Search Documents

By H. R. McCabe

"The study of a detailed series of structure and isopach maps of the Palaeozoic strata of southwestern Manitoba indicates that the principal Palaeozoic tectonic elements -the Williston Basin and Elk Point Basin -have been modified to a considerable extent by major tectonic features of the Precambrian basement. The principal basement feature is the break between the Churchill and Superior provinces, which coincides roughly with the Manitoba-Saskatchewan border. East-west-trending orogenic belts within the Superior crustal block may also be reflected to some extent in later Palaeozoic movements. In addition, the Superior crustal block, as a whole, appears to have had a slightly different response to the tectonic forces, giving rise to both basin subsidence and basin uplift. During periods of deposition, especially during Ordovician time, the Manitoba portion of the basin appears to have undergone a relatively higher rate of subsidence, whereas during periods of erosion relatively greater amounts of uplift and truncation have occurred. As a result, the depositional and erosional patterns for most of the Palaeozoic formations in southwestern Manitoba are somewhat anomalous relative to the regional basin framework.Some prominent Palaeozoic structures probably are the result of salt solution and differential compaction caused directly or indirectly by relatively minor tectonic movements related to Precambrian basement features. In particular, the prominent hinge line at the edge of the Devonian Prairie Evaporite salt basin may be due, in large part, to salt solution. Numerous other small structural lows, structural highs and isopach thicks, probably resulting from salt solution, occur along the salt edge and have been important in modifying and controlling Mississippian oil accumulation in the Daly-Virden producing area."

Jan 1, 1967

By O. J. Kensok

THE literature contains three previous studies of the chemical activities of Cd-Mg alloys: Trumbore, Wallace, and craigl obtained chemical activities of magnesium at 543" by performing electromotive-force measurements; Borg and irchenall calculated activities at 590°K based on vapor-pressure measurements of cadmium over Mg-Cd alloys by the Knud-sen effusion method; and Terpilouski and arcka measured the chemical activities of magnesium in the liquid state by means of electromotive-force measurements. In this study the vapor pressure of cadmium was determined over nine solid Cd-Mg alloys in the temperature range 571" to 697°K by the Knudsen effusion method. This study was prompted by the lack of precision in the data reported by Borg and Birchenall. Knudsen cells used during this study were fabricated from 0.020-in.-thick tantalum tubing. The tops and bottoms of the cells were cut from 0.010-in.-thick tantalum sheet, press-fitted, and welded in place. The orifice was drilled in the cell top and subsequently reamed to a knife-edge thickness. The diameter of the orifice was measured with a traveling microscope capable of reading 0.0001 cm. The sample was heated by means of a resistance

Jan 1, 1967

By J. B. Boniwell

The INPUT electromagnetic prospecting system was originally developed by Dr. A. R. Barringer in an effort to increase the sensitivity and penetration of airborne EM methods. Although brought to an operational state some several years ago, it is only through relatively re-cent modifications and testing that some of the potential of the system has been fully realised. This is brought into perspective by some recent results over known ore deposits and geologic environments.

