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By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By Donald S. Colby

This Bureau of Mines report is essentially a handbook, or manual, for making the type of mineral resource valuation commonly required for such public policy problems as mineral leasing. The principle of resource valuation through the capitalization of cash flow is well established. A mathematical procedure, based on a simplified accounting system, is detailed for calculating cash flow from revenue, plant costs, and operating expense. Variations of procedure cover cost depletion, percentage depletion, and depletion limited to 50 percent of net income. The influence of the depletion provisions of the tax regulations on the value of a resource to an owner and to an operator is analyzed. The relationship of royalty, bonus payments, and sales price to resource value is also described, and methods for approximating resource values using these payments as input data are developed.

Jan 1, 1969

The lead concentration of flotation feed ore slurries is determined using two ?-ray absorption gauges mounted directly on a 6 in. diameter flotation feed pipeline. One gauge is a conventional "density" gauge using CS137. The other is a "lead-sensitive" gauge, which depends on the preferential absorption. by lead of 225 key y-rays resulting from Compton backscatter of CS137 y-rays.Gauge outputs are combined using an analogue computer the output signal of which is directly proportional to the lead concentration of the pulp. The accuracy of measurement of the pulp lead concentration is ± 3·6 per cent for ore slurries with lead concentrations in the range 0'07-0·16 g/c.c. and pulp densities 1.43-1.60 g/c.c.This paper sets out the development of the technique and details are given of the two experiments (1964, 1966) conducted in the plant at North Broken Hill Limited. The installation of the two-gauge system inthe plant during May 1968 is described. Details are given of the calibration technique used and the results obtained.

Jan 1, 1969

By Ronald J. Roman

A mathematical model was developed for the grinding and flotation section of Union Carbide's Bishop mill and this model was used to indicate how variations in grind, retention time, and calcite and fluorite content effects the mill capacity, tungsten units produced, and the grade and recovery of the scheelite concentrate. A model such as this is a starting point in determining the economic optimum running condition for a mining and milling operation and an example of this is given.

Jan 1, 1969

By Valerie Kollonitsch

Functional mineral pigments are used in large quantities in paint, paper, plastics, rubber, textiles, agriculture, and several other industries. U.S. consumption in 1969 is estimated at over 5 million tons a year, valued at nearly $150 million, as shown in Table 1. Originally extender pigments were employed only to lower cost. They were thought of merely as adulterants to replace more expensive prime pigments and binders. However, over the years their role has become better understood, and today their main functions are: - Increasing strength, stability, and service life. - Improving surface properties. - Enhancing application and processing properties. - Extending prime pigments. - Controlling viscosity and package stability - Lowering overall costs of the finished product. The principal minerals used as functional pigments are kaolin, ground calcium carbonate, talc, and asbestos. Other minerals include barytes, attapulgite, diatomite, mica, ground silica, wollastonite, and nepheline syenite. Several synthetic products, including precipitated calcium carbonate; precipitated, gel, and fumed silica; alumina trihydrate; and barium sulfate, compete with mineral products. They are more expensive, but often have more closely controlled particle size or other properties because they can be tailor-made according to the requirements. This paper covers only natural products selling for $10 or more a ton, approximately the lower limit for pigment grades. Data refer only to consumption in pigment applications. For example, such applications as filter aids for diatomite are not included. Key properties of the major mineral pigments are given in Table 2. It is important to note that these properties are primarily physical rather than chemical. In general, these products are sold to performance specifications for what they can do rather than on chemical composition specifications on what they contain.

