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By D. W. Mitchell

While pure magnesium does not corrode rapidly the presence of even very small quantities of certain other metals accelerates corrosion remarkably. Because magnesium is such an electropositive metal (E° = +2.34 volts)' the presence of substances that permit galvanic activity is extremely undesirable. It is stated that as little as 0.017 pct of iron in magnesium causes a marked increase in the corrosion rate.2 Magnesium and its alloys are commonly melted in iron or steel pots; consequently the commercial metal has the opportunity to pick up iron if it has that tendency. Quantitative data on the solubility of iron in magnesium are of practical as well as of academic interest. Some magnesium alloy castings tend to have large grain size unless suitable treatment is given to the liquid metal just prior to casting. One method of grain refinement consists of "superheating" the metal just prior to casting. "Superhcating" is heating to a temperature 100 to 200°C above the casting temperature and holding for a short period of time. Superheated metal has a much finer grain than unsuperheated metal. A satisfactory explanation of this phenomenon has not been forthcoming. One hypothesis attributes the grain refinement in the superheated metal to precipitation of some phase that is mis-cible at the temperature of superheat but not miscible just below the casting temperature and which is thought to provide nucleating centers for crystallization. This phase, if the foregoing hypothesis is correct, would probably be a metal or an intermetal-lic compound. Of the metals likely to be found in magnesium alloys, iron is one of the most likely candidates for the role of grain refiner for iron occurs in small quantities in all commercial magnesium and magnesium alloys. A. Beck³ states that magnesium, in either the liquid or the solid state, cannot dissolve iron and that iron exists as a finely divided suspension which does not settle out because of its extreme fineness. Beck also presents a micrograph showing a large iron dendrite in magnesium but does not comment on the crystallization of iron from a solution supposed to contain none. It is doubtful that dendrite formation from suspended iron -would be possible. This suspension theory is the basis of patents4 covering the removal of iron from magnesium by allowing the iron particles to act as nuclei for the formation of primary magnesium crystals which can be separated by segregation. Also covered by patents is the removal of iron by the addition of another metal to form an intermetallic compound with the iron which, because of its increased particle size, is able to settle out of the molten metal. Here, too, quantitative information on the extent of iron solubility in liquid magnesium is of more than theoretical interest. M. Hansen,5 in his critical collection of the data on binary alloys, states that iron is not soluble in liquid magnesium. W. R. D. Jones% ho studied the physical properties of low iron magnesium alloys observed a 57°

Jan 1, 1949

By J. W. Spretnak, G. W. Cunningham

A study has been made of the growth and disappearance of voids in the interface of pressure bonded copper. The formation of visible voids is primarily due to spheroidization and coalesence of microvoids produced during the application of pressure. The microvoids could be prevented from forming by the application of high pressures or by increasing the ductility of the copper. Migrating grain boundaries were found to be more effective in void removal, than stationary grain boundaries. DURING the course of an investigation on the mechanism of pressure bonding, it was found that voids formed in the bonding interface which inhibited migration of the interfacial boundary and grain boundaries in the bond region. Therefore, an effort was made to determine the nature of the voids and how they form, grow, and disappear. This paper reports the results of such an investigation. The existence of interfacial voids is not solely a characteristic of massive components of metal which have been bonded by the application of heat and pressure, but is a phenomenon which has been observed in sintering as well. Simonsen attempted to study the sintering process by hot-stage microscopy and thereupon observed the formation of interparticle porosity as sintering proceeded. It was assumed that the porosity was due to grooves created at the location where grain boundaries joined the surface of the particle. Pranatis, Castelman, and seigle2 have also observed voids along the areas of contact in wound-wire specimens used for sintering studies. They did not discuss the point in detail since this behavior was not general, but they did suggest that the voids might develop as a result of stresses along the interparticle contact area. In previous investigations on pressure bonding, workers3 have suggested that voids may exist in the region where mating surfaces are placed in intimate contact, but the existence of the voids was not verified and no attempt was made to study the growth and disappearance of these voids. Durst noted the existence of pores in roll-clad structures prepared by cold reducing two sheets to force them in contact and then annealing to improve the bond. Since his unbonded regions contained a gas which he assumed to be insoluble, he proposed a mechanism which consisted of spheroidization of the unbonded regions and a growth of the contact area, but no speculations were made regarding disappearance of the gas filled pores. One interesting comment made by Durst was the suggestion that flattened voids with sharp corners which are produced during roll bonding will have a greater driving force for spheroidization than the more rounded pores created by pressing metal powders and thus spheroidization and neck growth will occur at lower temperatures. In this study it was necessary to demonstrate conclusively that voids can actually exist in the interfacial bond area. Experimental work was then directed toward a study of the mechanism whereby the voids grow and subsequently disappear.