Jan 1, 1967

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid binary and ternary Fe-Ni-Co alloys has been measured by the Sieverts' method between 1550°and 1700°C. Solubility data and standard free energzes and enthalpies of solution for nitrogen in the alloys are presented. Interaction parameters are discussed and presented for binary and ternary alloys. MOST of the studies of nitrogen solubility in liquid metals have been directed toward the dilute alloys of iron. Several of these investigations have included measurements of the nitrogen solubility in Fe-Ni al10s'- and in Fe-Co alloys.435 There has been some work, however, that has extended across the e-i-" and F-CO" binaries. This investigation was undertaken to determine the nitrogen solubility in both binary and ternary alloys of the Fe-Ni-Co system. It was also hoped that the differences between earlier studies might be resolved. EXPERIMENTAL METHOD This investigation was made using a Sieverts' apparatus described previously." The nickel (99.85 pct) and cobalt (99.9 pct) were obtained from Sherritt-Gordon Mines, Ltd., and the iron (99.95 pct) was Fer-rovac-E obtained from Crucible Steel Co. Recrystal-lized alumina crucibles were used throughout the entire investigation with no evidence of crucible-melt reaction. Melt temperatures were measured with an optical pyrometer and the temperature scale calibrated against the melting points of the three pure metals. The emissivity of the melt was assumed to be a linear function of composition for all alloys, as has been shown for Fe-Ni alloys.lZ The emissivity of the pure metals at 1600°C were taken as 0.43 for iron, 0.44 for cobalt, and 0.45 for nickel. Using these emissivities, the trans mis sivity of the system was found to be 0.51 i 0.01. The Sieverts' method was used for this study and followed the procedures outlined previously.l' The individual metals were weighed to give about 100 g of alloy. The alloys were melted in the crucible under a partial pressure of argon. The system was evacuated, and the "hot volume" was measured with argon. To avoid the errors caused by vaporization, the melt was held under vacuum only long enough to ensure that all of the gas in the system had been removed. The influence of any small amount of vaporization on the "hot volume" was shown to be negligible by measuring the "hot volume" after a run. This measurement agreed with that made at the start of the run within the implicit error, 0.2 cc, caused by the limitations in accurately reading the buret. The solubility-pressure relationship was measured in the pure metals and in several alloy compositions throughout the ternary system. These measurements were made by admitting measured amounts of nitrogen to the system, and then determining the equilibrium nitrogen pressure above the melt. This method has the distinct advantage of higher accuracy, particularly at lower pressures, than measurements made by withdrawing gas from the system to reduce the pressure after determining the solubility at 1 atm nitrogen pressure. This latter method has a practical lower limit of about 0.4 atm where an increased error is encountered because the buret must be emptied to permit further measurements at lower pressures. By determining the relation between apparent solubility and pressure, it was possible to make a good estimate of the initial nitrogen content of the metal from the intercept of the solubility curve extrapolated to zero pressure.11 DISCUSSION The solubility data corrected to 1 atm nitrogen pressure are summarized in Table I. The reported solubility has been corrected for the initial nitrogen content of the alloys. The initial nitrogen contents fell between 0.0002 and 0.0010 wt pct, and were lower in the iron and nickel than in the cobalt. Sieverts' law was obeyed in all alloys at pressures up to 1 atm. Examples of this behavior are shown in Fig. 1. The reaction for solution of nitrogen is Taking the standard state as 1 wt pct N in the alloy and the reference state as nitrogen at infinite dilution in the alloy, and noting the adherence to Sieverts' law, K becomes the solubility of nitrogen in the alloy at 1 atm pressure. Thus the solubility data of Table I were used directly to calculate the standard free energy for the solution reaction. These results are also presented in Table I. The enthalpy of solution is also summarized in Table I as calculated from a form of the van't Hoff relation: Iron-Nickel System. The data for the solubility of nitrogen in liquid Fe-Ni binary alloys is presented in Fig. 2 along the with data of aito, Schenck et al.,' and Humbert and 1liott.l' The data for studies of nitrogen solubility in Fe-Ni alloys containing less than 20 pc t i'- are not presented in Fig. 2, although they are in good agreement with the present work. The results of this study are in good agreement with Schenck

Jan 1, 1967

By M. T. Heath

Numerous mineral deposits of somewhat limited extent and grade are associated with most of the Tertiary granitic intrusions in the Cascade Mountains of Washington. The Silver Star area in southwestern Washington is typical of many of these small, and at the present time, economically marginal mineralized areas. Small but fairly high grade deposits of copper, lead, and zinc sulfides are found within the borders of a small granodiorite stock, and in surrounding Tertiary volcanics. This paper will discuss these deposits and their genetic relationships with the intrusion.

