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By Daniel C. McLean

Chemistry plays a more important role in milling operations than is generally recognized, particularly in fluid- solid separation processes. Chemical aspects are also very important insofar as plant water quality is concerned, and in the manner in which this water quality effects plant design and operation. Aside from the inherent chemical characteristics of plant water, the mineral preparation industry is becoming increasingly more dependent on the use of mining chemical reagents--relatively new to the coal industry, but items of I standard usage in complex metal recovery plants. These chemicals have many useful properties and can produce significant improvements in operations and metallurgical efficiencies when used properly and intelligently. They can produce poor results and sometimes severe losses when used improperly. Most reagents are relatively expensive on a per pound basis, hence costs can be excessive if they are used wastefully or inefficiently.

Jan 1, 1968

By D. C. Hatch

At the MacIntyre Development of the Titanium Division of National Lead Company a magnetite-ilmenite ore together with gabbro-anorthosite waste is mined from an open pit by shovels and trucks. The ore from the pits is trucked to ore stockpiles for blending ahead of the crusher and to free the mine from crusher delivery schedules. The ore stockpiles are blended to yield a 16.5 to 17.0 % TiO, crusher feed. This requires mining on an assay cut-off rather than a visual grade cut-off. Highly mineralized ore runs from 20 plus % TiO2 and 30 plus % Fe to 15 % TiO2 and 40 plus % Fe as the ratio of ilmenite to magnetite changes. There are three major ore types in the present pit with magnetite ratios varying from about one to one up to three times as much magnetite as ilmenite. Ilmenite and magnetite together liberate from gangue down to about 10 mesh and this is the basis of the magnetic cobbing. Below 10 mesh the ilmenite and magnetite start to separate and ore cobbing pulleys will not hold the ilmenite.

Jan 1, 1968

By C. Barnett

"A description of the Geco orebody has been given by W .L. Brown and R.C.E. Bray (1). The mill flowsheet and equipment were described by M.J.S. Bennett, D. Wild and C. Lawton (2). Mill capacity is now 4, 150 tons per operating day of copper, silver, zinc and lead ore. A recent flowsheet has been published in the - Canadian Mining Manual (1966).Soon after the start of production in September 1957, it became apparent that large tonnages of sand would be required by the mine for backfill pruposes. Initial experimental work on the preparation of sand fill from the flotation tailings was begun in late 19 59. Cyclones of local manufacture, in a variety of sizes, were tested quite successfully. There were, however, several obvious advantages with some of the custom-built cyclones and a recommendation was obtained from the Techniquip Company. A single Krebs D-10-B cyclone was tested experimentally in 1960.INITIAL TESTWORKExperimental results showed that with our relatively coarse grind (in the order of 53 % minus 200 mesh) 75 - 80% of the flotation tailings could be recovered as backfill sand with one stage of treatment. Percolation rates of four inches per hour were obtained with cyclone inlet pressures in the range of 20 - 25 psi and feed densities of 20 - 23% solids."

Jan 1, 1968

By W. F. Hughes

The thermodynamics of an electromagnetic field-fluid interaction system is discussed. A review of the thermodynamics of linear media (the permittivity and permeability taken as functions of density and temperature) is presented; then an extension is made to nonlinear media (the permittivity and permeability taken as functions of the fields). Expressions for thermodynamic properties and reversible work are derived and the first law of thermodynamics for magnetohydrodynamic flow is discussed.

