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By D. J. Steynfaard

Sishen Iron Ore Mine is situated 280 km north-west of Kimberley in the Northern Cape Province of South Africa. The mine produces and sells high quality iron ore of various specifications to various national and international clients. The saleable product is derived from the blending and beneficiation of different types and qualities of hematite iron ore. This paper documents the new developments which were implemented (or are in the process of being implemented) on the mine in the long-term planning, medium-term planning, grade control and material tracking in the beneficiation plant with special attention being paid to the quality of the final, saleable product. The process starts with the long-term planning where the pit shell and pit optimization is determined by Whittle 4X. New developments include the introduction of a linear programming based scheduling system to enhance the long-term schedule generated by Whittle 4X. The LP route was decided on in order to take into account all the constraining factors of the final product that could not be configured in Whittle. To complement this the XPAC Auto Scheduler scheduling package was introduced to do the medium-term mine scheduling. This 18-month rolling plan includes cost parameters to enable the planner to extract a detailed operational budget from the scheduling while ensuring that production standards are maintained and grade constraints are met. The existing grade control system was enhanced with GPS capabilities and a computer system to do material tracking. The high precision GPS system introduced on the shovels allows for the accurate control of the loading procedures at the mining face. Because of the complicated geology and grade composition of blasting blocks it is imperative to accurately differentiate between different materials in the same blasting block and being able to excavate that with the loading equipment. The GPS system on the trucks allows for accurate location monitoring of dumping in order to keep track of specific material types. The state-of-the-art material tracking system developed for Sishen will enable the grade control officer to keep track and record various parameters of the material from its in situ position in the blasting blocks, through the crusher and onto different stockpiles, in various stages of the beneficiation process and onto the blending beds, into the dispatching trains and eventually into the ships for international distribution. These developments elevate the Sishen planning and grade control systems to a new level of service excellence from which management can obtain accurate and timely information on product status. It also enables Sishen to maximize resource utilization while still complying with the tough market constraints.

Jan 1, 2003

By Herman L. Bauer

The Robinson Mining District near Ely, Nevada, is one of the major porphyry copper districts in the world. Within the district is an east-trending zone of altered porphyry, metamorphosed sedimentary rocks, and sulphide mineralization surrounded by Paleozoic limestone, dolomite, shale and sandstone, Tertiary volcanics, and Quaternary alluvium. Six major disseminated ore deposits have been exploited in this eight-mile zone. About 20% of the district production has come from disseminated ore in metamorphosed sedimentary rocks found adjacent to altered quartz-monzonite porphyry. The following brief statements summarize the inter-relationship of porphyry, alteration, metamorphism, and mineralization: 1. Disseminated copper ore does not occur in unaltered porphyry or in unmetamorphosed sedimentary rocks 2. Sedimentary rocks have been only weakly metamorphosed where intruded, by unaltered porphyry. 3. Intensely metamorphosed sedimentary rocks are found only adjacent to, altered porphyry. 4. Many hydrothermal minerals are common to both altered porphyry and adjacent metamorphosed sediments. 5. Disseminated ore is found in altered porphyry and adjacent meta¬morphosed sedimentary rocks. 6. In general, there is a direct correlation between grade of ore in porphyry and copper content in the adjacent rocks. 7. Chemical changes in the altered porphyry facies and metamorphosed rock facies appear to be related:

Jan 1, 1963

By M. A. Klugman

[This paper represents a portion of a lager study, concerning dispersion patterns of major, minor and trace elements in wall-rock about ore-bodies in part of the Colorado Mineral Belt. This phase of the work pertains to the Mg/Ca ratio variations in wall-rock adjacent to ore-bodies in two mines of the Alma-Horseshoe Mining District of Central Colorado. The mining district is located 80 miles southwest of Denver (Figure 1) on the east flank of the Mosquito Range. The area is typified by rugged relief with altitudes from 10,500 to 14,000 feet.]

