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By A. Coskun, J. F. Elliott

The activity of aluminum in liquid Al-Fe alloys .has been measured by an improved version of the transportation method in which the metallic vapor has been collected by its solution in a metallic condenser. The results can be represented by the equation: log yAl = -3.0(1 - xAl2) (0.6 < XAl < 1.0) This equation applies at 1315°C. MORRIS and zellarsl adapted the transportation method for measuring the vapor pressure of a com- ponent of an alloy at high temperature. We have modified their technique further2 for use with metals that are strong oxide formers. In the present case the method has been applied to the Al- Fe system to obtain the activity of aluminum in the liquid region at 1315°C. Dried ultrahigh-purity hydrogen (Matheson) is the carrier gas. The operations, Fig. 1, of deoxidizing the gas, equilibrating the gas with the sample at 1315";, and then collecting the aluminum vapor are all accomplished within a single, continuous alumina tube to avoid contamination of the system by leaks. De-oxidation to a very low level of PO2 (<10-25 atm) is Obtained by passing the hydrogen through a tightly packed bed of aluminum powder. The temperature of this bed increases to approximately 550°C in the direction of the gas flow. The boat containing three pellets of the alloy is supported on the end of a

Jan 1, 1969

By R. J. Hopkins, L. B. Haney

On the basis of limited experimental work conducted at the Port Pirie smelter, it would appear that, by increasing the specific surface of sinter, and possibly that of coke as well, a marked increase in the rate and degree of sinter reduction in the furnace shaft can be achieved. Fusion-point tests have shown that this increased reduction means a much higher sinter fusion point and narrower plastic zone, while the more efficient utilization of coke in the furnace is inherent in the intensification of reduction by the provision of a more reactive sinter surface. Investigations aimed at increasing the ability to operate the blast furnace with a higher lead tenor of sinter reducing fuel cost proportionately, and at eliminating the loss in reduction potential in coke entering the furnace, as shown by the presence of appreciable proportions of CO in the top gases, are reported. Several lines for future investigations that could result in improved smelting methods are proposed. A SOMEWHAT informal presentation of ideas on lead blast-furnace smelting will be given in this paper. These ideas have been developed during observations of furnace behavior at Port Pirie and earlier at Mt. Isa, and have been guided by the results of laboratory experiments at Port Pirie. The authors do not intend to propound any particularly new theories, but present their ideas as a basis for discussion which may help toward a better understanding and improved control of blast-furnace operation. Performance variations of considerable magnitude occur from time to time at most lead blast-furnace plants. While Port Pirie is fortunate in having a very regular supply of high grade concentrates, it is no exception in this respect. Such irregularities are of considerable economic importance and they constitute a challenge to present-day metallurgists in their efforts to obtain an ever greater degree of control over furnace operation. In operating as Port Pirie does with a relatively high lead charge, it has been recognized for a long time that shaft conditions are ,of the greatest importance. A practical, or engineering, attack on the problem of accretions consisted of changes in furnace design, e.g., by widening the shaft to 10 ft above the bottom row of tuyeres, and by the provision of curved ends and vertical walls.&apos; That this attack has had a great measure of success is shown by the fact that barring down of these wide furnaces is rarely necessary, shaft conditions have greatly improved, and sensitivity to charge variations has been markedly reduced. These modifications, followed by some metallurgical changes (chiefly the incorporation of pig iron into the furnace charge in 1948), have brought furnace operation to a point where some variables which were previously masked can now be studied. Accordingly, over different periods of time during the last five years, such variables as could be given numerical values have been recorded and subjected to statistical examination. The objectives of this work were: 1—to reveal the true importance of the different variables and 2—to show the proportion of total furnace variation which is unexplained and therefore referable to causes not measured at present? e.g., shaft accretions, sinter structure, coke structure, and others. Statistical Study of Variables In this work factors relating to furnace speed and lead reduction have been examined: 1—slag com-