Jan 1, 1968

By Fred H. Perfect

The thermite process, now approximately 80 years old, has heretofore been practiced in ceramic vessels. This paper outlines the successful production of several million pounds of alloy produced in zuater-cooled copper vessels. THE high temperatures necessary to produce fluid high-alumina slags have probably discouraged earlier workers from attempting to utilize water-cooled vessels. The following is a report of the successful application of this method, together with a report of the physical and chemical problems which had to be solved to make the process practical. About 1955, when Reading Alloys was more concerned with the production of ferrotungsten than with most other types of alloys, it was found to be exceedingly difficult to predict the reaction rate that one would experience from one tungsten ore to another . This difficulty was increased for two reasons: the physical state of the ore as received was seldom uniform, and the size of the mass to be reduced is a very important factor in developing the proper mix for the final reaction rate and temperature. For example, the reduction of ferric oxide with aluminum would theoretically produce temperatures of about 2600°C, and, in spite of the losses due to radiation, the energy is quite sufficient to produce a very fluid slag and iron effecting a very clean separation. On the other hand, the reduction of ferrous oxide with aluminum, while it is not as energetic as the first reaction, nevertheless should give temperatures above 2000"C, which should cause separation of alumina and iron, but, in practice, this is not the case and good fluid slag is not obtained. The heat of reaction, calculated from the thermo-dynamic heats of formation of the constituents of the reaction, offers a convenient guide to the feasibility of a thermite reaction. Thus, the values listed in Table I can be used as an approximate guide for estimating the results which may be expected in the reduction of various oxides and combinations of oxides using aluminum as the reducing agent. As a generalization, those reactions releasing approximately 600 cal per g of total mass represent the lower limit at which to expect separation of slag and metal. On the other hand, those reactions which release 1100 to 1200 cal per g are too violent to be used successfully without the addition of considerable inert material, such as lime, fluorspar, and so forth. Reaction rate is also a very important factor. This, of course, is governed very largely by the sizing and intermingling of the oxidant and reductant and by the starting temperature of the reactants. This is why those figures shown in Table I can only be a general guide. Further, it must be understood, that by adding powerful oxidizing agents, such as nitrates, chlorates or metallic oxides, such as molybdenum trioxide or chromium trioxide, certain problems respecting low temperatures are not necessarily solved. This is true in the addition of oxidants, such as sodium chlorate. By adding too high a concentration of sodium chlorate as a booster for a particular reduction, explosions are generated. Generally, they are of an intermittent type so as to give a Roman Candle effect to the reduction itself; with each surge resulting from a minor explosion more and more material is thrown

Jan 1, 1968

By R. W. Freedman

The gas chromatographic method, devised by the Bureau of Mines for analyzing routine mine air samples, was compared with the infrared method used for confirmatory determination of methane in mine air. While maintaining the specificity of the infrared method for methane determination, the gas chromatographic method is more precise, much more rapidly performed, and more convenient.

Jan 1, 1968

By Arthur L. Hawthorne

10.1-1. Relative Position of Maintenance as Compared to the Overall Mining Costs. The basic issue regarding the importance of maintenance in the modern mining industry must be faced squarely by the top manage- ment of each company before any real progress can be made in organizing a maintenance program for optimum effectiveness. Just a few decades ago the maintenance at coal mines consisted primarily of a blacksmith for sharpening picks and shoeing mules; as a result, probably less than 5%of the total mining cost went to maintenance and some 80% was operating expenses (operating labor). With each succeeding advance in equipment design towards larger, more complex, and more productive units, the pendu- lum swings the other way. As an example, haulage trucks have progressed through various stages in the past 20 years from 15-ton units to a 240-ton truck now in the "shakedown" or experimental stage. The following com- parison between 15-ton, 50-ton, and 100-ton haulage trucks clearly illus- trates this changing cost pattern in terms of percent of overall costs for running each size unit. [Maintenance 24% 44 % 51 % Operating labor 59 % 33 % 16% Operating supplies (fuel oil) 4 %. 4% 3% Labor burden and vac. pay 6 % 4% 3% Depreciation Total] From the preceding figures it is interesting to note that, as a rule, operat- ing costs go down as the equipment gets larger and the maintenance costs increase with the larger units. This same trend in cost variation applies to nearly all mechanical equipment used in surface mining from the large

