Advanced Performance Materials 5, 201212 (1998) c 1998 Kluwer Academic Publishers. Manufactured in The Netherlands.

Magnesium Science, Technology and Applications

D. ELIEZER Ben-Gurion University of the Negev, P.O. Box 653, Beer Sheva 84105, Israel E. AGHION Dead Sea Works, Ltd., Potash House, P.O. Box 75, Beer Sheva 84100, Israel F.H. (SAM) FROES Institute for Materials and Advanced Processes (IMAP), University of Idaho, Moscow, ID 83844-3026

Abstract. The science, technology and applications of magnesium alloys are reviewed. The very low density of magnesium in combination with excellent castability is leading to increased use, despite poor galvanic corrosion resistance and a higher cost than aluminum, especially in automotive applications. Even further expansion of the magnesium market should come from an expanded design base, a better understanding of the scientic underpinning of magnesium alloys, and development of cost-affordable cast and wrought products. Keywords: automobiles, die casting, fuel economy, light metals, magnesium, reduced weight, transportation

Introduction Magnesium is the lightest of all the commonly used metals and is thus very attractive for applications in transportation. It also has a number of other desireable features including good ductility, better damping characterstics than aluminum and excellent castability. However, there are some negative features including high reactivity in the molten state, inferior fatigue and creep compared to aluminum and galvanic corrosion resistance which has been described as awful [1], a limited supply base, a lack of fundamental knowledge of the behavior of magnesium alloys, and a cost which is about twice that of aluminum [2]. However, with the dramatically increased emphasis on weight reduction magnesium is receiving a lot of attention as a material for use on next generation automobiles [1] especially using a casting approach. Magnesium is produced from sea water, brines and magnesium-bearing minerals which gives it a virtually unlimited supply of ore reserves, for example, it has been estimated that at current world use levels there is enough magnesium in the Dead Sea for at least 22,000 years. The main use of magnesium by far is as an alloying addition to aluminum alloys. Other major utilization includes desulphurization of steel, the production of ductile iron and as a structural material in its own right [2]. It is this latter use of magnesium that we will concentrate on in this paper.

202

ELIEZER, AGHION AND FROES

Magnesium metal for structural applications is processed into casting (die, sand, permanent mold and investment), extrusions, forgings, impact extrusions and at rolled products. Castings far exceed cast and wrought products for reasons which will be discussed later and die castings account for 70% of the castings shipped; with demand for automobile parts produced by this technique (about 85% of the die castings total) projected to reach greater than 100,000 metric tons worldwide by the turn of the century. Magnesium can be joined by riveting, or any of the commonly used welding methods. Magnesium can be machined faster and has the best strength-to-density ratio of any of the commonly used structural metals. Its use in a variety of applications, particularly in automobile components is expanding as knowledge of the interactions between forming processes, components design, component function /properties and cost increases. However, particularly for the new alloys this knowledge is as yet, incomplete [1]. Total magnesium shipments, by category, are shown for the rst half of 1996 and 1997 in Table 1 with internal Chinese and former Soviet Union consumption (20,000 tons each) not included. To put magnesium into perspective 1997 estimated shipments of the light metals (Al, Mg, and Ti) and steel are shown in Table 2. In this paper we will review the science, technology and applications of magnesium based materials with emphasis on new developments, and make some projections for the future.

Table 1.

Magnesium shipments (metric tons) . Category Al alloying Nodular Fe/ desulphurization Die casting Wrought products Others Total
Primary

1st Half 96 72.3 27.4 33.1 2.2 Bal. 150.6

1st Half 97 72.3 29.7 44.6 1.7 Bal. 161.9

Mg, World totals, 103 , Courtesy IMA.

Table 2.

Metal shipments (metric tons) 1997 estimates. Metal Titanium Magnesium Aluminum Steel Estimate 103 50 320 25,000 700,000

World totals, 103 , Courtesy B.

Clow, IMA.