Jan 1, 1963

By G W. Scott, H M. Lukey

The Lake Superior Region has been a producer of iron ore for over 150 years. Early mining operations concentrated on direct shipping ores, which are the result of post-depositional upgrading principally by deep weathering. As direct shipping ore reserves became depleted, the focus changed to the production of iron ore pellets from taconite. The post-depositional processes responsible for upgrading taconite are regional metamorphism, contact metamorphism and hydrothermal processes (Clout and Simonson, 2005). While these processes are important in iron ore genesis they can also contribute to liberation problems and in some instances reduced pellet quality (Han, 2004). Low-grade metamorphic mineral assemblages can negatively impact liberation and pellet quality. Low-grade iron formation may contain a suite of carbonate minerals including ankerite, dolomite, kutnohorite, siderite and magnesiosiderite. Variation in the distribution and composition of siderite and magnesiosiderite makes controlling the MgO content of pellets difficult. Carbonate minerals also require calcination in the pellet induration process, which requires additional heat to be added to the system, slowing down the induration process and reducing throughput. Prediction of carbonate mineralogy and carbonate mineral chemistry is an important goal of ore characterisation for pelletising properties. Contact metamorphism causes changes in mineralogy and grain size (Klein, 1973; Gunderson and Schwartz, 1962). Increasing the grain size of magnetite should improve its liberation characteristics. However, plant grinding targets may not allow the coarse-grained, more easily liberating magnetite ores to increase throughput and can actually result in decreased throughput due to recirculation. While magnetite and martite ores are well understood (Lukey, Johnson and Scott, 2007) late open-space filling microplaty haematite ores are not. These ores, while composed of similar minerals, have a unique genesis that results in fine grain size and complex textures that present liberation challenges and often make interpreting laboratory metallurgical test results more difficult.

Jan 1, 2007

By Alden B. Greninger, Victor G. Mooradian

Microscopic examinations of quenched (beta) 60:40 copper-zinc and quenched (beta) 74:26 copper-tin alloys have frequently disclosed long, thin parallel bands or markings within the polyhedral beta grains. Apparently, it has been accepted that these markings are mechanical twin bands, although there is no published account of experimental data that might tend to substantiate this belief for the copper-zinc system, and only meager evidence has been submitted for the copper-tin system. Johnsonl0 commented upon the markings he observed after deforming a quenched brass of 55.6 per cent copper and 44.4 per cent zinc. Clark's papers4 on the heat-treatment of Muntz metal contain many photomicrographs of markings in beta brass; these she referred to as Neumann bands (inasmuch as repolishing and re-etching failed to remove them) and stated that markings present in Muntz metal as quenched were the result of shock imparted during the polishing operation. Van Wert18 first suggested that these parallel markings in quenched beta brass (60:40) might be alpha precipitated along certain crystallographic planes of the matrix lattice. He showed that upon reheating the specimens to temperatures below 800" C., obvious precipitation of alpha within the large beta grains first occurred at the markings. In a discussion of this paper, Phillips stated (pp. 505-507) that in his opinion the markings observed by Van Wert were mechanical twins resulting from contraction strains produced during the quenching operation. In a study of segregate structures in beta copper-tin, Smith17 observed that in the quenched beta phase (containing 74.92 per cent Cu) parallel . bands or markings very similar to those in metastable beta brass could be

Jan 1, 1938

By Albert G. Zima

According to recently puhlished statistics, it is predicted that as much oil must be produced during the next 16 years as has been produced during the past 75, in order to satisfy the high rate of consumption of petroleum products. During 1934, over 17,000 oil wells were completed in the United States, and it is expected that over 20,000 additional wells will be drilled during the current year. Were it not for the remarkable progress made during recent years in the improvement of drilling technique and in the development of equipment used in the production phase of the oil industry, it is doubtful whether sufficient oil could be produced to meet present requirements. A few years ago, wells seldom were deeper than 3500 to 4000 ft., owing to the limitations of the drilling methods and equipment employed. Today, however, through the application of scientific drilling methods and the adaptation of modern equipment and improved materials, many wells range from 6000 to 8000 ft. in depth, and a few recent completions exceed 10,000 feet. Drill Tools Modern rotary drilling tools are the product of ingenious design and careful selection and adaptation of materials used in their construction. They must withstand terrific abrasion and, because of their compactness, must be designed to resist exceedingly high unit stresses. In bits, core drills and reamers, the bodies are made of either forged or cast alloy steels, heat-treated to develop a combination of high strength and toughness. To provide sufficient strength to the threaded portions and to protect the threads from distortion or damage, the box or pin sections of the tools are hardened to approximately 310 to 330 Brine11 hardness number. Drill and reamer cutters are generally of the movable type; i.e., serrated cones, cylinders or disks, which can readily be replaced when

