‘TE PRODUCTION OP FERROTITANIUM THA + dsc, TRANSFERRED-ARC PLASUA FURNACE Allon D, Brent, L. Bruce teRae, and Herman Lagendijk Council for Mineral Technology (Mintek), Private Bag XJ015, Randburg, 2125 South Africa NTRODUCTTON | persoticanion ie uted ana carbide staizer ‘tm some special steels and, in particular, in fercitic stainless steel. Two ranges of grad of-ferrotitaniua are available. The lover grades ‘eontaia between 20 and 50 per cent titanius and lave produced by the aluninothernic reduction of Aimeniee,! the higher grades contain betveen 165 and 75 per cent titaniua and are produced simply by the co-melting of iron and titanium scrap. Ta the lover grades (which have & content between 4 and 8 per cent), the ratio of titanium to aluniniua in between 2 end 8.35 io ‘ehe higher grades, it is bétween 15 and 150. The silicon contents of the higher-grade alloys range from 0.1 to 0.5 per ceat.? i1teon | | Tee grades with a noninal titanium content ‘of 70 per cent are preferred, not only becau of their higher tizanium contents but because of their lov melting points (1130 to 1200°), which ensures their rapid assinilation vheo they are added to the steel during ladle processing. Recent advances in methods for the resel~ ting of titaniua scrap to yield an acceptable [erade of matal for aerospace application has resulted in « decline in the availability of thie aerap for ferrotitaniun production. This trend has reneved the search for alternative | methods by which ferrotitaniua can be produced direct from mineral sources. Sona vork had been dona at the Council for Mineral Technology (Mintek) on the pro- duction of reactive aetals by the aluainothersic reduction of their pure oxides.? study, hovever, the feasibility of the direct In the present, production of a high-grade ferrotitanium from a high Mincek's dic. transferred-are research programe. Mintek recognized the potential benefits of plasna technology sone years ago, and currently hhas test facilities rated between 50 LVA and 3.2 WA, which are used in investigations on the suitability of thermal plassa for a vi y-eitania slag vas investigated as part of of pyronetallurgical processes. TTRANSFERRED-ARC PLASMA FURNACES The furnaces used during the preseat study consist essentially of a refractory-Lined steel vessel fitted with an anode "connection that penetrates the hearth refractories, a centrally positioned hollow graphite electrode that serves as the cathod to atabilize the arc, a roof with a stuffing box that closes the fursace and provides a seal round the electrode, and a readily controlled due, pover source. and through which argon is passed ‘THE REDUCTION OF Tio, Compared with other, sore expensive reactive metals, aluniniua is the sost practical agent for the reduction of titaniua dioxide to tita~ nium metal. The use of carboa results in the formation of carbide, and the Gibbs free energy, 46°, for carbide formation is aore favourable, at all practical tenperatures, than that for the formation of titanium metal, Reduction by sithcon is not possible since the 6° for the reaction is positive at all practical teapera~ eur ‘The 0° for the reduction of titanium di- oxide to titaniua metal by aluminium is negative but, unfortunately, the 46° for the formation of Brent and Mekae 1 “ Paver, No» 9798.titanium monoxide is even nore negative at aiailar tesperatur ther reduction of this oxide is positive at the reaction tesperatures and therefore the yield: of titanium metal vill be diainished to tose The freerenergy change for the fur~ degree. Eathalpy Considerations A cumber of metal thermic reductions, The term ‘aluninotheraic’ are, produced by alunino~ is usually caken to mean self-sustaining alu- miniua reduction reactions. In these proc the enthalpy of reaction is high enoughy 4 level such that, after the reaction has been ueficieae initiated: in one part of the charg thermal energy i ly ther ‘suitable reaction texsperature and to superheat Liberated to heat progressive fe of the reacting materials toa the metal and resulting slag to a temperature such that good separation of these tvo phases is achieved without the neéd of any other heat Dautzenberg states that, for a self-sustain~ © tntua.4 si) 3-201 ky per gramatom of alusiniua.’ The | reaction 1 2 Dae AnSyg 7128.3 KD per gramaton of aluminiun and the 4395, for the reduction of 74,0, and 720 is 618.2 and -440.3 tJ per gran-atoa of aluniniua | Feepectively. This linits the titaniua content of a/b tio, + AL + 3/6 T+ 4 A105 : 4 ferrotitaniua alloy that can be produced in a \elfeusaining reaction to tout 28 per cent. | yacarat tineatte of good grade, wich cone | talon sone 6 por cent eitunien dione, cannot ibe used for the usual practice fnvolving self | qustaining reactions. Hovever, if the ilnenite |e pee-taced and fed eo noltenalunfai fa ¢ ‘ pre-heated reaction vessel, « self-sustaining reaction can be maintained, Another option also exists for the produc~ tion of bigher-grade ferrotitentua alloys.