MAGNESIUM SCIENCE, TECHNOLOGY AND APPLICATIONS

203

Figure 1.

Principle planes and directions in the magnesium unit cell [3].

Science General behavior Magnesium has a hexagonal crystal structure (gure 1), and its alloying behavior because of a favorable size factor (atomic diameter 0.320 nm), is characterized by an ability to form a solid solution with a variety of elements particularly those which are of commercial importance including Al, Zn, Li, Ce, Ag, Zr, and Th. Cast alloys predominate over wrought products, in part because of difculties in fabricating mill product forms (Mg alloys are hot worked above 250 C to allow additional slip systems to operate). The hexagonal closely packed structure and a large and variable grain size have led to less than optimum mechanical properties. Development of alloys to compete more effectively with wrought aluminum alloys has suffered from a substantial difference in the understanding of the phase transformations occurring in magnesium alloys compared to aluminum alloys; a direct result of the amount of research conducted on the magnesium alloys. A discussion of the behavior of magnesium alloys cannot occur without consideration of its corrosion behavior. The electrode potential of magnesium places it high in the electrochemical series. The Mg(OH)2 lm which forms, while offering protection in rural environments, is nonadhering. Problems also occur with galvanic corrosion requiring protection when there is contact with other metals; however, good design and appropriate protection concepts can alleviate these concerns [3]. While magnesium alloys generally exhibit good corrosion resistance during atmospheric exposure, their susceptibility to corrosion in chloride environments has been a serious practical limitation to wider application of these alloys. Magnesium is at the active end of the galvanic series, and galvanic corrosion is an ever existing threat. Moreover, magnesium oxide is not thermodynamically stable in neutral environments [4]. In spite of these limitations, signicant improvements have been made during the past decade in the corrosion resistance of alloy AZ91 (Mg-9.5Al-0.5Zn-0.3Mn) by reducing the heavy metal impurity level (Fe, Ni, and Cu), alloying with manganese [57] and heat treatment [8].

204

ELIEZER, AGHION AND FROES

Figure 2.

Effect of iron on the corrosion of pure magnesium (3% NaCl solution) [3].

The presence of noble metal impurities represents the most detrimental factor inuencing the corrosion properties of commercial magnesium alloys [3, 5, 9, 10], see gure 2. Of these, iron is generally of most concern since it is introduced to the melt from steel pots and casting molds and is present as an impurity in the alloying elements. The deleterious effect of iron has been attributed to the galvanic coupling between the magnesium matrix and the dispersoid of iron particles [9, 11]. Iron is very effective in catalyzing the reduction reaction, especially hydrogen evolution, which is responsible for the corrosion process. Alloy AZ91 is often alloyed with manganese because, when added in small amounts (fraction of a percent), manganese in general improves the corrosion resistance of magnesium alloys [7, 11]. In the absence of manganese, all iron precipitates as Al3 Fe. When manganese is added, several types of intermetallic phases are formed in the Al-Mn-Fe series depending on the method of alloying.

Technology Extraction The two principal extraction processes in use today [1214] are (a) electrolysis of molten magnesium chloride and (b) thermal reduction of magnesium oxide. Both processes are used to produce signicant quantities of magnesium, although currently the majority of production on a worldwide scale is by the electrolytic method.

