Scielo RSS <![CDATA[Journal of the Southern African Institute of Mining and Metallurgy]]> vol. 112 num. lang. en <![CDATA[SciELO Logo]]> <![CDATA[<b>ZrTa2011 New Metals Development Network Conference , 12-14 October 2011 , Mount Grace Country House & Spa , Magaliesburg</b>]]> <![CDATA[<b>The manufacture of plasma-dissociated zircon (PDZ) via a non-transferred arc process utilizing three 150 kw DC plasma torches</b>]]> South Africa produces about 400 Kt zircon (ZrSiC>4) per annum. This represents about 30 percent of the global demand. However, very little is beneficiated locally and more than 95 percent is exported with little or no value addition. Zircon is a very inert material and needs to undergo high-temperature alkaline melting processes to produce valuable zirconium products. The conversion of zircon to plasma-dissociated zircon (PDZ) produces a chemically reactive species (ZrO2.SiC>2) which consist of finely divided submicron monoclinic ZrO2 crystals dispersed in a SiO2 matrix. In this paper, an in-flight, non-transferred arc pilot plasma plant with a capacity of 100 kg/h and which consists of three 150 kW DC plasma torches, is described. The optimization of the plant, which includes the use of different zircon concentrates, the influence of particle size, feed rates, plasma gas, and energy utilization, is discussed. <![CDATA[<b>Phase transformations and surface characterization of the platinum-chromium coated system</b>]]> This research involves the investigation of phase transformations in the platinum-chromium coated system. Single-layer 0.1 ìçé platinum coatings were deposited via electron beam deposition on 99.98 percent pure chromium substrates. Specimens were subjected to systematic heat treatment in a vacuum furnace at 900°C for up to 20 hours. Phase formation and the changes in surface morphology were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Both CrPt and Cr3Pt phases are formed during heat treatment for different times at 900°C. Significant changes in the morphology of this coated system were detected after heat treatment at 900°C for 20 hours. <![CDATA[<b>As cast and heat-treated alloys of the Pt-Al-V system at the Pt-rich corner</b>]]> The Pt-based alloys have a high potential for replacing some Ni-based superalloys (NBSAs) used in the highest temperature and most aggressive environments, and vanadium would be a beneficial alloying element. Six alloys of average compositions Pt-26.6Al-9.1V, Pt-23.1Al-17.8V, Pt-9.6Al-21.1V, Pt-17.4Al-6.4V, Pt-22.3Al-7.9V, and Pt-6.0Al-10.1V (all in at.%) were manufactured by arc-melting and examined in the as-cast condition using scanning electron microscopy and X-ray diffraction (XRD). Five samples were heat treated at 1 000°C for 1 500 hours and water quenched, then examined. The phases were identified using energy-dispersive X-ray spectroscopy and the identities were confirmed by XRD. In most of the samples, the phases existing in the as-cast condition were different from those at 1 000°C after ~1500 hours heat treatment. A solidification projection, an isothermal section and a liquidus surface projection were determined for the Pt-rich corner. <![CDATA[<b>Microstructural, mechanical, and oxidation property evolution of gamma-TiAl alloy with addition of precious metals</b>]]> Titanium aluminide of composition Ti-47.5 at.% Al was prepared by melting titanium and aluminium of commercial purity with additions of precious metals of 0, 0.2, 1, 1.5 and 2 at.% content. The microstructure, hardness and oxidation properties were assessed. It was found that at 47.5 at.% Al, the microstructure of plain TiAl alloys was duplex, consisting of duplex lamellar grains and γ grains. The lamellar grains consisted of alternating lamellae of γ (TiAl) and α2 (Ti^Al), with overall aluminium content in the range of 43-47 at.%. The γ grains had a aluminium content above 50 at.%. The addition of precious metals to the TiAl alloy resulted in the formation of a new phase, with a high precious metal content, occurring mostly in the γ phase, without any major change to the microstructure. Increasing the amount of precious metals resulted in an increase of the new phase amount, at the expense of the γ phase. The hardness of the different alloys was around 300HVi0. Overall, the research has shown that addition of precious metals to TiAl resulted in a slight increase in hardness and a significant improvement of the oxidation resistance. This shows that alloying TiAl with precious metals, at the addition levels investigated, does not alter the mechanical properties very much, but improves oxidation resistance. <![CDATA[<b>Characterization of Au catalysts</b>]]> A range of supported gold catalysts was prepared by ion exchange, varying many of the preparation variables, including concentration in the precursor solution, washing procedure, as well as drying and calcination procedures. These catalysts have been characterized extensively. TEM images show essentially the same crystallite size distributions, between 2-5 nm, for almost all catalysts, the only exception being catalysts not washed in ammonia, which did not show any small crystallites. Additional characterization with SEM yielded an interesting