Jan 1, 1969

By S. W. Zehr, G. S. Murty, W. A. Backofen

AN observation by Squires, Weiner, and phillipsl has stimulated interest in a mechanism of deformation at high temperature (above -0.5 of the absolute melting point) that is not usually thought to be involved in the creep of metals. They found precipitate-free or "denuded" zones along grain boundaries normal to the stress axis in tensile specimens of a hydrided Mg-1/2 wt pct Zr alloy after slow straining at 450° and 500°C. Their suggestion that the zones were a result of directional diffusion of magnesium atoms was supported with calculations from Harris and Jones2 which also tended to identify the process as Nabarro-Herring (N-H) creep3,4—a process that is characterized by Newtonian viscosity, with stress (o) directly proportional to strain rate (C), and one that proceeds by lattice diffusion. Material transport by diffusion along grain boundaries is an alternative basis for Newtonian viscosity, as demonstrated by Coble,5 and is favored over N-H creep for fine grain size and lower temperature.6 In either case, the strain rate sensitivity of flow stress, defined as m = d log o/d log E (which commonly appears in the empirical a = KEW), is unity. The experiments to be described here gave metallo-graphic indications of diffusional creep which were no less clear than those just cited, but the associated m (as measured by the method of Ref. 7) was much more like that of a Bingham material. For true Bingham behavior, (a — ao) E, where oo is an initial yield stress. Therefore, even if flow after yielding should occur by diffusional transport, m must increase from 0 as < is raised to reach unity only in the limit as One result is that the resistance to tensile necking conferred by Newtonian viscosity is lost, which would become increasingly apparent through the formation of more sharply defined necks as 6 is lowered. That trend appeared in these experiments. Most of the work was done on an extremely finegrained alloy of magnesium with -6 wt pct Zn and ½ wt pct Zr (Mg ZK60); the initial mean-intercept grain diameter, L, was 0.55 µ. Shown in Fig. l(a) is a germanium-shadowed carbon replica of the surface of a specimen that was coated with silicone oil,* heated to 270°C under a helium atmosphere, and then stretched locally -200 pct at an initial E = 3.3 x 10-5 sec-1. Under

Jan 1, 1969

Jan 1, 1969

By J. T. McCartney

In an effort to correlate the size of pyrite particles in coal and coal-particle association with the removal of pyrite before burning, the Bureau of Mines conducted a study of 61 coals presently being used for electric power production. The results were obtained by visual microscopic studies of polished briquets of minus l4-mesh samples. Mean pyrite particle sizes ranged from 20 to 400 microns and proportions of pyrite contained in coal particles to an extent greater than 50 percent by volume (estimated) ranged from 20 to 95 percent. These parameters were correlated with reductions in pyrite accomplished by float-sink tests at 1.60 sp gr on 14-mesh, 3/8-inch, and 1-1/2-inch samples. The correlation coefficients between pyrite removal and mean pyrite particle size were 0.89, 0.84, and 0.79, respectively, for these samples. Correlation coefficients between pyrite removal and coal-pyrite association parameter were 0.92, 0090, and 0.85, respectively. It is apparent that extent of pyrite removal can be fairly well predicted from microscopic analysis.

Jan 1, 1969

By R. F. Abernethy

Analytical results, including ash fusibility data, are presented by the Bureau of Mines for 10 major constituents in coal ash from 373 samples of commercial U.S. coals. Determinations of Si02, Al2O3, Fe2O3, and P2O5 were made by colorimetric methods, Na2O and K2O by flame photometry, Ti02, CaO, and MgO by a spectrochemical method, and SO3 by a gravimetric method. In bituminous coal ashes the silicon, aluminum, and iron calculated as oxides often make up about 90 percent of the ash.

Jan 1, 1969

By William O. Rasmussen

Exploration requires processing highly varying kinds and amounts of geologic information. Successful discovery dictates that this be done quickly with maximum confidence. Most phases of exploration are more or less applicable to computer reduction on a routine basis. The use of digital computers to reduce raw data into interpretable form, lets the exploration geophysicist concentrate on interpretation and presentation, and to consistently apply more sophisticated and comprehensive analytical techniques, not practical before. In applying these concepts for the past several years, various efficient programs have evolved which provide more complete evaluation of all data including the pro- vision for more unique solutions. This has resulted in greater refinement and ability to select the most advantageous drill sites in a minimum time at a minimum cost or, in rejecting as soon as possible a project on which additional effort is no longer justified. Practical examples of computer applications in magnetics (air and ground), induced polarization and resistivity are discussed.

