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By J. C. White

This paper, after a brief introduction giving the history and geology of the area, deals with mining operations at the Copper Mountain mine of Gaspe Copper Mines, Limited. It discusses development operations, and then goes into the mining methods employed, covering drilling, grade control, blasting practice, loading and hauling, and the road and service machines used.

Jan 1, 1969

By J. J. Frawley, W. J. Childs

The dynamic nucleation of supercooled bismuth and Bi-Sn alloys has been studied over a frequency range of 15 to 20,000 cps. For low-frequency vibration, a minimum vibrational energy was required for enhancement of nucleation. Above this critical energy, the dynamic supercooling was less than static supercooling showing that vibration promoted nucleation. The amount of dynamic supercooling continued to decrease with increasing vibrational energy until a minimum or threshold value was reached. This minimum value of supercooling for nucleation remained constant joy all further increases in vibrational energy. For higher frequencies, similar results were observed. This behavior has been related to the necessity of cavitation for dynamic nucleation. When a liquid is cooled to a temperature below its equilibrium melting point, the solid phase is more thermodynamically stable. However, for solidification to occur, a two-step process, nucleation and subsequent growth of the solid phase, must occur. When a liquid is supercooled, that is cooled below the equilibrium melting point, the controlling process for solidification to begin is the rate of nucleation. Once nucleation has occurred, the solidification process is controlled by the rate of growth. Nucleation can be induced by two factors: either by a catalyst or by the use of mechanical shock. Numerous investigators1-4 have studied the effect of nucleation catalysis but much less systematic study has been made of nucleation by mechanical shock waves. The influence of vibrations on grain size in castings and ingots has been studied by many authors but no clear understanding of the mechanism or accurate prediction of the effect has been presented.5 It would be intuitively expected that the further the departure from equilibrium (i.e., the greater the supercooling), the easier it would be to induce nucleation. This has been quantitatively demonstrated both by walker6 and later by Stuhr,7 that the greater the degree of supercooling the easier it is to nucleate by a shock wave. Stuhr also attempted to obtain the mechanical energy required for nucleation of bismuth as a function of supercooling. He vibrated a crucible containing supercooled metal at low frequencies and various amplitudes and noted the corresponding dynamic supercooling obtained. The amount of supercooling was inversely proportional to the mechanical energy applied. Limitation of his experiment was the problem of the confinement of the liquid in the crucible without splashing and minimizing other unwanted modes of vibration. Tiller et al.8,9 did similar work on tin and Sn-Pb alloys using an electromagnetic stirring device. Their conclusions were that the magnitude of the magnetic field strength did not affect the amount of undercooling at which nucleation was initiated. While conclusive experimental results have been lacking to explain this effect of mechanical vibration on inducing nucleation, a number of theories have been proposed. Two of these theories are discussed below. 1) The Change in Melting:- Point Locally Due to the Change in Pressure (Clapeyron Equation). According to Vonnegut10 the most plausible explanation for the nucleation of a supercooled melt by cavitation is the effect of changing the melting point by a change in pressure. For materials where the volume decreases on solidification, an increase in pressure raises the melting point; for materials which expand on solidification, the melting point is raised for a decrease in pressure, i.e., rarefaction. Using the Clapeyron equation, the melting point of a metal can be calculated as a function of pressure. If it is assumed that the equation can also be used to calculate the temperature of nucleation of a supercooled melt as a function of pressure (i.e., the temperature of heterogeneous nucleation will increase with pressure at the same rate as the melting point), the amount of supercooling required for nucleation will be constant at all pressures as shown in Fig. 1. It is obvious that an isothermal change which results in an increase in melting point results in an equal increase in supercooling. This increase in supercooling may now be sufficient for nucleation. A pressure of 80,000 atm was calculated, using the Clapeyron equation, as the pressure required to increase the temperature of nucleation of nickel by 200°C. According to Lord Rayleigh,11 this very large pressure could be generated for a very brief period of time by the collapse of a cavity. This pressure wave is radiated in all directions from the collapsed cavity. If the temperature of the melt is slightly below its equilibrium melting temperature at atmospheric pressure, stable growth can follow; that is, once nucleation occurs, growth becomes the main driving force of the solidification process. This proposal has been extended to water which expands on freezing by assuming that nucleation occurs during rarefaction following the pressure pulse. This negative pressure pulse should follow immediately after the positive pressure pulse with its magnitude approaching the critical tensile strength of the liquid. The negative pressure developed during this period would raise the melting point of water and thus promote nucleation. Hunt and jackson12 have suggested this for water. Similarly, it could be postulated that bismuth which also expands on freezing could be nucleated during the negative pressure pulse. 2) Nucleation by a High-pressure Phase. An extension of the Clapeyron equation to systems where density decreased on freezing at atmosphere pressure has been proposed by Hickling.13 The phase diagram for water initially shows the well-known decrease in