discovery. Catalysts that appear identical on the TEM also contain some large crystallites in the range of 50-500 nm. Differences in dispersion due to the drying procedure not seen on the TEM can now be observed. Oxygen chemisorption is being investigated as an additional method to characterize gold based catalysts to complement the typically used electron microscope techniques. <![CDATA[<b>Electrochemical studies of Fe-21Cr-1Ni duplex stainless steels with 0.15 wt% ruthenium at different temperatures</b>]]> The 2101 lean duplex stainless steel has wide potential application in storage, heat exchangers, and in the oil and gas industries. This work investigates the electrochemical behaviour of 2101 duplex stainless steel with an addition of 0.15 wt% ruthenium, using potentiodynamic techniques in 1M H2SO4 at 25°, 40°, 60°, and 80°C. The microstructures of samples were characterized using optical metallography and scanning electron microscopy. The results showed that the ruthenium addition moved the corrosion potential of alloy 2101 to a more positive potential. All samples containing ruthenium displayed longer passive regions at 25°C and 80°C compared to those without ruthenium. Alloys without ruthenium had higher critical current density (?'crit) values when compared to the alloys with ruthenium. Ruthenium additions decreased the passive current densities and inhibited anodic dissolution. At room temperature the corrosion rate of alloys with ruthenium was lower than these without ruthenium. <![CDATA[<b>On the development of bainitic alloys for railway wheel applications</b>]]> The ferrite-pearlite microstructure is the most popular microstructure for alloys used in structural applications, including railway wagon wheels. These alloys have been designed through alloying and thermomechanical processing to have a refined microstructure. Ferritepearlite alloys are low cost, weldable, have good fabricability, and are reliable under extreme conditions. Given these performance attributes, it seems unlikely then that their dominant position as structural steels would ever be challenged by alternative microstructures. One major achievement in the development of ferrite-pearlite steels has been in the refinement of their interlamellar spacing to very fine distances of the order of < 0.3 μηι. A refined microstructure increases the hardness of the alloy, thus increasing its life under wear conditions. The interlamellar spacing in pearlitic steels has, however, been refined almost to its theoretical limit. The increasing demand for speed and increased axle loading on railway wagons requires the use of stronger, tougher, and more durable materials. This has opened the window for the development of novel bainitic steels. Bainitic alloys have a higher level of microstructural refinement than pearlitic ones. They have shown to have good wear resistance and rolling-contact fatigue resistance, and high toughness. This paper will discuss the progress to date on the development of bainitic railway wheel alloys. Four alloy chemistries have been chosen for possible further development. <![CDATA[<b>Gas-phase fluorination kinetics of Ta<sub>2</sub>O<sub>5</sub> with elemental fluorine</b>]]> The aqueous chemistry of niobium and tantalum compounds with hydrofluoric acid is a mature field of investigation. In contrast, very little attention has been paid to reactions of these compounds in non-aqueous environments. Similarly, reactions of elemental fluorine with niobium and tantalum compounds have received little more than cursory attention in literature. This work discusses the isothermal reaction kinetics derived from thermogravimetry, using a less redundant approach than is currently the standard. We also discuss the most likely kinetic models for this reaction. <![CDATA[<b>TEM studies of Pt-Al-Cr-Ru Alloys</b>]]> Pt-based alloys are being developed for high-temperature applications with the aim of replacing some of the currently used Ni-based superalloys (NBSAs) in the highest temperature applications. The Pt-based alloys have a similar structure to the NBSAs, and since Pt is more chemically inert than nickel and has a higher melting point, they can potentially be used at higher temperatures, up to 1 300°C, and in more aggressive environments. Several experimental Pt-based alloys were studied at Mintek, and an optimum composition was found to be Pt84:Aln:Ru2:Cr3 (at.%). On the basis of hardness and microstructure, a later study identified a new optimum: Pt78:Aln:Ru5:Cr6 (at.