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By D. B. Kibler

The Florida hard-rock field extends from Suwanee and Columbia Counties in northwest Florida to south of Croom, Florida, in Hernando County. This area is approximately 100 miles long and varies from 2 to 30 miles in width. Florida hard-rock phosphate was discovered at Hale Springs, about one mile northwest of the town of Dunnellon, Marion County, in the year 1888, by Alber-tus Voight, who lived within a few hundred yards of the spring. Soon after this discovery there was a great influx of land speculators and wildcat operators into the vicinity of Dunnellon. A few years later phosphate was found in Alachua, Levy, Citrus and Hernando Counties, and a great number of small crude plants were built from Newberry, Alachua County, all the way to Croom, Hernando County. Phosphate was found in many places as "outcrops." Looking for outcrops was the first method used by the early prospectors in searching for deposits. Several years passed before any systematic method of prospecting was used. Early Mining The early method of mining hard-rock phosphate was with picks and shovels, wheelbarrows, mules and wagons. The pick-and-shovel method was used altogether until about 1900, when some of the larger operators began to use railroad-type steam shovels of from ½ to I-yd. capacity Picks and shovels, with negro labor loading the phosphate ore (called "matrix") into wooden side-dump skip-cars, was continued until about 1907. From the discovery of hard-rock phosphate until approximately 1905, overburden was removed with mules and scrapers. At some places, the overburden was loaded into side-dump skip-cars by negro laborers and the cars were then pulled up an incline with a steam hoisting engine. The maximum depth of overburden that could be economically removed by hand labor, mules and scrapers was approximately 15 feet. About 1905 one of the companies erected a producer-gas power- I house near Dunnellon and generated its own electricity and about the same time the larger companies began using hydraulic methods for the removal of overburden. From the year 1888 through the year 1939 approximately 75 companies were operating at one time or another in the hard-rock territory, on approximately 500 locations. The hard-rock deposits are more irregular and have higher mining costs than the pebble-rock deposits, therefore 1 they have not been competitive in the domestic market, but because of the higher grade of the hard rock it is in demand for I the export trade. Discovery of phosphate outside of the United States has made it increasingly difficult in recent years for the hard-rock companies to survive, so today i only three companies are operating. These

Jan 1, 1942

By Bryan J. Travis, Thomas L. Cook

INTRODUCTION Our growing concern for adequate and secure sources of energy and minerals has stimulated vigorous exploration for new sources, research toward a better understanding of geological processes, and development of new extraction technologies. The need for control, or at least prediction, of subsurface fluid flow is important for many of these technologies for example: primary, secondary and tertiary recovery of oil; ground water and waste management; in-situ fossil energy extraction (oil shale, coal, tar sands); and solution mining of uranium, copper and other minerals. These technologies, especially the last two, are characterized by highly complex systems. A partial list of the physical processes occurring would include flow in porous/fractured media, multi-phase and multi-component flow with heat transport, chemically active fluids and soils, tracers, diffusion and dispersion, fracturing and dissolution. A great deal of understanding of how these processes behave and interact can be obtained from models. MODELS Theoretical models are valuable because they: 1) provide a frame of reference for interpreting results of laboratory and field experiments; 2) once validated by experiments, allow a variety of geometries, injection/production strategies, etc., to be examined (at relatively low cost) for efficiency and stability; 3) can provide guidance to the design of experiments and field operations. Most models are based on the fundamental principles of mass, momentum and energy balance. But from this starting point, many paths can be taken. For example, there is the theory of Payatakes (1973) which concentrates on the microscale dynamics. In this approach, the rock or soil matrix is represented by a complex of characteristic channels (such as periodically constricted smooth tubes). Detail of flow within the characteristic channel is calculated very accurately. A difficulty with this model is that description of a representative channel can require several parameters which may not be easily measured. Also, it is not clear how the channels can be combined practically to model a large scale flow. Another type of model is the "global" one described by Bear (1972). Here, the continuum equations for conservation of mass, momentum and energy are averaged over a distribution of pore channels, resulting in a set of conservation equations in which the small scale structure of the medium is replaced by quantities such as porosity, permeability, dispersion coefficients and tortuosity. This approach allows computation of large scale flows. However, additional constitutive equations are needed which relate averaged quantities such as permeability to observables such as local saturation, particle size distributions, and others. An important difference between models is the way they handle the momentum equation. Payatakes' model solves the full equation. In others, it is replaced by a simpler relation such as Darcy's law (valid for slow flow rates) or by Forchheimer's equation which extends Darcy's law to higher flow rates. These simple relations can nevertheless match a great deal of experimental data (Dullien 1975). The permeability term which appears in Darcy's law and in Forchheimer's expression has been related to other quantities such as porosity and particle surface area. The Kozeny-Carmen equation is a well-known example, valid for some ranges of porosity and particle sizes and for some materials. Several other semi-theoretical, semi-empirical formulations have been devised, none of which are entirely satisfactory. One goal of researchers has been the ability to predict permeability of a porous material from basic measurable quantities such as grain size distributions without recourse to adjustable parameters. This effort has proceeded from consideration of distributions of idealized, non-intersecting channels, to intersecting channels, to consideration of both distributed pore radii and pore neck radii. This last approach has been used successfully to predict permeabilities (ranging over several orders of magnitude) in sandstones (Dullien 1975). Additionally, studies on explicit networks of channels (e.g., Fatt 1956) and percolation theory (e.g., Larson et. al. 1981) have been used to examine interconnectivity effects in porous media with the hope of eventually being able to predict permeability accurately. To be of more than theoretical interest, a model must be compared s controlled laboratory conditions where boundary and initial conditions and relevant material properties can be accurately determined. Also, extraneous forces can be eliminated so that the interactions between processes of interest can be clearly seen and flow models can be vigorously tested. In contrast to the well-defined environment and