Jan 1, 1969

By T. E. Scott, D. H. Sherman, C. V. Owen

Mechanical properties and optical metallographic characteristics of vanadium containing 53 ppm (wt) H were investigated from, 77° to 298°K. A sharp ductile to brittle transition induced by the presence of hydrogen was observed between 238° and 223°K and a mar-tensitically formed hydride appeared at 200°K. While there appears to be a subtle relationship between the hydride formation and the ductile-brittle transition, it was concluded that the hydride per se was not sufficietzt to cause the severe em brittletnent. On the basis of the metallographic experiments and the results of a Petch analysis it is suggested that the mechanism of the embrittlement involves a reduction of the true surface energy, or cohesion, of the uanadiunz. THAT hydrogen can severely embrittle vanadium is well-documented;'-5 however, the mechanism by which hydrogen induces the observed embrittlement has not been established. It is not known whether the embrittlement of vanadium is caused by the formation of vanadium hydride or by a more subtle role of hydrogen. Until very recently6>' the solid solubility of hydrogen in vanadium at temperatures in the,range of the embrittlement was not known to a useful accuracy. In general, a severe embrittlement of the type produced by the presence of hydrogen in vanadium can be caused by changes in either of two properties of a metal. Either the yield stress of the metal is raised to the extent that plastic deformation at the tip of a crack cannot occur or the cohesive properties of the metal are reduced, at least locally, to the point at which cleavage is the natural response to applied loads. Of course a combination of these is possible. It is not known which of these properties of vanadium is influenced most by the addition of hydrogen. The purpose of this investigation was to determine the role of hydrogen in the embrittlement of vanadium. Accordingly, the solubility of hydrogen in vanadium in the temperature range where embrittlement is most severe was determined, the appearance of vanadium hydride was examined in relation to the initial ductile to brittle transition temperature, and an attempt was made to evaluate the effect of hydrogen on the yield stress and cohesive properties of vanadium. MATERIAL AND PROCEDURES Sample Preparation. The vanadium used in this investigation was prepared by the iodide refining process described by Carlson and owen.' Three ingots, 3 in. diam by 6 in. long, were cold-swaged to 0.096 in. diam, cut into short lengths, and then arc-melted under purified argon into one ingot. This process was repeated to insure a uniform composition in the final ingot. Chemical analysis of the metal is given in Table I. On the basis of work of Loria et a/ .' the following sequence of treatments was performed in order to obtain a uniform equiaxed ultimate grain structure: a) cold swage q-in.-diam ingot to 0.230 in. diam; b) anneal 6 hr at 1000°C in vacuum; c) by cold swaging reduce 81 pct in area in three steps: 0.230 to 0.187 in. diam, 0.187 to 0.150 in. diam, 0.150 to 0.096 in. diam. This sequence provided the desired grain structure after subsequent annealing treatments. Because annealing in evacuated quartz capsules resulted in contamination by oxygen, all anneals in this investigation were performed in a 304 stainless-steel chamber under a dynamic vacuum of 10- I Torr with the vanadium wrapped in tantalum foil. Prior to all annealing treatments the wires were electropolished for 1 min at 16°C in an 80 pct methanol-20 pct sul-furic acid electrolyte at 12.5 v. Following the final reduction the 0.096-in.-diam wire was cut into 2-in. lengths. A 1-in. gage section was reduced to 0.090 in. diam by electropolishing as above. Five different grain sizes were obtained by annealing the 2-in. samples at different temperatures for 8 hr to insure uniform grain size and residual hydrogen removal. The annealing temperatures used and the resulting grain sizes are given in Table 11. The final step in sample preparation was to charge half of the specimens of each grain size with hydro-

Jan 1, 1969

By G. Knight

"Results of a program of dust research carried out at the Mines Branch Laboratory, Elliot Lake, indicate that dust-concentration estimates vary greatly, depending on the sampling instrument, the assessment technique and the properties of the dust cloud. The wide range of the ratio between the estimates by any pair of instruments shows that the correlation between the health hazard and dust-concentration estimates by most existing sampling instruments must be questionable. Important studies are being carried out to permit the definition of mine environments in more precise technical terms. The influence of size selection, the physical property measured, composition and sampling period on the assessment of the health hazard are discussed."