MAGNESIUM SCIENCE, TECHNOLOGY AND APPLICATIONS

205

Electrolysis of molten magnesium chloride. Three different methods of cell-feed preparation for the electrolytic process are currently being practiced. The most difcult part of the cell-feed preparation after eliminating such minor impurities as boron and sulfates, is to separate the magnesium chloride from the six molecules of water that are chemically bound to it. The rst 4 1 molecules of water can be driven off simply by heating, but the last 1 1 2 2 molecules will hydrolyze and form undesirable products upon further heating. Each of the three methods deal with this problem in a different way. About half of the energy required to produce electrolytic magnesium is consumed in the cell feed preparation. In the Dow process, magnesium hydroxide is precipitated from sea water by slurring with calcined dolomite, and then converting to magnesium chloride by reacting it with hydrochloric acid. This product is dried to 1 1 molecules of water and introduced directly into 2 the cells. The by-product chlorine from the electrolytic cells is recycled into hydrochloric acid used at the front end of the process. In the I.G. Farben process magnesium hydroxide is calcined in oxide and chlorinated in presence of carbon to yield anhydrous magnesium chloride cell feed. The by-product chlorine from this process is recycled to the chlorinator. The most recent technology is called the anhydrous process, which starts with a magnesium chloride rich brine which is puried and concentrated by conventional methods. The nal dehydration is carried out by proprietary methods to yield anhydrous magnesium chloride. The by-product chlorine from this process is marketed since it is not needed in the cell-feed preparation. Two types of electrolytic cells are in use today. The Dow cell which is an externally heated rectangular steel pot, and the I.G. Farben type cell which is lined with insulating refractory brick contained in a steel tank without provision for external heating. There are advantages and disadvantages for each type. Thermal reduction of magnesium oxide. There are two thermic processes in use today for the production of magnesium. Both of them use calcined dolomite as ore and ferrosilicon as the reductant in a vacuum furnace. The basic process, as developed by L.M. Pidgeon, uses a 28 cm diameter retort that is externally heated. The magnesium evolves as a vapor and is condensed in the water-cooled end of the retort. This process produces a very high purity magnesium and is still used in Japan and Canada. A variation of this process uses internally heated retorts which allows the use of larger retorts and bigger batches. These are currently used in Italy and Brazil. The Magnetherm process, developed by Pechiney-UgineKuhlman in France, employs an electric furnace with liquid slag. Aluminum or bauxite is added to the charge and acts as a catalyst to keep the calcium silicate slag molten so it may be tapped out in the liquid state. The process is currently used in France, the United States, and Yugoslavia. In the nal step for both electrolytic and thermally produced magnesium, it is rened, alloyed as necessary, and cast into ingots or billets. Production Casting. Most magnesium alloy components are produced via high pressure die casting. Cold chamber machines are used for the largest castings and molten shot weights of >10 kg can now be injected in less than 100 ms at pressures that may be as high as 150 MPa [15, 16]. Hot chamber machines are used for most applications and are more competitive for smaller

206

ELIEZER, AGHION AND FROES

sizes owing to the shorter cycle times that are obtainable. Magnesium alloys offer particular advantages for both these processes [17, 18]: (a) most alloys show high uidity which allows casting of intricate and thin walled parts (b) magnesium has a low specic heat per unit volume compared with other metals, thereby allowing faster cycle times and reduce die wear (c) high gate pressures can be achieved at moderate pressures because of the low density of magnesium (d) iron from the dies has very low solubility in magnesium alloys which is benecial because it reduces any tendency to sticking. Magnesium alloy components can be successfully prepared by sand casting and by gravity casting into permanent molds. However, conventional pouring practice can cause problems owing to turbulent metal ow which may introduce oxides and dross as a result: of the reactive nature of magnesium. Squeeze casting has also been used to prepare higher quality castings from existing alloys such as AZ91 and to produce castings into alloys that could not be cast successfully using conventional processes [19]. Wrought alloys. Production of wrought magnesium alloy products is usually carried out by hot working, mainly by extrusion, rolling and press forging at temperatures in the range 300500 C [20, 21]. Melting. In the molten state, magnesium alloys react with oxygen in the air. This reaction is a comparatively slow oxidation of the metal surface, provided that fumes can escape and that the metal does not become overheated. At temperatures above 700 C the reaction increases rapidly. When melting and rening magnesium [22], the molten metal surface must be protected to prevent oxidation. Various uxes, sulfur, sulfur dioxide or sulfur hexauoride are used for this purpose. In the technique most commonly used, primary metal and scrap metal are melted and rened in a separate melting furnace, and later transferred in molten form to one or more holding furnaces. However, it is also possible to melt and rene scrap metal in the holding furnace. Applications The four principal uses of magnesium [2325] are shown in Table 1, and can be summarized as alloying with aluminum, iron and steel processing, as a structural metal, and electrochemical and other uses. In the following text we will only consider structural uses. Aircraft Magnesium is employed extensively in aircraft engines, airframes and landing wheels [26, 27]. The main factors dictating the use of magnesium have been strength/density ratio in casting and stiffness/density ratio in the wrought forms, combined, as required, with factors such as good elevated temperature, fatigue and impact properties, always with good machinability. The alloys ZE41 (Mg-4.2Zn-0.7Zr-1.3MM), QE22 (Mg-0.7Zr-2.5Nd2.5Ag), and particularly WE43 (Mg-4Y-3.25Nd-0.5Zr) are commonly used for aircraft applications due to their improved corrosion and creep resistance.