Jan 1, 1935

By Alden B. Greninger, Victor G. Mooradian

Microscopic examinations of quenched (beta) 60:40 copper-zinc and quenched (beta) 74:26 copper-tin alloys have frequently disclosed long, thin parallel bands or markings within the polyhedral beta grains. Apparently, it has been accepted that these markings are mechanical twin bands, although there is no published account of experimental data that might tend to substantiate this belief for the copper-zinc system, and only meager evidence has been submitted for the copper-tin system. Johnsonl0 commented upon the markings he observed after deforming a quenched brass of 55.6 per cent copper and 44.4 per cent zinc. Clark's papers4 on the heat-treatment of Muntz metal contain many photomicrographs of markings in beta brass; these she referred to as Neumann bands (inasmuch as repolishing and re-etching failed to remove them) and stated that markings present in Muntz metal as quenched were the result of shock imparted during the polishing operation. Van Wert18 first suggested that these parallel markings in quenched beta brass (60:40) might be alpha precipitated along certain crystallographic planes of the matrix lattice. He showed that upon reheating the specimens to temperatures below 800" C., obvious precipitation of alpha within the large beta grains first occurred at the markings. In a discussion of this paper, Phillips stated (pp. 505-507) that in his opinion the markings observed by Van Wert were mechanical twins resulting from contraction strains produced during the quenching operation. In a study of segregate structures in beta copper-tin, Smith17 observed that in the quenched beta phase (containing 74.92 per cent Cu) parallel . bands or markings very similar to those in metastable beta brass could be

Jan 1, 1938

By A. J. Phillips, C. G. Grant, Wm. B. Price

ADMIRALTY nickel is a new corrosion-resisting and heat-resisting white metal alloy composed of 70 per cent. copper, 29 per cent. nickel and 1 per cent. tin. It has been given the trade name "Adnic." In 1924, Wm. B. Price1 described this alloy and its successful use as a diaphragm metal. The physical properties of Adnic at ordinary and elevated temperatures were given in Mining & Metallury.2 A patent3 was granted on Adnic, April 28, 1925. Work was first started on this alloy during December, 1921. An investigation of the patent situation in this country and abroad, and also a search of the literature, did not reveal any work on the ternary diagram, copper-nickel-tin; and the only wrought copper-nickel-tin alloy found was that known as "Newloy," composed of copper, 64 per cent.; nickel, 35 per cent.; tin, 1 per cent. This was being manufactured and sold by Wm. Gallimore & Sons, Ltd., Sheffield, England, for unplated spoon and fork stock, and first came to our attention in January, 1922. The preliminary work in connection with the development of Adnic was started by casting four binary copper-nickel alloys of the compositions shown in Table 1. Various amounts of tin were added to each of these mixtures, to produce the series of ternary copper-nickel-tin alloys also given in Table 1. A 200-gm. sample of each of these was cast by melting in a clay graphite crucible and allowing the melt to slowly cool with the furnace. A longitudinal section from each of these castings was polished and etched for examination. The castings were not homogeneous solid solutions, but showed the usual cored structure associated with cast alloys. However, from an examination of these sections we roughly determined

Jan 1, 1928

By Albert G. Zima

According to recently puhlished statistics, it is predicted that as much oil must be produced during the next 16 years as has been produced during the past 75, in order to satisfy the high rate of consumption of petroleum products. During 1934, over 17,000 oil wells were completed in the United States, and it is expected that over 20,000 additional wells will be drilled during the current year. Were it not for the remarkable progress made during recent years in the improvement of drilling technique and in the development of equipment used in the production phase of the oil industry, it is doubtful whether sufficient oil could be produced to meet present requirements. A few years ago, wells seldom were deeper than 3500 to 4000 ft., owing to the limitations of the drilling methods and equipment employed. Today, however, through the application of scientific drilling methods and the adaptation of modern equipment and improved materials, many wells range from 6000 to 8000 ft. in depth, and a few recent completions exceed 10,000 feet. Drill Tools Modern rotary drilling tools are the product of ingenious design and careful selection and adaptation of materials used in their construction. They must withstand terrific abrasion and, because of their compactness, must be designed to resist exceedingly high unit stresses. In bits, core drills and reamers, the bodies are made of either forged or cast alloy steels, heat-treated to develop a combination of high strength and toughness. To provide sufficient strength to the threaded portions and to protect the threads from distortion or damage, the box or pin sections of the tools are hardened to approximately 310 to 330 Brine11 hardness number. Drill and reamer cutters are generally of the movable type; i.e., serrated cones, cylinders or disks, which can readily be replaced when

