Metallurgical Uses – Fluxes for Metallurgy

A metallurgical/flux is a substance that is added to combine with gangue (unwanted minerals) during ore smelting, with impurities in a molten metal, or with other additives in metal refining processes to form a slag that can be separated from the metal. Because slags are immiscible with the metallic melt and are of lower density, a separation of the slag and metal occurs if the viscosity and surface tension are of the proper values. The chemistries of slags are adjusted to provide the proper melting point, viscosity, surface tension, conductivity, specific heat, density, or chemical properties to effect the desired task. In addition to absorbing impurities from the metal, the purposes of the slag are to thermally insulate the metal bath, protect the molten metal from the atmosphere, and control the chemical potential of the system. Several excellent references on slags and metallurgical fluxes are available (Boynton, 1980, Lankford, Jr., et al., 1985, Turkdogan, 1983, Rosenqvist, 1974, Fine and Gaskell, 1984). The function of the slag might vary at different stages within a process prior to final melting. For example, the slag composition and behavior will change as materials descend in the iron blast furnace, or as they melt in the early stages of formation of steel- making slags. Selection of the chemistry for a slag might be influenced by factors outside the primary function as when blast furnace slags are used to make cement, rock wool insulation, or fertilizer supplements. Sometimes slags contain a sufficient amount of valuable recoverable elements to be sold as raw materials for other processes. Fluxes are often referred to as acid, basic, or neutral. Acid fluxes are those that generally form acids in water and bases are those that would generally form bases in water. Typical acid fluxes are silica, alumina, and phosphorus, although alumina can function as either an acid or base. Typical basic fluxes are lime and magnesia. Fluorspar, or calcium fluoride, is a neutral substance because it can be viewed as the reaction product of a base and an acid. The degree of acidity (ratio of acids to bases) or basicity (ratio of bases to acids) is often specified to characterize the slag chemistry for a particular system. The system might also be referred to as acid or basic depending on the choice of slag, for example, basic steelmaking uses slags with more bases (lime and magnesia) than acids (silica and alumina). Many forms of minerals and compounds have been used as fluxes depending on the process requirements, availability, costs, requirements for recycling of intermediate products, and environmental concerns. Because slags are most often mixtures of oxides and silicates, fluxes are usually oxides, carbonates (which decompose to oxides) and silicates. Slags comprising phosphates, borates, sulfides, carbides, or halides have also been used (Rosenqvist, 1974, Moore, 1981, Szekely et al., 1989). In ironmaking and steelmaking, some acidic components are sometimes added. In nonferrous processes slags and fluxes are acidic with silica as the primary component, and although the use of basic flux such as limestone or lime is not extensive, some amount is used to modify slag properties and some refining slags are lime based. The production of iron is accomplished by smelting of ores, pellets, and sinter in blast furnaces with subsequent refining of molten iron and scrap in oxygen-blown processes. The electric furnace is used to make steel, stainless steels, ferroalloys, and special alloys, whereas ferromanganese is often made in blast furnaces. Fluxes are used in all of these processes, and either limestone or lime is the major flux component with some dolomite, dolomitic lime, silica, alumina, and fluorspar being used. In ironmaking, the flux is added either by direct charging or through sinter and fluxed pellets. In steel refining by the basic oxygen process, flux is added as lime and dolomitic lime that are either charged as lumps or injected as fines. Some small amount of limestone is sometimes used. Fluorspar is often added as lumps or mixed with other fine materials in briquettes. Alumina is sometimes added to blast furnaces either by direct charging of sized lumps or through sinter. Typical acid fluxes are sand, gravel, quartz rock, used silica brick, or raw siliceous ore (Lankford, Jr., et al., 1985). Olivine, which is a magnesium-silicate mineral, has been added to iron blast furnaces to enhance removal of alkalis (Lankford, Jr., et al., 1985). Alumina in the form of bauxite, aluminiferous clay, and recycled alumina brick has been used as flux. Alumina can function amphoterically as either an acid or base, for example it can form aluminum silicate in high silica slags or calcium aluminate in lime-bearing slags (Lankford, Jr., et al., 1985). Limestone (calcium carbonate) and dolomite (magnesium-calcium carbonate), or fluxstones as they are sometimes called (Boynton, 1980), and their calcined forms, lime and dolomitic lime are the major basic fluxes. In the latter cases, the carbonates are de- composed in a kiln-type process to drive off carbon dioxide that might otherwise interfere with the subsequent smelting or refining process or require expensive forms of energy to effect the decomposition (e.g., by combustion of coke in the iron blast furnace). Limestone is considerably less expensive than lime because it is not calcined; however, lime is far more difficult to handle and reacts readily with water. Dolomite and dolomitic lime are used for their magnesia content. Fluorspar is a neutral flux often used as an additive in steel- making slags to improve fluidity, but it has also been used in combination with lime as a primary slag in electroslag refining (Duckworth and Hoyle, 1969). Fluorspar is available in several grades, with the lowest grade often used for steelmaking. When the price of fluorspar has risen, substitutes including aluminum smelting dross, borax, manganese ore, titania, iron oxides, silica sand, and