Magnesium Technology 2003 Edited by Howard I.

Kaplan TMS (The Minerals, Metals & Materials Society), 2003

TECHNOLOGIES FOR EFFICIENT MG-SCRAP RECYCLING

Gerhard Hanko1, Gernot Macher2
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University of Leoben; Franz-Josef Strae 18; Leoben, 8700, Austria ecka granules-non ferrum; Brmooser Landesstrae 19; St. Georgen, Salzburg, 5113, Austria Abstract primarily for decorative and corrosion protection. Depending on what is expected of the finish, mechanical and chemical finishing methods are available. The wide spread field of magnesium appliances along with its diversified alloy composition and its different surface treatments make recycling tremendously difficult.

Currently, only high grade clean Mg-scrap without impurities can be recycled easily into high purity alloys. More complex handling is required for old magnesium-base or post consumer scrap e.g. automotive parts and electronic devices. The additional process steps determine the economical attractiveness of Mg-recycling. This article will provide a detailed overview of the current research activities of ecka granules - non ferrum, Austria, in cooperation with the department of non-ferrous metallurgy at the University of Leoben, Austria, concerning different Mg-Recycling technologies. Aim of the investigations is the optimisation and implementation of refining methods in consideration of metal loss reduction.

The Secondary Magnesium Industry Magnesium is a highly recyclable material, consuming only 5% of the energy required to manufacture the primary metal. Currently only high quality magnesium scrap can be recycled easily into high purity alloys. As magnesium becomes specified for an increasing number of applications, the recycling of secondgeneration components from the recovery of end of life products is likely to play an increasingly important role in the supply of magnesium in the long term. To realise this prediction, effective recycling technologies must be installed in the industry. The effort for the magnesium recovery depends on the chemical and physical quality of the scrap. Preliminary treatments for efficient recycling can include shredding, sorting, briquetting and delaquering. The additional process steps required for effective magnesium melting determine the economical attractiveness of recycling. The demand by designers and end users for high purity magnesium alloys for the majority of new applications suggests that, unlike for other materials, a two-tier system of alloys, i.e. primary and secondary, is unlikely to evolve. In todays marketplace, recycled alloy ingot is required to meet the same ASTM quality criteria as primary metal in terms of chemical composition and oxide content. Utilising post consumer scrap in the iron and steel industry is also an option for recycling. Magnesium is used as an external hotmetal desulfurisation reagent and in the production of nodular iron. In most of the cases the steel producer has the flexibility to inject lower cost raw material into the molten iron. Magnesium used can be derived from low-quality streams or alloy scrap, which is then ground into a coarse powder. However, when the magnesium market is very tight, post consumer scrap may be considered more seriously. The European Mg-Recycling industry has installed a capacity of 75,000 tpy. In Europe Hydro Magnesium is the largest recycler of magnesium scrap. In 2002 the cast house in Porsgrunn, Norway, started remelting operations with a capacity of 20,000 tpy. It also has a 7,500 tpy recycling plant at Bottrop, Germany. Magnesium Elektron has two refining centers in Manchester, UK, with a total melting capacity of 14, 000 tpy. The new facility in Litvinov, Czech Republic, has a melting capacity of 10,000 tpy. Therefore
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Introduction It is the use of magnesium as a strategic lightweight material in the automotive industry that has spurred the growth of magnesium in the high pressure die casting sector over the last decade at an annual rate of 15%. This growth is dedicated to continue at a rate of 12% per annum for the next ten years. Several specified magnesium alloys containing lithium, scandium, yttrium, zirconium or rare earth elements can meet the requirements for improved corrosion performance, for creep resistance and for excellent castability. Magnesium has a long tradition of use as a lightweight material in the field of automotive and aerospace constructions. In the recent years the information and communication industry has also recognised the benefits to be gained of noise and vibration reduction, of rigidity and strenght in smaller components, of great heat conductivity and of electromagnetic shield by utilising magnesium alloys. Chassis for cameras, projectors, notebooks are manufactured from magnesium alloys using high pressure die casting, thixomoulding and press forging technologies. Due to is unique physical and chemical properties, magnesium is now be considered for a broader range of household appliances. In typical magnesium die casting operations, only around 50% of the metal input is converted into components. The residual implies scrap descending from different stages of the die casting process. Casting return material can contain biscuits, sprues, runners, flash, overflows, dross, sludge, scrap parts and uncoated rejects from a later step in the finishing process. If a magnesium part is to perform satisfactorily in a particular application, it has not only be designed to meet the mechanical requirements but environmental factors, finishing and assembly methods must also be properly considered. Surface treatments are applied to magnesium parts