Jan 1, 1967

By P. H. Turnock, R. D. Pehlke

The effects of mutual interactions between elements on the solubility of nitrogen in liquid iron alloys containing chrormium, columbium, molybdenurn, nickel, or silicon have been determined. The equilibrium nitrogen solubilities in the liquid iron alloys were measured by the Sieverts method. The second-order effects caused by the presence of chrormium, columbium , or silicon in the melt were found to be significant. The solubility of nitrogen in liquid iron alloys containing several alloying elements has also been measured as a function of melt temperature and nitrogen pressure. The heat of solution of nitrogen in microcomponent iron alloys has been found to be a function of the logarithnz of the activity coefficient of nitrogen, irrvespectilje of the composition of the melt. The heat of solution of nitrogen in pure liquid iron was determined to be 1265 ± 450 cal per g-atom of N over the temperatxue range 1600° to 1800°. Sieverts ' law was obeyed for all melt compositions studied in the pressure interval 0.4 to 1.0 atm. The solubility of nitrogen in liquid pure iron and in many dilute binary liquid-iron alloys has been the subject of many investigations. Pehlke and Elliott' made a comprehensive investigation on this subject in which they summarized and compared previous researches. However, the practical application of these solubility studies requires prediction of the nitrogen solubility in the multicomponent alloys encountered in operating practice. The interaction parameter as defined by wagner2 has been used to predict the behavior of a solute in a complex alloy, and a modification of this approach has met with reasonable success in several instances.'1"5 The necessity for extending the nitrogen solubility data on binary alloys is caused by the lack of direct measurements of the solubility of nitrogen in molten alloy steels. A direct comparison between measured solubilities and those predicted for multicomponent alloys based on data in binary systems has been made in only a few instances, and most of these were reviewed by Langenberg,6 who developed a graphical technique for predicting nitrogen solubilities in multicomponent iron alloys. The solubility of nitrogen has also been studied over the entire Fe-Cr-Ni ternary system by Humbert and Elliott.? Both studies compared the solubilities computed from binary iron alloy data with those measured in ternary alloys in the liquid state at 1600°C. Most of the nitrogen solubility measurements referred to above were for iron alloys at 1600°C; thus, the ability to predict nitrogen solubilities in molten iron alloys has been restricted primarily to alloys at 1600°C. Recently, Nelsson8 devised an approximate method for calculating the change in nitrogen solubility in molten iron alloys as a function of temperature, but an assumption of regular solution behavior limits the applicability of the method. Chipman and Corrigan9,10 have developed an empirical correlation. based on the activity coefficient of nitrogen in the iron alloy at 1600°C, which facilitates the estimation of nitrogen solubilities at higher temperatures. This method also has limitations, due to the necessity of calculating the activity coefficient for nitrogen in a multicomponent iron alloy at 1600°C from the nitrogen solubility data for binary iron alloys. The shortcoming of such a straightforward approach to the problem of predicting nitrogen solubilities is the disregard of mutual interactions between elements in a complex iron melt. This investigation was conducted in an attempt to provide a more reliable method of predicting nitrogen solubilities in multicomponent iron alloys. The effects of the mutual interactions between chromium, nickel, silicon, molybdenum, or columbium in iron were studied, using the Sieverts' technique1,7 to measure the effects of alloy composition, temperature, and pressure on the solubility of nitrogen in ternary liquid iron alloys.

Jan 1, 1967

By R. F. Waters

Laboratory-scale selective volatilization methods developed by the Bureau of Mines to recover germanium and gallium concentrates from coal fly ash and phosphorus furnace flue dust are summarized. In the better experiments between 85 and 98 percent of the germanium was recovered as the lower oxide and as sulfides, and between 75 and 97 percent of the gallium was recovered as the lower oxide and as the trichloride. Grades of the condensates were inconsistent and varied between a few tenths of a percent and 8 percent, depending on the method used. In the primary extractions of germanium alone the degree of enrichment surpassed 100 to 1, and for gallium the best ratio was 30 to 1. Upgrading of condensates by vaporization retreatment and by leaching and precipitation is discussed. An appreciable degree of mechanical preconcentration by attrition scrubbing and elutriation was possible on two fly ash samples.