MAGNESIUM SCIENCE, TECHNOLOGY AND APPLICATIONS

207

Helicopter components For military helicopters [26, 27], the good ballistic tolerance of ZE41 has made it the most common alloy used, although QE22 has been used where higher strength is required at elevated temperatures. Currently both alloys are being replaced by WE43 and WE54 (Mg5.1Y-3.25Nd-0.5Zr) alloys due to the excellent corrosion and creep resistance of these latter alloys. Cars and light trucks Use of magnesium in automobiles despite its high cost compared to competing metals (conventional steel and aluminum) is justied on the basis of component integration and the near-net shape castability. The most promising applications for magnesium are those where aluminum or plastic are not desirable substitutes for heavier materials such as steel; i.e., substitution for either of these light-weight materials in existing applications is unlikely [2]. This is borne out by the 1997 model cars in North America in which increased use of magnesium has occurred largely at the expense of steel. The use of magnesium in the new models ranges from about 1.4 to 9 kg per vehicle giving an average of 2.9 kg per family car, about 16% more than for 1966 models. The dramatic benet that reduced automobile weight can give in terms of improved fuel consumption is shown in gure 3 [28]. Hence the great interest in magnesium on Partnership

Figure 3.

Fuel economy versus vehicle weight [28].

208

ELIEZER, AGHION AND FROES

for a New Generation of Vehicles (PNGV) automobiles such as the Ford stretched Mondeo/Contour P2000 which is expected to achieve nearly 80 mpg (3.4 l/100 km) [1]. In addition to new power train requirements, this aggressive fuel efciency goal requires that the vehicles body weight and chassis must be reduced by nearly 50% and the total mass be reduced by some 30% or 450 kg (from 1450 kg down to 950 kg) [1]. This has led to extensive evaluation of the potential use of magnesium components to levels in excess of 103 kg (10% magnesium) from a present 2.6 kg; a magnesium intensive vehicle [1]. The magnesium industry has made great efforts to educate the automotive industry on the benets of utilizing magnesium to reduce vehicle weight, cost, and /or complexity. Applications for magnesium in automobiles, using the die casting approach, has been in components such as instrument panels, steering wheels, steering columns and seat risers which take advantage of magnesiums high strength-to-density ratio, excellent ductility combined with attractive energy absorbing characteristics. The most common automotive alloy today is AZ91D and AM60B (Mg-6Al-0.3Mn). In addition, alloy AS41B (Mg-4Al-0.3Mn-1Si) has some North American automotive applications. Magnesium parts in production include: accessory drive brackets (AZ91D), automatic transmission clutch piston and stator (AS41B), clutch housing (AZ91D), door mirror brackets (AZ91D), headlamp retainers (AZ91D), upper and lower inlet manifolds (AM60B, AZ91D) oil lter adapter housing (AZ91D), power window regulator housings (AZ91D), seat frames (AM60B), steering wheel armatures (AM50 [Mg-5Al-0.3Mn], AM60B) and valve and cam covers (AZ91D). Typical applications for magnesium in automobiles are shown in gures 4 and 5. Missiles and space exploration Strength and rigidity at minimum weight, coupled with ease of fabrication are important for missile and space applications. However, the designer of missiles and space probes needs other properties in his materials of constructions. Conditions in space ight are

Figure 4.