Jan 1, 1935

By W. O. Philbrook

Reduced-scale models have long been used in hydrodynamics, aerodynamics, and heat transfer for studying fundamental flow relations or the performance of prototype designs under prescribed conditions. The pilot plant is a common tool of chemical engineering for investigating process variables and as an integral step in developing a new process. The metallurgical industry was rather slow to recognize the applicability of these techniques to some of its established and rather complex processes, but there has been a rapidly increasing number of applications of the principles of modeling in process metallurgy since World War II. Not only have pilot-scale operations been employed for developing methods of extracting metals that have recently achieved commercial importance, as well as new processes for some of the commoner metals, but models have also been used for engineering studies aimed at better understanding of the controlling, variables of time-honored conventional processes, It appears that the principles of similitude have become accepted as a useful tool, when properly applied, in metallurgy as in other fields of engineering. Much of the work of the Pyrometallurgical Laboratory, Region V, involves study of high-temperature smelting and refining processes for ferrous and related metals in pilot-scale equipment, such as the experimental blast furnace, converter, open-hearth, arc furnace, and rotary kiln. It was appropriate for the work of this laboratory that guiding principles for designing apparatus and interpreting results should be set down and that a bibliography of related work should be available for reference. A summary of the principles of model study and a brief review of some of the more noteworthy general papers have been published elsewhere.3/ Also, the Bureau of mines plans to publish a report of investigations describing its experimental work in this field. The bibliography is presented here as a service to others who may have use for it.

Jan 1, 1958

By R. Maddin, A. Lawley

Single crystal Mo-Re alloys (99.99+ purity), grown by electron bombardment floating zone heating, were deformed in tension at temperatures from -196° to +200°C. At -196oC, Mo-6 pet Re and Mo-20 pct Re alloys deform by slip on systems of the type (101) [1ll]. Above-78oC, the operative slip system is of the type (112) [111], (101) [1ll], or (211) [1ll], depending upon orientation. Mo-39 pct Re alloys deform by twinning and slip at all test temperatures with a (112) [111] type twinning system. Critical resolved shear stress for slip and twinning is calculated as a function of composition and temperature, and the mechanical properties compared with those of less Pure polycrystalline alloys. HEXAGONAL close-packed rhenium, c/a = 1.615, is highly soluble in molybdenum. The bee molybdenum-rich solid solution extends to approximately 42 at. pet Re* at 2500°C,' Fig. 1. Recent work on polycrystalline alloys has shown conclusively that the addition of rhenium to molybdenum improves both the fabricability and the low-temperature ductility.2"5 Similar behavior is observed for W-Re and Cr-Re alloys.5 Initially, Geach and Hughes2 found that the Mo-30 pct Re alloy could be cold rolled to approximately 90 pct reduction before the onset of cracking. The remarkable effect of the rhenium was later confirmed by Jaffee et al. 3-5 with an optimum condition of maximum strength combined with maximum ductility at the Mo-35 pet composition. At higher rhenium contents, the ductility was severely impaired due apparently to the presence of brittle tetragonal s phase, Fig. 1. In the Mo-35 pet Re alloy, at least 110 ppm (parts per million) oxygen could be tolerated before cold workability was reduced. By comparison, the corresponding tolerance figure in unalloyed molybdenum is ~ 10 ppm. The effect of rhenium was considered in terms of: 1) a reduction in oxygen solubility in the lattice; 2) a redistribution of intergranular oxide from grain boundary films to isolated spheres; and 3) the promotion of twinning as a further mode of plastic deformation. Paradoxically, twinning is often associated with brittle fracture in iron and the silicon irons.6'7 Work to date has been restricted to are-melted and powder metallurgy polycrystalline material of ~ 99.9 pet purity. The present investigation was initiated for the purpose of determining the mode and crystallography of plastic deformation of a series of bee Mo-Re alloy single crystals over a wide temperature range from -196o to +200°C. Using high-purity zone-melted material (~ 99.99 + pet purity), the specific role of rhenium in the molybdenum lattice may be understood more fully since effects due to grain boundaries and oxide redistribution will be absent. At the same time, the study provides a comparison of single and polycrystalline deformation behavior. EXPERIMENTAL TECHNIQUES A) Preparation and Purity of Single Crystals. Alloys in the form of either are-cast and swaged or sintered and ground bar, 0.120 in. diam, were obtained from the Chase Brass and Copper Co. Alloy single crystals ~ 8-in. long were grown from the

Jan 1, 1962

By H. W. Maynor, C. J. McHargue

DURING the course of an investigation of materials suitable for use as thermocouples at elevated temperatures by one of the authors, several nlolybdenum-rhenium alloys were prepared. Micrographs of an annealed alloy containing 25 pct Re (intended concentration; analysis not obtained) showed a number of twins, Fig. 1, suggesting a face-centered cubic structure. This note reports the structure and recrystallized wire texture of an alloy containing 25 wt pct Re. Alloys were prepared from 99.9 pct Mo (Fansteel Metallurgical Corp.) and rhenium obtained from the University of Tennessee (purity unreported). Powders were combined and briquetted at 56,000 psi and sintering was carried out at 2400°C for 5 hr in vacuum. Ingots so prepared were swaged at 982.2" to 1037.8oC into wires 0.036 in. diameter, a reduction in diameter of 85.6 pct. These wires were vacuum-annealed 1 hr at 2000°C. A North American Philips 114.59 mm powder camera and nickel-filtered copper radiation were used for structure determination. For the texture determination a Laue-type camera was used with zirconium-filtered molybdenum radiation and, because of the high background, aluminum foil was mounted next to the film. Exposures were taken with the wire perpendicular to the X-ray beam and tilted by 10". It was found that the X-ray pattern could be indexed on the basis of a face-centered cubic structure. Because of difficulties associated with obtaining a good X-ray pattern for this material, accurate parameter determinations were not made. An indicated parameter value of 3.70A was obtained. The X-ray data are given in Table I. The annealed wire texture was observed to be a sharp [111] texture. The spread about this fiber axis was k8" at the surface of the 0.036 in. wire. The annealed wire textures of aluminum have been reported as retention of the [Ill] deformation texture for anneals below 500°C and a new [1121 texture for anneals above 600°C.1 In copper wires, with a [Ill] plus [loo] deformation texture, results indicate a retention of this texture for annealing at lower temperatures and new components or the disappearance of components for annealing at higher temperatures.' The presence of the strong [I111 texture in the molybdenum-rhenium alloy after a 2000 °C anneal suggests that the deformation texture was the same. Acknowledgment The wires used in this study were prepared and heat-treated at the Institute for Atomic Research, and Ames Laboratory, Iowa State College, and the authors wish to express their thanks to the Institute for allowing the use of the material and permission to publish the results.