Jan 1, 1962

By A. M. S. Hussein, B. E. Rogers

Progressively more stringent emission limits and advances in regulations and enforcement have made air compliance more difficult for metallurgical facilities. This has historically required improved collection and treatment of stack sources. Fugitive emission reductions are now increasingly required to achieve compliance. Typically small in magnitude, fugitive emissions have a disproportionate impact on ground level concentrations, can be visible to the public and can influence workplace health and safety. Moreover, these emissions are complex, as they are spread over multiple sources, distance and time and are affected by various activities and conditions. As such it is difficult to find, define and monitor these emissions and their impacts. This difficulty translates to the design of emission reduction measures and operational requirements. This paper presents an overview or ‘heuristic’ of fugitive emissions management for compliance in existing operations. This includes aspects such as the impact of regulations on project scope, approaches to developing a comprehensive emission inventory, considerations for solution development and the plant’s role in sustaining compliance once achieved. Case studies are presented to demonstrate how portions of this approach have been applied.

Jan 1, 2015

By H. N. Lawrie

Introduction. THIS study was undertaken on account of the lack of definite knowledge concerning the influence of bismuth on wire-bar copper, and the small elimination of bismuth from copper-matte during the smelting-operations. The early workers who studied the influence of bismuth on copper confined their investigations to malleability and ductility-two physical properties which are related to the others so intimately that their determination is of primary importance. Karsten ' and Levol,2 using bending- and mealleability-tests, seem to have been the first to take up the subject, and while their results are incomplete, they agree in the main with the later work of Hampe.3 The bending-tests used by the first investigators consisted in bending the specimen until it failed. The malleabilitytests were made by beating the material to a knife-edge with a hammer. Hampe not only determined the percentage of bismuth which would cause red-shortness and cold-shortness of the alloy, together with other influences of bismuth on the malleability and ductility of copper, but also took up the influence of the bismuth protoxide, BiO, on copper, and of bismuth sesquioxide, Bi2O3, on the copper protoxide, CuO. Hampe's conclusions of the influences of these two latter compounds of bismuth on copper are as follows "If the protoxide of bismuth be alloyed with metallic copper, it is not changed to metallic bismuth, but remains mechanically distributed throughout the copper.

Sep 1, 1909

By D. K. Deardorff

The purpose of this work was to investigate the hafnium-carbon phase diagram. Alloys used to study this system were prepared from high-purity components by both consumable-and nonconsumable-electrode arc melting. Data for the diagram were obtained on the alloys by metallography, optical pyrometry, thermal analysis, heat treatment, and X-ray diffraction. The data indicate that a carbide compound occurs over considerable range of composition, and that one of each of the following types of reactions occurs in the hafnium-carbon system: Peritectoid, peritectic, and eutectic. The maximum melting temperature of hafnium carbide is 3,840° C at 49 to 50 atomic percent carbon, and the composition range of hafnium carbide at temperatures of 2,150° to 2,380° C is from 37.0 to 48.5 atomic percent carbon. The hafnium a-S transformation temperature is raised on alloying with carbon from 1,750° to 1,890° C, where a peritectoid reaction isotherm occurs. Alloying hafnium with carbon increases the hafnium melting temperature from 2,190° to 2,250° C, at which temperature a peritectic reaction occurs. Hafnium carbide and carbon react at 3,055° C to form a eutectic of 68.3 atomic percent carbon.

Jan 1, 1967

By N. Tatalias, P. Ilunga, M. Lampi, J. Edwards, K. Valkama, M. Nicolle, D. Samal

"Developing a greenfield mining project is a complex exercise: doing so in an increasingly volatile, uncertain, and ambiguous global economy adds significantly to this complexity. In the context of an elevated cobalt price, this paper outlines the metallurgical and process development of the Mutoshi copper–cobalt project for copper cathode and cobalt hydroxide production in the Democratic Republic of Congo. Chemaf has a long production history on the Copperbelt, a region widely perceived to be tough to operate in. This history stretches back to 2001, during which time the company has developed two copper–cobalt processing facilities. The experience gained in the development and operation of these two facilities has been used extensively in the Mutoshi copper–cobalt project. The metallurgical test work, process design, and project delivery approach are presented. Additionally, the decisions taken to minimize risk and maximize upside to the project are discussed. IntroductionChemaf (Chemicals of Africa), a mining company located in Katanga province of the Democratic Republic of Congo (DRC), has been operating since 2001 with two major copper– cobalt processing facilities: the Usoke and Etoile plants. In 2016, Chemaf acquired the Mutoshi mine, which belonged to Gecamines and had been explored by Anvil Mining since 2004 under a joint venture with Gecamines. Chemaf appointed African Mining Consultants Ltd (AMC) to undertake a preliminary economical assessment, then develop a JORCcompliant Mineral Resource estimate and finally a full life-of mine feasibility study. Both a Mineral Reserve and Mineral Resource were developed and the final life-of-mine feasibility study is to be published shortly. A metallurgical test work programme was initiated and carried out by Chemaf’s research and development laboratory with assistance from the Chemaf process team. After completion of the initial test work, Chemaf developed a process design criteria document for a 20 kt/a copper cathode and 8 kt/a cobalt in hydroxide production plant, followed by a flow sheet and supporting METSIM mass balance. As the drilling progressed, the plant design capacity was revised to 16 kt/a cobalt production. The life of the mine at this production rate is over 40 years."