Jan 1, 1982

By H. D. Outmans

Present first-order theory for frontal stability and viscous fingering of immiscible liquids is improved by including the nonlinear terms in the equations describing conditions at the interface of the liquids. This leads to the revision of several conclusions which were based on first-order theory. They concern the growth rate and changing shape of a sinusoidal disturbance, particularly in relation to the wave number of this disturbance. Nonlinear aspects of effective interfacial tension are discussed and it is shown that this tension is not simply a positive proportionality constant in a linear relation between pressure difference and curvature at the interface. Scaling requirements are determined from the dimensionless groups which govern fingering. Gravity and interfacial tension invalidate a previously formulated conclusion that the shape of a finger after a given displacement is independent of the displacement velocity. Also, similarity of fingering (and, hence, of sweep efficiency in case of an unstable front) requires geometrical similarity of the initial disturbance in the model and the reservoir with a scale factor which is the same as the one for scaling down the dimensions of the reservoir. INTRODUCTION The critical velocity at which the transition zone in the vertical displacement of immiscible liquids becomes unstable was calculated by ill. More recently, the same was done for nonvertical displacements and it was also shown that the stability is affected by an effective interfacial tension between the liquids. 2-4 Although in the oil reservoir a stable front is always desirable from a recovery point of view, the necessary velocity may have to be so low that the corresponding production rate is not economical. In that case, a knowledge of the fingering unstable front is necessary for predicting recovery at break- through. Studies in this direction have not gone beyond the very moment at which fingering first occurs.5,6 Conclusions about stability and fingering in these references are all based on linear theory. In this theory the nonlinear terms in the equations describing conditions at the front are neglected. The usual justification for this lack of mathematical rigor is that the nonlinear terms can be made small relative to the linear terms and, supposedly, small causes produce only small effects. It has been recognized, however, that this is not necessarily true in the nonlinear problems of hydrodynamics.7 The hydro-dynamic stability and fingering of the front between two liquids, accelerated in a direction normal to the front, for instance, is strongly influenced by the nonlinearity of the boundary conditions.8-10 Since these boundary conditions are not unlike those arising in the problem of stability and fingering of the front during a slow immiscible displacement in porous media, it was thought that there, too, the nonlinear terms should be taken into consideration. A summary of the results obtained in linear theory and a comparison with experimental data precede the nonlinear theory developed in this paper. This summary serves to introduce some quantities which will be used in the further develop ment. It should also be pointed out that the method of higher-order approximation by which the nonlinear stability problem is solved has application in other reservoir studies.11 SUMMARY OF LINEAR THEORY 1. A plane interface remains stable if its velocity is smaller than a critical velocity. vc = (p2-p1)gn/(l/A2- l/A1 .........(1.1) This equation is derived for uniform flow in a thin layer inclined to the horizontal plane. The displacement takes place in a direction normal to the intersection of this layer and the horizontal plane. The undisturbed (line) interface is normal to the velocity. Fluid 1, the upper fluid (gas), is displacing Fluid 2 (oil). (VcQS would be the injection rate in cc/