Jan 1, 1954

By Richard Paul Seelig

The following review covers published information on pressing of metal powders at room temperature. Only those operations are considered which occur between the time the powder is filled into the cavity and the compact is ejected from the die. Thus, this review does not concern hot pressing, coining or sizing feed or flow problems, commercial presses nor designs. It was also necessary to disregard to a large extent the effect of pressing on subsequent operations and on properties after sintering. 'The pressing operation is considered independently in its function to compact loose metal powder into useful shapes which can subsequently be handled. There are some comments by the writer in connection with a few of the findings quoted in the literature in order to stimulate thought and discussion. The selection of references quoted in the text is in some cases arbitrary although an attempt was made to favor papers containing novel ideas, techniques or results which mag stimulate future research. In order to enable the reader to check further into the subjects mentioned, the original, rather extensive, bibliography is appended even though not all the references are touched on in the printed version of this review. The equipment used by various workers, for example a die design created by Bridgman,22 is very interesting. 'The die insert has a conical external surface. The vertical pressure exerted on the punch transmits itself to the die which in turn is pushed harder into its tapered retainer. Thus, the higher the pressure exerted on the punch, the higher also the pressure exerted inwards on the die inserts. Inasmuch as this pressure counteracts the internal pressure from the compact the two stresses balance each other so that it is possible to obtain tremendous pressures without breaking the die. The die collar was made from an oil hardening tool steel, heat treated to a tensile strength of some 300,000 psi. The die was closed at the bottom by a plug made from special tool steels. Bridgman found that there is no steel which will withstand a com-pressive stress of 700,000 psi without continuous slow flow or immediate fracture. Therefore, the only material suitable for use in the pressing punch was sintered carbide. In view of the ingenious design it was possible to use special tool steel as die material. Jones22 raises the question whether this method of pressing has practical application in powder metallurgy. Although these tremendous pressures cannot readily be utilized without many special precautions, the tapered die and retainer idea is believed to be useful even for lower pressures. Bridgman, himself," alls attention to the fact that the properties

Jan 1, 1947

By Roe-Hoan Yoon

INTRODUCTION In 1960, coal accounted for 49% of the world energy consumption, an amount that was reduced to 29% in 1973 because of the availability of cheap oil. At that time, it seemed that oil would remain available for a long time in unlimited quantities. However, this situation changed drastically in 1973/74 when a series of closely spaced price increases from $3 per to $12 per bbl by mid-1974 hit both industrialized and developing countries. Another sharp price increase in 1979/80 to the $34 to $38 per bbl level also hit the world economy hard and, at the same time, set in motion powerful technology development forces for increased coal utilization. At this point, the price of coal was approximately $1.50 per MM Btu, while that of oil approached $6.00 per MM Btu. This huge price differential offered an incentive for developing new coal technologies including liquefaction, gasification, fluidized bed combustion, coal-water mixture (CWM), etc. The CWM technology was of particular interest to the utility industry, which consumes more than 80% of the coal mined in the US for power generation. In this technology, a powdered coal is mixed with water to produce a stable slurry that can be stored for an extended period of time without settling and is readily pumpable. Various reagents in the amount of approximately 1% by weight of the coal are added to inhibit sedimentation during storage and to reduce the viscosity for atomization in burners. The coal loading is in the range of 50 to 80% solids, depending on the particle size and its distribution. With very fine particles, it is difficult to increase the coal loading above 50%, and a binomial distribution helps increase the coal loading. The presence of water consumes a relatively small amount of the heating value of the coal during combustion; for a coal-water slurry containing 30% water, less than 5% of the calorific value of coal is usually consumed due to evaporation. The major advantage of burning coal as a slurry is that many of the oil-burning furnaces can be converted to coal-burning with a minimum retrofit cost. Considering the substantial price margin between coal and oil, the pay- back period for retrofit costs can be relatively short. Nevertheless, the retrofit cost can be further reduced if low-ash coals are used as feedstocks for CWM; there will be savings in the capital cost of installing bag filters or electrostatic precipitators that are designed to remove the ash from the combustion gases. Furthermore, the use of low-ash coals can minimize derating of boilers because the velocity of the combustion gases can be maximized without creating erosion

