Scielo RSS <![CDATA[Journal of the Southern African Institute of Mining and Metallurgy]]> vol. 111 num. 3 lang. pt <![CDATA[SciELO Logo]]> <![CDATA[<b>Tickle four: Future foresight</b>]]> <![CDATA[<b>President's Corner</b>]]> <![CDATA[<b>Rheological assessment of titanium MIM feedstocks</b>]]> Titanium is an exciting structural material that can offer significant strength-to-weight advantages over currently used alloys. However, its Achilles' heel is its costly, energy-intensive production process that effectively eliminates it from competing with aluminium and high-strength steels, apart from critical applications where titanium forms only a small component of the total cost. Current attempts are being made to reduce the cost of titanium products and these recognize the importance of minimizing the costs over the total production chain. Powder metallurgy (PM) technologies play a crucial role within this, as the output of the existing and potential primary metal production methods is in the form of sponge or powder. By using PM, costly remelting and forming operations can then be avoided, except in the manufacture of large components. Metal injection moulding (MIM) is an effective process for producing complex net-shape components in large volumes from metal powders. Nevertheless, the commercial use of titanium powders in this process is still in its infancy. The only major supplier of feedstock utilizes a polyacetal-based binder. This gives good green strength but requires a catalytic nitric acid process to remove most of the binder prior to thermal treatment. As this involves additional and expensive equipment and is a potentially hazardous process, there is interest in finding an alternative binder system that can be debound either purely thermally or that involves a less hazardous, more environmentally friendly solvent. This paper describes the use of capillary rheometry to characterize the influence of temperature and shear rates on the flow behaviour of potential binder systems for titanium MIM feedstock. <![CDATA[<b>Leachability of nitrided ilmenite in hydrochloric acid</b>]]> Titanium nitride in upgraded nitrided ilmenite (bulk of iron removed) can selectively be chlorinated to produce titanium tetrachloride. Except for iron, most other components present during this low temperature (ca. 200°C) chlorination reaction will not react with chlorine. It is therefore necessary to remove as much iron as possible from the nitrided ilmenite. Hydrochloric acid leaching is a possible process route to remove metallic iron from nitrided ilmenite without excessive dissolution of species like titanium nitride and calcium oxide. Calcium oxide dissolution results in unrecoverable acid consumption. The leachability of nitrided ilmenite in hydrochloric acid was evaluated by determining the dissolution of species like aluminium, calcium, titanium and magnesium in a batch leach reactor for 60 minutes at 90°C under reflux conditions. The hydrochloric acid concentration (11%, 18% and 25%), initial acid-to-iron mole ratio (2:1, 2.5:1 and 3.3:1), and solid-to-liquid mass ratio (1:8.33 to 1:2.13) were varied. The results indicate that a hydrochloric acid concentration of 25 wt% supplied in a 2:1 acid-to-iron mole ratio would produce the most favourable upgraded nitrided ilmenite product. The dissolution of iron in this solution reached 97 per cent after only 60 minutes. The total dissolution of calcium and titanium species was 0.01 and 0.11 wt% respectively. Hydrochloric acid can therefore be used as lixiviant to remove metallic iron from nitrided ilmenite. <![CDATA[<b>Titanium production via metallothermic reduction of TiCl<sub>4</sub>in molten salt: Problems and products</b>]]> Industrial production of titanium occurs via the batch-wise reduction of titanium tetrachloride (TiCl4) with a reducing metal, being magnesium in the Kroll process, or sodium in the Hunter process. In the search for low cost titanium, the CSIR is developing a continuous process to produce titanium powder directly via metallothermic reduction of TiCl4 in molten salt, dubbed the CSIR-Ti process. The move to a continuous process has been attempted by a number of organizations, but was until now always met with failure, due in no small part to challenges inherent in the process chemistry. The reaction between TiCl4 and the reducing metal can occur directly, when TiCl4 or any titanium sub-chlorides present, comes into contact with suspended or dissolved reducing metal. The reaction can also occur indirectly, without any physical contact between the reacting species, via an electronically mediated mechanism. The reaction mechanism via electronic mediation