Jan 1, 1955

By Joseph Gurland

EVERAL carbide-cobalt compositions were pre-^-5 pared for the purpose of determining the transverse rupture strength of various carbide-binder systems. The binder content was held at 10 and 37 volume pct Co, so as to be representative of low and high bjnder compositions. The carbides used, WC, Tic, TaC, CbC, VC and ZrC, were selected on the basis of availability, knowledge of their properties, and small solid solubilities in the binder metal at room temperature. The methods of preparation and carbon analysis of the carbides are summarized in Table I. The carbides with cobalt added were ball milled, pressed, and sintered. vacuum sintering was used throughout, except for the WC-Cs alloys, which were sintered in hydrogen. The sintering temperatures ranged from 2500" to 2750°F for the low binder alloys and from 2300" to 2550°F for the high binder alloys. Compositions and properties of the sintered com- pacts are presented in Table 11. For the transverse rupture strength, the average and range of the five best samples of each alloy are listed. Discrepancies between the actual and theoretical densities are attributed to carbon deficiencies in some samples. The theoretical densities were calculated by assuming mixtures of carbides of stoichiometric compositions and cobalt. Representative microstructures are shown in Figs. 1 to 6. The porosity was A-2 or better&apos; in all alloys except those with ZrC. A grain size of about 3 p was

Jan 1, 1958

By M. Dayne Aldridge

A discussion of the definition of automation in mine ventilation applications is presented. The results of theoretical studies, experiments, and practical experience from work in the United Kingdom, Belgium, Poland, the Soviet Union, and the United States are summarized Conclusions are drawn from these efforts and the prospects for the future development of automatic mine ventilation systems are explored.

Jan 1, 1980

By E. E. Schumacher

IN a laboratory devoted to the furtherance of the science of communication, the breadth and variety of the problems encountered are challenging to a metallurgist. In my own long association with the Bell Telephone Laboratories, our metallurgical group has dealt with a vast number of alloys, both ferrous and nonferrous, and with many materials in the border range of metallic properties., The objectives of our design engineers embrace every phase of telephony, and the properties they desire in metals are generally unusual, frequently unique, and often conflicting. Commercial alloys have not always been available with properties to meet a special requirement in the telephone plant, and many alloys have had, therefore, to be custom-made. Anyone who has had the opportunity to observe the results of tests of all types on numerous such alloys, both commercially and specially produced, or who has taken part in the development of an alloy of some necessary, but new or unusual combination of properties, could not fail to be impressed by the frequency with which a desired goal has been reached or adequately approached through the presence of decimal quantities of alloying elements. Nor could One fail to be struck by the occasions when, conversely, of a minute amount Of impurity element has rendered an alloy useful. It is no exaggeration to state that the content be- hind the decimal point often spells success or fail-ure, and the critical content is sometimes far to the right of the decimal point as I shall later illustrate. The great effects of small additions have long been recognized and have, in fact, been described by many investigators. The importance of the minute, however, cannot be overemphasized. Therefore, in this discussion, I propose to illustrate for you some of the startling instances, drawn primarily from our own experiences, wherein small, even vanishingly small, proportions of stranger elements in otherwise common aggregates have com-pletely changed the customary pattern of behavior. No one property has a monopoly as to being dis-proportionately affected by minor elements. Nearly all properties are affected, but there is time here to include only a selected few. I have chosen, there-fore, three of general interest: strength, magnetic, and electrical properties. I shall inquire into both the mechanisms and consequences of these disproportionate effects and try to share with you the fascination and challenge of this field. Strength Properties of Lead and Lead Alloys To illustrate the effect of the minute on strength properties I have selected lead and its alloys, with which we have worked extensively for many years. Lead has the advantages of being available in quantity in a state of high purity and of being fairly easy to melt and fabricate without contamination to any extent detectable by the spectrograph. It has the interesting disadvantages of recovery and recrystallization at room temperature. Whether I