Nov 1, 2018

By Ray D. Peterson

The hydrothermal enrichment of chalcopyrite by CuSO, occurs in the absence of oxidizing or reducing reagants. Kinetics of the enrichment process were determined under autoclave conditions in the temperature range of 398°K (125°C) to 473°K (200°C). Covellite (CuS) formed first, followed by digenite (Cu,,,S), with rejection of iron to the solution. The kinetics have been explained by a model which includes diffusion during the first stage formation of covellite followed by surface reaction rate control when digenite be. The effects of particle size, temperature, pH, and cupric and ferrous ion concentrations on the leaching kinetics were examined. Additions of ferrous ion to solution markedly increased the rate of reaction.

Jan 1, 1994

By K. Perry, B. Lusk, Q. Huang, R. Honaker

"Rock dust is applied in underground coal mines to prevent the propagation of coal dust explosions. The application is conducted either dry or wet. Both methods have advantages and disadvantages however the formation of caked rock dust particles is cited as a significant concern for wet applications. A study was conducted to evaluate the effect of modifying the rock dust particle surfaces to repel water and each other by the addition of oleic acid (OA) and sodium oleate (NaOL). At a NaOL dosage of 2 lbs/ton, a contact angle of 112o was measured indicating strong surface hydrophobicity and ability to repel water. FTIR studies indicated a chemisorption mechanism which is necessary for long term stability of the surface modification. The dispersion rate of the modified rock dust samples was elevated by the application of both OA and NaOL thereby indicating a significant reduction or elimination of the detrimental effect of caking. Tests in an explosion chamber showed a 79% reduction in the dust explosion potential relative to untreated rock test applied by the wet technique. INTRODUCTION Mine explosions have been a long-time threat to underground coal miners attracting significant attention to the accumulations of combustible dusts and gasses. In the presence of sufficient oxygen and heat, the accumulations of combustible dust and gass can lead to large-scale underground coal mine explosions [Harris et al., 2010]. To alleviate the problem, rock dust such as limestone can serve both as a thermal inhibitor and a heat sink to inert the coal dust explosibility thereby prohibiting the occurrence of dust explosions [Richmond et al., 1975; Amyotte et al., 1995; Dastidar et al., 1997; Man et al., 2009]. The dispersibility of the rock dust is an important characteristic that determines the degree of explosion prevention [Greenwald et al., 1938; Mozumdar et al., 1974; Amyotte et al., 1995]. Unfortunately, the environmental conditions of an underground mine has the potential to cause caking of the rock dust which reduces the dispersive characteristics needed. The dispersive property of rock dust can be enhanced by modification of the particle surface properties by the application of chemical additives [Greenwald et al., 1938; Mozumdar et al., 1974; Spence, 2004; Vogt, 2011; Doidge et al. 2014]. The major mechanism for rock dust caking is the adsorption of water which forms liquid bridges at the particle-particle contact points where saturated solutions of soluble powder ingredients are present. Changes in temperature or relative humidity result in solvent (water) evaporation and the formation of dry bridges [Rumpf, 1958; Specht, 2006]. One method to prevent caking is creating hydrophobic rock dust to repel water from the solid surface thereby preventing the formation of liquid and solid bridges."