> Uae can be made of chenical boosters such barium peroxide or potassiua perchlorate to generate the required extra thermal energy. This practice has the disadvantage that rela: nium unite are used tively expensive alu essentially as a fuel co provide the enersy requirenent of the process. Constitution of the Charge ‘The reaction of metal oxides by aluainius produces high-melting-point aluniniua oxide. For geod slag-eetal separation, a flux aust be added to lover the melting point of the remaining oxide phase. Line is very suitable for this purpose decause it foras a lov-melting-point (1455°C) eutectic vith aluinium at a Lime-to-alusina ratio of 55:65. Hovever, the use of line results in the production of large volunes of slag. The ‘amount of Line needed as a flux depends, of course, on the efficiency of the aluainothernic reaction. The presence of unreacted netal oxide in the amount of Line needed to lover the liquidus ag can have a narked influence on the temperature of the slag to a suitable level, as vas found in the manufacture of ferrotiteniua, Choice of Rav Material A local source of titanla-rich slag contain- ing 85 to 87 per cent titanium dioxide vas avail- able and it was decided that an attempt should be made to produce ferrotitaniua from that source and to supply the shortfall in energy required for tha completion of the reaction and the separation of the metal and the slag by electri- cal means. Tt vas hoped that this would allow the optimum usage of sluniniua as a reducing agent. Redsons for the Choice of a d.c. Transferred are Plasna Furnace . Taltially, attempts vere made to produce ferro- titanium in a 6OkW single-phase submerged-are furnace, The operation was very difficult becaus Brent and Motae 20Gf-thie very bigh conduttivity of the titaniferous slag. The penetration of the electrode into the bath could not be maintained at 4 constant level, and violedt fluctuationd ceeurred in the current dram from the transforser. Operation ia a seni~subserged-are mode vas necessary, but this raised the temperature of the top of the bath to ‘a high level, and the reflected heat damaged the furnace roof. Also, the material in the lover part of the furnace tended to freeze and, thus, Limited the amount of reaction that could take place. Various ways in which the constituents of the charge could be introduced to the furnace vere tried, but the. operation did not improv Although on mogt occasions sone slag could be tapped from the furnace, the bulk of the product, of the snelt had to be renoved by digging-out the furnace vhen it had cooled. It vas frequent= ly found that large sasses of metal vere held up in the slag, end that ‘eéntact of the elec~ trodes with this metal probably caused che wild fluctuations in the current being drava. Although an alloy contained 61.6 per coat and 15.1 per cent it vas felt jtitanium, 9,0 per cent iron, luniniva vas produced in oce tat that an azersoeltiag operation vould not be commercially viable, since {8 vould be. too | erratic co be easily controlled, and chat som8 jother heating system, in vhich there would be no Vcoutect betvasa the electrode and the charts, | should be used, The tranaferce | turaace appeared to offer as attractive altar- wre plasna ‘native and, as a preliminary study, four t |e shoe dation ware carried out ia 100 KA "furnace voing Genito and che itanlacontelae | ing slag as a source of titanium, ‘The tests demonstrated that the use of & transferred-are plassa furnace for this particu | tar reduction reaction was feasible, The opera~ "elon of thle furnace, unlike ehat of the aze | furnace, wae extranely stable. An alley contain ‘tag 31.2 per cent titanium vas produced from ilmenite, vhile one containing 63.5 per cent ttaniud vas Sbtained from the titaniferous slag. The eitaniva content of this metal vas sinilar. to that obtained in the are furnace except that the aluainium content vas 7.9 per cent as against 15.1 per cent. Hovever, the id high- Light sone problens. Tt vas not possible to cap preliminary tests ‘metal from the furnace, and an exanination of the contents of the furnace after they had cooled shoved a poor slag-netal separation. The slag produced vas tovards the magnesite lining of the furnaci although, theoretically, the slag should have jen to be very corrosive and contained no