Jan 1, 1991

By D. Shishin

Continuous integrated experimental and thermodynamic modelling work is conducted in Pyrometallurgy Innovation Center (PYROSEARCH). The target is to develop a tool, which is capable to predict the compositions of phases, phase equilibria and enthalpy balance for pyrometallugical processes with higher accuracy. All these can be achieved by thermodynamic calculations based on Gibbs energy minimization algorithm. Recent developments made it possible to predict important factors, such as the chemical solubility of Cu in slag as a function of matte grade, temperature, P(SO2), Fe/SiO2 ratio in slag, wt% Al2O3, CaO and MgO in slag. In industrial practice, it is not only chemical solubility, but the overall amount of slag, which affects the recovery of copper and other valuable metals. It will also impact the energy balance. The presence of solids in the slag matrix influences the physical entrainment of matte in slag. Oxygen enrichment which is sometimes used to control the temperature of the furnace, may also affect the volatilization of minor elements into the gas phase. Same is true if additional fuel is used to compensate for heat balance. In other words, all key process parameters mentioned above are interrelated. Present study demonstrates the ways thermodynamic modelling can be used to link those process parameters on the example of copper smelting. INTRODUCTION Research methodology involving integrated thermodynamic modelling and experimental approach has been recently reported by the authors (Shishin, Hayes, & Jak, 2018 Shishin, Hidayat, Jak, Decterov, & Belov, 2016). Present paper reviews the updates and discusses challenges in the development of a large self- consistent thermodynamic database. The database covers the Al-Ca-Cu-Fe-Mg-O-Pb-S-Si-Zn-(Ag, As, Au, Bi, Ni, Sb, Sn) chemical system. The database works in the environment of FactSage software Bale et al., 2016 and related family of products: ChemApp (Petersen & Hack, 2007), ChemSheet and SimuSage. A list of phases, and thermodynamic models is shown in Table 1. For the copper industry, most important phases are Gas, Slag, Spinel and Liquid matte/metal/speiss. Black-colored elements represent the base system, elements in green can be considered as slag modifiers (slagging elements), and elements in red are minor. Ni is highlighted because it was included recently, in 2019, and currently under development. In addition to copper, the database covers the conditions typical for lead and zinc pyrometallurgical extraction. It is developed in consistency with the experimental results for high concentrations of Pb and Zn. Examples of applications in the present study include the thermodynamic analysis of fluxing for an agitated copper reactor to show the effect of Fe/SiO2, and calculations of copper slag cleaning using reductant.

Jan 1, 2019

By Richard Paul Seelig

The following review covers published information on pressing of metal powders at room temperature. Only those operations are considered which occur between the time the powder is filled into the cavity and the compact is ejected from the die. Thus, this review does not concern hot pressing, coining or sizing feed or flow problems, commercial presses nor designs. It was also necessary to disregard to a large extent the effect of pressing on subsequent operations and on properties after sintering. 'The pressing operation is considered independently in its function to compact loose metal powder into useful shapes which can subsequently be handled. There are some comments by the writer in connection with a few of the findings quoted in the literature in order to stimulate thought and discussion. The selection of references quoted in the text is in some cases arbitrary although an attempt was made to favor papers containing novel ideas, techniques or results which mag stimulate future research. In order to enable the reader to check further into the subjects mentioned, the original, rather extensive, bibliography is appended even though not all the references are touched on in the printed version of this review. The equipment used by various workers, for example a die design created by Bridgman,22 is very interesting. 'The die insert has a conical external surface. The vertical pressure exerted on the punch transmits itself to the die which in turn is pushed harder into its tapered retainer. Thus, the higher the pressure exerted on the punch, the higher also the pressure exerted inwards on the die inserts. Inasmuch as this pressure counteracts the internal pressure from the compact the two stresses balance each other so that it is possible to obtain tremendous pressures without breaking the die. The die collar was made from an oil hardening tool steel, heat treated to a tensile strength of some 300,000 psi. The die was closed at the bottom by a plug made from special tool steels. Bridgman found that there is no steel which will withstand a com-pressive stress of 700,000 psi without continuous slow flow or immediate fracture. Therefore, the only material suitable for use in the pressing punch was sintered carbide. In view of the ingenious design it was possible to use special tool steel as die material. Jones22 raises the question whether this method of pressing has practical application in powder metallurgy. Although these tremendous pressures cannot readily be utilized without many special precautions, the tapered die and retainer idea is believed to be useful even for lower pressures. Bridgman, himself," alls attention to the fact that the properties