By W. J. Schuster

Safety in coal mines depends largely upon adequate training of the foreman. Although management must provide modern and safe equipment and at all times keep mines in first class condition from a safety viewpoint, final results will be determined by the quality of supervision. HANNA COAL CO., Division of Pittsburgh Consolidation Coal Co., operates three large underground mines in eastern Ohio. The section of Pittsburgh No. 8 coal seam in which these mines are located varies in thickness from 52 to 64 in. It is immediately overlain by a stratum of shaly material 12 to 15 in. thick locally known as draw slate, which is structurally very weak and which disintegrates rapidly upon exposure to atmosphere. Immediately above the draw slate as it is normally found is a band of extremely high ash material 6 to 12 in. thick known as roof coal or rooster coal, and above this is a stratum of conglomerate material varying from 4 to 10 ft in depth. Overlying the conglomerate is a relatively thick stratum of limestone, the first stable material above the Pittsburgh coal seam in eastern Ohio. With the method of full-seam mining that has been adopted, draw slate is shot down, loaded with the coal, and removed in the preparation plants. The roof coal then becomes the permanent roof. The major problem in mining the No. 8 seam in eastern Ohio is control of the roof. Since the strata above the draw slate contains no material with a structure firm enough to provide self-support, the roof begins to sag in a relatively short time after the coal and draw slate have been removed. The problem thus becomes one of getting temporary safety posts under this roof as quickly as possible to prevent a break or separation from occurring either in the roof coal or in the conglomerate above it. Haulage System The Pittsburgh No. 8 seam in eastern Ohio is relatively level, with only minor local dips. Throughout the Hanna Coal Co. mines, entries are generally 12 ft wide. Rooms are driven on a 60" angle on 30-ft centers and are 22 ft wide. No attempt is made to extract the 8-ft pillars between. The entire length of main line haulage is gunited in one mine, and a major portion in another. Two of the mines have single-track main haulage roads with passways. The third, a new mine, is double-tracked, and the roof is supported by steel crossbars, 60 lb or heavier, spaced on 4-ft centers and lagged. In recent years timbering on main line and secondary haulage roads has been accomplished by one of two methods: 1—crossbars are supported on a small section of post set in a hitch hole in the rib, or 2—or a hole is drilled in the rib about 12 in. below the roof, of sufficient depth to fasten securely a short length of 40-lb rail, the bottom of the rail facing the roof, on which a short post is set directly under the crossbar. At present the hitch-hole timbering method is favored. At two of the mines the main line haulage locomotives are 26-ton, 8-wheel units. These locomotives are of the axleless type, each wheel being individually mounted on the frame. The motorman's compartment is encircled by 3-in. armor plate for the protection of the occupants. At the third underground mine conventional 15-ton locomotives are being used. However, these locomotives have been completely rebuilt in the company's shops. Equipment has been streamlined and quarters have been provided for two people, who are protected by heavy steel plate in much the same way described above. This modernization program has been completed on all secondary haulage locomotives at the three mines, and the company is well on the way to similar equipment of the 6-ton section locomotives. The following additional features have been included in their modernization: 1—additional support for the motors to prevent their falling to the middle of the track and derailing the locomotives should a break occur in the suspension bar support; 2—installation of additional bracing to prevent brake rigging from becoming displaced and causing derailments; 3—enclosure of all electric wiring in conduit or raceway; 4—provision of an enclosed compartment for the storage of re-railers, jacks, and other equipment, so that they need not be carried on the outside of the motor; and 5—redesign of the end of the locomotive opposite the operator's compartment to prevent anyone's mounting from that direction. It is interesting to note that some

