Extractive Metallurgy Division - Melting Points in the System TiO2-CaO-MgO-A12,O13

The melting points of mixtures of titanium dioxide and other titanates have been reported to a limited extent as binary systems and some results have been reported in conjunction with silicon dioxide. The limited data indicated that a low melting zone might exist in a ternary or quarternary system of CaO-MgO-TiO2-Al2O3, since the eutectics reported in the binary systems of MgO.TiO2-TiO2, Al2O3TiO2-TiO2 and CaO.TiO2-TiO2 were of about equivalent composition of TiO2. The importance of a low melting region with a high titanium oxide value in the developing of high titanium slags is fully appreciated by metallurgists. A comprehensive study was undertaken to establish basic information on low melting titanate mixtures. Compounds in the System CaO-MgO-TiO2 -Al2O3 Preparation of the titanates of CaO, MgO and Al2O3 confirmed reported data that the following compounds could be formed under oxidizing conditions in solid state reactions: CaO.TiO2, 2MgO.TiO2, MgO.TiO2, MgO-2TiO2 and Al2O3.TiO2. Under oxidizing conditions it was not possible to react MgO with TiO2 in mol ratios higher than 1:2 without having unreacted TiO2 in the product, nor was it possible to form calcium or aluminum titanates with a higher mol ratio of CaO and A12O3 to TiO2 than 1:1. By fusing mixtures of Al2O3-TiO2 and MgO-2TiO2 together a series of solid solution products were obtained, which showed an MgO-2TiO2 X ray diffraction pattern shifted to smaller inter-planar spacings. Range of Investigation Data in the literature1 indicated that these titanates had melting points which ranged from 1645 to 1860°C. Since the purpose of the study was primarily to provide useful data for smelting titaniferous ores, the work was restricted to the zone of the system which would include the crystalline phases present in the slags. The explored limits were bounded by CaO.-TiO2-MgO.TiO2-TiO2in the base plane. The system was extended to a fourth component Al2O3-TiO2 since many titaniferous ores contain appreciable amounts of A12O3. In the quarternary system CaO-TiO2-MgOTiO2-TiO2-Al2O3TiO2, a tetrahedron was used to represent graphically the components, with one component at each point of the tetrahedron. In the base plane, mixtures were pre- pared to represent fairly uniform changes of composition over the desired range expressed on a mol percent basis. Al2O3-TiO2 was brought into the system in increments of 10 mol pct up to 40 pct. Mixtures were then made up for each of the Al2O3-TiO2 planes. The ranges employed were then represented by five planes cutting the tetrahedron at 10 mol pct Al2O3-TiO2 intervals. Choice of Equipment Although it was necessary for all smelting work to be done in a strongly reducing atmosphere, it was decided that all melting point determinations should be done under oxidizing conditions. This decision was prompted by the fact that TiO2 reduced to lower oxides in a reducing atmosphere with consequent changes in melting points. The use of a micropyrometer and a platinum strip furnace for work of this type is adequately described in the literature.2 With modifications, equipment was selected which provided a fairly rapid method of determining melting points of refractory oxides. The final assembly, which was used, consisted of a platinum strip furnace and a Leeds and Northrup disappearing filament optical pyrometer attached to a special telescope which magnified the sample about 20 diam. The furnace assembly consisted of a platinum strip 0.005 X 0.3 X 2.2 in. mounted on brass posts on a refractory base. This was enclosed in a black steel shell which had a 2-in. opening at the top for purposes of sighting the telescope. The platinum strip was in series with two 0.04 ohm nichrome resistors connected to the secondary of a 2 kw transformer which supplied 17 volts. The current to the primary was varied