Jan 1, 1947

By L. Kaufman

An equation is derived relating AF a", the difference in free energy between austenite and martensite, to temperature and composition in the iron-chrmnium and iron-chromium -nickel systems. This equation is used to calculate at M,for low-carbon stainless steels. A method for utilizing the energetic equations to calculate M, in stainless steels is suggested. In addition, an explanation is given for the anomalous effect of chromium in forming a y loop concurrent with the lowering of M, in iron-base alloys. It has been demonstrated that the effect of alloying elements on the Ms temperature is strongly dependent upon the influence of the alloying element on the thermodynamic properties of the y and a phases. Notwithstanding the fact that alloying elements affect the Ms temperature by changing the lattice parameters, elastic constants, and inter-facial energies of the a and y phases, their primary role is a thermodynamic one. Thermodynamic analyses have been presented for the iron-carbon'-4 and iron-nickele systems in which equations are derived for Fa and FY, the free energies of the b.c.c. (or b.c.t.) and f.c.c. phases. These equations, which can be obtained with the aid of the equilibrium diagrams, can be used to help predict the Ms vs composition curves. This paper deals with a calculation of the thermodynamic properties necessary to compute AFffLY for iron-chromium alloys. In view of the lack of direct information concerning the activity of chromium in the a and y phases of iron, the regular solution approximationa,g was utilized to bridge the gap. After the necessary equations were derived for the iron-chromium system they were used to calculate AFff— Y for stainless steels by combining them with the previous results obtained for iron-nickel alloys. The results of these calculations offer a means of rationalizing the anomalous behavior of chromium in iron-base alloys. The latter depends on the regular solution approximation in contrast to the explanation offered by zener , which is based upon the "magnetic specific heat effect." THERMODYNAMICS OF THE IRON-CHROMIUM SYSTEM If y represents the atomic fraction of chromium in an iron-chromium alloy, then the free energy of the b.c.c. phase Fa, the f.c.c. phase FY, and the difference in free energy between the f.c.c. and b.c.c. phases of the same composition are given through [3] and Fmy represent the free energies of mixing of the a and y phases; while @era -' and uFea 4Y represent the difference in free energy between f.c.c. and b.c.c. chromium and iron respectively. The values of AEFe0ff4Y in the temperature range between 0" and 900K ( .

Jan 1, 1960

By F. H. Spedding

From thermal, metallographic, X-ray, dilatometric, and electrical resistance data a Phase diagram is proposed for the La-C system. TWO compounds are formed, body-centered-cubic Laz C, having a large range of solid solubility, and body -centered-tetrago-nal Lac2 . The former melts incongruently at 1415°C, and at 25OC it has an electrical resistivity about two and one-half times that of bure lanthanum. The latter melts congruently at 2356°C and at room temperature has an electrical resistivity about equal to that of bure lanthanum. The addition of carbon to La lowers the melting Point of La about 115' C, raises the higher (B-Y) transfomzation about 10" C and appears to have no effect on the lower ( a-0) transformation. The addition of carbon appears to lower the oxygen content in the metal and improve the machinability; however, the tendency to oxidize is increased. Two eutectics are formed in the system. The first occurs at 2.2 pct C and melts at 806" C, while the second occurs between Lac2 and C with a melting point of2271"C. PETTERSSON,~ in 1895, was the first to prepare lanthanum dicarbide by heating the oxide with carbon in an electric furnace. He showed that this yellow, crystalline but brittle carbide had a formula corresponding to LaCz and that it reacted with water with the evolution of hydrogen and hydrocarbons and the formation of the hydrated oxide. Von Stackelberg's investigation of the crystal structure of the MCz carbides showed that the lanthanum dicarbide is of the tetragonal calcium dicarbide-type structure. He found the lattice parameters were a = 3.92 and c = 6.56.* Bredig,' using X-ray methods, showed that the room-temperature form of lanthanum dicarbide is stable up to 1750 °C and that above this temperature it transformsoto a face-centered-cubic structure, a = 6.0 ± O.lA, probably of the pyrite, FeSzstruc- typ? The reported discovery of two new cerium carbides, suggested that a corresponding face-centered-cubic lanthanum monocarbide and a body-centered-cubic lanthanum sesquicarbide might exist. This paper describes work on the lanthanum-carbon system which is part of a study of the rare earth metals and their alloys now in progress in this laboratory. EXPERIMENTAL PROCEDURE Source of Materials—The lanthanum metal was prepared at the Ames Laboratory by metal1o;hermic reduction of the fluoride with calcium metal. The results of spectrographic and chemical analysis indicated the presence of 0.01 pct Y, Al, Cu, Fe, and Si; 0.02 pct Ca and Mg; 230 ppm C; and 115 ppm N. The carbon used was of two types: 1) "National Special Graphite Spectroscopic Electrodes," and