Jan 1, 1951

By A. C. Fraker, H. H. Stadelmaier

In the systems Mo-Fe-C, Mo-Co-C, and Mo-Ni-C the phase boumdaries of the cubic Ij carbides were determined at 1000°C and the variation of the lattice parameter with composition was measured. In the system Mo-Fe-C a single ternary carbide, Mo3Fe3C, was observed. In Mo-Co-C and Mo-Ni-C two new n phases of the type M12C were found: Mo6C06C and Mo6Ni6C. At 1000°C they coexist with the M6C phases MO3-4,CO3-2C and Mo3-4Ni3-2C, respectively. Mo3C03C and Mo4C02C are not separate phases but parts of a single M6C phase region, and the same is true of Mo3Ni3C and Mo4Ni2C. THE n carbide structure type has been known since it was determined by westgren&apos; in 1933, yet reliable information on phase compositions of this type is ap-parently scarce. The following selection of suggested formulas illustrates the extent of the confusion con-cerning compositions: W2-3Fe4-3C,1W6Fe6C,2 W2_4Fe4-2C,3 (W,Fe)6C,4 Tj.-W4Co2C and nz-W6Co6C,5 n1-W3Co3C and n2-w4Co2C,5 W3C03C and w6Co3C2,7 MO3Fe3C,8n2-M04Fe2C,9 (MO,Fe)6C,4 MO3CO3C,8 n2-MO4CO2C.9 Many of these compositions obviously overlap, some disagree in carbon content. The use of the designations 77, and n2 is not consistent. There is uncertainty whether two carbides M6C coexist or whether there is only one M6C with a wide range of substitution of one metal for the other. The existence of M12C seems questionable altogether if one ignores the results of a neutron diffraction study of W6Fe6C supporting that particular metal to carbon ratio.&apos;&apos; More reliable information is available for the iso-typic oxides studied by Nevitt,11 Nevitt, Downey, and orris," and Meussner and carpenter.l3 That n car-bides and oxides are structurally identical, particularly with respect to the location of the metalloid atom, has been demonstrated clearly by Stadelmaier and Meussner14 and also by Parthe, Jeitschko, and sadagopan.15 Therefore the present paper, which attempts to establish the phase boundaries of n defini-tively for three carbon systems, has implications for the whole family of filled Ti2Ni types. EXPERIMENTAL PROCEDURE The samples were prepared in two stages. Pellets weighing 3 g were compacted from powders of the elements and presintered in a closed tube of fused silica that had been evacuated to lO-4 mm Hg. This was fol- lowed by arc melting the sintered samples under argon. Remelting the button once was sufficient to produce homogeneous specimens. The metal powders had the following minimum purities in wt pct: molybdenum 99.5, iron 99.0, cobalt 99.7, nickel 99.9, graphite 99.94. Carbon determinations by the gas volumetric method were obtained from thirty-one of the one hundred samples in the annealed condition. They were limited to compositions that were critical to placing a boundary line in the isothermal sections. The carbon losses were comparatively low and averaged less than 1.5 at. pct. For annealing, the samples were sealed in tubes of fused silica evacuated to 10-4 mm Hg. The annealing schedule was 20 hr at 1250°C followed by 150 hr at 1000" ±10°C. For the water quench the silica glass tubes were broken mechanically to speed the quench. The specimens were examined in the as-cast and annealed condition by standard metallographic techniques. Some of the as-cast and all annealed samples were studied by X-ray diffraction using a 114.6-mm powder camera with filtered Co radiation. The lattice parameters of the n phases were determined by graphic extrapolation to 8 = 90 deg on a plot against sin2 8. It is estimated that the maximum error in the lattice parameters is ±0.002A.. The phase fields were determined by the disappearing phase method, relying on X-rays for phase identification and on microscopy to detect small amounts of a phase. RESULTS Pertinent information on the binary side diagrams has been summarized by Hansen and Anderko16 and Elliott17 and will not be discussed further. Photomicrographs documenting the equilibria at 1000°C have been selected to avoid redundancy due to the similarity of the three systems. Thus there will be only one picture showing an equilibrium with Mo2C, and so forth. Molybdenum-Iron-Carbon. An isothermal section of most of the Mo-Fe-C system at 1000°C is shown in Fig. 1. No attempt has been made to distinguish between a and y iron or to determine their phase boundaries. A conspicuous absence is the phase Fe2 1Mo2C6 with the Cr23C6 structure, supporting the suggestion by Krainer4 that it decomposes by annealing at high temperatures. The only ternary phase is found in a narrow range around Mo3Fe3C (MO43Fe43C14). A microstructure with a two-phase mixture of Mo + n is seen in Fig. 2. The variation of the lattice parameter of n with the estimated composition is shown in in Table IA. The phase diagram does not agree with the results of Kuo9 who reported n2-Mo4Fe2C. Our lattice parameter Varies from 11.095A at the iron-rich end to 11.140Å at the molybdenum-richoend of the phase field whereas Kuo9reported 11.26Å for Mo4Fe2C. We are in agreement with the older work