Jan 1, 1969

By D. M. Steelman

Digital systems have been employed in industry as an aid in process evaluation and control for about 20 years. The earlier systems were quite simple and did little more than periodically scan a multitude of process variables, perhaps comparing them to alarm limits, and print out the results. As time passed, the needs of industry and the imagination of process engineers became more demanding. Rather than perform only alarm checking and logging, operating guides were generated to help the operator gain optimum performance from the process. Eventually, systems were entrusted with the job of manipulating the set points of the local analog control loops in a (DDAC) digitally directed analog control mode. Today digital systems are used to gather all-the process information, including both analog and digital variables; to make the necessary data manipulations; and to control the process end elements in a (DDC) direct digital control mode. During these years of transition from the very simplest systems to the complex systems of today, the demands upon the system engineer have been every increasing. The process engineer has required, among other things, more computational ability at high speeds, faster input and output rates, greater flexibility, better communication facilities (man-machine interface), (process oriented software), and finally, greater reliability at lower cost.

Jan 1, 1969

By William E. Bruce

The Bureau of Mines performed drill calibration tests on two industrial percussive drills of 2-5/8- and 3-1/2-inch piston diameters to determine operating characteristics for their use in conjunction with penetration rate data in developing drillability equations and furthering the knowledge of percussive drills. The use of a linear velocity transducer for measuring piston velocities and application of its instrumentation are described. Data presented include relationships between maximum piston velocity and feed air pressure other results confirm the theory or data of previous investigators, and some comparisons are made with the performance prediction formulas of other investigators.

Jan 1, 1969

By R. L. Klueh, W. W. Mullins

During the course of a study on the periodic precipitation (Liesegang phenomenon) of water vapor bubbles in solid silver, some interesting observations were made concerning the formation and growth of these bubbles. Under certain conditions it was found that the bubbles which formed in the single crystals led to the formation of large blisters ad cracks, and when poly crystalline specimens were used grain boundary cracking was observed. These two phenomena were examined in some detail, and it was found that an important step in the formation of the blisters and grain boundary cracks was the impingement of neighboring bubbles. DURING the study of Liesegang precipitation in solid silver,' some interesting observations were made concerning the formation and growth of water vapor bubbles. The bubbles were formed by annealing oxygen-saturated silver in hydrogen. Because of the similarity of this phenomenon to the hydrogen embrittlement of tough pitch copper,' it is known in the literature" as the hydrogen embrittlement of silver. In some respects it appears that the hydrogen embrittlement of silver is similar to the processes of hydrogen attack of steel5 and blister formation.' Hydrogen attack results from the high-temperature reaction of hydrogen with dissolved carbon or carbides in the steel to form methane (usually at grain boundaries). Blister formation occurs in steel and other materials as a result of hydrogen produced by corrosion, pickling, and so forth. Because of these similarities, some speculations were made concerning these other processes. EXPERIMENTAL PROCEDURE Water vapor bubbles were formed in 99.999+, 99.99+, and 99.9 pct Ag by annealing in a partial pressure of oxygen (pq) until saturated and then in a partial pressure of hydrogen (pH,). The hydrogen diffuses into the silver and reacts with the dissolved oxygen to form water vapor which precipitates in the form of bubbles. The specimens were then sectioned, silver-plated, mounted in cold-setting plastic, ground and polished through a preliminary polishing, and finally chemically polished.' The bubbles were visible without etching.

Jan 1, 1969

By Robert M. Jimeson

The competitive market potential for solvent refined coal is estimated. Market advantages of solvent refined coal are enumerated. Markets are possible in combustion, railroad locomotion, and carbon electrodes. The combustion characteristics are consistent with expected air pollution restrictions on the emission of sulfur and particulate matter. A market potential of sufficient size exists to support the initiation of solvent refining in the United States. The market analysis should help fuel producers determine the advisability of their undertaking the solvent refining of coal.