Jan 1, 1955

By T. J. Neil, C. B. Manula, O&apos

This paper describes a simulation model developed to analyze truck haulage problems as they are found in the open pit mining and construction industries. The model, using a computer, cycles trucks between their assigned loading and discharge points over a measured haulage route. Required parameters for model operation include the number and type of operating trucks and loading units, maximum truck acceleration and velocity, a realistic vehicular deceleration rate, and the ratio of ore to total material loaded at each origin. Equipment performance characteristics, system profile characteristics, and service time distributions are also included. Records are kept of all waiting times at the loading and discharge points and of any truck interference on the haulroads (moving queues), and a current journal of ore and waste production is maintained. In the pursuit of reduced truck haulage costs, management is confronted with three particular problems in truck and shovel mines. 1) What is the best assignment of trucks to shovels in the system? 2) If new equipment is needed, which new shovels and trucks will operate most effectively in the system? 3) Are any physical changes in the haulage layout warranted to increase productivity? For small open-pit mines the answers to these questions may be obvious. However, for larger operations complex problems are encountered with production and system configuration relationships usually being unknown. The mining simulator discussed here was developed to aid management in evaluating alternative pit-haulage schemes to reduce the risk involved in the selection and assignment of equipment in open-pit truck and shovel mining systems. There are two fundamental differences between this model and other truck haulage simulators: one is a difference of degree, the other a difference of kind. This model can simulate more complex systems than previous models by allowing transportation of material from multiple mine faces to multiple mine destinations and by being readily adaptable to a wide variety of mine layouts. The second difference that characterizes the model is the standard simulation of truck movements. This technique enables each vehicle to perform according to its mechanical capabilities and the physical profile of the haul road. Among the similarities between other truck haulage simulators and this model are the recognition of the probabilistic nature of certain service times in the system and the use of a digital computer to operate the model. The computer inherits the staggering computational and bookkeeping work loads and provides a means for compressing the time scale by allowing several days' operations to be simulated in a matter of minutes. DISTRIBUTION SYSTEM Basic aspects of the system analyzed here may be brought into focus by referring to Fig. 1, a schematic of the typical open pit truck-shovel operation programmed into the simulation model. A single stage materials handling scheme is employed to transport both ore and waste. Loaded trucks are directed to a crusher or stockpile if ore is being mined, while overburden is conveyed to a waste dump. Each shovel has a given number of assigned trucks and has two associated haulage routes, one for waste and one for ore. Up to 5 shovels and as many as 10 trucks per shovel (or a total of 50 trucks) can be operated in the model. Essentially the model, using a computer, cycles trucks between their assigned shovels and the proper discharge points over measured haulage routes. Required input parameters for model operation include the number of shifts to be simulated, operating time per shift, number and type of operating trucks and shovels, maximum truck acceleration and velocity, a realistic vehicular deceleration rate, and the ratio of ore to total material loaded at each shovel. Equipment performance characteristics, system profile characteristics, and service time distributions are