the Elektron-group melting capacity is 24,000 tpy. Remag is an independent Austrian metal trading company operating melting plants in Hungary and the US for the recycling of magnesium. The recycling plant at Schalgotarjan, Hungary, has a capacity of 5,000 tpy. In October 2003 Remag expects to start production at its 10,000 tpy magnesium recycling plant in Delfzijl, Netherland. ecka granules-non ferrum at St.Georgen, Austria, opened a state of the art recycling plant with a melting capacity of 3,500 tpy in May 2000.
others 5,000 REMAG Delfzijl 10,000 tpy REMAG Schalgotarjan 5,000 tpy ecka granules non ferrum St. Georgen 3,500 tpy Hydro Magnesium Porsgrunn 20,000 tpy

The removal of metallic contaminants by pyrometallurgical refining with the aid of manganese, zinc, cobalt, beryllium, boron, titanium or zirconium additives is based on intermetallic compound formation. Addition of these refining reagents form intermetallic particles with the impurity contaminants, which then precipitate out of the melt. At the present the recycling and refining of magnesium is focused on the remelting process. Distillation seems to be an alternative method for recovering non class 1 by products such as dross and sludge, machining chips, floor sweeping or other contaminated scrap. Most of the impurities are less volatile than magnesium and get enriched in the remaining residue. Figure 2 shows the recycling circuit of end of life products.

Hydro Magnesium Bottrop 7,500 tpy

Decoating / Delaquering In order to maximize magnesium recovery it is essential to remove organic coatings such as lacquer, paint or oil prior to melting as completely and as economically as possible with minimal interference to the magnesium surface. Thermal treatment has become the most widely used decoating process; the use of solvents is an expensive method and not very acceptable from the environmental point of view. The three principal decoating technologies are the rotary kiln, the belt decoater and the fluidized bed decoater. An important benefit of a decoating step is that gaseous emissions, arising from the organics, can be easily confined and thus controlled and neutralized.
Gas and Tar CO and CO2

Magnesium Elektron Litvinov 10,000 tpy

Magnesium Elektron Manchester 14,000 tpy

Figure 1: Recycling capacity in Europe

Recycling Scenarios Sorting magnesium residues correctly is essential for the recovery into products, which meet specifications. Mg-scrap, which is classified into several categories /1,2/, may be restored to products by selecting the correct recycling process. The recycling method is determined by the chemical and physical composition of the scrap; after sorting big Mg parts must be shredded, paint or oil removed and fine fractions compacted. Mg scrap containing high quantities of oxides require special precautions during recycling. While the amount of oxides and certain metallic impurity elements can be diminished when remelting postconsumer scrap, it is not possible to eliminate elements such as nickel and copper. If present in excessive amounts, these elements can have a detrimental impact on alloy performance, particularly corrosion resistance.
Shredding Thermal Treatment

Organic Magnesium

Heat Volatilization

Char

O2 Combustion

C and MgO

Gas and Tar Relative Amount of Organics Released Volatilization

C and MgO Combustion Decoating Time

Figure 3: Principle of decoating /3/

Mg-Scrap

Rotary Kiln

Mg-Zn Masteralloy

Mg-Alloy for Desulfurisation

Distillation Column

Melting / Batching

Briquetting

By eliminating residual moisture in the magnesium scrap, the safety of the melting process also gets improved. The level of organics on magnesium scrap does not exceed 10%. Paint and laquer that adhere very thightly on the magnesium surface, represent 2-5% of the coated scrap weight. Oil contaminated magnesium chips are first centrifuged so that the amount of residual oil gets reduced to 7-10%. Despite the pyrophoric characteristics of thin walled magnesium alloy die-castings and magnesium chips the thermal treatment is a safe and efficient method of removing paint and oil. The temperature range for an entire decomposition of the organic coating depends on the process atmosphere, on the melting point of the magnesium alloy and on the composition of the organics.
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Melt Transport/ Ingot Casting