Jan 1, 1969

By R. A. Corley, W. R. Wilcox, J. R. Teviotdale

Chemical vapor deposition of hafnium carbide yielded whiskers, needles, dendrites, faceted crystals, and adherent coatings. The gas stream compositiom and the mass transfer conditions determined the habit of the deposit. The deposits were obtained at temperatures ranging from 1100" to 1800°C. HAFNIUM carbide has the highest melting point of any binary compound; therefore, its various potential applications are a subject of vital interest to the aerospace industry. The experiments described herein were performed to investigate the chemical vapor deposition of hafnium carbide with particular interest being placed upon the possible production of high-strength single-crystal whiskers for composite materials. In 1931 Moers 1 used a gaseous mixture of HfC14, Hz, and toluene to vapor deposit crystalline hafnium carbide on a tungsten filament heated to 2400°to 2800°C. More recently Lepie 2 deposited hafnium carbide on graphite using HfC14 and methane in a helium gas carrier. The pyrolytic depositions described here were accomplished in graphite tubes by using various gas mixtures and dopants. The resulting crystal habits included whiskers, needles, needle dendrites, bulbous dendrites, faceted crystals, and smooth, adherent poly-crystalline layers. EXPERIMENTAL The depositions were carried out in an induction-heated graphite tube, 1.2 cm ID, which was contained in a vertical 9-cm-ID quartz tube. (A more detailed account of the experimental procedures and results is given in Ref. 3.) Refractory oxide fiber and tubes and graphite felt were utilized jointly and singly for therma1 insulation. A typical temperature distribution is shown in Fig. 1. The reactant gases were introduced at the top and removed at the bottom of the tube. Table I summarizes the experimental conditions and results. Many deposition habits were obtained. X-ray analyses showed that they possessed the hafnium carbide structure. Almost invariably these formed well above the point of maximum temperature in the graphite tube. The habit depended strongly on the gas composition. In a series of runs (e.g., run A) using HfC14 and toluene in H 2, hafnium carbide coatings, Fig. 2, were reproducibly obtained at the position where the tube wall was 1400°C, and bulbous dendrites, Fig. 3, were

Jan 1, 1969

By H. T. Kennedy, J. E. Little

An empirical equation for the prediction of the viscosity of several pure paraffin hydrocarbons and nitrogen is presented. It involves temperature, pressure and six constants of the material, and it applies reliably to both liquids and gases. The equation is similar in form to van der Waal's equation of state. For the paraffin hydrocarbons methane through r-hexane and nitrogen, an average absolute deviation of 1.9 percent was obtained on 1,006 data points described in the literature by 14 authors. When this equation is extended to complex, liquid hydrocarbon mixtures, a correlation was obtained with an average absolute deviation of 9.9 percent. INTRODUCTION Equations describing the flow of gas and liquid through porous media contain the viscosity coefficient of the fluid. If other pertinent variables remain constant, the volume rate of flow is inversely proportional to this coefficient. In dealing with condensate fluids and volatile oils, however, the compositional effects resulting from changing pressure materially affect the viscosity. The effect of compositional changes also may be significant in certain secondary recovery or pressure maintenance processes, notably miscible displacement or gas injection. Early attempts to describe the performance of reservoirs utilized a volumetric material balance method wherein gas and liquid in the reservoir were identified as produced gas and liquid at the surface. This method of analysis proved adequate for reservoirs at moderate temperature and pressure that contained gas with moderately low amounts of condensable materials. The volumetric material balance procedures for "black oil" reservoirs leave much to be desired when applied to condensate and volatile oil reservoirs because phase behavior and compositional changes are relatively more important in these cases. The alternative is a compositional material balance, which in turn, requires a correlation of properties of the reservoir fluid with composition. This paper supplies this correlation in regard to viscosity, for reservoir crude oils. REVIEW OF LITERATURE The literature contains many empirical equations describing the effects of composition, temperature and pressure on the viscosities of pure liquids and binary liquid mixtures. However, the applicability of a majority of these equations is limited to very low pressures and to a small number of systems. Most of them, when applied to complex hydrocarbon systems, are of little value. The lack of utility of the majority of equations results from the fact that they were developed to show the separate effect of temperature, pressure or composition on viscosity, but not to predict the viscosity as a function of all three variables. And with the few exceptions noted below, they were developed to apply to much simpler systems than hydrocarbon mixtures. Eakin1 developed an equation for the viscosity of pure light hydrocarbons applicable in the gas, liquid and dense fluid regions, and in its most general form is written as µ - µo =A(ebP - e-cpk) The pure component viscosity at atmospheric pressure and temperature T, µo, was calculated using the Sutherland equation: µo = BT3/2/T + S The constants in Eakin's equation permitted the term e-CPk to become quite small at high densities (above 0.215 gm/cc), and the general equation would simplify to

Jan 1, 1969

By Rex B. McLellan, W. A. Oates

FROM a consideration of the application of the Gibbs-Duhem equation to multicomponent systems arken' derived the following equation applying to dilute solutions of a solute, 2, dissolved in a binary solution, 1-3:

Jan 1, 1969

This paper reviews the manpower requirements of the Australian mining industry. It has been necessary to provide general background information in order to support the view that university education in mining and mineral process engineering should be strengthened rapidly in Australia to provide graduates for the industry.