Jan 1, 1967

By C. S. Yust, C. S. Morgan

ThIS note reports the observation of masses of dislocation etch pits around the weld necks of small single-crystal particles of calcium fluoride sintered to a cleaved face of a larger CaFz crystal. Crystal particles in the -50 +I00 mesh size range were placed on freshly cleaved CaFz surfaces and heated at 1250°C for 30 min in a tantalum container in an argon atmosphere. The sintered specimens were then etched at room temperature for 40 to 50 min in a 2 pct sulfamic acid solution which is a selective etch for dislocations in caF2.' Figs. 1 through 3 show the masses of dislocation etch pits observed around weld necks after etching. In some cases, particles were gone after removal of the specimens from the furnace although weld necks were readily visible. In other instances, no etch pits formed around a weld neck. A possible cause of concentrations of dislocations on the crystal surface is mechanical deformation of the base crystal when particles are dropped on it. If such a deformation does occur, it would be much smaller than that caused by the light punching of a crystal with a sharp instrument which results in large concentrations of etch pits. However, crystals deformed by punching with the sharp instrument and annealed at the conditions of these experiments (1250°C for 30 min) before etching showed no concentrations of dislocation etch pits. It is obvious that dislocations from the much smaller deformations, possibly created when particles are placed on the surface, would also anneal out. Etching of large crystals which had particles placed on them in the usual manner but which were not heated showed no dislocation concentrations such as shown in Fig. 1. The magnitude of dislocation etch-pit concentrations did not vary with extensive variation of the cooling rate. The appearance of many of the etch-pit clusters is typical of a well-annealed condition, indicating that the dislocation concentrations formed before the specimen temperature was lowered. Therefore, it is evident that thermal stresses in the neck area did not create the deformation indicated by the presence of the dislocations. The possibility exists that the etch-pit concentrations at places where particles had been removed may be the result of deformation accompanying the fracture of the sintered bond. That this is not so was demonstrated by breaking off particles around which no etch pits occurred. Re-etching never resulted in the large concentrations observed at sintering sites. The stress available to effect material movement during sintering of two particles will depend on the geometry at the contact point but can easily exceed the macroscopic yield stress in CaFz systems. It appears that the plastic deformation observed results from sintering or simply from the weight of the small particles. It has been previously argued that plastic flow makes an important contribution to the initial densification of oxides having the fluorite crystal structure.2p3 If plastic deformation occurs, it would begin as soon as the temperature is sufficiently high

Jan 1, 1967

By Roger V. Pierce

"WITHOUT mineral wealth, modern man would not exist. True, man could survive on a stone-age basis with an average life expectancy of, say, 25 to 30 years -once he got past infancy.However, no metal would tip his arrow in a hunt for protein; no steel plough would break the soil for the organized planting of seed; and no coal, nor oil, nor natural gas nor uranium fuels would pro-vide him with light or beat or safety from either beasts, or other men, or an unkind nature that threatened him and his family.Modern agriculture, fishing and forestry represent the other three wealth-producing industries. With-out metals, non-metallics and energy minerals, however, it would be impossible to fit any of these to man's modern needs."