magnesiua oxide, it vas found to con~ tain 16 per cent. SMALL-SCALE BATCH TESTS TN A SO kVA ATER-COOLED FURNACE The prelininary large-scale tests vere done before the small-scale teste veré started. How ever, the investigations vei 4 later stage, and modifications to equipsent and done in parallel at lessons Learned in the small-scale te applied, wherever possible, in the large-scale teste, Equipment and Procedures The Mintek 50 kVA facility vas used in these tests. A schenatic diagran of the later develop- ment of this furnace is shova in Figure 1. The najor features of this furnace are: the use of & pre-fired high-magnesia refractory crucible (200m in diameter and 400m in height) inside the vate cooled steel shell, an anodic connection consis~ ting of a single steel rod (50am in diaseter) that penetrates centrally through the bottos of the crucible, and a pencilled electrode (25am in iameter) that vas to centralize the arc. The fidveate of argon through the electrode vas 6 Main. In prelininary ¢ dissolution of the magnesia crucible into the slag. The reduction of this sagnesia by the alu- there vas considerable Brent and Metae 3 “Ainiua-in the ‘furnace charge resulted in lov efficiencies of reducing agent and poor racove~ ries of titanium, Crucibles made from a range of other refactory' materialé (@.g: alumina, magzi sartitania, ete.) did not succeed in withetand= ing slag attack. This problem w tually by the use of the water-cooled jacket shova in Figure 1. This vater-cooled jacket permitted # protective skull of frozen slag to form on the walla of ehe erucibie, This, approach vas found £9 be highly avecessful, and no further problens with refractories were encountered. The heat losses to the vater-cooled jacket were aonitored continuously as a precaution ‘against any impending failure-of the crucible refractory. These heat-loss weasurenents vere ‘also used as a moans of operational control of the power requirenents of the furnace. A typical test took approxinately 1 hour, and the average ‘are pover was about 30kW. Objectives of the Experimental Work The affecte of the folloving vaciables vere tavestigated during the snali-scale vests (1) the snount of Line added as a flux, (2) the sluainiua added to the charge as a proportion of the stoichlomstric requize- pest, and |G) the influence of the addfeion of tron to | the charze. Sie ‘qucted, each series being dedicated to the study esate ecreet ree ‘reproducibility of the results was found to be + excelent in all cases, and titaniua recoveries | of over $0 per ceut vere obtained, Alumina fatflctenctas (bused only on the qusctity of! feanton reduced to mate) of op ba 69 per emt ‘vere reatized, Effect of Lime flux - As vas mentioned ear~ ° Lier, Lime is componly used as a flux for the alu- mina generated during aluainothermic reduction: ‘The formation of a slag with a lov melting point iu particularly iaportant in an autothersic pro~ coss vhere the enthalpy of the reduction reactions hhas to provide the necessary thermal energy, not only to melt the slag, but to temperature that it has sufficient fluidity to eonure good disengagenent of the metal and the ‘slag phases. Tn an electric furnace, hovever, nore refractory slags can be" tolerated since the energy input is not dependent on process at it to auch a chemistry. Extended periods of superheating can aleo be used to inprove slag-setal separation. A zajor incentive to the inclusion of saaller quantities of Line in the charge isthe substaa~ tial reduction in slag volume that results. The Line addition required to give a calciua oxid wuaina ratio of | results in a 9] ‘to-metal ing ray material that vas selected is smelted. An appre: ble quantity of thermal energy is therefore required to heat a aaterial that is required only 1s a flux and is essentially inert in the redue~ tion reactions, Sone undesivable contaminants (e.g. carbon and silicon) that tend to concen~ duced via the lise. in the ferrotitanium alloy are also intro~ The effects of varying additions of lise flux to the sneiting charge can be seen in Table Z. An sluainivn addition of 100 per cent of the stoichionetric requirenent vas used in t tests. This requirenent vas calculated on the basis of the total reduction of ferrous oxide, titanium dioxide, and silica contained in the titaniferous slag to their respective metals. The jag-to-uetal ratio obtained with de~ creasing line additions is also shova in Table I, and significant decrease can be seen. Although the titanium content of tha alloys produced venained relatively constant at about 55 per cent, it may be noted that a decrease in the quantity of Lime in the charge