Jan 1, 1969

By M. Bevis, E. O. Fearon, P. C. Rowlands

Fe-Ni and Fe-Ni-C martensite specimens have been deformed in compression at room temperature and the habit planes of operative deformation twins determined by two-surface optical trace analysis. The full orientations of the martensite crystals were determined from divergent X-ray beam diffraction patterns. The experimental results are in excelled agreement with predicted twinning modes. In particular, the habit planes of some deformation twins in bcc martensites are consistent with a "Type XI compound'' twinning mode with Kl, Kz, 71, 77~ elements given by {5, 8, 11) {ioi}, (33) (ill) Tetragonal derivatives of this mode are operative in bct martensites. UnUSUAL deformation twinning modes have been reported by Richman' to occur in Fe-Ni-C martensites with bcc and bct structures. The twin habit planes were determined by single-surface trace analysis (pole locus method) and the remaining twinning elements were determined from the geometry of twin-twin intersections. The indices assigned to the observed habit planes are (3 101, "(089)" and "{0, 1,13)" or "{1,2,7} ", and only in the first case do the twinning elements correspond to a predicted twinning mode. This is mode 1.4 in the paper by Bevis et al. The results presented in Ref. 2 indicate that previously unpublished bcc and bct modes should be operative in preference to the (130) mode and anomalous modes reported by Richman. In view of these results and the uncertainties involved in determining habit planes from single-surface trace analysis and twinning elements from twin-twin intersections5 a two-surface trace analysis of deformation twins in Fe-Ni and Fe-Ni-C martensites has been carried out. EXPERIMENTAL PROCEDURES Two alloys with compositions Fe-23 pct Ni-0.6 pct C and Fe-30.4 pct Ni were prepared from 4N pure materials by induction melting under a vacuum of 10"5 mm Hg. The alloys were homogenized at 1350'~ for 5 days. Both of these alloys are austenitic at room temperature with M, temperature - — 50"C. The aus-tenite grain size of the Fe-Ni-C alloy was approximately 300 to 400 p. The Fe-Ni alloy was remelted in a vertical tube furnace and the melt lowered slowly from the hot zone of the furnace to produce s ingle -crystal austenite specimens. Specimens approximately 10 by 5 by 5 mm were cut from the ingots and quenched to various temperatures below the Ms temperature. The specimens were elec-tropolished in a 10 pct perchloric acetic electrolyte before being deformed in compression at room temperature. Martensite plates which exhibited profuse deformation twinning were selected for analysis and the specimen polished on a second surface such that the two surfaces which contained the martensite plate enclosed an obtuse angle of approximately 145 deg. The specimens were then electropolished to reveal the traces of the deformation twins on both surfaces. The full orientations of the martensite crystals were determined using a divergent X-ray beam technique (Kossel line technique) employing an AEI SEM2 electron probe microanalyzer. Details of this technique which include a detailed description of the Kossel camera attachment to the microanalyzer used in the present experiments have been discussed elsewhere.3 Only additional details relevant to this investigation are discussed here. The specimens were mounted with one surface normal to the incident electron beam as illustrated schematically in Fig. 1. The martensite plates to be analyzed were located using the normal scanning equipment of the microanalyzer. The position of the electron beam and hence the position of the source of divergent X-rays generated within the crystal could be located to within 1 p. Exposure times of approximately 8 to 10 min were required for back-reflection Kossel patterns and it was found that useful diffraction patterns could be obtained consistently from heavily deformed martensite plates. A reference line (carbon contamination mark) produced on the two surfaces of the specimen by scanning the electron beam in a direction having a known relationship with the reference !ine in the X-ray camera enabled the full orientation of the crystals to be determined. Martensite plates with widths as small as 8 p could be oriented using this procedure. The Kossel line patterns were interpreted using the charts developed by Rowlands and ~evis~ as generally