Jan 1, 1968

By H. L. Overton, J. B. Lipson

The concept of sodium single-ion equivalent activity as developed by Gondouin, Tixier and Simard,' was used to determine the filtrate resistivity-activity relationships for 150 laboratory and 49 field drilling muds. With the exception of the native and phosphate high-resistivity muds and the calcium-treated muds, the filtrate resistivity-activity relationships were found to be within 20 per cent of that for pure sodium-chloride solutions. Gondouin, et al,* previously suggested a method of treating the high-resistivity muds in quantitative electrical log analysis. A new treatment is presented which uses the P-alkalinity of the filtrate as a correlating parameter in handling the calcium-treated muds in quantitative electrical log analysis. INTRODUCTION Gondouin, Tixier, and Simard in 1957 introduced new interpretive procedures for analyzing the self-potential curve of electric logging. They re-emphasized the previous work of the Schlumberger brothers, Wyllie and others, and re-defined the activity concept in terms of a number which they termed the effective resistivity. Their procedures are particuarly effective when the connate-water resistivities are less than 0.08 ohm-m or greater than 0.3 ohm-m. For gyp muds where the calcium content is known, a procedure was presented which allows calculation of the connate-water resistivity with improved accuracy. These procedures assume that one of the fluids in the system is a pure sodium-chloride solution, but they are not limited by the assumptions. For the fresh and saline connate waters, for instance, it is assumed that the drilling mud filtrate is a pure sodium-chloride solution. For the gyp mud interpretive procedure, it is assumed that the connate water is a pure sodium-chloride solution. Brown,' on the other hand, has suggested that it would be extremely fortuitous if drilling mud filtrates could all be treated electrochemically as sodium-chloride solutions, and he cites some examples where discrepancies exist. A study has been made of the deviations of sodium single-ion equivalent activities, an of drilling mud filtrates from that of pure sodium-chloride solutions. Drilling fluids in common use on the Texas and Louisiana Gulf Coast and laboratory-controlled muds were investigated. Using a cell patterned after Gondouin, et al, (Fig. I), the equivalent activities were measured. It should be remembered here that the activity measured is merely an index which uses numbers that represent the sodium single-ion equivalent activity a,., of the mud filtrate. The membrane potential developed across the cell was determined with a null-type potentiometer. The resistivities of the solutions were measured by the four-electrode method. The resistivity system was calibrated by using saturated KC1 solution as a standard. Chemical properties of the drilling fluids studied were measured with standard API-approved equipment for the particular property in question. For the activity measurements, two shale discs were chosen to serve as cationic membranes. These two discs were both 1 1/4 in. in diameter and, respectively, 1/4 and 1/8 in. in thickness. The membrane potential, Em, was determined using the shale discs as cationic selective membranes separating two standard sodium-chloride solutions of known mean activity. Then by comparing the constant Km in the following equation, with the theoretical value of — 59 mv at 75OF, the perfection of the membrane was determined. The variation of Km for the two membranes used in this experimental work, as well as one of the many unsuitable membranes, is shown in Fig. 2. The measurement of the activity of mud filtrate involves the balancing of its combined individual activities against a standard solution of known mean activity. At the point where there exists zero potential across the membrane cell, the activity effects may be assumed equal for all practical purposes. The mechanics of making a null reading of this sort requires having a large number of different mean activity solutions. A more practical method involves

By Arthur B. Yates

Diamond drilling has advanced and expanded during the past few yean. Along with this increase there has been a marked trend to rely more and more upon drilling for the outlining of ore for reserve purposes. This is especially true underground, where men have not been available for opening up ore by crosscuts, drifts and raises. During the recent heavy call upon known ore reserves, more drilling has been done for exploration and it has become expedient to drill longer lateral holes from underground and deeper holes both from surface and from exploration headings in the mines. Furthermore, these deeper holes have to be drilled closely enough to warrant calculation of "probable" if not "proven" ore, from the results obtained therefrom. Interpretation of diamond-drill results has become more precise and reliable with the growing knowledge and understanding of the geologic structures that control the geometry of ore distribution, and this has broadened the field of usefulness of the drill. All of this has created a necessity and a demand for more accurate control of the hole as to direction, a more precise and reliable method of surveying for position, and a need for better and more complete core recovery, as well as larger cores, to provide an adequate sample. At depth the control becomes more difficult and, at the same time, more important. Control A close study of drilling in various parts of the world for a period of more than 20 years has brought to light one definite rule, practically invariable; namely, that diamond-drill holes tend to deviate into a position normal to any structure existing in the rocks, such as bedding, schistosity, gneissosity, or even parting or jointing— even if the hole is started at almost any angle other than parallel with the structure. It also appears that the better developed the structure is, the more quickly will the hole get into a position perpendicular to it. It has often been said that there is a tendency for holes to "drift" in the direction of rotation. This is obviously untrue, for in a vertical hole the measure of deviation would depend upon the azimuth chosen as zero, and there is an infinite number of choices. It has been proved. however, that in homogeneous rocks there is a tendency for the hole to corkscrew, and that the direction of the spiral is the same as the direction of rotation. This may account for the belief that holes drift in that direction. Some tests have been made using right-hand and left-hand rods, and these show that no matter what the direction of rotation the hole will swing into a position perpendicular to the structure. Methods of Control The foregoing empirical rule may be used as an indirect method of control. If the prevailing structure is known, it may be advantageous to start the hole as nearly normal to it as possible, for the