Jan 1, 1970

By George M. Fowler, F. E. Gregory, William M. Agar, Joseph P. Lyden

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

By William M. Agar, F. E. Gregory, Joseph P. Lyden, George M. Fowler

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

By F. E. Gregory, George M. Fowler, William M. Agar, Joseph P. Lyden

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

By B. F. Oliver

Equilibrium and kinetic segregation coefficients for the dilute high-temperature system tantalum in iron have been experimentally determined in a levitating zone melter. The equilibrium segregation coefficient, ko, is 0.43 * 0.03. Planar interface solidification is possible up to a freezing velocity of 4 in. per hr but not at 6 in. per hr. Precise concentration control of the solid is possible over this range of freezing velocities. The momentum boundary layer thickness, and the diffusion boundary layer thickness, 6, are such that either 6, > 6 or ALTHOUGH considerable data exists in the literature concerning the stability of planar-solidification fronts, little data exists for high-temperature metallic systems. The study of fundamental aspects of solidification in high-temperature iron-base systems is complicated by the extensive solvent power of liquid iron. In order to minimize such effects a levitating zone melter was used to study the segregation of tantalum in iron.&apos; The solute tantalum was selected because: 1) the ko value was, according to the literature, initially thought to be less than 0.1, thus increasing the precision of the method used;2,3 2) the vapor pressure and is a constant, fixed by induction stirring, 6, the diffusion boundary layer, is 5150 u. At 400 rpm and 6 in. per hr freezing velocity the cast structure exhibits circular macroporosity and banding concentric with the axis of the rotation of the interface. Electron-beam microprobe analyses indicate that the tantalum content is highest at the center of rotation (1.2/1) and decreases with increasing radius as the fine-grained bands become sharper. This entire structure exhibits microseg-regation of tantalum. of tantalum in 1 atm of H2 is small, assuring conservation of solute during redistribution; and 3) spec-troscopic analyses were available for the appropriate range of tantalum considered. Additional objectives were 1) to determine kinetic segregation coefficients for well-stirred zones with constant boundary conditions and thus quantitatively calibrate solute-segregation behavior in the levitating zone melter, and 2) to examine the range of freezing velocities over which smooth solid-liquid interfaces could be controlled in an iron-base alloy under the restrictions of the thermal gradients imposed while levitating a zone. The single-pass zone-melting method was used to calculate individual k values.&apos;

Jan 1, 1964

By D. W. Fuerstenau

On page 1243, column 1, the first line of the author&apos;s reply should read "D. W. Fuerstenau (author&apos;s reply)---," rather than D. E., as printed. In the sentence immediately preceding the first equation (page 1243, column 2)&apos; the word "none" was omitted. The sentence should read: "However, if enough ore is put into the mill [so] that none of the energy put into the mill is wasted on metal-to-metal impact, then the product should have size modulus determined by the relation: ..."