Jan 1, 1969

By James P. Connell

The Berkeley Pit of The Anaconda Company is located on the southeast slope of the Butte Hill, the legendary "Richest Hill on Earth," and is one of the largest pit operations in the world completely dependent on truck haulage. Through October 31, 1968, the Berkeley stripping and mining operations have moved more than 442,589,000 tons of material. Present scheduled production is at the rate of 260,000 tons per day, with a record quantity of 306,900 tons having been hauled on September 23, 1968. Although the Berkeley Pit has been in production only a little more than ten years, it has been the proving ground for many of the presently used large trucks. Beginning with the original R. G. LeTourneau 75-ton electric truck in 1960, Unit Rig 85- and 100-ton electric drives, Haulpak 65- and 105-ton electric drives, and Caterpillar 100-ton electric drives have all been tested under production conditions. In addition, engine development has kept pace with both 1000-hp diesel and 1100-hp gas turbine engines now under test. As the size of the Berkeley operation has grown, the truck fleet has changed in size and appearance in order to maintain economic mining costs. The original fleet consisted of forty-three 36-ton trucks with conventional mechanical drives. The present fleet is made up of eighty-nine trucks: nineteen 85-ton Unit Rig electrics with 700-hp diesel engines; sixty-nine 100-ton Unit Rig electrics with either 700- or 1000-hp diesel engines; and one 100-ton Unit Rig electric with an 1100-hp gas turbine engine.

Jan 1, 1969

By Mohan Dutt

This paper is concerned with applied platinum resistance thermometry which involves many considerations absent in precision thermometry. The historical development of the Callendar-Van Dusen Equation which describes the resistance- temperature relation of pure platinum is discussed. The advantage of using platinum resistance temperature sensors over thermocouples is described, and the improvements in design and construction of these sensors that have come about in the past few years are discussed. Integral and remote bridges that convert resistance changes into voltage together with signal conditioning techniques and equipment for voltage or current signals are described. Errors encountered in temperature measuring schemes and methods to reduce these errors are summarized.

Jan 1, 1969

By J. V. Vogel

Jan 1, 1969

By R. D. Nelson

The purpose of this technical note is to briefly present some data on a phenomenon—recrystallization with concurrent deformation—that has been found to occur in a plutonium. This phenomenon is unusual because a plutonium is considered brittle, not easily deformed, and not easily recrystallized; the a phase is simple monoclinic having 8 atoms per unit cell and it is stable below about 115°C. The properties of the recrystallized metal were different from the as-cast metal. Even though a plutonium is difficult to deform, Ianniello successfully rolled it&apos; and he also observed some recrystallization at 120°C.2 Pavlick and Hanson3 detected some recovery at 109°C but they observed no recrystallization. Gardner4 and Bronisz5 studied the compression properties up to 100°C but they did not report having seen recrystallization. In the present deformation studies of electrorefined plutonium pronounced recrystallization took place concurrently with plastic deformation in compression between 24" and 115°C. The metal contained less than 300 ppm total impurities with the major impurities being 100 ppm Am, 30 ppm C, 40 ppm W, and 25 ppm U; all other impurities totaled less than 100 ppm. The compression specimens were machined to dimensions of 1.2 cm long and 0.8 cm diam from as-cast rods having a density of 19.65 g per cu cm. They were heated to the test temperature in a high-temperature silicone fluid that was evacuated to 10-4 Torr. With this procedure the specimens oxidized a negligible amount, and the temperature was maintained within ±0.2°C for times up to 3 weeks. Deformation and recrystallization

Jan 1, 1969

By J. P. McGee

A 1,000-hour test with a gas turbine at 1,200° F showed a working fluid of 1 gr of ash per 100 scf of power gas (79 percent of the ash 7 to 35 microns in diameter) to be excessive for acceptable blade wear for commercial practicability. Blades in the turbine consisted of about 20 percent each of chromium, cobalt, and nickel; 3 percent molybdenum; 2-1/2 percent tungsten; and smaller amounts of manganese, columbium, and tantalum. Erosion of both the fronts and backs of the turbine nozzles was particularly heavy, the trailing edges being worn to a featheredge. Erosion of the buckets was less marked, although the leading edges were somewhat pitted. A refractory-lined combustor performed efficiently and with little abrasion of the lining by the ash-laden gas.