Jan 1, 1946

By E. W. Filer, L. S. Darker

ONE of the primary purposes of this investigation was to determine how far blast-furnace metal and slag depart from equilibrium, particularly with respect to sulphur distribution. In studying the equilibrium between blast-furnace metal and slag, there are two approaches that can be used. One method is to use synthetic slags, as was done by Hatch and Chipman;' the other is to equilibrate the metal and slag from the blast furnace by remelting in the laboratory. In the set of experiments here reported, metal and slag tapped simultaneously from the same blast furnace were used for all the runs. The experiments were divided into two groups: 1—a time series at each of three different temperatures to determine the t.ime required for metal and slag to equilibrate in various respects under the experimental conditions of remelting, and 2—an addition series to determine the effect of additions to the slag on the equilibrium between the metal and slag. An atmosphere of carbon monoxide was used to simulate blastfurnace conditions. The furnace used for this investigation was a vertically mounted tubular Globar type with two concentric porcelain tubes inside the heating element. The control couple was located between the two porcelain tubes. The carbon monoxide atmosphere was introduced through a mercury seal at the bottom of the inner tube. On top, a glass head (with ground joint) provided access for samples and a long outlet tube prevented air from sucking back into the furnace. The charge used was iron 6 g, slag 5 g for the time series, or iron 9 g, slag 7 % g for the addition series. This slag-to-metal ratio of 0.83 approximates the average for blast-furnace practice, which commonly ranges from about 0.6 to 1.1. A crucible of AUC graphite containing the above charge was suspended by a molybdenum wire in the head and, after flush, was lowered to the center of the furnace as shown in Fig. 1. The cylindrical crucible was 2 in. long x % in. OD. The furnace was held within &3"C of the desired temperature for all the runs. The temperature was checked after the end of each run by flushing the inner tube with air and placing a platinum-platinum-10 pct rhodium thermocouple in the position previously occupied by the crucible; the temperature of the majority of the runs was much closer than the deviation specified above. The couple was checked against a standard couple which had been calibrated at the gold and palladium points, and against a Bureau of Standards couple. The carbon monoxide atmosphere was prepared by passing COz over granular graphite at about 1200°C. It was purified by bubbling through a 30 pct aqueous solution of potassium hydroxide and passing through ascarite and phosphorus pentoxide. The train and connections were all glass except for a few butt joints where rubber tubing was used for flexibility. The rate of gas flow was 25 to 40 cc per min. As atmospheric pressure prevailed in the furnace, the pressure of carbon monoxide was only slightly higher than the partial pressure thereof in the bosh and hearth zones of a blast furnace—by virtue of the elevated total pressure therein. Simultaneous samples of blast-furnace metal and slag were taken for these remelting experiments. The composition of each is given in the first line of Table I. There is considerable uncertainty as to the significant temperature in a blast furnace at which to compare experimental results. This uncertainty arises not only from lack of temperature measurements in the furnace, but also from lack of knowledge of the zone where the slag-metal reactions occur. (Do they occur principally at the slag-metal interface in the crucible, or as the metal is descending through the slag, or even higher as slag and metal are splashing over the coke?) The known temperatures are those of the metal at cast, which averages about 2600°F, and of the cast or flush slag, which is usually about 100°F hotter. To bridge this uncertainty, remelting temperatures were chosen as 1400°, 1500" (2732°F), and 1600°C. For the time series the duration of remelt was 1, 2, 4, 8, 17, or 66 hr; crucible and contents were quenched in brine. The addition series were quenched by rapidly transferring the crucible and contents from the furnace to a close-fitting copper "mold." Of incidental interest here is the fact that the slag wet the crucible

