Materials Technology

The Significance of Nickel and Molybdenum in Steel

The prices of alloying constituents like nickel and molybdenum have gone up dramatically in recent years. The price increases have a major effect on all parts and assemblies made of materials that contain these alloying constituents. This keeps raising the question whether one cannot do without these two cost boosters, at least on some applications.

Anja Dwars

Before proceeding to change the material composition of the parts one manufactures, however, one should remember that these two alloying constituents play a major part in a materials performance and also determine the fields of application for which it can be used. Molybdenum (Fig. 1) Molybdenum takes its name from the Greek molybdos, which translates into lead. During the Middle Ages, this name was used for all leadlike materials. It is estimated that approximately 0.00015 weight-% of the earths crust consists of molybdenum. Although relatively rare, molybdenum is found all over the world. In nature,

Fig. 1: Molybdenum

molybdenum is only found as a compound. The countries which export molybdenum are the United States, China, Chile, Canada and Russia. The most important molybdenum-bearing minerals are molybdenite, powellite and wulfenite. These are often recovered as by-products of copper mining. Molybdenum is a soft, formable, silveryshining heavy metal with a cubic body-centered lattice. It does not corrode in air because it is protected by a thin oxide layer. It is also resistant to water, most acidic and alkaline solutions. It does decompose in the presence of concentrated sulphuric acid or nitric acid, however. Its chemical properties are similar to those of tungsten. Important molybdenum compounds are molybdenum oxide and molybdenum sulphide. In 2003, the annual production stood at approximately 129,000 tons world-wide. At the end of the 19th century, the engineers developing steel armour plate for use in warship building discovered that the hardness, corrosion and heat resistance properties of steel could be much improved by adding even a small amount of molybdenum. In its pure form, molybdenum is used in filament supports in electric lamps. A further area of use is in catalysts in the chemical industry. These are some of the reasons why there is an enormous demand for this element from all technical fields and why it is so expensive. While one ton of molybdenum cost around 5,900 US Dollars back in 1999, it cost 73,300 US Dollars in January of this year (reference: Federal Institute of Geosciences and Raw Materials, Germany). Nickel (Fig. 2)

Fig. 2: Nickel

In medieval times, worthless nickel ores were

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generally referred to as nickel. Although the ancient Greeks already used nickel alloys, they manufactured these materials without any knowledge of the metal itself. In the Middle Ages, European miners considered it a useless substance that got into their way when extracting copper ore. It wasnt until the Englishman Michael Faraday introduced his electroplating process in 1843 that the metal first gained some economic significance. The earth crust contains approximately 0.009 weight-% of nickel. In small amounts, its minerals are found practically everywhere. The most important of these are garnierite, millerite, pentlandite, pyrrhotite (pyrrhotine) and nickeline. Of these, pentlandite and garnierite are of economic significance. Deposits worth being worked are found in Canada (pentlandite), the Commonwealth of Independent States, Australia and Cuba. In 2003, the annual production volume totalled approximately 128,000,000 tons world-wide. Nickel is a formable, silvery-white metal with a very dense lattice structure. It forms a thin oxide layer on its surface, which makes it highly resistant to air and water. It easily forms an alloy with iron, copper and manganese. It is estimated that there are 63 million tons of nickel left in the world that are worth being worked. Today, between 500,000 and 900,000 tons of nickel are won all over the world each year. Nickel is an important alloying constituent which has its principal area of use in steel refining. Metal surfaces are rendered corrosion resistant by means of nickel-plating. Another use for large quantities of nickel is in the electrical industry, where it is applied in the manufacture of electric batteries and storage batteries. The price of a ton of nickel was around 4,269 US Dollars in 1999; in January 2005 the same amount had a price tag of 16,300 US Dollars (reference: Federal Institute of Geosciences and Raw Materials, Germany). Molybdenum-free materials pose problems in acids and chloride-containing fluids The question whether substantial cost savings can be achieved by using a lower alloy material depends on whether the substitute material is suitable for the intended use. It only makes sense to use a better priced pump or valve material, if the material has the required corrosion resistance in the liquid to be pumped, and if the material has