Jan 1, 2015

By L Klemettinen, J Biswas, W Malan, D Sukhomlinov, D Lindberg

In order to mitigate the effects of climate change, our society must be able to drastically reduce its CO2 emissions. As the metallurgical industry is a considerable contributor to these emissions, new greener technologies must be invented and developed. One option could be the direct production of metals from oxides using renewable electricity. The aim of this study was to investigate the possibility of using high-temperature molten oxide electrolysis (MOE) for iron and ferrochrome production. FactSage™, ver 8.2 (by Thermfact Ltd and GTT-Technologies) was utilised for estimating a feasible equilibrium electrolyte composition, and the experiments were conducted at 1550–1580°C in conical alumina crucibles with iridium wire as the cathode and platinum wire as the anode. The sources of iron and chromium were either pure FeO powder or industrial chromite pellets. Voltage was applied to the electrolysis cell for 6 hrs and the resulting current was measured, along with oxygen concentration in the off-gas line. The electrolyte comprised of SiO2, Al2O3, MgO and CaO. First, the effect of FeO concentration on iron reduction efficiency was investigated using only pure oxide powders as starting materials. The results indicated that 10 wt per cent FeO mixed with the electrolyte resulted in more efficient iron reduction compared to 20 wt per cent. In further experiments, industrial chromite pellets were ground and mixed with the CaO-free electrolyte. Iron and chromium reduction efficiencies were higher when approximately 19 wt per cent of the total sample mass consisted of pellets compared to increasing the pellet amount to 37 wt per cent. Generally, the chromium solubility in the liquid electrolyte was relatively low, and most of the chromium was confined to the spinel solid solution, from where its dissolution to the liquid electrolyte was very slow, resulting in slow reduction kinetics. For larger scale applications, economically more viable electrode materials should be investigated.

Jun 19, 2024

By E. H. Christiansen

Gem-quality red beryl in the Wah Wah Mountains of southwestern Utah formed as a post-magmatic mineral in a topaz rhyolite flow. Unlike topaz, this beryl occurs along fractures in devitrified rhyolite, rather than in lithophysal vugs. The flow occupies a graben and perhaps a significant paleo-drainage. Beryl occurs at medial depths within the eroded flow, about 170 m below overlying mafic lava flows. Both beryl-bearing fractures and the host rhyolite show an unusual amount of argillic alteration compared with other topaz rhyolite flows. Alteration may be related to the incursion of surface water along shrinkage fractures within the flow. Whole-rock concentrations of CaO within the host rhyolite are very low (<0.01 % to 0.18%) compared with other topaz rhyolites and Be concentrations (about 20 ppm) are about average. Low Ca activities prevented fluorite precipitation and allowed Be transport as fluoride complexes. Beryl probably grew at subsolidus temperatures (-300-650°C), but above the temperature of kaolin development (200-300°C) as fluoride-rich vapors, released by devitrification, encountered fractures and mixed with vapors derived from surface water flowing through the fractures. Beryllium fluoride complexes reacted with water vapor, silica minerals, alkali feldspar, water, and Fe-Mn oxides along fractures to produce red beryl. Continued reaction of the cooling flow with surface water at lower temperatures probably produced a boiling, more acidic fluid that produced the argillic alteration. Consequently, eruption of low-Ca topaz rhyolite followed by entrance of surface water into medial portions of a devitrifying and still hot lava flow appear to be critical factors that led to red beryl formation.

Jan 1, 1996

By Ihsan Berk Tulu

The complex interaction between multiple seam pillar extraction panels and variable topography can generate unexpected ground control problems. This case study describes stress-related damage in multiple seam workings that resulted in difficult operating conditions and compromised the safety of the support crews. The damage appeared to be caused by horizontal stress but the unexpected location of the damage baffled the authors. A 2D Finite element analysis was conducted of the mine layout and surface topography in an attempt to explain the observed failure. It was discovered that the topography resulted in the rotation of the major stress at the location of the current workings. The stress rotation caused asymmetrical interactions between the workings on the different coal beds, which can explain the unexpected response observed in the mine. Consequently the layout of the next panel was changed by locating the vulnerable entry 30 ft away from its originally planned position. The new location was selected to locate the entry in favorable stress conditions. The change in layout resulted in a significant improvement in conditions when the next panel was mined. At the time of writing this paper, a full panel has been developed using the modified layout without undue ground control problems. The case study demonstrates that numerical models can help engineers to interpret and solve complex multi-seam interaction problems.