Jan 1, 1953

By L. E. Snow, L. F. Pett

AT the Utah Copper Pit of Kennecott Copper Corp. a versatile mobile drill unit has been developed and tested. Through increased drilling speed and additional available drilling time, an improvement of 233 pct in drill performance has been realized. Operators using drill power can quickly and easily convert the unit from a vertical to a toe hole drill. Drilling is done with the machine in line with the unit or at right angles to it. Table I covers the 1950 drill record at the mine, showing the types of machines used and the footage obtained. [ ] Development of the new units was prompted by a desire for solution of the following problems: 1-The ever-expanding operations within the Utah Pit, requiring some 65 miles of transmission pipe lines radiating from a central compressed air plant, have now taxed this compressor plant beyond capacity. While 100 lb per sq in. pressure is maintained at compressors, transmission losses from innumerable small leaks result in low terminal pressure at the drills. Fig. 1 illustrates that while terminal pressure varies according to size of air hose and fittings used, the average drill is operating on air pressures within the 60 to 70-lb range. The compressor plant is operated primarily for air rock drills. All drilling is done on day shift, but it is necessary to run two of the three 3720 cu ft capacity compressors during night shift in order to prevent drastic loss of pressure through leaks. On day shift all three compressor units are operated at capacity, so that there is no reserve safeguard available for extensive repairs to any compressor. The calculated volume of compressed air required for operation of 25 drills is but 33 pet of three day-shift compressors. While compressed air is being used to a minor extent for purposes other than drilling, it is felt that satisfactory substitute facilities could be provided in the event that air lines were no longer available. 2-Drill performance has increased beyond the capacity of present 3 ½ -in. drifter machines. 3-The installation, maintenance, and moving of air lines in routine mining is a growing problem. The 2-in. level lines are placed outside electrification towers and must be moved to new location upon completion of each shovel cut. In addition to these moves it is often necessary to dismantle level lines so that excessive shovel spillage, or material covering track following a blast, can be pushed in the clear with bulldozers. Where level room is limited, it is often necessary to remove air lines in giving bulldozers room to prepare grades for wagon drills. In spite of precautions taken, many level lines become buried, twisted, and constricted, with excessive air loss resulting. Excessive back break in blasting often leaves several sections of air line suspended in mid-air. Occasionally air lines come in contact with defective electric transmission towers, so that holes are burned through pipe. 4-Rail-handling of drilling equipment such as wagon drills from one location to another requires considerable locomotive crane crew time. Any new unit developed should travel under its own power. 5-Present practice requires accessory material including hose, water pressure tanks, water barrels, drill steel, and bits to be transported by means of push cars when drill locations are changed on any level. 6-In order to supply numerous drill locations with material, many stock piles of new drill rods, drill bits, and other essentials must be left at strategic points, usually in the vicinity of powder magazines. This practice makes for poor housekeeping and contributes to the loss of supplies. Planning the Unit It was felt that a mobile drill unit which would rectify the foregoing problems should meet certain demands: 1-It must furnish compressed air to operate a 4-in. rock drill at a pressure of 90 to 100 lb.

Jan 1, 1952

By Walter R. Hibbard, George H. Eichelman, William P. Saunders

INTEREST in the various products of the austenite eutectoid transformation in iron-carbon alloys, particularly as produced by the isothermal sub-critical techniques introduced by Davenport and Bain,1 has resulted in the application of similar heat treatments to other eutectoid transformations. Studies2.3.4 of the beta copper-aluminum alloy eutectoid transformation revealed microstructures very similar to those found in iron-carbon alloys. Investigations5,6 of the kappa phase in the copper-silicon alloy system have established the eutectoid type transformation of this phase into terminal alpha and intermediate gamma phases. This transformation has been reported' as forming a eutectoid type structure in a very sluggish manner by a long time isothermal treatment. The purpose of the present investigation is to study the products of the kappa eutectoid transformation as affected by transformation temperatures by means of microscopic and hardness methods. PREPARATION OF ALLOYS The copper-silicon alloy equilibrium diagram is shown in Fig I. The kappa field converges to a minimum silicon solubility at the eutectoid composition and all other completely kappa alloys are hypereutectoid. Thus, kappa decomposition involves first the proeutectoid precipitation of gamma, followed by the eutectoid transformation of a lower silicon content kappa (5.2 pct). Smith5 has indicated that alloys containing between 5.4 and 5.7 pct silicon could be hot rolled, but that the latter composition was desirable in order to permit a wider kappa temperature range. The alloy was prepared by adding Baker's commercially pure silicon to an ingot of copper-silicon alloy containing 2.34 pct silicon remaining from the investigation of Brick, Martin and Angier.7 Following the casting techniques of Krynitsky, Saunders and Stern,8 the ingot was melted under a heavy layer of dried charcoal in a clay-graphite crucible in a gas-fired pot furnace. Small lumps of silicon were held under the melt surface with a graphite rod. After the silicon had dissolved, the alloy was chill-cast and then remelted without a cover, stirred thoroughly, skimmed and poured into a preheated cast iron mold. The cast microstructure is shown in Fig 2. The casting, 10 X 4 X ¾ in., was annealed at 750°C for 21 brand furnace cooled. About 1/16 in. was milled from all surfaces. The plate was cut in half longitudinally and the bottom half analyzed by A.S.T.M. methods.9 The composition by weight was as follows: copper 94.24 pct, silicon 5.56 pct, iron 0.11 pct.

