INCTRODUCTION TO COBALT

Cobalt Atomic number Density, 20 C (68 F) Atomic weight Melting point Boiling point GENERAL Cobalt has few, but highly specialized, uses in alloy steels. Its behavior is similar to nickel, in that it forms a complete series of solid solutions with iron at elevated temperatures and is also extremely soluble in ferrite. It is a potent ferrite strengthener; this solid solution strengthening persists to quite high temperatures, and cobalt is therefore found in several grades of high speed tool steels, among others. Like nickel, cobalt is ferromagnetic. This led to its use in a series of magnetic steels as well as the widely-used Alnico alloys. Cobalt is an important constituent of the 18% Ni maraging steels and several other ultrahigh strength steels and is added to one grade of austenitic stainless steel. About one-quarter of the cobalt in the U.S. (depending on market conditions) forms the basis for a family of superalloys and corrosion and abrasion-resistant alloys. To a certain extent, it is interchangeable with nickel in this regard. Because of the high cleanliness standards imposed on these latter alloys, many of them are produced by specialty-alloy and stainless steel mills. Although large reserves are known to exist around the world, cobalt has often been in short supply - occasionally to the point of allocation. Political unrest in Africa and labor disruption in affiliated nickel production (see Nickel) have been major contributors to the cyclic supply situation. The U.S. is not self-sufficient in cobalt. 27 8.7 g/cm3 58.94 1492 C (2718 F) 2900 C (5252 F)

Sources of Cobalt

Cobalt is not a particularly rare metal and it ranks 33 in abundance. It is however widely scattered in the Earth's crust but is found in potentially exploitable quantities in several countries, 17 of which currently produce. Cobalt is only extracted alone from the Moroccan and Canadian Arsenide ores. It is normally associated with copper or nickel. 39% of World production is from Africa - D.R.C. (21%) and Zambia (15%) - where cobalt is a copper by-product. Table 1 - Where Cobalt is Mined - shows the current situation. Significant resources of cobalt are also present in the deep sea nodules and crusts which occur in the Mid-Pacific and are estimated to contain anywhere from 2.5-10 million tonnes of cobalt. At a world production level of 27,000 tonnes, this is 90 to 400

AVAILABLE FORMS Cobalt metal is supplied to alloy and steel producers in the form of briquettes, granules, broken electrolytic cathodes, rondelles, fines and powders. Purity generally depends on the means of production, but grades in the range 98-99.9% Co are most commonly sold. A metallurgical grade "grey oxide" analyzing 76% Co is also available. While not strictly an addition agent, scrap must be considered as an increasingly important source of cobalt. Unfortunately, superalloy scrap often contains high concentrations of nickel and is therefore not acceptable for tool steel production: however, maraging and ultrahigh strength steel producers can benefit from this additional source, as can suppliers of the superalloys themselves. years of usage. Current land sources are estimated at over 100 years, so no long term shortage is in sight. Table -1 Where Cobalt is Currently Mined and/or Refined Country Australia Botswana Brazil Belgium Canada China Cuba France Yes Yes Yes Yes 140 Mined Yes Yes Yes Yes Yes Yes Yes 750 1,200 4,000 1,100 Refined Yes 2,500 Approx. Refined Qty

Finland Japan Morocco New Caledonia Norway Russia South Africa Uganda D.R.C. Zambia Yes Yes TOTAL Yes Yes Yes Yes

Yes Yes Yes

7,500 220 1,200

Yes Yes Yes

4,000 3,500 400 500

Yes Yes

5,000 4,000 35,000 (Tonnes)

Cobalt in Steels
Cobalt is not an element commonly added to alloy steels. It does have some effects but these are also obtainable by other additives at lower cost and mostly with better results Molybdenum, nickel, etc. We have seen in other areas that cobalt does not form carbides and that in fact, it decreases hardenability (a measure of the depth to which a steel hardens on quenching). It hardens ferrite but only marginally and has only a small influence on the transformation temperature of iron. The factors above ensure that cobalt is unlikely to ever find a use in high tonnage low alloy steel production. It does however have some niche markets in steel. In martensitic steels, cobalt has the effect of delaying tempering and this can be shown by plotting hardness against a time/temperature parameter as in Figure 1 (T = temperature, t = hours). Increasing cobalt levels produces increased hardness and steels of this type 1%C, 12%Cr, 4%Mo and 7%Co have attractive properties.