Jan 1, 1961

By Hiroshi Oikawa, A. G. Guy

Recent experimental evidence has shown that it is often incorrect to neglect the reactions occurring at an interface with respect to the diffusion reactions. By introducing reaction-rate constants and k for the transfer of components 1 and 2 between the a and b phases, a phenomenological description has been devised for the coupled processes of diffusion and in-terfacial reaction. An illustrative example has been analyzed with the aid of a suitable computer program. The results indicate that for kab values on the order of 10&apos;1 cm per sec and Ð values of about 10¯10 sq cm per sec, the interfacial reactions are significant during the first 10 2 to l0 6 sec of a diffusion experiment. Among the observable effects of the interfacial reactions in this case appear to be the burying Kirkendall markers and an anomaly in the initial shifting of these markers. THE study of diffusion between two phases is especially important because of its direct connection to phase transformations. For example, the transformation of austenite to ferrite involves diffusion in the a and ý phases and also an interfacial reaction (trans formation) at the a/? interface. If ferrite and aus-tenite are the two members in a diffusion couple, the same two reactions occur during the diffusion process. The numerical values obtained for the diffusion coefficients and interfacial-reaction constants from diffusion experiments can then be employed to predict phase-transformation behavior. Refinement of the calculations of phase transformation is also suggested by the present method for treating two-phase diffusion. In the recent paper by Nolfi et al.&apos; only the solute com ponent is considered in the interfacial reaction accompanying a phase transformation. The present analysis demonstrates that both components must be considered. It is generally recognized that reactions of some kind must occur at the interface in a two-phase diffusion couple, but usually it is assumed that the interface reaction occurs so rapidly that its effect on the overall process is unobservable because the slower diffusion process determines the kinetics of the process. However, Seith and Heumann 2 pointed out that effects of the interfacial reaction should always occur in the early stages of diffusion, and recently Eifert et al. 3 have shown that interfacial reactions influence the composition and motion of the interface in a/ß Al-Cu diffusion couples during the entire course of prolonged, high-temperature treatments. A general procedure for handling the combined processes of interfacial reaction and diffusion in a binary, two-phase system is to introduce kinetic coefficients for the interface reactions and to develop the system of equations governing the interlinked processes of diffusion and interface reaction. The resulting equations, although not amenable to solution in closed form, can be usefully manipulated by a digital computer. INTERFACIAL REACTIONS IN TWO-PHASE DIFFUSION Consider the general case of diffusion between two solid solutions, a and ß, which are adjacent phases in a binary system, Fig. 1. Two semiinfinite bars having compositions c1 and c0ß are jointed at x = 0. If concentrations are expressed in volume fraction,4

Jan 1, 1970

pAbad, Leopoldo F., Min, Engr,, Div. of Mines, Bureau of Science Manila, P. 1. &apos;23 Abadilla, Quirico A,, Geol., Lago Pet. Corp Box 172, Maracaibo, Venezuela, &apos;20 Abbey, Robert Graham, The W. W. Sly Mfg, Co Train Ave., Cleveland, Ohio. &apos;21 Abbott, A. N., Mines Supt., Mazapil Copper Co., Ltd Concepcion del Oro, Mexico, &apos;28 Abbott, Clarence E., Mgr., Mines & Quarries, Tenn, Coal, Iron & R. R, Co,, 1242 Brown Marx Bldg,, Birmingham, Ala. &apos;04]