can cause TiCl4 to react at the outlet of the feed port, rapidly causing blockages of the TiCl4 feed line. The electrical conductivity of the metal reactor can also cause the electronically mediated reaction to favour the formation of titanium sponge on the reactor walls and internals, rather than titanium powder. Various methods were investigated to overcome the problem of blockages in the TiCl4 feed line, e.g. mechanical removal, sonic velocities, dilution of the TiCl4 and the use of ceramic feed lines. This article discusses problems experienced with the continuous feeding of reagents, and various methods attempted are shown and discussed. Information is also given on the morphology, chemical composition and suitability of the final titanium powder for powder metallurgical application as presently produced by the CSIR-Ti process. <![CDATA[<b>Effect of process control agent (PCA) on the characteristics of mechanically alloyed Ti-Mg powders</b>]]> This paper reports the results of a study to determine the effect of process control agent (PCA) on the characteristics of Ti-Mg powders during milling. It has been shown that a 2% increase in PCA content leads to up to a 40% increase in yield of the milled powder but reduces the kinetics of the mechanical alloying process. The introduction of 4% PCA decreases the mean powder particle size by up to 30%, whereas 6% PCA increases the mean particle size by up to 230%. The characteristics of the milled powders will be discussed in relation to the role of PCA in the milling process. <![CDATA[<b>Microstructure evolution in Ti-6Al-4V alloy during hydrogen dosing at elevated temperature</b>]]> The embrittlement of the Ti-6Al-4V alloy by hydrogen dosing at elevated temperature has been investigated. Metal coupons were subjected to isothermal treatments in a partial hydrogen atmosphere in the temperature range from 650ºC-950ºC and the degree of embrittlement after treatment was determined by dropweight impact testing. Embrittlement was found to be inversely related to reaction temperature as a result of the combined effects of greater hydrogen absorption and titanium hydride precipitation at the lower isothermal temperatures. <![CDATA[<b>The use of titanium hydride in blending and mechanical alloying of Ti-Al alloys</b>]]> Titanium sponge, which is almost pure titanium, is extremely ductile and not easily processed into titanium powder. One method of producing powder is the hydride-dehydride (HDH) process, where titanium sponge is hydrided to form brittle titanium hydride (TiH2). Titanium hydride is easily milled to produce powder and is then dehydrided to form Ti powder. In this work, titanium hydride powder obtained from titanium sponge was used as a starting material for blending and mechanical alloying with elemental powders. Firstly, titanium hydride powder was blended with aluminium elemental powder to produce a homogenized powder, which was then compacted and sintered to produce powder metallurgy compacts. Secondly, titanium hydride powder was mechanically alloyed with aluminium elemental powder and then compacted. The mechanically alloyed powder was characterized in terms of particle size distribution, morphology and microstructure. In both blending and mechanical alloying, the green compacts were characterized by assessing the green density, while the sintered compacts were characterized by their sintered density, microstructure, and hardness. The two processes have resulted in the formation of TiAl3 intermetallic compound. It was established that by simple mixing and homogenizing, titanium hydride can be used as a starting material to produce powder metallurgy components in which porosity is a benefit rather than a problem, much akin to metallic foams. From the products obtained in the TiH2-Al system, it appears that titanium hydride can be used as a precursor in mechanical alloying. However, the possible formation of complex hydrides may introduce detrimental properties, and needs to be further investigated. For the production of non-porous components, it would be advisable to dehydrogenate the TiH2 powder before milling i.e. producing titanium powder by the hydride-dehydride (HDH) method. <![CDATA[<b>The influence of Mn on the tensile properties of SSM-HPDC Al-Cu-Mg-Ag alloy A201</b>]]> A201 aluminium alloy is a high strength casting alloy with a nominal composition of Al-4.6Cu-0.3Mg-0.6Ag. It is strengthened by the Ù(Al2Cu) phase and the è'(Al2Cu) phase during heat treatment. Further strengthening of this alloy system can be obtained through the addition of transition elements, but care must be taken as other elements might have adverse effects on the mechanical