Jan 1, 1969

By Ashok K. Kakar

THE occurrence of superplasticity in Al-Zn alloys is of interest because of its possible industrial exploitation.' The eutectoid composition (78Zn-22A1) has been the most extensively studied;'-= neck resistant flow and high strain rate sensitivity of flow stress (characteristic of superplasticity) are associated with a micron-size grain conferred on the alloy by an homo-genization and quench.5'6 Compositions away from the eutectoid have received comparatively little attention, especially from the viewpoint of relating the structural

Jan 1, 1969

By J. D. Verhoeven

In the past 15 years a considerable amount of experimental and theoretical work has been done concerning the onset of convection in liquids as a result of interm1 density gradients. This work, which has been doue in many different fields, is reviewed here and extended slightly to give a rrlore quantitative understanding to the probletrz of conzection in liquid metal dlffusion experinletzts. In liquid metal systems the capillary reservoir technique is currently used, almost exclusively, to measure diffusion coefficients. In this technique it is necessary that the liquid be stagnant in order to avoid mixing by means of convection currents. Convective mixing may result from: 1) convection produced as a result of the initial immersion of the capillary; 2) convection produced in the region of the capillary mouth as the result of the stirring frequency used to avoid solute buildup in the reservoir near the capillary mouth; 3) convection produced during solidification as a result of the volume change; and 4) convection produced as a result of local density differences within the liquid in the capillary. The first three types of convection have been discussed elsewhere1-a and are only mentioned for completeness here. This work is concerned only with the fourth type of convection. Local density differences will arise within the liquid as a result of either a temperature gradient or a concentration gradient. It is usually, but not always, recognized by those employing the capillary reservoir technique that the top of the capillary should be kept slightly hotter than the bottom and that the light element should be made to migrate downward in order to avoid convection. In the past 15 years a considerable amount of work, both theoretical and experimental, has been done in a number of different fields which bear on this problem. This work is reviewed here and extended slightly in an effort to give a more quantitative understanding of the convective motion produced in vertical capillaries by local density differences. The Stokes-Navier equations for an incompressible fluid of constant viscosity in a gravitational field may be written as: %L + (v?)v = - ?£ + Wv - g£ [1] where F is the velocity, t the time, P the pressure, p the density, v the kinematic viscosity, g the gravitational acceleration, and k a unit vector in the vertical direction. A successful diffusion experiment requires the liquid to be motionless, and under this condition Eq. [I] becomes: where a is the thermal expansion coefficient [a =-(l/po)(dp/d)], a' is a solute expansion coefficient [a' = -(l/po)(dp/d)], and the solute is taken as that component which makes a' a positive number. Combining with Eq. [3] the following restriction is obtained: Since there is no fixed relation between VT and VC in a binary diffusion experiment, Eq. [5] shows that the condition of fluid motionlessness requires both the temperature gradient and the concentration gradient to be vertically directed. Given this condition of a density gradient in the vertical direction only, it is obvious that, as this vertical density gradient increases from negative to positive values, the motionless liquid will eventually become unstable and convective movement will begin. The classical treatment of this type of instability problem was given by aleih' in 1916 for the case of a thin fluid film of infinite horizontal extent; and a very comprehensive text has recently been written on the subject by handrasekhar.' It is found that convective motion does not begin until a dimensionless number involving the density gradient exceeds a certain critical value. This dimensionless number is generally referred to as the Rayleigh number, R, and it is equal to the product of the Prandtl and Grashof numbers. For the sake of clarity a distinction will be made between two types of free convection produced by internal density gradients. In the first case a density gradient is present in the vertical direction only, and, since the convection begins only after a critical gradient is attained, this case will be called threshold convection. In the second case a horizontal density gradient is present and in this case a finite convection velocity is produced by a finite density gradient so that it will be termed thresholdless convection. Some experimentalists have performed diffusion experiments using capillaries which were placed in a horizontal or inclined position in order to avoid convection. These positions do put the small capillary dimension in the vertical direction and, consequently, they would be less prone to threshold convection than the vertical position. However, if the diffusion process produced a density variation, as it usually does, it would not be theoretically possible to avoid thresh-