Jan 1, 1968

By H. C. Brassfield, R. E. Fryxell, E. C. Duderstadt, E. A. Aitken, P. K. Conn

Permeation rates of hydrogen through are-cast tungsten were measured at temperatures from 1300" to 2600°C with hydrogen pressure differentials of 1 and 0.1 atm across isothermal membranes. Rates were nearly Proportional to square root of pressure, were inversely ProPortional to membrane thickness, and were temperature-dependent according to the equation: p = permeation coefficient in cu cm (stp)-mm per sq cm-min-atmlr2, R = gas constant in cal per mole-OK, T = absolute temperature in OK. Permeation rates of oxygen through tungsten were deternlined in the range 1965" to 2300°C and at calculated oxygen (02) pressures of 3.3 x 10-4 to 2.2 x at?n using sealed capsules containing Kmown quantities of tungsten oxide. Permeation coefficients obtained in this manner had a temperature dependency in the range of 40 to 45 kcal per mole of permeating species. Permeation coefficients for oxygen were higher than those for hydrogen in the temperature range studied. This is probably the result of oxygen solubility being much greater than hydrogen solubility at these temperatures at a gzven pressure. The purpose of this investigation was to determine experimentally the permeabilities of hydrogen and oxygen through polycrystalline tungsten at temperatures ranging from 1300° to 2600°C. Permeation rates of hydrogen through tungsten have been measured at temperatures up to 925°C,but no previous measurements have been reported for the temperature range covered in this investigation. Some diffusion measurements3&apos;&apos; and solubility measurements3 have been made for hydrogen at temperatures below 2200°C. No previous permeability studies of oxygen through tungsten are known to the authors; however, efforts have been made to determine diffusion rates5-&apos; and solubilities PERMEATION THEQRY Permeation has been defined by ortton" as the overall steady-state flow process from the gas phase on one side of a membrane or wall to the gas phase on the other side and includes the steps of adsorption, solution, diffusion, exsolution, and desorption; in a given temperature range, any of these processes may be rate-controlling. For diatomic gases, which dissociate prior to diffusion, the quantity of gas which permeates through a membrane or wall at a given temperature is directly proportional to the surface area of the membrane, the length of time of permeation, and the difference between the square roots of the pressures on each side of the membrane, and it is inversely proportional to the thickness of the membrane when diffusion-controlled, thus: q = total amount of gas permeating a membrane, p = temperature-de pendent permeation coefficient, A = area of membrane exposed, / = time, p i = gas pressure of high-pressure side, p2 = gas pressure of low-pressure side, d = thickness of membrane. When the surface reactions are not rate-controlling steps and the solution of the gas in the metal follows Henry&apos;s law, the permeation coefficient, P, is equal to the product of diffusivity and solubility. The permeation coefficient is also temperature-dependent according to the equation: Po = permeation constant, Q = activation energy, R = gas constant, T = absolute temperature. MATERIALS The tungsten materials used in this investigation were greater than 99.9 pct pure. The interstitial impurities ranged from < 1 to 50 pprn C, 7 to 35 ppm O, less than 15 pprn N, and undetectable quantities of hydrogen. Previous high-temperature studies of are-cast tungsten have shown that thermal treatment similar to that which the hydrogen permeation cells experienced reduces the carbon content from starting levels of 50 to 60 ppm to about 30 ppm. Metallic impurities were in the low (1 to 50) ppm range. The argon gas used in this investigation contained about 8 ppm N. None of the following gases were

Jan 1, 1968

By Alexander Karim

This paper reviews the growth pattern in bauxite and alumina production, and primary aluminum smelting through 1980. Because the alumina and primary metal are intermediate products of the major integrated aluminum companies, it is not possible to determine their production costs. The costs indicated in this paper are order of magnitude costs based on published figures and the market price of these products. The conclusions in this paper indicate the general pattern of growth in the aluminum industry and are not meant to be a substitute for the feasibility and economic studies that are needed for individual bauxite mining, alumina refining and aluminum smelting projects.

Jan 1, 1968

By Allen V. Heyl

This old district is a major zinc and lead source and minor copper and barite source. Ores are chiefly in the Galena Dolomite and in limestones and dolomites of the Decorah and Platteville Formations, all of Middle Ordovician age. Locally, deposits have been mined from Lower Ordovician dolomites and Upper Cambrian sandstones. Small deposits of lead, zinc, and iron sulfides have been found in Upper Ordovician Maquoketa Shale and in Lower and Middle Silurian Edgewood, Kankakee, and Hopkinton Formations. No post-Precambrian igneous rocks are known in the region, and the granitic and metasedimentary Precambrian basement rocks unconformably underlie the district at depths of 1500 to 2000 feet. The strata are gently flexed and faulted, probably largely the result of gentle compressive and rotational adjustments in the underlying crystalline basement, especially along lineaments between basement blocks. Folds of three orders ·of magnitude are recognized, and many related reverse, strike-slip, and normal faults of small to moderate displacements are present. Zinc-lead deposits are commonly linear, arcuate, or elliptical in plan. Most ore occurs as vein fillings in fractures and as breccia fillings and lining vugs, but some is in bedded replacements and impregnations of wall rocks. The ore is in shears, small reverse and bedding- plant faults, joints, and solution-slump structures related to intermediate and small folds. The main primary minerals in their general sequence of deposition are quartz, illite, dolomite, pyrite, marcasite, cobaltite(?), sphalerite, galena, chalcopyrite, millerite, barite, and calcite. Wall-rock alterations include solution of the carbonate rocks, silicification, dolomitization, clay alteration, and sanded dolomite. Oxygenisotope, trace-element, lead-isotope, and sphalerite- stratigraphy studies are in progress. Fluid inclusions in sulfide and gangue minerals are filled with concentrated brines at 120° to 40°C. Sulfides are directly replaced by supergene minerals above the water table at 50 to 100 feet in depth. In this relatively cool climate and limestone environment, smithsonite is in pseudomorphs after sphalerite; solution transport and redeposition of supergene minerals are rare. Ore genesis is postulated by rising hot-water solutions-a mixture of heated connate, magmatic, and meteoric waters.