Jan 1, 1928

By Paul Weir

BLEACHING clays have been used extensively in the oil-refining industries for a number of years. Their use in water purification is relatively recent and less extensive. They are frequently classified as (1) those naturally active and (2) those active after artificial activation with acid. Fuller&apos;s earths fall within the general group of bleaching clays and gradually the commercial term "fuller&apos;s earth" has been applied to natural clays originating, for the most part, in the south-eastern section of the United States. Bentonitic clays are usually classed as activable and are prevalent in the southwestern section of the United States.1 Bleaching clays vary considerably in chemical and physical properties throughout the country, or even in different parts of one deposit (Table 1). TABLE 1.-Physical and Chemical Composition of Different Types of Clays Composition, Per Cent Constituents and Properties Bentonite Fuller&apos;s Mud Clay (Wyoming) Earth (P Peak)&apos; (Alluvial) Silica (SiO2) 60.0 69.6 61.67 Alumina (Al203) 19.0 14.3 20.34 Ferric oxide (Fe203) 2.8 3.90 7.70 Titanium oxide (Ti02) 0.13 0.70 1.01 Lime (CaO) 0.5 0.80 0.00 Magnesia (MgO) 2.0 1.00 0.24 Soda (Na2O) 2.4 0.40 0.31 Ignition loss 4.7 6.77 8.51 Moisture content 8.0 10.0 20.0 Isoelectric point, pH 9.2 9.2 6.5 Average swelling volume 15.0 0.0 0.0 Weight per cubic foot, lb 55.0 40.0 65.0 Material passing 200-mesh sieve, per cent 90.0 85.0 50.0

Jan 1, 1939

By Adrian C. Dorenfeld, Theodore Balberyszski, Strathmore R. B. Cooke

This paper reports results of studies of sulfidiza-tion of base-metal oxides and silicates with gaseous sulfur, hydrogen sulfide gas and pyrite and of their subsequent flotation with xanthate collectors. It has been established that a 100% conversion of the oxides of lead, zinc, copper and manganese into their respective sulfides is possible and is a function of reaction time and temperature. Sulfidization of chrysocolla (with malachite and azurite inclusions) resulted in a product containing covellite, chalcocite and digenite in proportions depending on conditions of sulfidization. Reacting cassiterite with gaseous sulfur, H2S or pyrite at various reaction temperatures resulted in its partial conversion to a tin sulfide. Flotation of the products of sulfidization indicated that their behavior is similar to that of natural sulfide minerals, the recovery being a function of the con-version of the oxides to their respective sulfides. The gradual depletion of high-grade sulfide mineral deposits has turned the attention of the mineral industry to the recovery of metals from the oxides and silicates. Anionic (fatty acid) and cationic collectors have in some cases made flotation of nonsulfides possible, although, in general, flotation of oxide ores is not as yet an economic process. Consequently, many attempts have been made to sulfidize the surface of the relevant oxide mineral and thus make it amenable to to In recent years, Bautista and sollenberger4 have investigated the conversion of a number of oxides to sulfides by reacting them with molten sulfur. This paper presents the results of .investigations carried out at the School of Mineral and Metallurgical Engineering at the University of Minnesota to study the flotation characteristics of some sulfidized minerals. It is divided into two parts: The first describes the sulfidization of a number of oxides and a silicate, and the second presents the flotation behavior of the products of sulfidization. SULFIDIZATION OF METAL OXIDES AND SILICATES Experimental Procedure: SULFIDIZATION WITH HYDROGEN SULFIDE GAS — Sulfidization with H2S gas was carried out in a horizontal tube furnace (Fig. 1). The temperature of the furnace was regulated by means of a Variac and determined with a chromel-alumel thermocouple. The constant temperature zone in the furnace was about 6 in. in length, and it was within this zone that the experiments were carried out. The gases employed were supplied from standard compressed gas cylinders, and passed through a glass-wool filtering tower before entering the Pyrex reaction tube. Gaseous products were bubbled through a water tower (used as a flow indicator) and excess H2S was burned off at the end of the outlet tube. Samples of reagents or minerals were placed in a 3-in. Alundum boat and inserted within the constant temperature zone of the furnace. Nitrogen gas (6 ppm O2 content) was passed through the tubes at room temperature to remove air in the tube, and continued to pass while the furnace was heating up. When the required temperature was reached, H2S was allowed to enter the tube and the supply of nitrogen was shut off. At the end of the reaction period, the reverse procedure was carried out, the samples being cooled to room temperature in a nitrogen atmosphere. The flow rate of H2S gas was maintained fairly constant in all experiments, although the rate was not determined. SULFIDIZATION WITH SULFUR POWDER - To study the sulfidization of minerals with sulfur (liquid or gaseous), samples of the mineral, together with a measured quantity of sulfur powder, were placed in a stainless steel (SS316) reaction vessel (Fig. 2). The reaction vessel was heated in a vertical resistance coil furnace, the temperature being regulated through a Variac. At the end of the experiment the vessel was cooled to room temperature before the sample was removed. Cooled products were leached with CS2 to remove any free sulfur. SULFIDIZATION OF TIN CONCENTRATES - Fifty gram samples of sulfidized tin ore were prepared by mixing -48 mesh Bolivian tin concentrate with -48 mesh Ottawa sand in various proportions and sulfi-dizing these samples with H2S in the horizontal tube

