Aluminum Overview

The Properties and Uses of Fluxes in Molten Aluminum Processing

T.A. Utigard, K. Friesen, R.R. Roy, J. Lim, A. Silny, and C. Dupuis
Gaseous and solid fluxes play an important role in the degassing, demagging, and fluxing of aluminum and its alloys. Inert as well as reactive gases, or hexachloroethane, may be used to remove dissolved hydrogen and sodium. Magnesium may be removed by chlorine or an aluminum-fluoride-containing flux. Fluxes based on a KCl-NaCl mixture may be used to cover and protect the metal from oxidation. To recover aluminum from drosses, a more reactive flux containing cryolite or some other fluoride may be used. In this article, the thermodynamics of aluminum melting and refining are analyzed in terms of the behavior of sodium, magnesium, and calcium. The coalescence of aluminum drops in salt fluxes improves with fluoride additions. With increasing MgCl2 contents in the flux, the effects of NaF and KF additions become much less pronounced. INTRODUCTION For the treatment of aluminum and its alloys, various molten-metal processing steps are necessary in addition to melting and alloying. Historic practices, such as fluxing, metal refining, deoxidation, degassing, and grain refining, are being used in addition to newer in-line technologies, such as metal degassing, fluxing, and filtration. The term fluxing is used to represent all additives to, and treatments of, molten aluminum in which chemical compounds are used. These compounds are usually inorganic and may perform several functions, such as degassing, demagging, cleaning, and alloying. Fluxing also includes the treatment by inert or reactive gases to remove inclusions or gaseous impurities. When melting aluminum scrap in open charging well furnaces, a salt-potashfluoride flux is often used on the open surface of the bath to eliminate the formation of oxides and to cause the agglomeration of small beads of aluminum, improving metal recovery. In other cases, fluxes are used to remove oxide build-up from furnace walls or to eliminate and/or reduce oxidation. While fluxes require energy, they are effective in lowering the aluminum content of the dross/mush, and the amount of alumiBoiling Point (C) 1,325 1,413 1,500 1,600 1,412 177.8 1,560 1,676 1,695 1,505 2,500 2,239 1,291* 600 380 400 high 1,689 high 1,124 1,310 high high 350 850

num that is skimmed from the furnace can be substantially reduced. FLUX COMPOSITIONS Solid fluxes are mainly blends of chloride and fluoride salts with additives to instill special properties. Most fluxes are based on a mixture of KCl and NaCl, which forms a low-temperature (665C) eutectic. Another common ingredient in fluxes is NaF, which forms a ternary eutectic with KCl and NaCl with a melting point of 607 C. A common cover flux contains about 47.5% NaCl, 47.5% KCl, and 5% fluoride salt. A low melting point is important since it will improve the fluidity of the flux. Other cover fluxes are based on MgCl2KCl, which forms a low melting eutectic at 424C, or carnalite (MgCl2KCl), which melts at 485C. These cover fluxes have high fluidity and can form a thin layer on the melt surface. However, MgCl2 is fairly expensive, so it is primarily used in sodium-free fluxes for alloys containing more than 2 wt.% magnesium. They may also be used where it is important to remove calcium in alloys of fairly high magnesium content. Many ingredients are available (Table I); these additives affect properties such as fluidity, wettability, and reactivity (Table II). Alkali-fluoride salts act as surfactants,1 decreasing the surface tension between the flux and the metal (Figure 1) and between the flux and the oxides. Chloride salts, as well as AlF3 and MgF2, exhibit this property to a much lesser extent,13 because with NaF- and KFcontaining fluoride salts, the aluminum easily picks up some sodium or potassium, which are both surface-active elements.46 Although rarely analyzed, it is expected that potassium has negative effects similar to those of sodium on the properties of the final aluminum product. Fortunately, due to their similar properties, the techniques used to remove sodium should also remove potassium. Alkali-fluoride salts have a slight (although very small) solubility of oxides, which facilitates penetration into oxide films that contain metallic aluminum in dross and build-up. This leads to improved wettability, favoring separation of oxide inclusions from the melt and JOM November 1998

Chemical LiCl NaCl KCl CaCl2 MgCl2 AlCl3 BaCl2 LiF NaF KF CaF2 MgF2 AlF3 Na3AlF6 LiNO3 NaNO3 KNO3 Li2SO4 Na2SO4 K2SO4 CaSO4 MgSO4 Li2CO3 Na2CO3 K2CO3 MgCO3 CaCO3
* Sublimes Decomposes

Table I. Characteristics of Materials Used in Fluxes Molecular Mass Solid Density Melting (g/mol) (g/cm3) Point (C) 43.39 2.068 605 58.44 2.165 801 74.56 1.984 770 110.99 2.15 782 95.22 2.32 714 133.34 2.44 190 208.25 3.92 963 25.94 2.635 845 41.99 2.558 993 58.1 2.48 858 78.08 3.18 1,423 62.31 3.18 1,261 83.98 2.882 209.94 2.9 1,010 68.94 2.38 264 84.99 2.261 307 101.11 2.109 339 109.94 2.221 859 142.04 897 174.27 2.66 1,069 136.14 2.61 1,450 120.37 2.66 73.89 2.11 723 105.99 2.532 851 138.21 2.42 894 84.32 2.96 100.09 2.71 1339

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