Jan 1, 1969

By M. Takeda, H. Majima

Pyrite has been subjected to xanthate adsorption experiments in order to determine the nature of adsorption. The identification of adsorbed species by means of IR spectroscopy, as well as UV, shows that the dixanthogen adsorption is undoubtedly predominant on pyrite surface. The rest potential measured in a xanthate solution coincides with the redox potential of the xanthate-dixanthogen couple. Considering all the factors together, the adsorption mechanism of dixanthogen on pyrite has been proposed as This mechanism is consistent with the "passive" character of pyrite. From the measurement of the redox potential of the xanthate-dixanthogen couple in the homologous series, a rule similar to that for surface tensions proposed by Traube is also applicable. The polarization experiments were conducted on pyrite in a solution containing xanthate. In the anodic polarization, xanthate is observed to oxidize to dix- anthogen, which depresses oxygen evolution on py rite at higher potential levels. In spite of the importance of the presence of pyrite in the flotation of sulfide minerals, not many studies have been made on the xanthate-pyrite system in the absence of an activator or a depressant. In an early study by Gaudin and Wilkinson,' it was pointed out that no ferric xanthate was formed on a pyrite surface, while in another study Gaudin and his collaborators2 proved the formation of a very small amount of ferric xanthate. Afterwards, Gaudin et al.3 studied the pyrite-xanthate system with a radiometric technique and found indications of the presence of adsorbed dixanthogen on pyrite surfaces. Mamiya4 studied the flotation behavior of the pyrite-xanthate system and also suggested the possibility of dixanthogen. Recently, Fuerstenau and his coworkers at The Colorado School of Mines5 studied the role of dixanthogen in the xanthate flotation of pyrite and discussed the problem in terms of such properties as oxidation potential, zeta potential, flotation recovery, pH of solution, etc. However, the mechanism of dixanthogen adsorption at the pyrite-water interface is not yet understood. This paper is concerned with an electrochemical in-vestigation through which the mechanism of dixanthogen adsorption on pyrite is interpreted. EXPERIMENTAL MATERIALS AND TECHNIQUES Pure potassium xanthates were synthesized by an

Jan 1, 1969

By J. D. Wright

This paper describes current milling practice at Endako Mines Ltd., a molybdenum producer in central British Columbia. The various steps in the crushing, grinding and flotation of the ore are outlined, with emphasis on the metallurgy of the latter operation. Tailings disposal and concentrate assaying methods are also described.

Jan 1, 1969

This list is part of the long-range conservation program of the Bureau of Mines and is intended for use by those interested in the Bureau's publications dealing with oil shale and shale oil. The items included represent 51 years of research by Bureau of Mines employees on oil shale and shale oil and are available at any U.S. depository library. DISTRIBUTION U.S. Bureau of Mines report series contain both free and sales publications. An asterisk (*) designates publications for sale. Such publications can be obtained from Superintendent of Documents U.S. Government Printing Office Washington, D.C. 20402

Jan 1, 1969

By H. D. Jacobs

The Bureau of Mines developed a concentration method to upgrade and utilize marginal natural or direct-shipping iron ores and fine-grained lean iron ores. Presently these ores receive little beneficiation and accordingly have low iron-silica (Fe-Si02) ratios. Ore samples were roasted with equal weights of solid reductant at 1,100° C for 1 hour to metallize the iron and for an additional hour at 1,200° C to promote grain growth. Concentration was effected by crushing and screening techniques and/or wet magnetic separation. Sized concentrates (minus 4 plus 35 mesh) derived from crushing-screening processes contained from 80 to 85 percent iron that was 90 percent metallized. Iron-silica ratios as high as 12:1 and iron recoveries from 75 to 94 percent were obtained. The sized concentrates were judged suitable for use as blast furnace feed. Minus 200-mesh metallized concentrates derived from roasted minus I-inch plus 8-mesh ore fractions and magnetically concentrated contained 90 percent Fe and 4 percent or less Si02, chemically qualifying them as feed for electric furnaces. Roasting minus 8-mesh ore with hydrogen, then magnetically concentrating it, produced iron concentrates containing 57 percent to 67 percent Fe and 3.6 percent to 8.4 percent Si02. The concentrates having Fe-Si02 ratios ranging from 8:1 to 12:1 were considered adequate for use as blast furnace feed. Overall iron recoveries for the 12 ores tested ranged from 56 percent to 94 percent with an average iron recovery of 86 percent.