Jan 1, 1969

By John Ward Smith

An analytical method developed by the Bureau of Mines to determine dawsonite, nahcolite, and nondawsonite alumina (called excess alumina) extractable from Green River Formation oil shales is presented. The method requires water extraction of nahcolite followed by HCI-extraction of dawsonite and an unidentified mineral yielding excess alumina from the water-leached residue. Instrumental determination of sodium in the water extract and sodium and aluminum in the HCI extract measures the sample&apos;s content of the minerals. Detailed evaluation shows the method to be adequately specific, precise, and reproducible and free from uncorrectable interferences. The method&apos;s results define precisely the production of sodium carbonates and alumina possible from a sample of oil shale and the interval it represents. Shale-oil yields, nahcolite contents, and yields of extractable alumina determined on 83 samples representing an 821-foot section of dawsonite-nahcolite-bearing shale from .Colorado Corehole No.3, drilled in the north part of Colorado&apos;s Piceance Creek Basin, are presented. These samples resulted in nahcolite contents to 53.3 percent, oil yields to 48.3 gallons per ton, and alumina yields to 5.80 percent. Use of these data to evaluate the production potential of a section of the formation are suggested.

Jan 1, 1969

By David A. Sterling

Approximately 50 percent of the uranium resource of the Free World is in deposits of Precambrian age, principally in lower Proterozoic conglomerates in Canada and South Africa (Uranium Resources, Joint Report, ENEA and IAEA, 1967). Most of the uranium resource of the United States is in Mesozoic and Cenozoic continental clastic sedimentary rocks that fill intracratonic basins. The Atomic Energy Commission is investigating the distribution of uranium and thorium in the Precambrian of the Western United States and the relationship of, time-space-facies patterns of uranium and thorium enrichment in the Precambrian to the major resources of uranium in the Mesozoic and Cenozoic host sedimentary rocks. This paper summarizes the results of preliminary studies of the Precambrian in the Southwestern United States including New Mexico, Arizona, southern Nevada, and southern California (Fig. 1). The host rock provenances for the major uranium resources in epigenetic deposits of Mesozoic and Cenozoic age in the Western United States were in areas of extensive Precambrian exposure along the eastern margin of the Phanerozoic geosynclinal belt (Fig. 2). Mesozoic continental clastic sediments in the Colorado Plateau contain about two-thirds of the uranium resource of the United States. These sediments formed from detritus derived from the Mogollon highland in the Southwestern United States where the Precambrian was extensively exposed (Stewart, et al., 19593 McKee, et al., 1959; McKee, et al., 1956; Craig, et al., 1955) (Fig. 2). A genetic relationship may exist between this provenance and the major uranium deposits of the Colorado Plateau. The Precambrian might be equally important in the genesis of uranium deposits whether the most important process in the formation of these deposits was the leaching of low-order intrinsic amounts of uranium from Precambrian granite or from Mesozoic pyroclastics derived from syntexis of the Precambrian basement rocks (Malan, 1968).

Jan 1, 1969

By W. L. Price

Since first introduced in the United States in 1964, rail mounted bucket wheel stacker-reclaimers have gained wide acceptance by users. The coal burning power plant group has adopted this new storage tool most quickly. The actual history is traced in this area in some detail. Installations in phosphate and steel mill ore storage and a listing of present users are included.