Jan 1, 1969

By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970

The Candelaria deposit was first discovered by Spanish prospectors in 1863; but its silver ore was not exploited on a large scale until 1873, when the Northern Belle mine was opened. The first Northern Belle mill was built at Belleville, 13 km (8 miles) to the northwest. From 1876 to 1886 the Northern Belle paid over $1 million in dividends each year. In 1882 a 43 km (27 miles) pipeline was built to Candelaria from the White Mountains to the west to furnish water for the mills and town at Candelaria; it was 100 mm (4 in.) in diameter, hand- riveted, and made in England. Sections of this pipe are used. as claim posts today. At its terminus at Metallic City, above Candelaria, a large concrete reservoir was built and called Metallic Lake. It is being used today by Candelaria Partners. Production at Candelaria declined after the mid-1980s, revived for a short period in the early 1890s, and during the 1920s a 300 ton mill operated for three years. Candelaria Partners is owned jointly by Occidental Minerals and Congdon and Carey, with Occidental being the operator. An engineering study done in mid-1979 resulted in engineering for the plant commencing in late that year and heap leaching being started in September 1980. Two million tons of ore per year containing 108 g Ag and 0.28 g Au per mt (3.15 oz Ag and 0.008 oz Au per st) will be mined from the Lucky Hill and Mount Diablo .areas about 1.6 km (1 mile) up Pickhandle gulch from the heap leaching operation. Waste -to -ore ratio is about 2:l. Ore is mined by front-end loaders and hauled by 85 ton trucks to the primary crusher, a 1,070 by 1,780 mm (42 by 70 in. ) gyratory. Primary crushed ore is conveyed to a stockpile of 10,000 tons live capacity from which it is reclaimed by hydraulic reciprocating feeders and conveyed to the crushing and agglomeration facility. This unit is composed of a 1.8 m by 2.6. m (6 ft by 12 ft) double deck screen, a 2.1 m (7 ft) standard cone crusher, and three conveyors. At the conveyor transfer points NaOH and NaCN solution is sprayed on the ore as it falls through a row of 75 mm (3 in.) hanging steel bars. During this process of turning and dividing the ore, the fines agglomerate with the coarse ore to give better percolation for the leach solution on the heaps. Provision was made for the later addition of 2 kg per mt (4 lb per st) of cement to aid in the agglomeration. Agglomerated ore at minus 50 mm (2 in.) size is then conveyed to a 390 mt (430 st) loadout bin where it is transferred to 85 ton rear dump trucks for haulage to the leach pads.