Batching Furnace

Melting Furnace

Figure 2: Recycling circuit

In air atmosphere a temperature range of approximately 200C 400C is required to remove the majority of the organic compound. When inert gas is used for the thermal process, the upper temperature limit can be increased to 450C and consequently the time for thermal decomposition will be diminished. Due to the decomposition of the organics the atmosphere around the particles gets reduced. That is the reason why oxidation of the magnesium surface is restrained. Products obtained from decomposition of organics are divided in a gaseous, liquid and solid phase. The liquid phase is usually known as tar. A mixture of inert substances and combustible material, called char, form the solid phase. The proportion of each phase formed depends on the nature of the organics, on the heating rate during decoating, on the final decomposition temperature and on the process atmosphere. When the temperature for thermal decoating rises, the formation of char and tar gets minimized while the amount of gas is increased. At the beginning of decoating gas and tar fractions are removed by volatilization. Following the step, a layer of residual char adheres to the surface of the magnesium shreds. The mixture of carbon and magnesiumoxide form a protective coating on the scrap. Therefore it is possible to expose hot magnesium parts to direct contact with air without the risk of ignition.

Removal of metallic and non-metallic inclusions A variety of melting processes are in current use, based on the use of refining fluxes as well as fluxfree methods. The magnesium recycling industry both in Europe and North America favour a combination of flux refining and inert gas sparging. Once the magnesium scrap is molten, the flux absorbs the oxide particles to form a conglomerate, which is significantly denser than the molten magnesium. Fine dispersed inert gas bubbles injected by an impeller treatment, float this conglomerate to the surface of the melt, while simultaneously removing much of the hydrogen. At the top of the melt a cluster of particles can be removed. The dross and sludge removed tends to catch fire in the open atmosphere and should be deposited in tight containers. Due to this refining method very high levels of metal cleanliness can be achieved, equal to that of primary metal. When the fluxing procedure is properly carried out, a melting efficiency of over 97% can be obtained in a single operation involving melting, flux refining and pouring.

Briquetting Briquetting fine magnesium chips dramatically reduces the volume, making the shipping of the material safer, easier and more cost effective. The compacting of oily chips should be carried out after the decoating step to minimize the risk of ignition. During the briquetting of the chips heat is generated. The grade of compacting achievable is above 90%. Impeller for fine dispersing inert gas Removal of floated conglomerates

Figure 5: Impeller treatment at ecka granules-non ferrum

Removal of iron Since magnesium scrap is normally processed in crucibles constructed from iron or steel, special precautions have to be taken to avoid enrichment of iron in the melt. The iron level in ingots is kept below the maximum limit of 0.004% by adding manganese while alloying the melt. Manganese is already present in magnesium alloys as an alloying addition between 0.17%0.50%. Further additions reduces the liquid solubility of iron. The excess iron is removed by precipitation and settling of intermetallic particles containing iron and manganese in combination with other alloying elements. Following this treatment, ingots saturated in iron are produced at the chosen casting temperature. Thus, provided, that excessive temperature fluctuations are avoided and the minimum manganese content is maintained, melting of ingots will not result in iron being picked up. Although this technique is successful in removing iron, the residual manganese content of the alloy can become variable, potentially leading to excessive sludging in the crucible. Zirconium can be used to precipitate iron from magnesium melts in form of insoluble compounds. Removal of iron by zirconium is mentioned by several authors /4,5,6/ and is widely practiced. The process works even with Al-Mg type alloys, despite the presence of aluminum. Iron contents of 0.002% are quite promptly achieved by addition of sufficient zirconium to induce a slight grain refinement followed by a settling period.
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Figure 4: Mg-Briquetts

Melting and pyrometallurgical refining Melting of scrap is usually carried out on a batch or semicontinuous basis using a flux or suitable protective atmosphere to ensure the molten magnesium does not react with air. Scrap magnesium must be refined of dissolved gases and metallic contaminants and of different intermetallic and non-metallic inclusions prior to being reintroduced into the die casting operation as feedstock material to ensure that the metal is free from impurity contaminants, which can have a detrimental impact on material properties. The types of inclusion, which can be found in melts are given in Table I. Therefore it is the refining process which forms the basis of a successful remelting operation.