Jan 1, 1960

By Richard Paul Seelig

THE following review covers published information on pressing of metal powders at room temperature. Only those operations are considered which occur between the time the powder is filled into the cavity and the compact is ejected from the die. Thus, this review does not concern hot pressing, coining or sizing feed or flow problems, commercial presses nor designs. It was also necessary to disregard to a large extent the effect of pressing on subsequent operations and on properties after sintering. The pressing operation is considered independently in its function to compact loose metal powder into useful shapes which can subsequently be handled. There are some comments by the writer in connection with a few of the findings quoted in the literature in order to stimulate thought and discussion. The selection of references quoted in the text is in some cases arbitrary although an attempt was made to favor papers containing novel ideas, techniques or results which may stimulate future research. In order to enable the reader to check further into the subjects mentioned, the original, rather extensive, bibliography is appended even though not all the references are touched on in the printed version of this review. EXPERIMENTAL APPROACH The equipment used by various workers, for example a die design created by Bridgman,22 is very interesting. The die insert has a conical external surface. The vertical pressure exerted on the punch transmits itself to the die which in turn is pushed harder into its tapered retainer. Thus, the higher the pressure exerted on the punch, the higher also the pressure exerted inwards on the die inserts. In as much as this pressure counteracts the internal pressure from the compact the two stresses balance each other so that it is possible to obtain tremendous pressures without breaking the die. The die collar was made from an oil hardening tool steel, heat treated to a tensile strength of some 300,000 psi. The die was closed at the bottom by a plug made from special tool steels. Bridgman found that there is no steel which will withstand a compressive stress of 700,000 psi without continuous slow flow or immediate fracture. Therefore, the only material suitable for use in the pressing punch was sintered carbide. In view of the ingenious design it was possible to use special tool steel as die material. Jones22 raises the question whether this method of pressing has practical application in powder metallurgy. Al- though these tremendous pressures cannot readily be utilized without many special precautions, the tapered die and retainer idea is believed to be useful even for lower pressures. Bridgman, himself,8 calls attention to the fact that the properties

Jan 1, 1947

By H. J. Rose, J. J. S. Sebastian

When coal is stored under ordinary conditions, progressive changes take place in its chemical and physical properties. These changes are largely caused by the reaction of atmospheric oxygen with the coal substance. Although this "oxidation" or "weathering" occurs slowly in the case of high-rank coals, it is nevertheless a matter of considerable importance, since even a small amount of oxidation may affect the value of coal for carbonization purposes. Coal storage is a necessity at all carbonizing plants. In normal times there are about 5,000,000 tons in storage at by-product coke ovens and gas retorts in the United States, as compared with an annual throughput of about 75,000,000 tons. In other words, the average coal reserve at such plants is slightly less than one month's supply. However, owing to the cost of storage and recovery, coal is usually left in stockpile for as long a time as the management thinks advisable. Storage for six to eight months is common practice and is, in fact, a necessity at certain plants which obtain their coal by water routes that are closed during winter months. Modern by-product coke ovens operate continuously, and they are not cooled down from the time that they arc put into operation until they are shut down for rebuilding—perhaps 20 years later. This continuous operation is imposed by silica-brick construction and high operating temperatures. It is therefore obvious that coke plants must at all times maintain an adequate supply of stored coal, in order to prevent a failure in supply from any cause whatever. Thus when strikes or other emergencies threaten, abnormally large coal stocks are accumulated and held at coke and gas plants. Many of these plants have been forced, at some time or other, to use coal that has been stored for several years. Such coal may fail to coke at all, or it may produce a dirty appearing, weak coke of reduced value. The yields of salable by-products may also be distinctly lowered. However, it must not be assumed that slight oxidation or heat effects are always injurious. Certain high-volatile coals produce a stronger, blockier

Jan 1, 1930

By D. Morin

A general study of gold refractory arsenopyrite-pyrite concentrate bioleaching has been carried out including two continuous bioleach testworks at different sizes, namely one at a laboratory scale with a 100 I unit at a 2 kg/d dry solid flowrate and the other at a pilot scale at a 100 kg/d dry solid flowrate. Both tests show a 80% bioleaching of arsenopyrite in about four days of treatment and with the same kinetic. Pyrrhotite is attacked at the earlier stage of the bioleaching but pyrite remains unaffected. The weak potential of oxidation associated with the decomposition of arsenopyrite and the abundance of arsenite leads to a high grade of elemental sulfur in the bioresidue which consumes the major part of the cyanide during the gold recovery. Furthermore. the arsenite and ferrous produced in solution have to be oxidized to obtain a stable precipitate in the waste products and as outlined in previous works of other authors on this subject the addition of iron to obtain a Fe/As molar ratio at least above 3 is necessary. The agitation equipment used in the pilot unit allowed an optimization study calculation for scaling-up the design and power requirements of an industrial installation. For the pretreatment of a gold refractory As high-graded concentrate the reagent cost has the greatest part in the operating cost of the biooxidation step due to the necessary retreatment of the biosolution. In that conditions the power cost is quite marginal. actually it is significant for the treatment of pure pyrite.

Jan 1, 1991