Jan 1, 1967

By G. S. Baker, S. H. Carpenter

Langenecker has reported significant reduction in strength of high-strength metals during ultrasonic t'ibration. Decreases in static yield stress an order of magnitude greater than the calculated stress amplitude of vibrations were reported by him for a stainless steel and for tungsten. in the present work, attempts were nzadc to verify such large reductions in yield and flats stresses using resonant librations of measured amplitudes. The results show that both the soft metals (copper and aluminum) and the high-strength metals (sleels) hare reductions in yield and .flow stresses no larger than the stress amplitude of libration. BLAHA and Langenecker,' investigating the effect of vibratory stresses on the deformation of zinc and aluminum, found a decrease in the static yield and flow stresses approximately equal to the vibratory stress imposed. Langenecker later extending this work to high-strength metals such as stainless steels and tungsten2 found a much larger effect. In these metals the static yield and flow stresses decreased by an amount more than an order of magnitude greater than the calculated vibratory stresses. It was suggested that this phenomenon could be a serious hazard to high-strength structures in an acoustic environment, such as a large rocket at launch, or could be used advantageously in the working of hard-to-work materials such as the refractory metals. Langenecker and others3 have investigated the effect of high-amplitude vibrations on many metal-forming operations. The results have been quite favorable with usually a large decrease in the energy necessary for the forming operation. The processes, however, involve large frictional forces and it is not clear whether the decreases in forming forces are to be ascribed to decreased friction or to decreased flow stresses. The present paper reports an attempt to determine the effect of accurately known vibratory stresses on the static yield and flow stresses. I) EXPERIMENTAL TECHNIQUE The standard multicomponent resonator technique for measuring internal friction has been adapted to allow simultaneous high-amplitude vibration, internal-friction measurement, and tensile deformation. This has been described in detail elsewhere.4 Longitudinal oscillations of approximately 50 kc frequency are excited in a multicomponent resonator by a quartz transducer. A second transducer measures the amplitude of vibrations. Fig. 1 shows a schematic drawing of the resonator and grip arrangement and the displacement pattern produced. Since the centers of the dummy bars are at displacement nodes, they represent points where attachments will not materially affect the vibrations. The force is applied by a standard Instron tester. The sample may be deformed while simultaneously vibrating at up to 104 strain amplitude. 11) EXPERIMENTAL RESULTS The effect of high-amplitude vibrations on the yield and flow stresses of copper. aluminum, tantalum. a soft iron, and a stainless steel has been measured. In addition samples of tungsten vibrating at stress levels up to 10' dynes per sq cm have been subjected to static stresses near the static yield stress with no indication of macroscopic deformation. Fig. 2 gives typical results for 99.999 pct polycrys-talline copper. A vibratory stress of 7 x 107 dynes per sq cm is applied at points "a" and removed at points "h". The behavior of aluminum is identical. In agree-

Jan 1, 1967

By John E. Miller

A high accuracy Burnett apparatus for use at 12,000 psi and 0° to 65° C has been constructed at the Bureau of Mines Helium Research Center. The apparatus is patterned after Burnett's original apparatus, but the working pressure is much higher and elastic distortion can be essentially eliminated. An operating procedure to permit faster experimental measurements is suggested.