properties. The objective of this study is to determine the influence of Mn on the tensile properties of rheo-processed Al-Cu-Mg-Ag alloy A201. ThermoCalc software was used to predict the different phases that can be expected in the alloys, and scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS) was used to investigate the actual phases that formed. The influence of these phases on tensile properties is quantified. SEM and ThermoCalc revealed that there is an increased amount of the Al20Cu2Mn3 with increasing Mn. The tensile properties showed that high amounts of Mn do have adverse effects on the tensile properties of alloy A201, especially the ductility. <![CDATA[<b>Nitriding of ilmenite and high-grade slag fines</b>]]> Titanium bearing resources can selectively be chlorinated at temperatures below 200ºC if the TiO2in the feed is nitrided before chlorination. However, the nitriding reaction is highly endothermic, requires highly reducing conditions, is only thermodynamically favourable at elevated temperatures, and is affected by mass and heat transfer restrictions. At the required processing conditions, problems might also be experienced with sintering and with melting of slag forming components in the raw materials. A test programme was undertaken to study the effects of raw material type, temperature, gas composition, bed depth, carbon to raw material ratio and residence time in order to simulate conditions required for scaling up a nitriding process. In contrast to previous experience with low-grade titaniumbearing slag containing about 30% TiO2, ilmenite and chlorinateable slag do not form melting phases under the studied nitriding conditions and hardly sintered at all. Both feed materials can readily be nitrided with conversions in excess of 90% at temperatures around 1300ºC and using bituminous coal as reducing agent with fixed carbon in excess of 1.1 times the stoichiometric requirement. The conversion decreases as the bed depth of the feed material increases and the N2/CO ratio in the gas decreases. Analysis of the relative rates of mass and heat transfer into the reacting beds of ilmenite and slag showed that the heat transfer rates are more limiting than the mass transfer rates. In order to increase the throughput that can be achieved in a kiln, it would be necessary to take special measures to enhance the heat transfer rates into the mass of reacting material. One such a measure is to pre-form the mass of reacting material into thin-walled, hollow brick shapes prior to introducing it into a kiln. Depending on bed depth, temperature and N2/CO ratio, required residence times in the high temperature zone of the kiln can vary between about 6 and 10 hours. <![CDATA[<b>Solidification of an Al-Zn alloy during semi-solid processing</b>]]> The semi-solid metal casting process results in a unique solidification path. The microstructural features that were identified during the characterization of the as-cast microstructure, were used as evidence of the process history in order to determine the solidification path followed during the evolution of the microstructure. The morphology of the grains was characterized using SEM and the extent and distribution of the elemental segregation within the grain structure was analysed using EDS. <![CDATA[<b>Monte Carlo simulation of Pt-Al thin film diffusion</b>]]> In this study Pt-Al thin films were prepared via electron beam physical vapour deposition (EB-PVD) with an atomic concentration ratio of Pt25:Al75. These films were heat treated at temperatures ranging from 150°C to 650°C for annealing times from 4 to 60 minutes. The resulting microstructure of these thin films were obtained via secondary electron imaging used in conjunction with depth profiling with the aid of scanning auger microscopy (PHI 700). Elemental maps of the micrographs were obtained. Simulations, based on a chemical potential Monte Carlo method1, were run for various interaction parameters. From these simulations theoretical depth-profiles and proposed microstructures were obtained. These were compared to the experimentally measured depth profiles and elemental maps. <![CDATA[<b>Fluid bed chlorination pilot plant at Mintek</b>]]> A chlorination pilot plant having capacity to produce 5-10 kg/hr of titanium tetrachloride is in operation at the chlorination facility in Mintek. The bubbling fluid bed chlorination plant can be operated in batch and/or continuous process to study the chlorination kinetics of various feedstocks. The chlorination of titaniferrous ores to produce titanium tetrachloride (TiCl4) was carried out during the commissioning of the pilot plant and also as part of the