Diecast magnesium alloy seat frame [3].

MAGNESIUM SCIENCE, TECHNOLOGY AND APPLICATIONS

209

Figure 5.

Steering column assembly composed of three magnesium diecastings [3].

rigorous, involving extremes of temperature from aerodynamic heating, sudden immersion in shadows, and proximity of some components to liqueed fuels: ozone and free radicals in the upper atmosphere: bombardment by short wave electromagnetic radiation, high energy particles and micrometeorites: vacuum down to 1011 mmHg. EZ33 (Mg-2.7Zn-0.7Zr-3.2MM) sand casting are used in the Skylark research rockets. Limited information is available on British missiles, but it is known that ZK51 (Mg-4.5Zn0.7Zr) and ZE41 castings have been used extensively for structural parts. American use of magnesium in missiles has been widespread and some of the more important types of application are listed in Table 3.
Table 3. American use of magnesium in missiles. Form of Mg Sheet Missile structure Body skins, stiffeners, formed bulkheads, and rings Control surface skins and ribs Engine air inlets and ducts, nose cones and cowlings External fairings Fabricated doors Radar antennas Pneumatic system bottles Bodies, stringers, etc. Support ttings, brackets Wave guides External tunnel fairing for wiring and plumbing Control surface stringers, integrally stiffened wing skins, leading and trailing edges Engine components and support components Body rings Fins

Extrusions

Castings

210

ELIEZER, AGHION AND FROES

Figure 6.

Thin-walled magnesium case and chassis for a hand-portable cellular telephone [3].

Nuclear energy industry With natural uranium as a fuel, it is essential to conserve neutrons by only using materials in the reactor which will not absorb them readily. Natural uranium plants with operating temperatures suitable for power production essentially determine the general reactor design and limit the canning material to magnesium and the coolant gas to magnesium dioxide. The advantages of magnesium over competing materials are: (a) low tendency to absorb neutrons, (b) does not alloy with uranium, (c) adequate resistance to carbon dioxide up to the highest service temperatures envisioned, and (d) good thermal conductivity. Appliances and sporting goods The trend has been for an increase in the use of magnesium die castings and examples are computer housings and mobile telephone cases (gure 6) where lightness, suitability for thin wall casting and the characteristic of electromagnetic shielding are particular advantages.

Future developments There are a number of developments occurring in the overall magnesium scenario which bode well for the future. In the science base there is an awareness that to see the greatest utilization of magnesium, both cast and cast and wrought, an adequate scientic underpinning is required. This includes development of deformation behavior in processing to obtain desired microstructures (thus mechanical properties) and near-net shapes (minimized machining). There is also the necessity to greatly improve our understanding of phase transformations to allow development of cast and wrought alloys paralleling those available in the aluminum system.