Jan 1, 1967

By Eugene S. Machlin

A classical theory of solid solutions involving neavest-nergkbor intevactions with both central and linked-central forces between atoms has been developed. It has been found that the theory, where it can be checked quantitatively, is in ageement with experiment. The theory encompasses a description of many diverse pkenomena, such as antiphase shift structures, size effect, relative stabilities of various solutions, lattice para,neters, and order-disorder transitions. In particulav. a quantitative prediction not involving adjustable pavameters is made concevning the deviation of the Au-Cu interatonlic distance in long-range ordered (Ll,) Cu-Au I fronl the average distance based on the distances in pure gold and copper. This prediction, which is in agreement with expel-intent, has not been encompassed by any preuious theory. The theory of order-disorder is fragmentary. That is, no one theory exists that can explain the variety of qualitative phenomena observed. Further, many theories are not in good quantitative agreement with experiment. This subject has been reviewed by Muto and Takagi, Tuttman, and Oriani.3 There exists no doubt that the quasi-chemical approximation is not a complete description and that the inclusion of strain energy using macroscopic elasticity theory concepts leads to results in disagreement with experimenL4 The observation of antiphase domains and ordering systems such as Cu-Pt has led to Brillouin zone treat-ment of the order-disorder transition as opposed to the classical Ising model. The objective of this paper is to demonstrate that it is possible to develop a pairwise approximation model that can explain many of the observed order-disorder phenomena that have puzzled investigators in the past. This theory is based upon an empirical model due to ergmman' for the elastic constants of metals. This model is generalized for multicomponent systems. As will be shown, the theory yields a short-range ordering energy for the disordered solution which differs from the ordering energy calculated from the differences in energy of disordered and long-range ordered solutions. It will be demonstrated that there is no necessary correlation between heats of formation and the tendency to order or between size effect and the tendency to order. Also, the existence of antiphase domains and iso-short-range-order systems that form superlattices (Cu-Pt) is predicted on the basis of the theory. Further, the relative stability of competing superlattices is calculable from the theory. If single-crystal elastic-moduli data are available for the pure components and one superlattice then there exists but one adjustable parameter in the calculation of lattice parameters for both the disordered and ordered solid solutions. In one special case, no adjustable parameters are required and a quantitative prediction is made. For the calculation of energies and partial order, there exists but one additional adjustable parameter, the pair-exchange energy V used in the quasi-chemical approximation (or the Ising model.) However, in these calculations, much more precise values are required for the single-crystal elastic moduli than available if the quantitative uncertainties in the predicted values of the energies are to be sufficiently small. THEORY ~er~man' has developed a model with which he was able to obtain fair agreement with experiment for the relations between the elastic constants for metals. This model which we shall call Bergman's model is a linear combination of his models I and 11. In effect, Bergman, in this model, considers that each interatomic distortion is composed of two components: a classical central force distortion with an associated central force constant and what we shall call a linked-central force distortion with an associated linked central-force constant. The linked-central force distortion component obeys the constraint that the sum of such distortions over all the bonds equals zero. No constraint is imposed on the classical central force distortion component. Bergman' derives the constraint on the linked-central force distortion on the basis of application of Pauling's relation between bond distortion and bond number to metals.ga This assumption is not logically necessary, however, and the Bergman model may be taken as a mathematical model for elastic constants, e.g., a purely empirical model without a physical basis. In the present work, the method of Bergman has been applied to two-component systems (solid solutions). In place of an external strain—which would allow a calculation of the elastic constants for the two-component system—it is considered that internal interatomic distortions exist as a consequence of having three potentially unequal distortion-free interatomic distances and but one "average" interatomic distance. It is assumed that the distortion-free interatomic distances between atoms of the same element are those found in the pure element having the same undistorted crystal structure as the solid solution. The distortion-free interatomic distance between unlike atoms is in general not measurable except in the probably nonexistent

Jan 1, 1967

Jan 1, 1967

By Leonard Obert

Before 1957 a number of investigators reported stress determinations made on or near the surface of underground excavations. The usual procedure was to measure surface strains and to calculate the stresses using laboratory-determined values of the elastic constants of the rock. In some instances strain gages were stress-relieved so that the measured stress was absolute. Also, several investigators reported near-surface absolute stress determinations made by the flat-jack procedure. In 1958, Hast1 described a procedure for making absolute stress determinations within a body of rock. In this procedure a diametral deformation gage was placed in a borehole and then the borehole was overcored to produce stress relief. The secondary principal stresses in the plane normal to the axis of the borehole were calculated from measured deformations and the elastic constants of the rock. During the past nine years a number of investigations have been reported1-20 in which this technique, or modifications of it, have been reported. Both the stress distribution in the walls of underground openings and the stress field at points as great as 200 ft from these openings have been determined. Considered collectively, these reports shed some light on the nature of the stress distributions in the proximity of underground openings and on the stress field, that is, the state of stress outside of the zone of influence created by openings. To summarize these findings first consider the stress distribution in the wall and structural components of openings. Fig. 1 (a) shows a typical theoretical stress distribution curve in a linear-elastic, isotropic, homogeneous material. Fig. 1 (b) is an idealized measured stress distribution curve for the same opening in a relatively unfractured uniform, but brittle,