Jan 1, 1968

By Carl D. Broadbent

The goal of slope mechanics is to achieve efficient and safe pit slopes. In the case of ultimate mine slopes the objective is to minimize the stripping ratio by steepening the slopes to their maximum stable limit. On the other hand, the inclination of working slopes is normally established by operating space requirements and the function of slope mechanics should be the continuous surveillance of slope conditions to assure long-term stability and to provide timely warning of impending slides so that corrective measures may be incorporated in production planning. In 1956 Kennecott instituted a program to provide the resources necessary to develop and maintain a slope mechanics capability, including technical knowledge, engineers, and instruments. Although the goal has not been fully achieved, very significant progress has been made. Other papers (3, 4, 7, 8, & 12) have described the purposes and detailed results of the most recent study carried out at the Kimbley Pit. The study has provided valuable experience and has given the industry a three dimensional picture of the stability variables that influence a mine slope. The study has better defined those areas which require further investigation and has indicated those design and analytical techniques which can be used with confidence. In effect, the study has paved the way for the next step; that of refining the design process and applying it for profit.

Jan 1, 1968

By G. S. Cole

The temperature has been measured ahead of stationary solid-liquid interfaces under conditions approximating luzidirectional heat flow and therefore unidirectional solidification. Natural convection flow patterns may be deduced from the temperature distributions , temperature fluctuations, and shape of the interface. Fluid flow increases with the height and the rate of heat transfev through the interface and this is further manifested by a deviation of the interface from aflat vertical plane. The influence of fluid flow on solute inhomogeneity during alloy crystal growth can be inferred from the observed temperature distributions. A buoyancy force exists in the liquid ahead of a vertical solid-liquid interface, caused by a difference in density between cold fluid near the interface and warmer fluid in the bulk liquid. When the viscous and inertia forces in the melt exceed this buoyancy force, a flow of fluid takes place, termed natural or free thermal convection. Natural convection in purely liquid systems has been extensively studied for many years. 1"u On the other hand, fluid flow during horizontal crystal growth has oniy recently been the subject of experimental investigation."-25 The requirements for horizontal crystal growth differ from other heat flow systems. The small aspect ratio (ratio of height of cold wall to length of fluid) has never been considered. The uniform furnace gradient which supplies heat radially (and not necessarily symmetrically) differs from previous boundary conditions of uniform heat flux at the cold and hot ends. And most important of all an isothermal s/l interface is present which can adjust its shape and position to conform to heat and fluid flow. All of these boundary conditions involve complexities which cannot be readily solved analytically. Preliminary observation has demonstrated the penera1 shape of the natural convective flow pattern in transparent media.20&apos;24&apos;25 The flow is circulatory, directed toward the interface at the surface of the liquid, down and away from the interface at the bottom, and then up at the hot end of the melt. During crystal growth such a flow may interact with the solute boundary layer at the s/l interface to affect solute incorporation.M&apos;1B|28&apos;i!T Evidence has also been presented recently to show that thermal convective flow will affect the structure of ca~tin~s.~~-~~ The rate of heat transfer (conduction plus convection) in a given fluid system is a function of the temperature difference between the hot end of the liquid and the s/l interface and the height of the interface. At the lowest values of these variables* all heat is *It has been shown&apos; that adverse temperature gradients as low as O.OOS°C oer cm are sufficient to cause convection. transferred by conduction. When the temperature difference or interface height are increased, laminar fluid flow commences and heat transport takes place by laminar convection as well as by conduction; turbulent heat transfer takes place at higher values of these variables. In the transition region between laminar and turbulent flow, boundary layer separation takes place; fluctuations in temperature are also noted and increase in amplitude and frequency as turbulence becomes dominant. In this paper, fluid flow patterns in the melt ahead of a stationary interface are deduced from observations of temperature distribution and fluctuations, heat flow rate, and interface shape. The fluid flow ahead of advancing interfaces and the effect of such flow on solute incorporation may be inferred from these measurements on stationary interfaces. Observations during enforced fluid motion will also be considered. EXPERIMENTAL PROCEDURE The metal was contained in a lava boat 10 cm in length, 1+ cm in width, and 2 cm in height, as shown in Fig. 1. A water-cooled, molybdenum block heat-sink is at one end of the boat; surrounding this assembly is a slotted stainless-steel tube noninductively wound with a nichrome heating element. Temperature was measured by 38-gage Chrome1 vs Alumel thermocouples sheathed in 0.05-cm-diam graphite-coated stainless-steel tubing, which were moved longitudinally and vertically through the melt by means of a two-dimensional motorized micrometer stage. In some experiments the thermocouple junction was exposed, but in the majority of experiments the junction was welded to the sheath tip; no significant difference