Jan 1, 2014

By T. L. Joseph

A DEMAND for specialized knowledge has directed engineering curricula towards competency in some particular field or occupation. Preparation for life in a broad sense of completeness has received little consideration. Ways and means are needed for weaving some of the threads of liberal education into the fabric of engineering education. Any effort to develop a humanistic-social stem of engineering education will depend largely upon the content of the courses and the type of instruction offered. Many of the courses in college curricula are intended to lay a foundation for more advanced courses to be taken later by those. who specialize in some particular field. Students in other fields lack the background necessary to take the advanced courses and have too much detailed information, soon forgotten, forced upon them if they pursue the foundation courses. To develop a humanistic-social stem for engineering education existing catalogue courses selected should follow some general plan aimed towards broad educational objectives. Courses packed with detailed factual information are necessary for the stu-

Jan 1, 1947

By E. D. Hummer

During the planning of the fine coal cleaning addition at the Gary, W. Va., Coal Preparation Plant of United States Steel Corp. careful consideration was directed toward the problem of minus 48 mesh refuse disposal. The plant flow sheet included wet screening the raw coal at ¼ in., pumping the minus ¼ in. raw coal to bowl desiltors for desliming, and then cleaning the deslimed raw coal on tables. The material to be removed from the circuit as minus 48 mesh refuse consisted of the minus 100 mesh desiltor overflow thickened in two 120 ft diam thickeners and minus 1 mm screened from the table refuse. Later a flotation plant was added to recover coal from the desiltor overflow, and a classifier replaced the screens to make a sharper size separation of the table refuse at 48 mesh. Today the minus 48 mesh refuse at Gary consists of thickened flotation tailing and thickened spiral classifier overflow. The transportation of large quantities of fine, wet refuse filter cake mixed with jig and table refuse over existing conveying equipment would have been neither dependable nor economical. Filtration was therefore impractical, and disposal of the fine materials was a problem. The decision was to pump the material to storage ponds.

Jan 3, 1965

By P. A. Davidson, D. J. Short

"In this paper we describe a 'non-contact' electromagnetic nozzle suitable for sprayforming and gas atomization processes. In such processes there is a need to control the flow rate and diameter of the liquid metal jet whilst minimising contamination of the stream. This can be achieved using an electromagnetic valve, which partially levitates the jet in freespace, using a segmented cylinder surrounded by an induction coil. This valve will significantly enhance the quality of the titanium alloys and nickel-based superalloys used in sprayforming and gas atomization. This paper describes the design and test of a laboratory prototype valve based on experiments performed with liquid tin.1. Introduction In many industries there is an increasing need for clean, high quality metals and alloys based on titanium and nickel. Two important processes are: 1) Spray deposition which allows the liquid metal to be converted to a near-net shape, thus alleviating the need for subsequent forging and extensive machining and; 2) Powder production of titanium by gas atomisation.In centrifugal spray deposition of titanium (see figure 1) the metal is induction melted in a cold crucible. The crucible consists of a number of water-cooled segments, which allows the high frequency magnetic field of the coil to pass through the crucible, and into the melt. The charge is melted by the induced eddy currents. Locally at the crucible walls the liquid metal solidifies, and is contained within a. 'skull' of its own solid, thus reducing contamination from the crucible wall. Once melted the metal is poured through an electrically heated graphite nozzle and into the spray forming chamber. The principal limitation of the process to-date, however, is that it currently uses a graphite and /or ceramic nozzle to direct the flow of liquid metal to the atomizing disk and as such there is considerable risk of nozzle erosion with inevitable effects in terms of contamination of the melt stream and variability in flow conditions. In this research programme we develop a. non-contact electromagnetic nozzle, which will totally eliminate refractories and/or ceramic materials from the melting and casting process. This will greatly enhance the technological capabilities of sprayforming and gas atomization processes."

Jan 1, 1999

By D. L. Millar

The hydraulic air compressor (HAC) is driven only by water, held up by a dam, to create relatively low head (typically 10-20 metres), such that the developed hydropower is used to cause flow in openings deeper underground. Air is entrained in the water at the inlet to the sub-surface openings (an air to water volume ratio of 1:1 is reported to be optimal) and is compressed as it is carried along by the deepening water flow. At depth, and with lower water velocities arising from larger cross sectional area tunnels, air bubbles separate out of the water flow and are collected in a receiver space above the flowing water. Water, free of air, then passes back up a return shaft (up-pipe) and rejoins the river or stream flow. In principle, an HAC can produce any pressure and flow rate required, given large enough shafts and enough water supply with head sufficient to overcome frictional resistance in the sub-surface tunnels. Practically, as air solubility in water increases with pressure, HAC installations with depths greater than 100 metres may lead to higher rates of compressed air loss, without special separation measures. A modern HAC application for mine refrigeration and cooling is presented.