MAGNESIUM SCIENCE, TECHNOLOGY AND APPLICATIONS

211

Current world operating capacity is 346,000 metric tons with increase forecast at existing plants such as Norsk Hydros Porsgrunn, Norway facility (8,000 tpy to almost 70,000 tpy) and B cancour, Canada (50% increase to 60,000 tpy). Dow is also considering increasing e capacity at Freeport, Texas (15,000 tpy to 91,000 tpy). New projects include the 25,000 tpy Dead Sea plant in Israel, Noranda (extraction of magnesium from asbestos mine tailings) Magnola Metallurgy (a joint venture between Noranda Metallurgy, die caster Aisin, SGF and SNC Lavalin). Other developments are occurring in Iceland using a new chlorinefree technology developed in the Former Soviet Union (Icelandic Magnesium, Salzgitter Anlagenbau, Consortium Magniy and Icelands Sudurnes Regional Heating Coop) with 50,000 tpy capacity. Activity is also occurring in China, and in the growth of secondary (recycled) magnesium [29]. The net result of these expansions could double the worldwide capacity by the early next century. The pressure, particularly in the USA to decrease the weight of automobiles in programs such as PNGV could see up to 103 kg of magnesium in vehicles such as the Ford P2000 [1]. This can do nothing but greatly increase magnesium use, particularly as design criteria is developed. Conclusions The science, technology and applications of magnesium and its alloys has been reviewed. Magnesium has a number of attributes and deciencies compared to competing lightweight metals such as aluminum and titanium. However, the very low density of magnesium, in combination with other attractive features such as castability is leading to an expanded market especially for automobiles. Increased use can come from an expanded design base, better understanding of the fundamentals of magnesium behavior, and development of cost-affordable cast and wrought alloys. References
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. G. Cole, Magnesium applications in Fords PNGV, Mondeo, 24. M. Nurse, MBM 1997, 52. I.J. Polmear, Materials Science and Technology (1994), vol. 10, pp. 114. M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions (National Association of Corrosion Engineers, TX, 1974), p. 141. J.E. Hillis, Light Metals Age (1983), p. 25. K.N. Reichek, K.J. Clark, and J.E. Hillis, Controlling the salt water corrosion performance of magnesium AZ91 alloy, SAE Technical Paper, No. 850417, 1985. O. Lunder, T.K. Aune, and K. Nisancioglu, CorrosionNACE (1987), vol. 43, pp. 291295. T.KR. Aune, O. Lunder, and K. Nisancioglu, Microstructural Sci. 17, 231 (1989). J.D. Hanawalt, C.E. Nelson, and J.A. Peloubet, Trans. AIME 147, 273 (1942). F.A. Fox and C.J. Bushrod, J. Inst. Metals 70, 325 (1944), 71, 255 (1945). H.A. Robinson and P.F. George, Corrosion 10(6), 182 (1954). A.M. Cameron, A.V. Hatten, and V.G. Aurich, Proceeding of Magnesium Technology Conference (London, 1987), vol. 119, pp. 717. J. Wiley and S. Inc, Kirk-Othmer, 3rd edition (1981), vol. 14, pp. 576590. P.S. Desikan, Light Metals: Science and Technology, Proceeding of an International Symposium (Switzerland, 1985), pp. 128223.

212

ELIEZER, AGHION AND FROES

15. F. Klein, Proc. Int. Conf. on Magnesium Alloys and their Applications (DGM Informationsgesellschaft, Oberursel, Germany, 1992), p. 53. 16. T.KR. Aune and H. Westengen, Ibid., p. 221. 17. J.E. Ebbesen, Ibid., p. 267. 18. G.A. Chadwick and A. Bloyce, Ibid., p. 93. 19. H. Westengen, Proc. Int. Conf. on Recent Advances in Science and Engineering of Light Metals (Japan Institute of Metals, Tokyo, 1991), p. 77. 20. C.V. Raynor, The Physical Metallurgy of Magnesium and its Alloys (Pergamon Press, London, 1959). 21. C.S. Roberts, Magnesium and its Alloys (Wiley, New York, 1960). 22. Magnesium Pure and Alloys, Norsk Hydro Report. 23. E.F. Emley, Principles of Magnesium Technology, 1st edition (Pergamon Press, 1966). 24. Magnesium Materials, A Publication of Magnesium Elecktron (1993), p. 1. 25. J.E. Harris, Light Metals: Science and Technology, Proceeding of International Symposium (Switzerland, 1985), p. 225. 26. E. Aghion, B. Bronn, and I. Schwartz, Magnesium Applications in the Aerospace IndustryA Review. 27. Magnesium Electron Limited, Magnesium Alloy Database, MATUS Databases, Engineering Information Co. Ltd., 1992. 28. S. Sugimoto, 53rd Annual Magnesium Congress (Ube City, Japan, 1996), p. 38. 29. T. Gill, MBM 1997, p. 63.