Jan 1, 1968

By Harold R. Larson, John F. Elliott

The standard free energies of formation of several nzetallic sulfides have been measured by a reversible electromotive-force cell employing stabilized zir-conia as the electrolyte. The oxygen potential at the cathode was fixed by the use of pure oxygen gas at 1 atm. It was established at the anode by bringing to equilibrium the reaction between the sulfide and oxide species present. Thus, Gf: for the sulfide could be obtained from the cell potential and the standard free energies of formation of the oxides participating in the reaction. The results in calories per cam rnole for the temperature range 850" to 1100°C are: Use of the reversible electromotive-force cell having an oxide-ion electrolyte to obtain the standard free energies of formation of some of the more stable metallic sulfides offers a convenient experimental method that is very productive. It also avoids some of the problems inherent in the experimental methods&apos; for such studies which rely on precise determination of gas compositions, particularly if these compositions lie near the limits of our capabilities for accurate chemical analyses. The reaction equilibrium between the lowest sulfide of a metal, SO2 at a fixed pressure, and an oxide of the metal has a characteristic oxygen potential. For example: and for metals whose lowest sulfide is much more stable than the oxides of the metal, the equivalent reaction might be:

Jan 1, 1968

By John E. Murphy, Ernest L. Ohle

Hematite-magnetite ore bodies at Iron Mountain, Missouri, have produced nearly 9 million tons of iron ore concentrates since 1844. The ore minerals occur principally as open-space filling in fractured and brecciated andesite porphyry with very minor replacement of the wall rocks. The enclosing rocks are Precambrian in age and consist of a series of dacite, rhyolite, and andesite flows aggregating about 2000 feet in thickness. All of the ore is in andesite and the mineralization is Precambrian in age. The shape of the ore bodies, the breccia character of the ore, and the gangue mineralogy are believed to be unique. One of the two main ore bodies is crudely dome-shaped with a tendency for development of concentric mineralized shells; the other is an elongated lense in plan but hook-shaped in cross section. Both have strong linear elements striking northeast, east-west, or northwest. Various modes of origin for the structures and for the tension breccias have been suggested, but none is completely satisfactory. Hematite is the main ore mineral; magnetite is subordinate. Important gangue minerals are andradite, quartz, calcite, actinolite, apatite, epidote, and chlorite. Although some evidence favors injection of an iron-rich melt, other evidence suggests ore formation by a high temperature, water-rich solution.