Some steels such as Jethete M120 have been developed for use at high temperature using the effect of cobalt to give high temperature strength in the range below which superalloys are more usual. The steels where cobalt has found its home (apart from the high speed variety) are termed maraging. This name is derived from the fact that they are aged in the martensitic form. The original steels used were 20/25% nickel steels with small additions of Al, Ti and Nb. The secret of these steels was and is, that simple air-cooling is sufficient to transform the Austenite high temperature phase to Martensite, the hard unstable lower temperature form. On reheating, the temperature to return to Austenite is found to be much higher than the Martensite forming temperature of 250C and is in fact over 500C. Reheating (aging) at an intermediate temperature retains the Martensite but allows precipitation of various hardening phases such as Ni3Mo, Ni3Ti, FeMo and these raise the hardness to up to 900 Vickers. The early steels were found to be brittle and cobalt additions solved this problem. As usual, the role of cobalt is obscure but it enhances the properties and accelerates the process. Table 1 shows a range of typical steels. Table 1 - Composition and Properties of Maraging Steels Composition, wt.% UTS Elong. Ni Co Mo Ti Al 103 psi MN/m2 % 18 8.3 3.25 0.2 0.10 210 1450 13 18 7.5 4.8 0.4 0.10 255 1750 13 18 9.0 4.8 0.6 0.10 285 1960 11 17.5 12.5 3.8 1.7 0.15 355 2450 9

Grade 18Ni (200) 18Ni (250) 18Ni (300) 18Ni (350)

Hardness Rc 43 50 54 58

13Ni (400)

13

15.5

10.8

0.2

390

2690

59

Their properties are not the highest possible but they score in that they can be air-cooled without distortion, machined without difficulty and finally, develop their properties with a relatively simple low temperature aging process. Maraging steels have found many uses in the aerospace and military industries where their strength coupled with workability has got them the job over possibly stronger materials. Typical applications are landing gears, arrestor hooks, torque shafts, rocket motor casings, gun barrels, bolts, fasteners, extrusion arms, etc., etc. There are the areas where cobalt steels are best.

Tool materials
High Speed Steel
Not all high-speed steels contain cobalt, but possibly the newest and the best ones do. High-speed steels are also steel but with large additions of refractory metals tungsten, chromium, molybdenum, vanadium and, in specialised cases, cobalt. The other element in steel, namely carbon, forms carbides in carbon steels with just iron and in high-speed steels, with all the alloying additions except cobalt which has other functions. So, in essence, a high speed steel is a steel containing large amounts of refractory carbides which proved hardness, high temperature strength, wear resistance to tempering, with cobalt enhancing high temperature strength. Structure is of paramount importance in tools steels and the aim is to get a very fine distribution of carbides. To this end, complex heat treatment schedules have been devised, often with two or even three tempering stages. Three current methods of manufacture have evolved: i) air melt cast and work, ii) vacuum melt cast and work, iii) atomise cold isostatic press sinter hot isostatic press and work. The newer ASP alloys made by method (iii) are superior to other grades and the best of these contain high levels of cobalt (8-10%). The benefit of the powder route is in the structure. Casting produces segregation by its very nature and further work and heat do little to change it. Atomising a homogeneous molten metal gives such rapid cooling that each mini-ingot (powder particle) is homogeneous unlike its large cast brethren. The rest of the process is to stick these little ingots back together into a porefree, homogeneous form.

Why is cobalt in high-speed steels?