Table I: Common contaminants in magnesium melt Contaminant Dissolved gases (hydrogen) Dissolved metallic contaminants (iron, nickel, copper,) Organic contaminants Intermetallic particles Salt Oxide/nitride particles Oxide films Origin Reaction with ambient atmosphere Descending from unsorted, unclean scrap; Picked up from the processing equipment Descending from paint, lacquer, oil Precipitate during refining process Electrolysis Reaction with air Reaction with air/SF6-SO2 mixture Characteristics of inclusion

Crystalline particles (0.5 to 15 m) Na, Ca, Mg or K-based chlorides Cluster of particles (1 to 100 m) 0.1 1 m thick; 10 150 m longfilms

Titanium, which has a very low solubility in magnesium, possesses the ability to form intermetallic compounds with iron. Hence titanium is also a most effective refining reagent in removing iron from the magnesium melt.

out in vacuum, the distillation of magnesium must be carried out with exclusion of air in an inert atmosphere.

Outlook The problem elements The term high purity was introduced in the early 1980s, to describe alloys with a low content of impurities like nickel and copper. In order to keep the level of nickel and copper in the alloys low, the raw materials have to be carefully selected. In addition, the materials used in equipment for processing the molten metal should contain no nickel or copper. Nickel is extremely detrimental to the corrosion resistance of magnesium alloys and must be limited to a maximum of 0.002% in the finished parts (0.001% in ingots). It is highly soluble in magnesium alloys. Copper also decreases the corrosion resistance of magnesium alloys although the tolerance limit is far higher than for nickel. Contamination from copper bushings etc. in recycled parts can cause enrichment of copper to levels higher than the allowable maximum limit. To date, no technology exists to refine molten magnesium of copper or nickel. The remelting of clean and compact magnesium material, which represents about 70% of all generated scrap, does not represent a challenge to a magnesium recycler any longer. The recovery of old magnesium base scrap, or postconsumer scrap, is still difficult. This type of scrap is dirty or corroded, contains all sorts of coatings and shows detrimental surface to mass ratios. To prolong the growth of magnesium applications in the field of automotive and aerospace constructions, in the information and telecommunication industry, the loop in the recycling circuit of magnesium should be closed.

References 1. J.F. King, A. Hopkins and S. Thistlethwaite, Recycling of By-Products from Magnesium Diecasting, Proc. 3rd Internatioan Magnesium Conference, Manchester, 10-12 April 1996, 51-61. H. Antrekowitsch, G.Hanko and P. Ebner, Recycling of Different Types of Magnesium Scrap, Magnesium Technolgy 2002, TMS, 2002, 43-48. W. Stevens and F. Trembay, Fundamentals of UBC Decoating / Delaquering for Efficient Melting, Light Metals 1997, TMS, 1997, 709-713. E.F. Emley, Principles of Magnesium Technology, Pergamon Press, 1966. W.G. Green and J.E. Hillis, Process for Producing High Purity Magnesium, U.S. Patent 4,891,065, 1990. Kh.Kh. Sabirov and G.N. Topalova, Development of Effective Technology for Deep Refining of Magnesium, Russian Journal of Non-Ferrum Metals, 41, (2000), 72-75.

Distillation Distillation of contaminated magnesium could be an innovative refining method. Almost all types of return materials can be utilized. The most of the impurities are less volatile than magnesium. Manganese, aluminum, nickel, copper, chrome and iron have high boiling points. The refining effects obtainable are determined by the equilibrium conditions, for instance, by the pressure of the reaction gases above the magnesium melt. Contaminated magnesium is charged into the distillation column where the less volatile elements as iron, copper and nickel get removed along with a part of the magnesium from the bottom. The rising magnesium vapor condenses at the top of column. Depending on the charged material purified magnesium or a zinc magnesium masteralloy can be obtained. It is also possible to utilize the residue remaining in the bottom of the column, as desulfurisation reagent in the iron and steel industry. By application of vacuum the distillation temperatures may be lowered, the evaporation rate increased and the possibility to enhance the separation of the components improved. If not carried

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