Jan 1, 1968

By Gerhard Derge

The rapidity of oxygen steelmaking has created renewed interesl in the mechanisms and kinetics of the various processes involved. These studies can now be approached with increased confidence because of the more adequate thermodynamics, physical chernislry, and relevant engineering infornzation available. These combine to offer promise of useful control and automation if the details of each specific problem can be sufficiently well-defined. The hot filament microscope provides new insig-hi into many of these problems by direct observation at temperature, allowing the appraisal of the relative importance of thermal gradients, convection, and intermediate phases. All of these have a direct bearing on the overall rates and control of most pyrometallurgical processes. It is one of the special privileges of the Howe Lecturer to become better acquainted with this distinguished man. All of us interested in the metallurgy of iron and steel have developed some sense of his widespread influence by the annual reference to his work in these Memorial Lectures. Each lecturer since 1923 has been able to identify his personal specialty with the broad interests of Professor Howe. This has become even more rewarding with the background information from Professor Gensamer&apos;s monograph, "Henry Marion Howe&apos;s Contributions to Metallurgy, which brings out his happy combination of intellectual and professional activities. Beyond this, I found my personal bond with Professor Howe in his book on The Metallurgy of Sleel first published in 1891.&apos; After a detailed discussion of the dephosphorizing action of slags, he relates the mineral species identified in the frozen sample to the chemistry of the fused slag with the question, "Is it not most philosophic to hold that these independent entities were wholly integrated in the initial magma; that their presence in it was wholly

Jan 1, 1968

By R. T. Hukki

The purpose of this paper is to present an analysis of the unit operation of grinding and the circulating load, of the unit operation of classification and the circulating load, and of the two superimposed into one operation to clarify the overall trend of events relating the circulating load to the capacity of the closed circuit grinding system, to the specific surface area of the final fine product, and to the energy consumption in the closed circuit grinding process. The capacity of the closed circuit is frequently, if not always, determined by the classifier, not by the mill." With these words a startling idea was expressed in 1934 by Dorr and Anable.1 Today, some 30 years later, grinding in closed circuit is universally accepted. The basic curve presenting the capacity factor versus circulating load by Dorr and Anable has obviously been so convincing that not a single authoritative investigation regarding its validity seems to have been conducted. The only major subject of discussion appears to have been the relative merits of the &apos;high&apos; and &apos;low&apos; circulating loads. It seems to be universally agreed that much still remains to be hoped for regarding sharpness of classification. BASIC CURVES FOR CONSTANT MILL LOADING Fig. 1 presents a series of basic curves for constant mill loadings in function of new feed rate and circulating load. The mill loading indicated by each curve is the sum of hourly tonnages of new feed and circulating load. For example, at point 0 where the new feed rate is 100 t/h and the circulating load 300%, or 300 t/h, the mill loading is 400 t/h. In closed circuit grinding, the new feed rate corresponds to the rate of finished classified material produced. Although at this stage the effect of classification is excluded in construction of the basic curves, the trend indicated by these curves is strongly in favor of closed circuit operation under relatively small circulating loads. A study of the curves reveals that, e.g., a mill operating under a load of 200 t/h at point P where the new feed rate is 50 t/h and the circulating load 300% will also operate under the same total load at point Q where the new feed rate is 100 t/h and the circulating load 100%. In other words, a reduction of circulating load from 300% to 100% would lead to doubling of the new feed rate and doubling of the rate of production of finished material, without a change in the total mill loading. The obvious question is, is it also possible by a reduction of the circulating load in a closed industrial grinding circuit to increase the production of finished classified material and, if so, how and to what extent? GRINDING TESTS BY DORR AND ANABLE In a series of open circuit grinding tests reported by Dorr and Anable1 limestone was ground at various feed rates in a 3-ft ball mill. The original data are reproduced in Table I. It can be seen that with the increased feed rate production of -65-mesh material increased and the energy consumption per unit weight of the -65-mesh product decreased in the reverse ratio. The data shown in Table I have been reproduced for our purposes in Table II for a scale corresponding to grinding in a large industrial mill. This reproduction

Jan 1, 1968

By M. J. Ferrante

The preparation and subsequent reduction of vanadium trichloride was investigated as a process for the production of high-purity vanadium metal. Chlorine was reacted with vanadium oxide in the presence of carbon to vanadium tetrachloride. The contaminant vanadium oxytrichloride was also formed and later converted to tetrachloride by reaction with chlorine in the presence of activated charcoal. Vanadium tetrachloride was stirred continuously during thermal dissociation to vanadium trichloride powder from which volatile contaminants were removed by distillation. The vanadium trichloride powder was reduced to vanadium sponge by controlled feeding of the trichloride into molten magnesium. Excess reductant and byproduct salt were removed from the vanadium sponge by high-vacuum distillation. Batches as large as 6.5 kilograms of sponge metal were prepared at an average reaction efficiency of 98 percent. Vanadium sponge after consolidation by arc-melting contained 820 to 11330 ppm of interstitial impurities and had a hardness between Rockwell B 40 and 70, This metal exhibited excellent workability at room temperature. The purification of impure vanadium metal by electron-beam melting resulted in lowering interstitial impurities from 1,890 to 504 ppm and hardness from Rockwell B 87 to 28.