results in a significant decrease in the residual aluniniva level in the alloy. The test im which no Line vas used (rua no. 4) resulted in the highest titaniue-to- aluniniua ase ratio being obtained in the ferro- titanium alloy (1.0, 3.1). theoretical Brent and Mcbae 02 aUefect of substoithioastric aluminiua addi~ tion ~ In the second series of tests, the influence of smelting under substoichiosetric redueing-agent conditions aa eximined. fo Line vas used in the: teats, The results obtained for four different substoichionetric levels of alusinium are given ‘though the ration of titanium to aluniniua in the ferro in Table II, from vhich can be seen that, titanium alloy may be disproved by suelting under substoichionstric reducing-agent conditions, this Amprovenent is accompanied by a rise in the oxygen content of the alloy, Mineralogical exa- mination of the lags produced in these tests revealed the presence of suboxides of titanium (110, 11,05), vhich bad resulted from the par- tial reduction’of titaniua.dioxide, et [mente was carried out in vhich metallic iron Effect of iron addition’= A of exper: vas included in the sselting charges. No Line vas used in these tests. These done ts ver (Hn an dtieipe to deteraise the influence of aided iron on the ratio of titanium to alusiaiun ‘in the alloys produced. The results of this | series of tests are shown in Table III. Metallic | eon in the fora of setallic flakes constituted 110 per cent (by mass) of each charge. An inme~ | diate benefit realized from this practice vas gnificant inprovenent in the slag-netal ia paration, This is attributed to the increase | in density of the ferrotitaniva, voich resulte from increased iron coucentratfons ia the alloy. Tha everage relative density of alloys produced | tn che first evo series of teste vas only 4.4 compared to an average value of 5.AZobtained in the third series. Table IIT shov} that the inclusion of iron in the eoelting charge hae very Little effect on the ratio of ftantua | ko aluainion, Interpretation of Results of the Saall-scale Teste ‘The substantial decrease in the elag-to metal ratio that occurred vhen no Line vas added to the suelting charge resulted in more efficient heat transfer to the lover regions of the bath, In the particular furnace configuration used in these test: most of the are energy is dissi- pated on the surface of the bath at the point of are attachaent.® As titania slags have high electrical conductivity, it may be assused that the degree of resistance heating in the slag is negligible, This improved energy transfer jures that the metal in the lover regions of ble to the bath rensine fluid and is therefor: participate in the reactions throughout a run. This effect, coupled vith the higher reaction teaperatures that prevail during operation with more refractory slags, is believed to be one of the reasons for the inprovenent in the ratio of titaniua to sluniniua ia the alloy as the lise additions to the charges were decreased. Another factor may be the increased activity of the ti: tanium dioxide in the slag, which is suppressed at high concentrations of Lime. Soelting with ubstoichionetrie quantities of aluniniua leads to W decvease’is thie residual aluminium in the alloys produced due to the nore favourable reaction equilibria that are est blished under these conditions. Hovever, it appears that a thernodynanic barrier is encoun tered that does not allo ferrotiteniua alloys vith a titaniutovaluainioa sass ratio higher than about 7 to be produced. Tt appears that ateempts to improve this ratio by further de- crease of the aluninius contained in the charge result only in a corresponding increase in the oxygen content of the alloy. LARGE-SCALE CONTINUOUS TESTS ‘The transferzed-are plasma furnace used in the large-scale tests is shova in Pigure 2. A graphite electrode of S0um diasater with a 10am axial hole for the argon is used in the furna: The desiga of the roof seal is similar to that of che 50 KVA furnace, The anodic connection is via three S0ma steel rods, vhich enter the bottos of che furnace and initially protruded some 20mm through the hearth refractory. As the project progressed, the furnace vas modified. The najor changes vere as follova. The moulded, doned, Seeeats“Mluatea refractory root vas replaced by a flat aceel roof, which vas faced with a layer of mag nesite refractory and, on its hot face, vith Layer of baked electrode paste, Finally, an‘ alusina-brick Lining w: was nade for Linited vater cooling on the furnace shell. installed, and provision The charge vas fed to the furnace via a totally enclosed vibratory feeder vhich vas a0) designed as to