the specified mechanical properties. Possible substitute materials are, for instance, stainless steel grades containing considerably less of the costly alloying constituent molybdenum. An example of such a steel grade is forged steel 1.4541, which contains no molybdenum. Below, the corrosion resistance as well as the mechanical properties of this molybdenum-free alloy will be compared to forged steel 1.4571 and duplex steel 1.4462, two steel grades that contain molybdenum. The majority of stainless steels are used in corrosive media. A materials corrosion resistance, therefore, is one of the main criteria for its selection. Corrosion resistance depends first and foremost on the chemical composition of the material. Besides chromium, molybdenum is the alloying constituent which is of greatest importance for the corrosion properties of stainless steels. Materials 1.4571 and 1.4541 differ considerably in terms of molybdenum content. As shown in Table 1, 1.4571 has a molybdenum content of between 2.00 and 2.50 %, whereas 1.4541 contains no molybdenum at all. A comparison of the other alloying constituents shows that the two materials do not differ greatly. Molybdenum generally increases the resistance of steel to acids. In fluids containing halogen ions, for example chloride (Cl-) and fluoride (F-), molybdenum, in particular, substantially improves a materials resistance to pitting and crevice corrosion. PRE a measure of a materials resistance The pitting resistance equivalent (PRE) is a measure of a stainless steels resistance in chloride-containing media. It is determined by the chromium, molybdenum and nitrogen contents. The higher the pitting resistance equivalent, the better the corrosion resistance of a material and the broader its field of application.

Forged steel grades

1.4571 1.4541 1.4462

Equivalent cast materials

1.4408 1.4308 1.4593 or 1.4517

Material
1.4571 1.4541

PRE
24.9 18.0

PRE = %Cr + 3.3 % Mo + 16 % N

Figs. 3 to 5 show the influence of the alloying constituents on corrosion resistance using the examples of sulphuric acid and phosphoric acid. Ferrous metals are deemed resistant to a given liquid if the corrosion rate is less than 0.1 mm/an-

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Materials Technology

num. The conditions at which the corrosion rate is 0.1 mm/annum are marked with continuous lines. The diagrams show that materials not containing molybdenum are decidedly less resistant to acids than materials containing molybdenum. Fig. 4 shows the effects of chloride content on corrosion resistance in sulphuric acid. It gives a clear indication of the positive effects of molybdenum. If as little as 200 ppm chloride is added, material 1.4541 is no longer suitable for use in this fluid, irrespective of the concentration of the sulphuric acid. When comparing the corrosion resistance of materials 1.4571 and 1.4541, the following points stand out: Material 1.4541 is an austenitic chromiumnickel steel which is considerably less corrosion resistant in acids and chloride-containing fluids than material 1.4571 which contains molybdenum. An

exception are oxidizing acids such as nitric acid; in some applications, molybdenum-free materials can be used in the presence of these acids. In a chloride-free, alkaline environment such as sodium hydroxide solution, the resistance levels of materials 1.4571 and 1.4541 are very similar. The said facts also apply to other, highly corrosion resistant materials, for example to ferriticaustenitic material 1.4462 (Table 1), which, as far as its corrosion resistance is concerned, is clearly superior to both 1.4571 and 1.4541. Comparable mechanical properties? As far as the mechanical properties of 1.4571 and 1.4541 (molybdenum-free) are concerned, i.e. if we compare the strength and ductility figures, the materials are very similar (Table 2). However, if we compare their strengths at elevated temperatures

Material 1.4541 1.4571 1.4462

C 0.08 0.08 0.030

Si 1.00 1.00 1.00

Mn 2.00 2.00 2.00

P 0.045 0.045 0.035

S 0.015 0.015 0.015

Cr

Ni

Mo ------2.00-2.50 2.50-3.50

N ----------0.10-0.22

Cu ----------------

Ti 5xC- 0.70 5xC- 0.70 ------

Mean PRE 18.0 24.9 34.5

17.00-19.00 9.00-12.00 16.50-18.50 10.50-13.50 21.00-23.00 4.50-6.50

Table 1: Chemical compositions (% b.w.)