Jan 1, 1968

By J. M. Steininger

The mechanism of flotation of sphalerite with sulthydryl compounds of different acidities has been interpreted in terms of chemisorption of unionized collector molecules on hydroxylated zinc surface sites. At a constant collector concentration of 1.5 x 10 -4 M, the upper pH limit of flotation has been found to be directly and closely related to the negative logarithm of the collector acidity constant, pKa The experimental results indicate that flotation is prevented when about 95% of the collector is ionized. At low pH, collector adsorption decreases because of the reduction in number of hydroxylated zinc surface sites. These two effects explain why sphalerite does not float with the more acidic sulfhydryl compounds. Typical anionic collectors for sulfide minerals are short chain xanthates or dithiophosphates which are nearly completely ionized in the generally alka- line flotation circuits.1,2 Flotation mechanisms have therefore been usually interpreted in terms of ionic collector adsorption and competition with ionic depressants of the same sign as the collector. A few attempts have been made, however, to consider adsorption of neutral collector molecules. Contact angle measurements obtained by Wark and cox3 have been interpreted by Cook and Nixon4 as representing adsorption of the free acid molecules on sulfide minerals such as pyrite, galena, chalcopyrite, and sphalerite. Cook and Nixon tried to show that the free acid concentration of the collector was substantially constant along the curves relating collector addition and minimum pH for bubble adherence. However, in a review of the subject,5 Sutherland presented new data on the flotation of pyrite with mercaptobenzothiazole which did not support the hypothesis of constant concentration of either collector ions or collector free molecules. He further showed that, with the assumption of constant occupation of surface sites, both theories lead to relations between pH and collector addition having similar mathematical expressions. In fact, with the more likely assumption of variable occupation of surface sites which results in more complex relationships, it appears impossible to

Jan 1, 1968

By R. K. Koch

The vapor pressures of liquid molybdenum and liquid zirconium were determined by the Langmuir free-evaporation method. An electron-beam furnace with a water-cooled copper crucible was used for melting. Temperature was measured with a two-color ratio pyrometer. The vapor-pressure data led to the following equations: [log p (atm) = 5.429 - 28,380 T for liquid molybdenum in the range 2,890° to 2,990° K, and log p (atm) = 6.521 - 30,940 T for liquid zirconium in the range 2,229° to 2,795° K.] Third-law evaluations of each data set gave mean heats of sublimation (298.15° K) of 157.6 ± 1.8 kcal/mole and 148.4 ± 2.4 kcal/mole for molybdenum and zirconium, respectively, where the uncertainties are two standard devia¬tions. Second-law standard heats of sublimation determined from sigma plots and tabulated enthalpies were 143.5 ± 2.7 kcal/mole and 149.2 ± 3.8 kcal/mole for molybdenum and zirconium, respectively. The better agreement in heats of sublimation for zirconium is attributed to the 566° K temperature range studied which permitted a more accurate definition of the vapor pressure curve than could be obtained from the 100° K span for molybdenum. This supposition was verified by making a sigma-prime plot which utilized solid vapor pressure data for molybdenum to extend the evaluation range by 800° K. This gave a standard heat of sublimation of 155.2 ± 1.6 kcal/mole which is in good agree¬ment with the third-law value. The plot also gave a standard entropy of sublimation (298.15° K) of 35.73 ± 0.48 eu.

