in Table 3. The performance of the completely austenitic high alloyed steel 654 SMO was clearly superior in this test.

Phosphoric acid, reactor solution

H3PO4+40 g/l H 2SO4+5 g/l F, 100 g/l Al2O3, T=82C 5C, duration 5 h
400
mg/m2xh

350 300
Loss of material

+82 5 C 5h 338

250 200

260

Summary
Modern duplex steels highly alloyed with nitrogen are commonly used as pump materials. The completely austenitic 654 SMO highly alloyed with molybdenum and nitrogen has proven to be a very good pump material in demanding corrosive applications. This steel grade also features good abrasive erosion resistance in severe service.

ASTM A743 CN-7M

186 150 100 50 0 124 127

148

Accuracy in the test 21 mg/m2xh

References
1. B. Wallen, M. Liljas and P. Stenvall, Acom, Avesta Corrosion Management, Vol 2, 1992. 2. A. del Villar, 39. Internationaler Giessereikongress Philadelphia, 1972, Paper 12. 3. K. Rhrig and G. Tither, Proceedings of 1986 Annual Conference, SCRATA, Nottingham, 1986, Paper 4. 4. H. Lling, K.R. Repetzki, F. Schilling, A. del Villar and H. Zeuner, Giessen fr die Kerntechnik, Zentrale

Figure 5. Corrosion and abrasion test. Duration five hours. Same reactor solution in short time test (5h) on the plant site as in fig. 4. Additional abrasive 100 g/l fused alumina.

Average Values
18 16 14 12
Weight loss mg

A743 CF-8M

A890 Grade 3A A743 CA-6NM

fr Gussverwendung, Dsseldorf, 1975, 54-55. 5. J.W. Flowers, F.H. Beck and M.G. Fontana, Corrosion, Vol 19, 1963, 186-198. 6. E. Alfonson and R. Qvarfort, Acom, Avesta Corrosion Management, Vol 1, 1992, 2. 7. P. Lacombe, B. Baroux and G. Beranger, Stainless Steels, Les Editions de Physique Les Ulis, France, 1993, 279.

10 8 6 4 2 654SMO 0 0 5 10
Test time h

A890 Grade 5A

A747 CB7Cu-2

15

20

Avesta 654 SMO

A 890 1B

A 744 CN-3MN

A 890 Grade 3A

25

Figure 6. Cavitation Erosion test in tap water. Rotating disc, D= 300 mm, u= 42,5 m/s