%). There are at least two Pt3Al allotropes, and the high-temperature cubic structure has better properties than the lower temperature tetragonal form, and so needs to be stabilized. This work describes the latest results obtained in transmission electron microscopy (TEM) studies of the quaternary Pt-based superalloys. These results are both interesting and important, because the samples have a higher precipitate density compared to those from earlier work. The precipitate morphology is mainly cubic, with minor areas having irregular-shaped precipitates. The high volume fraction of the precipitates is a major breakthrough, since the objective of this work is to improve the alloys. A prior disadvantage was that the proportion of the precipitates was too low in samples before this work, especially compared with the work from Germany on Pt-Al-Cr-Ni-based alloys as well as the NBSAs. TEM ~Pt3Al diffraction patterns were studied, and for each diffraction pattern, many possible lattice point combinations were tried, with the angle between the lattice spots as well as interplanar spacings being calculated for each phase (cubic or tetragonal) to match the measured results. An overall analysis of the diffraction results indicates that the cubic phase fitted the experimental lattice points with much lower errors compared to the tetragonal phase. Thus, with the close match achieved with the cubic structure, the structure of ~Pt3Al precipitates is likely to be cubic. X-ray diffraction has been carried out on selected samples, and the results confirmed the presence of cubic -Pt^Al and (Pt). Different X-ray diffractometers were used to further verify the results, and the results were also compared with those from TEM. <![CDATA[<b>Manufacturing of anhydrous zirconium tetrafluoride in a batch reactor from plasma-dissociated zircon and ammonium bifluoride</b>]]> Anhydrous zirconium tetrafluoride can be used as a precursor for the manufacturing of nuclear-grade zirconium metal. This can be done by fluorinating plasma-dissociated zircon with ammonium bifluoride in a batch reactor. This paper describes the batch process. It was proved that anhydrous zirconium tetrafluoride can be manufactured by this route as confirmed by X-ray diffraction. The process shows potential for scaling up to the kilogram scale and possibly the tonnage scale. <![CDATA[<b>Safety considerations when handling metal powders</b>]]> Metal powder compaction offers unique advantages in the manufacture of net-shape components using techniques such as laser sintering, conventional press and sintering, metal injection moulding, direct rolling, direct forging, and hot isostatic pressing. If the output from the primary metal production process is in powder form, then considerable cost and energy savings can be realized by direct conversion to semi-finished or final shapes. This possibility exists for titanium and possibly also for Ta, Zr, Hf, and Nb metals. However, these attractive benefits are associated with some significant risks. The high surface-to-volume ratio of powder particles coupled with the reactive nature of these metals means that special care must be taken when handling them. Powder explosions are unfortunately still a regular occurrence internationally and these often result in serious injury and loss of life. Even seemingly 'safe' compounds such as sugar, flour, and grain can be extremely hazardous when handled or milled and dust clouds are produced. In addition, exposure to airborne particles can have adverse effects on the human body, especially when particles are inhaled on a regular basis. Furthermore, the medical consequences of these are not fully understood, especially in the case of nanoparticles. The impact is often not observed immediately and debilitating illnesses may emerge only years or decades later. As far as is known, there are no South African guidelines for handling of metal powders. This paper attempts to provide an awareness of the risks associated with metal powders (including those produced indirectly by other metalworking/finishing operations) as well as some guidelines for their safe handling, based on international best practices. <![CDATA[<b>Platinum promotion of Au/A1<sub>2</sub>0<sub>3</sub> catalysts for glycerol oxidation</b>: <b>activity, selectivity and deactivation</b>]]> Gold has been demonstrated as a possible catalyst for oxidation reactions. Some evidence for a possible promotion effect of platinum has also been recorded. The influence of platinum as promoter for Au/y-Al2O3 prepared via anionic ion-exchange for the oxidation of glycerol was investigated in a batch reactor at 60°C. It is inferred that the addition of platinum reduces the catalytic activity and the rate of deactivation, resulting in an overall higher final conversion of glycerol with increasing platinum loading. The addition of platinum to the catalyst favours the formation of the desired product, glyceric acid. <![CDATA[<b>Beneficiation of zircon sand in South Africa</b>]]> South Africa and Australia are the biggest suppliers of zircon sand to the international zirconium industry. However neither South Africa nor Australia is well known for zircon beneficiation. Geratech Zirconium Beneficiation Ltd (GZB) continued with additional research on sodium hydroxide (NaOH) cracking of zircon sand during 2002-2003. In 2003 GZB started extracting zirconium from zircon sand by means of NaOH cracking on a commercial scale. Experience has shown that temperature profile and atmospheric control inside the furnace is crucial for the beneficiation of zircon sand. Silica carryover to zirconium chemicals could result if a high temperature is used. Once the sodium silicate is extracted from the sodium zirconate and dissolved in hydrochloric acid, two distinct routes can be followed to precipitate various zirconium chemicals. The most common route is to precipitate zirconium