Aug 1, 2013

By R. F. Hammen

Copper is one of the most widely used metals in industrial processes and is also present in most mining operations. Extraction of copper from solutions often proves difficult due to the presence of complexing agents. ChromatoChem, Inc. has developed a Solid Phase Extraction (SPE) support (HiPAC) for removal and recovery of metals from wastewater. The HiPAC SPE support employs chelating agents covalently coupled to a long linker molecule. Several solutions containing copper and complexing agents were tested including 1) copper and carbonate, pH 9.8, 2) mixed metals and anions with copper and cyanide, pH 11, and 3) copper and the chelating agent EDTA, pH 11. The copper was extracted from solutions one and two at high pH, but the EDTA containing solution needed the pH lowered to make the copper available for capture. In each example, the copper concentration was significantly reduced by HiPAC SPE treatment.

Jan 1, 1994

By Jiongtian Liu, Jianjun Wu, Yongzhou Wan, Li Feng

"Mechanical Thermal Expression (MTE) is a developing non-evaporative lignite dewatering technology. It has been shown to effectively dewater high moisture content in low rank coals via the application of mechanical force and thermal energy at elevated temperatures. In this paper, the dewatering behavior of Yunnan Xiaolongtang lignite during the MTE-process was studied. Furthermore, how variations in temperature and pressure during the MTE process affect the surface oxygen functional groups and pore structure were also discussed using Fourier transform infrared spectrometer (FTIR) and mercury intrusion porosimetry (MIP). Increases in MTE temperature and pressure resulted in significant reductions in residual moisture content and moisture holding capacity, along with the increase of fixed carbon content and reductions of other elements content, especially oxygen content, which have been largely attributed to the destruction of the surface oxygen functional groups and porosity in lignite. The optimized technology conditions are temperature 150~220°C and pressure 7~10MPa. The residual moisture content of the lignite treated by MTE under the conditions of 200°C and 10MPa is decreased to 8%, while the dewatering rate exceeds 76 % and the calorific value approaches 22 MJ/kg. The experimental results offer a deeper understanding of the influence of process parameters on the lignite stuctures and properties. The reduction in residual moisture content, surface oxygen functional groups and pore volume under increasingly severe MTE conditions are suggestive of the structure changes that accompany increased coalification (rank) within the lignitic range."

Jan 1, 2014

By Richard B. Reese, George R. St. Pierre, Robert A. Rapp

The vapor pressures of pure iron and pure chromium have been measured using a Knudsen cell coupled with a mass spectrometer. The experimental results agree well with some previously reported data; heats of sublimation and vaporization have been calculated. From vapor pressure rr~easurernents, the activities of iron and chromium in their binary alloys have been determined for NcY = 0.10 to 0.65 over a 1400" to 1700~ temperature range. The activity of chromium in the liquid alloys was found to exhibit positive deviation from ideal behavior when referred to solid chromium as the standard state; however, for the activity of chromium referred to nonequilibrium undercooled liquid chromium as standard state, the activity behavior is almost ideal. ALTHOUGH the Fe-Cr system is important as the basic system of alloy steels, the thermodynamic properties of this system have not been thoroughly investigated at elevated temperatures. In view of the potential practical applications of such data as well as their contribution to alloy theory, further study of the Fe-Cr system was undertaken. In addition, further development of experimental techniques for equilibrium measurements at high temperature is required. The present research involved an application of the Knudsen effusion method in conjunction with a time-of-flight mass spectrometer. Belton and ~ruehan&apos; have measured the activities in Fe-Ni and Fe-Co alloys by a similar method. Speiser, Johnston, and lackbburn&apos; have determined the vapor pressure of pure solid chromium between 1283" and 1561°K by a Langmuir free evaporation technique. The vapor pressure of chromium was described by the expression: over the temperature range 1283" to 1561°K. McCabe, Hudson, and paxton3 have measured the vapor pressures of pure iron and pure chromium by the Knudsen cell technique around 1500°K. The vapor pressure and heat of sublimation at O°K, AH,", for pure chromium agreed within experimental error with the measurements of Speiser et al. at 1200°C. Kubaschewski and HeYmer~ determined the vapor pressure of pure solid chromium in the temperature range 1170" to 1400°C by the Knudsen effusion technique combined with a radioactive tracer analysis of crS1. Their results agreed with the work of previous investigators. Edwards, Johnston, and Ditmars5 have measured the vapor pressure of pure solid iron by the Langmuir technique between 1356" and 1519°K. The vapor pressure of solid iron in the temperature range studied was given by: The data of McCabe, Hudson, and paxton3 on the vapor pressure of pure iron around 1500°K by the Knudsen effusion technique were in good agreement with those obtained by Edwards et a~.~ Hultgren, Orr, Anderson, and Kelley give the selected values for the AH: of pure iron and pure chromium as 98,990 *200 and 94,340 * 500 cal per mole, respectively. These values are the average values determined in the several investigations by different methods. The Fe-Cr phase diagram7 is shown in Fig. 1. Previous determinations of activities in this system have been carried out by several investigators, but most of the work has been done on solid alloys. Using a Knudsen effusion method with cr5&apos;, Kubaschewski and Heymer4 reported that the Fe-Cr system exhibits positive deviation from the ideal behavior for compositions ranging from NCr = 0.0398 to 0.699 at 1170"