Material

Designation

Tensile strength Rm (N/mm) 500.0 700.0 500.0 700.0 650.0 880.0

1.4541 1.4571 1.4462

X6CrNiTi18-10 X6CrNiMoTi17-12-2 X2CrNiMoN22-5-3

Mechanical properties (standard values at room temperature) Elongation after Charpy-V notch impact Yield strength Rp0,2 fracture energy AV (J) (N/mm) A5 (longitudinal) (%) Longitudinal Transverse 190.0 40.00 100.00 60.00 (-196 C) 200.0 450.0 40.00 25.00 100.00 100.00 60.00 (-196 C) 40.00 (-40 C)

Table 2: Mechanical properties (according to DIN EN 10272)

Fluid pumped Highly corrosive

Pump Series Material variants CPK X X X X X X X X X X X X X X X ETA KWP X KRT / HGM Amarex X HGM - RO X X Multitec MultitecRO X UPA X X SEZ X X RDLO OMEGA RPH X (X) X X X X

Duplex stainless steel 1.4593 or 1.4517/1.4462 Cr-Ni-Mo steel Corrosive 1.4408/1.4571 Slightly 13% chromium steel corrosive 1.4317 or 1.4008/1.4313 or 1.4021 Upon special Cr-Ni steel (molybdenum-free) 1.4308/1.4301 (special request applications in the chemical industry) Slightly to Grey cast iron JL-1040 or GP240GH+N etc. non-corrosive (impeller in bronze or 1.4408 as required)

Table 3: Material variants for some pump series (Reference: applicable KSB type series booklets)

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and their tensile creep strengths, the molybdenumcontaining material has the better properties (Figs. 6 and 7). Material 1.4462, a ferritic-austenitic material, shows a different picture. Owing to its two-phase microstructure of ferrite and austenite at a ratio of approximately one to one, its tensile and yield strengths are much better than those of austenitic, molybdenum-free material 1.4541, and its ductility is good (Table 2). However, as material 1.4462 tends to become brittle, it cannot be used at temperatures in excess of 280 C as laid down in DIN EN 10088-1. This means that any design must be checked and adapted, if necessary, with a view to the mechanical properties of possible alternative materials, before effecting a change of materials. Conclusion Material 1.4571 can only be replaced with molybdenum-free 1.4541 for an application involving an acidic or chloride-containing environment if the maximum permissible applicable limits are lowered at the same time (Figs. 3-5). For components that will not come into contact with the fluid

pumped, 1.4571 can be replaced with 1.4541, seeing as these two materials have approximately the same strength and ductility characteristics. However, this is only true for those applications, where the lower strength at elevated temperatures and the lower tensile creep strength of the molybdenum-free material is of no relevance. In a corrosive atmosphere, e.g. in the chemical, potassium or salt industry, or near seawater, it has to be checked on a case-to-case basis whether it is safe to use the substitute material. Both from the points of view of its corrosion resistance and its mechanical properties, ferriticaustenitic material 1.4462 is superior to austenitic materials 1.4571 and 1.4541. Table 3 lists the materials selected for a number of pump series. High alloy stainless steel grades that do not contain molybdenum could be used for applications involving drinking water, fully demineralized water, permeate or boiler feed water. The materials laid down in customers specifications should also be examined against this background. The costs incurred by the change of materials and its benefits have to be checked on a case-to-case basis.

Equivalent material designations: 18-10 corresponds to 1.4541, 17-12-2,5 corresponds to 1.4571

Fig. 3: Corrosion resistance of stainless steel grades in sulphuric acid (reference: Corrosion Handbook Stainless Steel (Sandvik Steel))

N/mm2 240 220 200 180 140 120 100 100 150 200 250 300 350 400

1.4571: 0.2 % offset yield strength 1.4571: 1.0 % offset yield strength 1.4541: 0.2 % offset yield strength 1.4541: 1.0 % offset yield strength

Fig. 4: Corrosion resistance of stainless steel grades in sulphuric acid containing chlorides (reference: Corrosion Handbook Stainless Steel (Sandvik Steel))
450 500 550 Temperature C

Fig. 6: Elevated temperature strength of 1.4571 and 1.4541 according to DIN EN 10272

N/mm2 300 250 200 150 100 50 0 550 560 570 580 590 600 610 620 630 640 650 1.4571: tensile creep strength at 104 h 1.4571: tensile creep strength at 105 h 1.4541: tensile creep strength at 104 h 1.4541: tensile creep strength at 105 h

Fig. 5: Corrosion resistance of stainless steel grades in phosphoric acid (reference: Corrosion Handbook Stainless Steel (Sandvik Steel))
Temperature C

Fig 7: Mean tensile creep strength of 1.4571 and 1.4541 according to DIN EN 10272

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