Jan 1, 1967

By R. L. Hopkins

Some typical thiacyclopentanes and thiacyclohexanes were synthesized to provide reference compounds needed for the identification of sulfur compounds in crude oils. Two general methods of synthesis were employed: (1) cleavage of 2-alkyltetrahydropyrans with hydrogen bromide followed by the reaction of the resulting dibromoalkanes with sodium sulfide and (2) the catlyzed reaction of cyclic ethers or 1)4-or 1)5-alkanediols with hydrogen sulfide. Both methods produced mixtures of 2-alkylthiacyclopentanes and 2-alkylthiacyclohexanes with 2-alkyltetrahydropyran as the starting material. The structures of the reaction products were established by analysis for sulfur; desulfurization; gas-liquid chromatography (GLC); mass, infrared, and nuclear magnetic resonance (NMR) spectra; and an alternate synthesis. The synthesis of the cyclic sulfides contributed substantially to the identification of 10 members of this class of sulfur compounds in crude oil.

Jan 1, 1967

By H. M. Woodrooffe

This paper deals with the laboratory facilities at the Mines Branch for carrying out research in the industrial minerals field, and also reviews current programs in ceramics and construction materials, in non-metallic minerals and in the milling of industrial minerals. It then discusses the application of these pro-grams to industrial problems.

Jan 1, 1967

By Charles B. Kenahan

The effects of ultrasonic radiation on the electrodeposition of copper-zinc, copper-cadmium, and copper-tin alloys from cyanide baths were investigated by the Bureau of Mines at frequencies of 18.5 and 38 kilocycles per second, and at acoustic intensities up to 0.5 watt per cm3. Significant changes occurred in the composition of the deposited alloys; some of these deposits were brighter, harder, more adherent, or of finer grain size than nonirradiated deposits. The irradiated deposits were also smoother and less porous, and they afforded better corrosion protection for the substrate metal in sodium chloride solution. The limiting current densities of the cyanide baths were increased by the application of ultrasonics. Anode and cathode current efficiencies also were increased, and cell voltages were lowered; the relationship of these effects to current density is discussed. Electrode potential measurements showed significant depolarization effects at both electrodes during ultrasonic irradiation. The resulting decrease in cell voltage was due chiefly to depolarization at the anode, and the anode became less passive.

Jan 1, 1967

By Calvin L. Stevenson

The probability of a particle passing through a maze is predictable and consistent. This principle may be utilized to effect a particle size separation of materials by presenting a physical maze to a stream of material that will allow the fine particles to pass, while deflecting the coarse particles. A maze is effective even though all apertures encountered are many times larger than the particles being separated. By designing a machine that allows the probability parameters to be controlled and varied without changing physical dimensions, probability sizing becomes a useful tool for the separation of granular materials.

Jan 1, 1967

By F. L. Wideman

Materials handled at metal and non-metal mines in the United States increased 10 percent compared with those of 1965 as a result of expansions in output at existing mines and development of others to meet increasing demands for mineral products. The tonnage of commercial materials mined or quarried increased as did the quantity of waste handled. Crude material from which metal or nonmetal products were derived comprised 71 percent (75 percent in 1964) of the total materials handled. Great strides were made in mining technology and there were indications that, in the future, earth moving by the mining industry will involve materials-handling systems of increasing size and complexity. Materials Handled.-Output of ore and waste at metal and nonmetal mines and quarries in the United States in 1966 totaled 3,518 million tons (3.213 million tons in 1965). The quantity of materials handled has increased at an average annual rate of 5 percent since 1962. Ore production increased 4 percent over that of 1965, also comparable to the average annual rate of increase in the last 5 years. Waste removal in 1966 increased 25 percent over that of the previous year.

Jan 1, 1967

By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,' and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.' Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8'7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8'9 Copper minerals sometimes yield elemental sulfurlo'" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,'5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967