mininize the ingress of air. The furcace vas initially povered by a 100kW pover source, vhich consisted of a three-phase trans forner and a vater-cooled diode rectifier. At Later stage, a thyristor-controlled system, hich Ae nominally rated at. 200k and ie part of a Larger plasna-furnace installation, becane avail~ able and vas used. This larger facility vas used purely for convenience; operation of the unit was easier, and a higher pover level could be achieved. ‘The prinary objectives of the firet caspaiga were: the establishaent of an acceptable nase balance, ixprovenent of the grade of alloy pro- duced in terms of its titanium and aluniniua contents, and determination of the efficiency of utilization of che aluainium in larger-scale operation. Table IV gives the composition of the metal recovered from the hearth after an extended test Tia which six consecutive batches of feed vere | charged to the furnace but only a fev hundred {grams of metal vere present in the slag for each ta eee conte erese ees |ageen of te elem, oe, td einen ! rae etleteey of atuntlin sage bn ee | reduction of titaniun dioxide and silica by alu- j miniua vas calculated as being only 45.5 per cont. Ree peed Sree cetedt eee ‘facut of cnt our fond fn te eg iy | mar peamoct ws fu go te eben oft ‘nesium oxide that had been dissolved from the furanca Lining. The magnesium that formed vas volatilized and then re-oxidized at the south of the gas offtake, gi fumes, Confiraation that this is vhat had occur to copious unite red vas obtained vhen a sample of fume vas col~ lected at a later stage. Analysis shoved that the uajor constituent of the fune was sagnesiua oxide (64.4 per cent). An attenpt vas made to improve the quality of the magnesite Lining by sintering of the Lining vith the are before use. The arc vas struck om 4 graphite block placed on top of the anodes in the furnace. No improvenent vas noted, and the slag produced atill contained 14 per cont nagnesiua oxide, For this particular test, the alusinius in the charge had been reduced to 90 per cent of the stoichiometric requirement. The metal pro- duced had a titanium content very sisilar to test under that produced in the small: similar conditions, but the titeniva-to-aluniniua ratio vas 8.1, vhich is « great improvenent. ‘At that stage, it vas decided thar the fur~ nace should be relined with alunina bricks. It vas hoped that, because of their nore dense structure, these bricks vould better vithatand the corrosive action of the slag. A test of short duration vas conducted so that the of the alusina refractory could be observed. It vas toon obvious that even this material vas srformance Inadequate because severe undercutting vas seen ae the elag Lint Because the suall-scale tests had shove that vater cooling of the refractory vas an effective means vhereby ittack could be avoided, a vater-cooled circumferential panel vwab fitted to the furnace shell. The area that could be cooled vas linited in extent because of the design of the furnace shell, but vas ade~ quate since it covered the most critical ares Brent and McRae 6FURTHER EXPERIMENTAL, WORE A further campaign vas then mounted 40 that, thie sodification could be tested, and soma of che operating conditions vere changed, Because the higher-povered thyristor drive vas being used at chat scage, a higher feed rate and an in exeased pro-rated pover vere used in an attempt to shorten the time of reaction and, hence, to nininize the time for reaction betveen the alloy formed and the creased by half, and the aluniniua addition vas reduced to 80 per cent of the atoichionetric . The Line addition was de- requirenent. Control of the snelting operation vas easy at this higher pover level but, although the slag i was readily tapped, the metal still remained in | trained slag) gradually eau This accumlation of metal (and en- d the level of the the furnace bath to rise, vhich increased the thermal load on the furnace roof. Attempts ‘to flush out the accu~ mulation of the addition of extra Line and tita- nia slag set with only moderate succes ‘The cooposition of the first 10 slags tapped froa the furnace is given in Table VL. ‘The couposition of the samples of metal dug from the furnace hearth is given in Table VII. Te Le obvious from the wide fluctuations in couposition of the slags that this campaign suf- fered from 4 lack of metallurgical control pita careful monitoring of the feed rate and rate of energy input. The titanium content of the F metal dug out of the hearth was lov, except for sample 1, but the titaniumto-aluniniua ratio vas encouragingly high in sone cases. The oxygen! content of the metal was