Jan 1, 1969

By R. D. Pehlke, W. M. Small

The effect of added alloying elements on the solubility of nitrogen in a liquid alloy of 74 wt pct Fe. 18 wt pct Cr, and 8 wt pct Ni has been studied. At 1600°C and 1 atm nitrogen pressure, aluminum, chromium, columbium, manganese, molybdenum, tantalum, and vanadium increase the solubility of nitrogen in the liquid 18 Cr-8 Ni alloy, whereas additions of cobalt, copper, nickel, silicon, tin, and tungsten decrease the solubility. Interaction parameters based on a constant ratio of iron, chromium , and nickel have been used to quantitatively define the changes in nitrogen solubility. INVESTIGATIONS on the solubility of nitrogen in liquid iron have usually treated the pure metal, and often the influence of a single added element. Pehlke and Elliott1 carried out a comprehensive study on the influence of alloying elements on nitrogen solubility in liquid iron, and compared their results with previous studies. Turnock and pehlke2 have recently reported a study on the solubility of nitrogen in multicomponent liquid iron alloys. The original interaction parameter proposed by wagner3 was successfully employed in these studies. The need for obtaining information on the gas solubility in more complex alloys is indicated by the increasingly significant role played by dissolved gases in the processing of iron-based materials. The commercial stainless steels, for example, represent an area where data on nitrogen solubilities are required as a function of composition, temperature, and gas pressure. The nitrogen solubility in liquid Fe-Cr-Ni alloys has been studied by Humbert and Elliott.4 Their investigation covered the entire ternary system, and attempted to use data from binary alloys to predict nitrogen contents in liquid ternary alloys. Langenberg,5 using a method developed by Morris and buehl,6 calculated the nitrogen solubilities in multicomponent iron alloys from data available on binary iron alloys at 1600°C. Nelson,7 using a regular-solution model, extended this prediction to include the effect of temperature. Chipman and corrigan8 and Turnock and pehlke2 also employed empirical methods to calculate nitrogen solubilities in liquid multicomponent iron alloys. In order to provide a basis for predicting nitrogen solubility in liquid stainless steels, and to extend the data available for thermochemically modeling systems of this type, the following investigation was carried out. The study involved measupements of nitrogen solubility in a nondilute alloy and examination of the influence of a small addition of an alloying element on the nitrogen solubility. The study was focused on a very narrow range Of composition in the vicinity of 18 wt pct Cr-8 wt pct Ni (herein referred to as 18-8) with special emphasis on the change of.nitrogen solubility with the addition of a fourth metallic element. EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus, described previously,1,2 was used in this investigation. The charge materials were contained in a recrystallized alumina crucible and inductively melted. Additions were dropped from a glass side-arm. All materials were hydrogen-refined and vacuum-treated to eliminate or minimize the oxygen content. The source and purity of materials is given in Table I. The initial metallic charge was heated to approximately 1000°C and held under vacuum for 30 to 45 min as a means for removing hydrogen and adsorbed gases. Argon was used as the calibrating gas to determine the "hot volume". The average hot volume of the system was approximately 50 cu cm STP and a few experimental runs were made using a reaction bulb with a hot volume of 80 cu cm. The temperature range studied was from 1550° to 1700°C and the temperature was measured optically. THEORETICAL PRINCIPLES General Discussion. Nitrogen dissolves in liquid iron alloys according to the reaction: 1/2N2(g) = N (wt pct in solution) [l] The equilibrium constant, K1, for this reaction is written as:

Jan 1, 1969

By W. H. Yarroll Discussion by W. A. Griffith

W. A. Griffith (Head, Research Department, Phelps Dodge Corp., Morenci, Ariz.) - It is gratifying to see the increasingly common use of classical statistical procedures by metallurgical researchers. Mr. Yarroll has given excellent illustrations of the utility of multiple correlation analysis of complex metallurgical data. Our experience in applying these procedures to historical plant operating data has differed, however, from that which he suggests. The uninitiated frequently assume that the volumi-

Jan 1, 1969