Jan 1, 1981

The Pueblo Viejo Mine, a 7, 250 mtpd (8,000 stpd) gold-silver cyanidation plant built by Rosario Dominicana S. A., was described in Volume I of this monograph. At the time of writing that volume, Pueblo Viejo had not yet gone on-stream and operating data or costs could not be presented. Since that time this information has been obtained and several interesting modifications and an expansion have been made to the plant. Because Pueblo Viejo is the largest open-pit gold mine in the world and one of the world&apos;s leading gold-silver operations with production of approximately 31 kg (1,000 oz) gold and 125 to 155 kg (4,000 to 5, 000 oz) silver per day, the authors have updated the previous data and flow sheet. The Dominican Government, which held a 4670 interest in Rosario Dominicana S. A., completed purchase of the mine to gain full control in 1979. Rosario Resources will continue to manage the mine, at least until the end of 1980. Gold was produced at Pueblo Viejo almost 500 years ago with initial production in the year 1505. Rosario Resources became interested in the property in 1969 and found surface oxidation had rendered the upper portion of the ore body amenable to direct cyanide treatment. The treatment of the underlying gold-bearing sulfide zone is still undergoing metallurgical studies. The ore is considered to be a laterite; and because there appeared to be few boulders in the ore zone, only a 400 m (16 in. ) square grizzly was initially installed ahead of the mills when the plant went on-stream in late 1974 at a design capacity of 7,250 mtpd (8,000 stpd). Operation also proved the ore to be harder than was originally anticipated. During 1967 a 1. 25 m by 1. 5 m (48 in. by 60 in. ) jaw crusher was installed to -feed the 1, 000 mt (1, 100 st) mill bin. Minus 200 mm (8 in.) crushed ore is fed directly to two 5.5 m by 1. 8 m (18 ft by 6 ft) semi-autogenous mills re-powered with 750 km (1,000 hp) motors and 50 mm (2 in.) grates. Each mill product is screened at 13 mm (1 /2 in.) by a vibrating screen. Screen oversize from each mill is combined on a single return belt equipped with a magnetic head pulley for grinding ball removal. The non-magnetic oversize is then split into two fractions for return to the primary mills. Originally, a minus 6 mm (1/4 in ) product was made on each screen and fed to a 300 kw (400 hp) 2.6 m by 3. 7 m (8-1/2 ft by 12 ft) regrind mill. During a plant expansion in 1978, an intermediate mill of 746 kw (1,000 hp) was installed to operate in open circuit on the combined primary mill

Jan 1, 1981

By Harry Klemic

Zirconium and hafnium minerals are used industrially both as minerals valuable for their chemical and physical characteristics and as ores of zirconium and hafnium. The principal zirconium-hafnium-bearing minerals, their composition, and their ranges in content of zirconium and hafnium dioxides are listed in Table 1. The supply of zirconium and hafnium is based almost entirely upon the supply of the minerals zircon and baddeleyite. Eudialyte may eventually also be of importance as a source of these elements. Zircon, which generally contains nearly 49% zirconium and between 0.4 and 1.5% hafnium, is the principal industrial mineral of this group. Baddeleyite, a commercially important but less abundant mineral, contains as much as 73% zirconium and 0.4 to 1.7% hafnium. Eudialyte has a wide range in content of these elements, but analyses of material from several localities indicate values of 6 to 11 % zirconium and 0.07 to 0.4% hafnium. Zircon is a mineral consisting principally of zirconium, silicon, and oxygen that crystallizes from magmas during the formation of igneous rocks. Zircon also occurs in veins and in metamorphic rocks. It is in the tetragonal crystal system. It commonly forms as small well-developed prisms having pyramidal terminations but also occurs as irregular-shaped grains. Zircon has a hardness of 7.5 on the Mohs&apos; scale. Its specific gravity is commonly between 4.68 and 4.70 (Dana, 1932), but the specific gravity varies somewhat depending upon com- position and state of alteration. Zircon has no good cleavage directions and is brittle, breaking with a conchoidal fracture. Zircon of the composition ZrSiO, would contain 67.2% Zr02 and 32.8% SiO2. However, in addition to about 1 % of hafnium, minor amounts of thorium, uranium, rare earth elements, yttrium, calcium, magnesium, iron, aluminum, phosphorus, and hydrogen, and trace amounts of other elements are commonly present in the mineral (Frondel, 1957). Radiogenic lead and other daughter products from the radioactive decay of uranium and thorium also accrue in the mineral. Radiation damage to the structure of zircons that contain appreciable amounts of uranium and thorium may alter the internal structure of the crystals to

Jan 1, 1975