A good question as it doesnt form carbides. The reasons that have brought cobalt to prominence in these latest alloys are the same as they always were. Cobalt dissolves in iron (ferrite and austenite) and strengthens it whilst at the same time imparting high temperature strength (temperature on cutting surfaces can be 850C) During solution heat treatment (to dissolve the carbides), cobalt helps to resist grain growth so that higher solution temperatures can be used which ensures a higher percentage of carbides being dissolved. Steels are quenched after solution annealing and the structure is then very hard martensite, plus the retained high temperature phase austenite plus carbides peppered throughout the structure. Tempering will precipitate the ultrafine carbides still in solution and maximum hardness will be attained. Here, cobalt plays another important role, in that it delays their coalescence. This is important as it means that during cutting, the structure is stable up to higher temperatures. Thus, cobalt-containing tool steels are capable of retaining strength to higher temperatures They cut faster for longer. Tools, however, are not longer as simple as they were. The surface can be modified by coating with TiN or TiC for example, put on by plasma or vapour deposition. These coatings increase cutting life by large factors (4 or 5 times) and do so even after regrinding.

Cobalt in Cemented Carbides

The ability to cut metal faster and faster is to a great extent at the heart of the economic growth in the 20th Century. Up until World War I, cutting tools were made from high carbon steels and cutting speeds of 25 ft/min were the norm. 1896 saw the start of tungsten carbide manufacture when Moissan in France melted/fused tungsten and carbon together to make diamonds. He didnt but WC resulted. Although mixtures of WC and MoC did get used for cutting, the great leap forward came when Schroeter and Osram produced a carbide material consisting of crushed tungsten carbide in cobalt. Iron was the first choice but it was cobalt for reasons which only became clear subsequently, which was the most successful binding material. The need for a binder is paramount as carbide alone is brittle and has little impact strength. The actual driving force however was not for cutting tools but as wire drawing dies. Osram was cut off by a blockade from its sources of diamonds for dies and the carbide route was the alternative they developed. The cutting properties however were quickly exploited and by the 1920s, 150 ft/min cutting speeds were commonplace. Although nickel has also been used as a binder, cobalt reigns supreme. Why should this be? There are several criteria which govern the performance of a binder for carbides: a) It must have a high melting point Cobalt: 1493C b) It must have high temperature strength Cobalt does

c) It must form a liquid phase with WC at a suitable temperature Cobalt does at 1275C. This pulls the sintered part together by surface tension and eliminates voids. d) It must dissolve WC Cobalt forms a eutectic with WC at 1275C/1350C and at that temperature dissolves 10% WC. e) On cooling, WC should reprecipitate in the bond in cobalt it does, giving hardness combined with toughness. f) The binding agent should be capable of being ground very finely to mix with the hard carbide particles cobalt can be produced very finely and grinds down to << 1. On grinding, it reverts to the close packed form which is brittle although in the carbide product, it retains the more ductile cubic form at room temperature. Cobalt fulfils all the needs of a binder whilst others, like Ni, Fe, etc., only fulfil some. It is this fact that has kept it irreplaceable in carbide

Wear Resistant Alloys & Coatings

Cobalt is used in two ways to give hard, corrosion/erosion resistant, high temperature coatings. Firstly, carbide coatings containing up to 17% cobalt can be deposited by flame and plasma guns on to softer substrates to give the finish and hardness of carbide work rolls, mixers, grinders, etc. The main interest in this section is the metallurgical alloys based on cobalt, whose primary aim is wear resistance and which may be applied by surface coating or used as castings and forgings.

Secondly, alloys used in this field are based on the Stellite alloys developed in the early 1900s, although coatings have moved on into cobalt-containing nickel based alloys as well, strictly for corrosion resistance. The Stellites were originally used as cutting tools and whilst this use has mainly been replaced by carbide, it does remain. More often now however, the CoCrW alloys are used to coat other metals or are used as castings wherever their unique erosion resistance and high temperature properties are needed. They also form the basis of the prosthetic alloys used to produce hip and knee replacement joints.

The spray alloys used for plasma or flame spray are in powder form and contain silicon and boron to form a low melting point eutectic which allows fusion with the substrate with minimum distortion. In general, the cobalt-based alloys can be deposited by:

Welding both rods and strip are available MIG, TIG, submerged arc, oxy-acetylene, etc. Plasma/flame spray powders are available for both these processes or rod feed can be used

They can be cast and used as complete parts or as inserts i.e. titanium hip joint with Co/Cr ball