also high, but it was | felt that this could have been partly due to slag entrainnent as vell as to the effect of « reduced aluainiua addition. MELTING POINT OF THE ALLOY At that time, sone attention sive tthe Liquidue tesperature of the alloy being pro- duced," Samples of alloy vere selected, and atteapts vere made to melt then ia a graphite ance furnace under an argon atmosphere. The sasples ve and the furnace wat so constructed that the contained in alunina crucibles, samples could be observed vhile being heated. The tenperature vas neasured by means of an optical pytoneter. The temperature at vhich the sample slumped vas taken as the aelting temperature. The melting teaperatures together vith the composition of the samples, including their oxy- gen and nitrogen contents, are shova in Table VEIT. Tt can be seen that, except for sample 5, which had a high aluminiua content, the melting points were in excess of 170%, This, no doubt, vas the reason vhy the etal froze in the furnace. The high Liquidus temperature is probably attri- butable to the oxygen and nitrogen contents of the toy. ‘ME_ADDITION oF TRON TO THE cHARGE The application of vater cooling to the fur~ nace thell successfully stopped slag attack on the refractory, Hovever, it had still not been possible to tap an appreciable quantity of alloy from the furnace, ‘A further campaign vas conducted, therefore, in which a quantity of ixon vas included in the charge, The amount of iron added vas equal to 40 per cont (by mass) of the titania-rich slag in the charge. The objective vas to lover the Moy by diluting it sg-netal separa- ture of the Liquidua cenper with iron, and to isprove the ‘ton by increasing the density of the alloy. This vas only moderately successful and, while slag and some metal vas tapped from each heat, there vas again a build-up of saterial in the furnace, The composition of the metal tapped from heats 5 to 15 is shon in Table IX, vhich indicates that a fairly consistent grade of metal vas produced. The oxygen contest and the nitrogen content were also considerably reduced. Brent and McRaeThe melting teaperature of the metal produced vas deternined to be about 150°C. Tew calculated that the recovery of titanium.as metal in the tapping tray vas only 40 per cent. The rest remained in the furnac: entrained in the slag. After being allowed to cool, the furnace was dug out, and the major proportion of the frozen material vae recovered as a solid ball. Th ball had an outer layer of black slag, which had forned against the furnace walls, and a low material and sone layers of silvery metal (which vere later shown to be iron) in-the centres ass of greenish) Mineralogical exanination of the greenii yellow slag shoved that the material contained etal globules in a slag matrix. Each of these globules contained threa phases, each vith a different iicanium-to-iron ratio. There vas also 4 fine dispersion of yellow material throughout + This vas determined to be titaniua the nitride. Te vas obvious from this that the exclusion of air from the furnace vas inadequat though attempts had been made to control it. even FURTHER FURNACE MODIFICATIONS A further campaign vas conducted in which cer effort vas mada to control the ingress of air to the furnace. The gas offtake vas sodified, and the joint betveen the roof, and the body of the furnace vae caulked vith refractory cenent. Attention vas also given to the 1 in the stuffing box. I addition, the furnace vas fed at a high rate so that the tine available for reaction of the metal with nitrogen or oxygen would be as short # possible a far gre trode ‘These attempts were in vain, since it vas still not possible to tap metal from the furnact Hovever, the dig-out revealed no signs of titanium ateride in en Nevertheless, it vas clear that major redesign of the furnace and feeding aystem vas necessary if success vas to be achieved. AU SCALE_ SEALED FURNACE A sual Je (SOkW) sealed plasma furnace, which had been developed from the pot-test faci- Lity, was available, and it vas decided that tests should be conducted in that furnace before the 200kW facility was aodified. Figure 3 shovs the design of the furnace, which uses the that used in the other small-scale experiments. The aim in the deteraination of the oxygen and nitrogen contents of tha alloy pro- duced under aiz-free conditions as vell as the effect of iron additions on the concentrations of these elenents, Table X compare of the metal produced in three tests in the 51 furnace vith that of three Alloyd ‘prodied in che unsealed furnaces but having similar titaniua and iron contents, une type of magnesia crucible cests vai the