oxychloride crystals (ZOC), with subsequent purification from all contaminants (crystal route). Less known is the process (liquid route) that involves the direct precipitation of zirconium basic sulphate (ZBS). This route will yield a less pure product, with contaminants such as silica and titanium. An important factor in this route is the prevention of silica gel formation, which could hamper final product filtration. For applications like paint drying (zirconium octoate) or antiperspirants (zirconium hydroxychloride) low levels of contaminants have no effect on the final product. The advantage of the liquid route is fewer production stages compared to the crystal route. The disadvantage of the liquid route is that the market for the products will be significantly smaller. The optimum solution could be a plant design that could cater for both routes. Another example of an application of zirconium chemicals is the use of ammonium zirconium carbonate (AZC) in the paper industry. Zirconium basic carbonate (ZBC) is dissolved in ammonium carbonate to produce AZC solution. AZC is used mainly in European countries in the paper industry. For example, carton boxes were initially produced with formaldehyde as the binder, however, it has now been replaced with AZC since formaldehyde is considered toxic. AZC reacts with the cellulose fibres in the paper to act as the binder. The resulting product is not toxic, and printing ink dries very quickly due to the porous paper structure. Other applications of zirconium chemicals involve the use of acid zirconium sulphate tetrahydrate (AZST), zirconium orthosulphate (ZOS), potassium zirconium carbonate (KZC), and zirconium hydrous oxide (ZHO). Fluoride-based zirconium chemicals like zirconium tetra-fluoride (ZrF4) and hexafluoro-zirconic acid (H2ZrF6) are used in the aluminium industry. Zirconium oxide (ZrO2) can be produced from any of the abovementioned precipitated chemicals via a high-temperature decomposition process. The physical properties of such oxides can differ tremendously, depending on the final application. The fired density of sanitaryware is typically 5.8 g/cm3, compared to milling media at >6.1 g/cm3. The required fired density is achieved by controlling the precipitation and decomposition conditions for these two oxides. The same applies to stabilized and mixed oxides, for example where zirconium oxide acts as an oxygen carrier in fuel cells. <![CDATA[<b>Metal dusting on Alloys 602CA and 800</b>]]> Metal dusting is a corrosion phenomenon that occurs in strongly carburizing gas atmospheres at elevated temperatures. Reaction kinetics and product characterizations of Alloys 602CA and 800 were examined by scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDX) and X-ray diffraction (XRD). The results showed that Alloy 602CA is more resistant to metal dusting than Alloy 800. Visual examination and SEM surface analysis showed that Alloy 800 suffered metal dusting attack after a relatively short exposure period. The amount of coke deposits increased on Alloy 800 with increased exposure from 96 to 336 hours. X-ray diffraction on the reacted surfaces identified graphite and austenite in both alloys and some iron oxides/spinel for Alloy 800. <![CDATA[<b>Kinetics and thermodynamic parameters for the manufacturing of anhydrous zirconium tetrafluoride with ammonium acid fluoride as fluorinating agent</b>]]> More than 30 percent of the global demand for zircon (ZrSiC>4) is supplied by South Africa. A significant amount of the zircon is exported, and beneficiated products are then imported for industrial applications locally. Beneficiating the zircon locally could have a positive impact on the local market, since zircon is only one of many such cases. Ammonium acid fluoride serves as an alternative anhydrous fluorinating agent for zircon in the synthesis of several metal fluoridesi,2. It provides an effective dry fluorinating method and is easier to handle than hydrogen fluoride or fluorine gas. Zircon exposed to extreme plasma temperatures dissociates and becomes more reactive. The reaction of the plasma-dissociated zircon (ZrO2SiO2) with the ammonium acid fluoride (NH4FxHF, where x= 1 to 5) forms two main intermediate compounds (NH4)3ZrF7(s) and (NH4)2SiF6(s), the latter decomposing to form volatile products at relatively low temperatures, providing easy separation of the silicon and zirconium compounds. The ammonium zirconate compound decomposes to form zirconium tetrafluoride (ZrF4), which can be further manufactured into zirconium metal, to name but one product. Data on the kinetics of the reaction of ammonium acid fluoride with zircon and plasma-dissociated zircon, combined with the thermo-dynamic parameters of the reaction, is essential for the development of an industrial process for the production of a precursor for the manufacturing of zirconium metal, namely anhydrous ZrF4. Both the reaction kinetics and reaction parameters will be included in this study, as well as some proof that the reaction proceeds to ZrF4 on a small batch scale. If the exact reaction parameters can be pinned down, a wide spectrum of anhydrous metal fluorides can be synthesized through this fluorination route.