titanium programme carried out at Mintek. TiCl4 is a basic raw material for producing commercial titanium dioxide pigment and titanium metal. This paper discusses the challenges faced during the commissioning and operation of the chlorination pilot plant. It also discusses the effect on the auxiliary facilities and instrumentation as a result of the harsh operating conditions of +1000°C and use of corrosive gases like chlorine and titanium tetrachloride. It discusses the effect of physico-chemical properties of the titanium tetrachloride and iron chlorides. The effect on the chlorinator refractory lining due to heating and cooling of the chlorinator is also discussed. Besides the special provisions made during the design of the chlorinator, this paper also discusses the operational experience and possible solutions to be implemented in future. <![CDATA[<b>In search of low cost titanium: The Fray Farthing Chen (FFC) Cambridge process</b>]]> This article explores the Fray Farthing Chen (FFC) Cambridge process, a novel method for the electrochemical deoxidation of metal oxides in molten salt, discovered at the University of Cambridge in 1997. The process was hailed as a highly promising, potentially low cost, novel method for the production of titanium metal direct from its oxides. The article should inform researchers in the field of some of the challenges in the commercialization of a novel, high profile process involving multiple stakeholders. The author, former senior process engineer at British Titanium Plc, the company originally tasked with commercializing titanium production via the FFC Cambridge process, reviews the latest literature and discusses past and present progress in the pursuit of low cost titanium metal via this process. Topics explored include the history of the process, attempts at commercialization, NASA's alternative application, and present status of the process. <![CDATA[<b>Production of titanium metal powder by the HDH process</b>]]> Laboratory-scale tests were conducted at Mintek for the production of titanium powder from particulate Kroll sponge by the hydrogenation-dehydrogenation (HDH) process. The aim of this work was to produce titanium powder for powder metallurgical consolidations. The work involved the production of titanium powder at optimized conditions, which included hydrogenation in a horizontal tube furnace at 600°C for 2 hours, milling using planetary and roller mills, and dehydrogenation in a vacuumed retort fitted in a muffle furnace running at 700°C for 36 hours. The titanium powder produced in this project matched the elemental specifications of commercially available titanium powder, except for high carbon content. Nevertheless, the powder has been tested further in mechanical alloying and has been found suitable for the production of powder metallurgical compacts. <![CDATA[<b>Establishment of rapid prototyping/additive manufacturing in South Africa</b>]]> South Africa had a late start with rapid prototyping (RP), with the first system being available in 1991. Up to 1994 only three systems were available in SA. Through active research participation from the CSIR and a number of universities, supported by technology transfer programmes and industry awareness workshops, adoption of RP technologies started to grow. Internationally, RP grew to the extent that several country-based member organizations were formed, and an initiation meeting of the Global Alliance of RP Associations (GARPA) took place during the SME Rapid Conference in Dearborn, USA in 1998. South Africa (SA) was invited under the auspices of the Time Compression Technologies Centre (TCTC) launched by the CSIR, and received an invitation to become a member of GARPA through the launch of a national, inclusive organization. The latter gave rise to a RAPDASA planning/launch meeting held at the University of Stellenbosch, which culminated in the first RAPDASA international conference held in November 2000 at the CSIR, and the election of a first RAPDASA management committee, also at the 1st AGM held during the conference. RAPDASA has been a pillar of strength since then, with an annual international conference being presented. As South Africa's RP awareness grew through the RAPDASA and independent activities, so did the availability of RP platforms in SA. SA also became a benchmark for other countries/late adopters to follow, as slowly a position of following became a position of leading through innovative applications. The paper highlights SA's development approach and history, together with the discussion of case studies in various fields. Contribution to the light metals industry will also be discussed.