composition Tt can be seen that snelting in a sealed furnace bas a significant influence on the nitro— gen content of the alloy produced, but does not appear to influence its oxygen content. Tha oxy- gen content appears to be « function of the equi- Libria reached by the reacting species. concwustoNs Alloys of titaniua and fron have been pro- duced by the reduction of « titaniarrich slag with aluainiua in a d.c, transferred-are plarma fura- ace of the molten-anode configuration. Teste vere conducted at SO KYA and 200 kW. A typical ferro- tatanium alloy that can be produced contains 56.5 per cent titanium and has « titaniur-to~ aluminium ratio of 4.2, Factors such as the amount of Lime flux added as vell as the proportion of the stoichionetric ‘addition of aluniniva have an effect on the ratio of titaniua to aluminiva and, in both cases, a Brent and Herse : 8 “decreased addition ieproves this ratio. Hovever, at 4 lover aluainiue addition, che recovery of | titanium {a lover and the residual oxygen content of the metal is higher. ‘The residual oxygen and the nitrogen have a very marked and deleterious effect on the liquidus temperatures of the metal. It had been thought that, because of the design of the furnace, the use of argon as a plasma ga and the large slag volumes, the alloy vould be protected from the nitrogen in the atmosphere, Hovever, the results show that this vas not so, and that an especially sealed furnace vas needed to produce am alloy containing less nitrogen. The use of this furnace resulted in a tenfold de- but the oxygen content still ranged betveen 3 ‘and 5 per cent. This shovs that the oxygen con tent is not primarily a function of oxidation by the atmosphere but of the degree to which the reduction Feaction proceeds, 1.4. at whatever concentration of reactants and products equi~ Libriua ie reached. in the nitrogen content of the alloys, This study has shown that the aluninothernle reduction of titaniacrich slag to meet 4 tite- ‘ium-to-aluminiua specification 1s probably not ible in a single practically or theoretically f stage operation. Tvo options a} ble, as follows, sar to be possi- ' (1) Bxcess aluminium could be used to fora a titaniumaluniniua alloy vith an oxygen content sufficiently lov for the alloy to be tapped. (this practice should enhance the recovery of the titanium.) The aluainium vould have, to be renoved subsequently, by, for example evapo- ration in an electron-beam or plarna furnace.” ‘This approach would probably be very costly, and would not be economically viable while adequate are available (2) The influence of iron additions on the Ligquidus tenperatures of alloys (containing 30 to 40 per cent titanium and having an improved titaniua-to-aluainiva ratio and, it is hoped, 4 lover bxygesi content) needs to be investigated fon the larger scale in a sesled furnace, This approach seens to be the one most Likely to succeed. Acorowmcmenrs ‘This paper is published by peraission of the Council for Mineral Technology. We acknow- ledge the sponsorship of Middelburg Steel and Alloys (Pty) Ltd, of a large portion of this work, and the able assi of that company during the experinental york. tance of Mr G, Henderson sponsored part of the REFERENCES 1. V.B. Hlyutia, ef al., "Production of Ferro~ alloys. Blectronetatlurgy," B. Shapira (translator), Israel Programe for Scientific ‘Translations, Jerusalen, 1962, pp. 314-340. 2, International Standard, Ref, no, 150 150 S454~ 19802, "Ferrotitanium ~ Specification and Conditions of Delivery,” International, Organization for Standardization, 1st Edition, Dec. 1980, 3+ M.A, Bareza, G.W, Dreibrodt and J.A. Theron, ‘the aluminotherale reduction of the oxide of reactive materials,” S.A. Pat 84/0245, 1988, 4. W, Dautzenberg, "Das Metallothernische Ver- bitten ohne Zufuhr Hlektrischer Energie," Metallurgia der Ferrolegierusgen, G. Volkert, and K.-D. Frank, (B4s.), Springer-Verlag, Berlin, 1972, p. 65. ‘ + Ray Behera, of als, "EEfect of energisers on the production of ferrotitaniua from ‘deach sand ilmenite," Trane. Indian Inst. of Vol. 34, no. 6, Dec. 1981, pp. 421- Stevart, "The dissipation of energy in .e. transferred-are plamma furnaces and the Brent and eRae 9 4consequences for the production of ferro~ alloys," MINTEK 50, LF. Haughton (E4.), * 6 Council for Mineral Technology, Randburg, n 2 1985, Vol. 2, pp. 803-816, 7. G.W. Fletcher, "Inproved aluninetheraic process," U.S. Pat, 169722, 1979. Fig. I Scheaatic representation of the 50 kVA water-cooled batch furnace. (1) Argon 4 supply to hollow graphite electrode, (2) Electrode support nechaniss, clamp, 0 sod over cable, (3) Water~cooled elec trode seal, (6) Cas