Jan 1, 1969

By M. J. Duggin

Structural similarities between the E, X, and iron carbides are illustrated. Experimental evidence regarding phase transformations occurring during ternpering reactions in finely divided carbides, thin-film carbides, and carbides which occur in steels is considered and possible mechanisms for the E — x and x — 9 transformations proposed. HOFER1 has shown that within the appropriate temperature ranges carbon monoxide will react with finely divided a iron to form either iron carbide or x iron carbide. He has shown that at an elevated temperature the E iron carbide will transform to the x iron carbide (Hagg carbide) which, upon further elevation of temperature, will transform to 9 iron carbide (cementite). Jack,2,3 using X-ray diffraction methods, has observed that during the tempering reactions occurring in steel the E iron carbide formed in the first stage of tempering passes into two-dimensional platelets of 0 iron carbide during the second stage of tempering. The three-dimensional form of the 0 carbide is formed during the third stage of tempering. Jack suggested2 that the two-dimensional platelets of 0 carbide could be related to the faulted x iron carbide. Okada and Arata4 investigated a Swedish steel containing 1.05 wt pct C and approximately 1.0 wt pct Mn using permeability measurements at low field strength. A Curie point of 360°C was observed in the quenched steel, which indicated the presence of E iron carbide. On tempering at 400°C the specimen developed a Curie point at 230°C, indicating the presence of x iron carbide, and on tempering at 700°C the specimen developed a Curie point at 190°C which was assigned to 0 iron carbide. The carbides were extracted electro-lytically and the use of X-ray diffraction techniques4r5 indicated the carbide with a Curie point of 230°C to be x iron carbide. The Curie points of the carbides are 10 to 22°C lower than the accepted values which is probably due to the presence of manganese in the carbides, since it has often been observed (e.g., Ref, 6) that a partial substitution of manganese for iron in cementite will lower the Curie point of this carbide. Hofer' summarizes additional evidence of the tempering reactions in steel in which E iron carbide, formed during the first stage of tempering, transforms to x iron carbide during the second stage of tempering. During the third stage of tempering, the x carbide disappears as the 0 carbide is formed. By carburizing thin iron films in a CO gas stream, ~a~akura' has been able to produce the E, X, and 0 iron carbides. He found that below 250°C the E iron carbide was formed; between 250" and 350°C the x iron carbide was formed and above 350°C the 0 iron carbide was formed. He has shown that the E iron carbide transforms to form x iron carbide at 380" to 400°C and that the x ir°n carbide transforms to form the 0 iron carbide at approximately 550" C; both of these phase transformations are irreversible. Hofer' presents a review of evidence to show that the sequence of reactions occurring during tempering processes subsequent to the formation of E iron carbide formed by the direct carburization of finely divided a iron is the same as the sequence of reactions which occur during the tempering processes subsequent to the formation of E iron carbide in steel during the first stage of tempering. It is evident from Nagakura's work that identical tempering reactions are found in thin films of iron which have been carburized to form iron carbide. The purpose of this paper is to discuss the structural similarities between the E, X, and 0 carbides and to suggest a possible mechanism by which regions of the E carbide, formed during the first stage of tempering, may transform to the x carbide during the second stage of tempering. For the finely divided or thin film carbides a mechanism will be proposed for the transformation of the x carbide to the 0 carbide during the third stage of tempering, although it will be suggested that there is evidence that such a transformation may not occur in steels. STRUCTURAL DATA OF THE E, X, AND 0 IRON CARBIDES € Iron Carbide. It is evident from X-ray diffractions and electron diffraction', investigations that the metal atoms in the E iron carbide form an hcp structure with lattice constants ah = 2.752A, ch = 4.3534, using electron diffraction, reports the lattice paramet$rs of the superlattice cell to be a = 4.767A, c = 4.354, c/a = 0.9134. He finds that the carbon atoms occupy the octahedral voids in the metal atom structure so as to form a hexagonal stacking sequence with its basal plane parallel to that of the metal atoms. Considerable long-range disorder occurs in the positioning of the carbon atoms, however, which is in agreement with the possible range of composition Fe2C-Fe3C discussed by Hofer.' Barton and ale" have made X-ray diffraction measurements on a sample of E iron carbide extracted from a catalyst in an organic process. Although there were few reflections recorded on the obtained X-ray powder diffraction pattern, they have proposed that the structure could belong to one of the three possible space groups p3m1, P63/mmc, or Pbcn if one assumed the composition to be Fe2C. Nagakura, using electron diffraction data, suggests a space group of P 6322 for a specimen of c iron carbide of apparent composition Fez.&. x Iron Carbide. The x iron carbide has been studied by Duggin and Hofer" and by Jack and wild,' who

Jan 1, 1969