Jan 1, 1968

By P. L. Weston, S. E. Khalafalla

A systematic study was made by the Bureau of Mines on the effect of so me hypothesized accelerators for the process of wustite reduction in carbon monoxide. When small concentrations of promoter materials in the order of 0.69 at. pct were added to the reducible charge, the rate of reduction to iron was increased. Promotion phenomenon prediction was made in light of a suyface reduction mechanism with the aid of Vol&apos;kenshtein&apos;s effect regarding the propagation of crystal lattice disturbances by small amounts of relatively larger interstitial ions. The acceleration produced by a typical promotor, such as potassiunl, increases with protnoter concentration up to a maximum, beyond which the reduction rate decreases. Concentration for maximum promotion depends on the nature and physicochemical properties of the promoter. The extent of reduction rate enhancement is found to be directly proportional to the atomic volume and electronic charge of the additive. DESPITE the enormous volume of literature on iron oxide reduction, very little is reported concerning additive or impurity effects on this important metallurgical process. The beneficial effect bf calcium compound additions on the reducibility of iron oxide sinters has been reported by Tigerschiold,1 vor dem Esche,2 and Edstrom. Doi and Kasai~ found that the addition of lime or limestone to iron ores helps to break up any unreducible compounds, such as fayalite or ilmen-ite. and thus free the combined iron for reduction. Schenck et al. 5 suggested that the increased reduction rate obtained when adding lime could be accounted for by the instability of wustite in the presence of lime. Acid-base slagging reactions resulted in wustite disproportionation according to The dicalcium ferrite formed will yield iron and calcium oxide during reduction. Regenerated calcium oxide dissociates more wustite. This mechanism has been used by Seths and white7 to explain their experimental results. Recently, Strangway and ROSS&apos; attributed the calcium carbonate acceleration of iron oxide agglomerate reduction to increased porosity, both initial as well as that developed during reduction. Aside from calcium carbonate, or oxide, no other promoter was noted in the literature, except for a brief mention by Barrett and woodg on the effect of sodium carbonate and aluminate as activators for the hydrogen reduction of magnetite at 600°C. The present investigation systematically studied a host of other promoters, including calcium and sodium, in an attempt to elucidate the mechanism by which promotion takes place and to fit the results into a simple chemical model. To attain this goal, the effect of promoter physical properties, such as atomic volume, electronic charge, and concentration are related to wustite reduction kinetics in this paper. Wustite reduction to iron, rather than the overall hematite reduction, was chosen since this reaction is known to be the slowest, and hence the rate-deter mining step for the overall iron oxide reduction process. EXPERIMENTAL PROCEDURE Raw Materials and Their Preparation. The pure or impregnated wustite pellets were prepared from minus 400-mesh chemically pure hematite powders. A known weight of hematite was thoroughly and uniformly mixed with a calculated weight of the additive. The mixed paste containing 35 wt pct water was gradually heated from 400" to 1200° C and fired at 1200°C for approximately 4 hr in an air atmosphere. After cooling, the sinter was pulverized to minus 100 mesh and pelletized into minus 4- plus 5-mesh spheres. Pellets were fired, similarly to the paste mix, air-cooled, sized, and stored. An appropriate weight of the charge (20 g) was placed in a zirconia reduction tube maintaining a uniform oxide bed height of 1 cm and a cross section of 7.1 sq cm for all of the test runs. The samples were supported in the vertical reaction tube by a bed of fragmented insulating firebrick plus 3- to 6-mesh alumina beads. The hematite was then transformed to wustite by reduction with a 30 pct CO2-70 pct CO gas mixture at 1000°C in a globar furnace. Complete conversion to wustite was ascertained by a continuous infrared gas analyzer recording the CO-CO2 content of the effluent gas until no carbon monoxide was absorbed from the inlet gas, and inlet-outlet gas analysis remained constant for 30 min. The wustite sample was then reduced with 100 pct CO at 100WC. From the recorded data, an initial rate of reduction was determined by the initial slope of the graph percent reduction vs time. In order to estimate the accuracy of the data, five separate determinations of the reduction curve of pure wustite, under otherwise identical conditions, were performed. The maximum deviation from the average reduction at 14 min amounted to 2 2 pct reduction. This deviation corresponds to 3.8 pct variation based on the percent reduction of the sample. Aiiy impurity effect below the limits of this maximum deviation was considered a spurious result. If the effect exceeded + 4 pct, then it was considered as a positive one. Considerable care was exercised in determining the initial rate from the slope of the initial segments of the curve. Each reduction curve was examined separately on large graph paper and the best tangent to the curve at zero time was drawn. The slope of this tangent was taken as a measure of the initial fractional reduction per minute. Although the time required to reach 50 pct reduction may be of special practical significance, initial rate measurements are invaluable in fundamental studies. These rates provide a measure of the process kinetics on the initial

Jan 1, 1968