offtake, (5) Steel roof vith cagnesia Lining, (6) Ceramic fibce insulating gaskecs, (7) Water= Jacket, (8) Replaceable refractory cru efble, (9) Anode connection, (10) Cra~ phite'block, (11) Feed por: Fig. 2 - Schematic representation of large-scale furnace (coninally 200k). (1) Argon supply to hollov graphite electrod (2) Electrode support mechaniea, clamp, and pover cable, (3) Feed chute from sealed feeder, (4) Doned refractory roof (ater replaced vith a steel-backed, electrode~paste hot~faced magnesia roof), (S) Rammed magnesia Lining (later re- placed by aluaina brick Lining, (6) Vater cooled panel (fitted at later stage), + (8) Tap hole launder, (9) cas (Wo) Water-cooled electrode seal. Depth 60am (ater increased to 750m), Disneter 500m, Fig. 3 ~ Schematic representation of sealed furnace. (1) Argon supplied to vater-cooled hollow copper~graphite coxposite electrode, (2) Electrode support mechanism, clamp, aod ‘i - pover cable, (3) Staiate: 1 Bellows and electrode seal, tion vindow, (5) Off-g with waters 1 cooled baffle box, to water + seal, (7) Replace: crucible iA vith’ anodic cot LL (8) Graphite plate vith extercal anodic connection, (9) Refractory-lined bottom portion of furnace, (10) Water-cooled iddle section of furnace, (11) Refract tory Lined upper portion of furaace, (12) Feed pipe froa sealed hopper. ta ‘ a e a Brent and McRaeRefact of Line Flux Table T - Saall-scale Bach Te Rua Line Stag/ Chemical composition of metal produced Chenical composition addition as metal (Eby mass) of slag produced CA0:A1,0, ase (Eby mass) mass ratio THe ained for ThoFe al Si 0 OMG OTK/AL Th Anoy Gao 1 50:50 5.2, $5.4 9,42 25,6 3,03 1,3 0.95 0.57 2.2 13.6 37.2 36.7 2 40260-36544 13.7 21,7 2,85 168 0.30 0.19 2.5 13.7 45.0 32.5 3 30:70 2b ++ $7.2 10.0 21,3 1.69 2.7 0.26 “0,06 2,7 WS 545 273 4 02100 1S 548 1S 17.9 1,89 245 0,462 0.09 3.1 18.5 73.5 <0 Table IZ > Small-scale Batch Testa: Effect of Substoichionetric Aluainium Gheaical conyosition of aetal produced Grenical composition (@ by ase) of lag produced stoichionetric (& by mass) Fequireneat G0 era ee a eb eta HALO, ratio 1 30 57.6 106 14.029 052 Al 18.7 78.4 2 80 58.8 119 106 3.6 0295.7 22.3 70.0 3 7 57.219 9,782.8 0425.9 24.9 64.8 4 6 Shs 1407.9 1260.52 8.5 30.6 62.0 Table IIT - Soall-scale Batch Tests: Effect of Iron Additions Rua Aluminium as Ghesical composition of metal produced Chealcal composition percentage of by mass) of slag produced Stoichiomeric by mass) requireneat, u ve a T/A mae HAO; ratio 1 30 0 351139 32 16.7 83.2 eo Ree tse) ioe 45 aa 347 3 415 40.0 6479 6 6.8 616 4 6 40.2 42.2 6.58 61 Ba 633 : “ Breat and McRae n “Table TV - Large-scale Test No. 11 Composition Table V © Large-aeale Test No. 1: Recovery and of the Metal : Accountability of Titanium and Aluminium tt Fe si aL TiAl, — ei : A oe Elenent Metal ~—«-Slag Accountability x x x S64 1S 2B IS an —_ 1m 46.5 40.1 89.1 Fe 81.2 60.9 M421 aL Ma 646 79.8 Slag Origin 110, Feo «SiO, 0 0, ! a z z x 1 z 1 Beart 6a oss 22 78 0.60 26 36 2 Meat 2 38,3 100130 16.8 0.60 2.1 3 Meats 278 O18 1038 0.52 ane ' 6 wears 36.0 3.33068 15.8 0.59 27.0 Sweats 3.0 028 © 032178 0.60 25.6 6 wears 25.9 O72 0.50 2. Test 7 295. 0.72 1000 052 31.0 8 mata 47.0 1700.95 9.4 0.60 20.1 i 9 Reat9 30.2 12160 15.3 0.42 22.8 10 Heat 1033.0 055 055 2246 0.68 24.8 tobe VEE ~ tageesaate Tees oo, 1 Cenpottion of une tanpan fran Hasta ' ° | anes a a a Hi Boe z z z z z Mass ratio Ta a tan ; 2s ss so 8 fess Bs 1 ita soma Seige ate teeta : Brent and WeRaeSample 1h Te AL st 0, % Liquidus temp. z z eet 2 x °c agree 16 eee (30s ea 0 esi 9o ates > 1740 Cis 0) = OS) ) > 1720 Th eer} 1200 52.9017 2002? 1406 By = 1507 60.0 - 9.65 12.9 © 1185.2 0.8 > 1700 57.6 10.6 1.009592 > 1700 25 6.8 5.0090. 1503 Bb 56ST 003 1489 539.0 16.8 10.8 3S D2 > 1700 366 173 6128 > 1700 r 1 EE ee Table VIII - Composition and Liquidus Teaperatures of Selected Alloys SS “Commercial 70 per cent alloy ‘tALloy made in argon atmosphere Heat TL Te aL st ° x, TAL C8 x x x x X Mase ratio eee eters 132082002 Od 6 269 ae. 0,29 ma 7 th 1130448 6.5 8 28 126 0,63 66 9 thB Mas 0.39 58 10 24.2 118 + 0.56 0,025 no 25s 1.10. Outs ns 12 280 i220. 0,66 18 13 25,7 1,04 1 132 ae 0.72 15.0 1527.0 64.6 101 0.05 56 Table IX - Large-scale Test no. 3: Composition of Tapped Alloy Brent and McRae 3 “Table X ~ Comparison of the Couposition of Metaln Produced im the Sexted and Open Furnaces Furnace Feed recipe mo ooaY me Sk Liquidus x x x x oe a A 1002 AL 56.8 167 16.02.28 0.08 1580 i al 55.0 17.0 1018801 Bo 100K ALSG.5E Fe 49.0 12.2 28,7 2.020.039 1650 a! 48.0089 2707 16 40S © OK ALSO Fe M6770 1650 ct CH ty Ey 0) A th : Sealed furnace. Open furnaces i j i I / : e