Jan 1, 1969

By D. N. Seidman

In the course of a study of the electronic and thermodynamic properties of Pb-Se alloys it was found necessary to have an accurate knowledge of the phase diagram. However, the literature is in disagreement as to whether or not a monotectic reaction occurs in the lead rich portion of the phase diagram. Pelabonl reported only a two-phase region consisting of lead-rich liquid and solid PbSe extending from almost pure lead to the compound PbSe, and gave the melting point of PbSe as 1065°C. The data of Friedrich and Leroux2 are in general agreement with this type of diagram, with the melting point of the compound being 1088°C. However, Nozato and Igaki by inverse rate thermal analysis observed a monotectic reaction isotherm exlacing at 860°C with a monotectic composition of 20.5 at. pct Se. The miscibility gap in the liquid state extends from 7.5 to 20.5 at. pct Se. Hansen and Anderko4 accepted Nozato and Igaki&apos;s phase diagram in the region of the lead-rich monotectic. To reinvestigate this portion of the phase diagram, both thermal analysis and metallographic examination of various compositions were performed. The thermal analysis apparatus was constructed according to the specifications of the National Bureau of Standards. A t/t-l pct Rh thermocouple was calibrated against the melting point of copper (NBS), zinc (NBS), and antimony (A. D. Mackay), the emf being measured with a Rubicon Type B potentiometer sensitive to lpv. The absolute accuracy of the thermal analysis obtainable with this system is ± 0.5oC. Starting materials were semiconductor grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999 pct pure with only trace impurities detected upon spectroscopic examination. One hundred galloys were sealed in quartz crucibles with a central thermocouple well under a vacuum of less than 1 p. This procedure prevented any composition change due to vaporization during the run. Cooling curves were obtained on the alloys listed in Table I. Data was taken by the direct method at cooling rates ranging between 1/2 to 2°C per min. The alloys were heated well above the liquidus and shaken vigorously to insure homogeneity. No evidence of an arrest indicative of the monotectic reaction was observed, and the two-phase region reported by Pelabonl and Friedrich and Leroux? was confirmed in general, although our data give higher liquidus temperatures than Friedrich and Leroux. The melting point of stoichiomet-ric PbSe determined for two different samples was 1080.7 0.5oC. The results of this investigation are compared with Nozato and Igaki&apos;s data in Fig. 1. To Complement the thermal analysis data, an 86 at. pct Pb specimen was examined microscopically. This composition was in the center of the miscibility gap reported by Nozato and Igaki.3 The alloy was heated to 1000°C, held for 1/2 hr, and water quenched. The specimen was polished using standard metallographic techniques for lead. The alloy was etched with an acetic-nitric acid etchant for 10 min at 45°C. Microscopic examination did not indicate the existence of two separate layers or solidified droplets imbedded in a matrix, as would be expected if a miscibility gap were present. The mi-crostructure shown in Fig. 2 consists of uniformly dispersed, dendritic PbSe in a lead-rich matrix.

Jan 1, 1962