Jan 1, 1948

By Lawrence H. Van Vlack, Otto K. Riegger, Gerald I. Madden

The microstructural variations of periclase (MgO) in the presence of oxide liquids are examined under the steelmaking variables of: 1) temperature, 2) liquid composition, and 3) FeO additions under different oxidation levels. Attention is given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. Silicate liquids penetrate more extensively between individual periclase grains than do liquids containing high percentages of Fe2O3 Higher MgO solubilities in the liquid and lower MgO contents of the solid favor more rapid grain growth. The presence of a second solid phase reduces the periclase grain growth rate and increases the amount of the solid-to-solid contact within the oxide microstructures at high temperatures. The service suitability of a refractory depends on many factors. Two are of major importance and include 1) the thermal resistance to melting, and 2) the mechanical resistance to loads at service temperatures. Neither is a simple consequence of the service temperatures because service conditions will alter compositions, produce partial melting, and induee phase changes. Consequently, the equilibrium phase relationships have been rather thoroughly studied and give a knowledge of the thermal resistance to melting, but do not give full information about the mechanical properties because two refractories with the same types and quantities of phase may have different microstructures. Although variations of microstructures with time, temperature, and composition have been subjects for extensive investigation in metals, only a limited amount of comparable microstructural work has been performed for refractory materials.' This study was an attempt to evaluate some of the consequences of service parameters upon the microstructures of refractories so that bases may be established for the analyzing of high temperature mechanical properties. Periclase (MgO) was chosen as the refractory oxide; variables included those which are encountered under steelmaking conditions such as 1) temperature, 2) liquid composition, and 3) FeO additions under various oxidation levels. Specific attention was given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. The most closely related work on microstructures of polyphase materials is that of Van Vlack and Rieg-ger2 on the microstructure of magnesiowüstite [(Mg,Fe)O] in the presence of silica. In that work which pertained to solid solutions with less than 40 pct MgO, most of the quantitative work was performed on FeO microstructures. The chief conclusions concerning these relatively low-melting oxide solids were as follows: 1) the rate of crystalline grain growth is inversely proportional to the grain diameter, 2) grain growth proceeds more rapidly at higher temperatures but is slightly retarded by additional liquid content, and 3) a Silicate-containing liquid penetrates as a film between the individual magnesiowüstite grains independent of time, temperature, amount of liquid, or the MgO/ FeO ratio. The above observations are in contrast to prior work3 on the microstructure of silica in the presence of iron oxide-containing liquids where the liquid does not penetrate as a complete film between solid grains. The phase relationships for the compositions of the present work are shown in Fig. 1 which is a summary of the work of several investigators.4 Of importance is the fact that CaO forms a more stable structure with SiO2 and Al2O3 than do either MgO or FeO. The oxygen potential has little effect on periclase unless iron oxide is also present. The iron oxide is ferrous at moderately low oxygen levels, changing to ferric as the Oxygen potential is increased so the spinels, magnetite, and magesioferrite are formed.5 These two phases are relatively stable in air at steelmaking temperatures. I) EXPERIMENTAL PROCEDURE ractory were made with reagent grade Oxides. The magnesium oxide used was 99 pct MgO after ignition, and the iron oxide raw material had a minimum content of 99 pet Fe2O3. The CaO, SiO2, and A12O3 were also reagent grade raw materials. After mixing, the required compositions were pressed into pellets at a minimum pressure of 5000 psi to insure compaction of the raw materials and prevent excess void content. A silicon carbide element tube furnace was used with thermocouple control for sin-

Jan 1, 1963

By O. N. Carlson, H. A. Wilhelm, J. M. Dickinson

On the basis of microscopic studies, melting-point observations, and X-ray analyses, a phase diagram is proposed for the Cb-V system. A complete series of solid solutions is formed with a minimum in the solidus at 1810°C near 35 wt pct Cb. No compounds or intermediate phases were found in the system above 650°C. THERE is an ever increasing need for better structural metals and alloys for use in nuclear reactors. In addition to the normal properties of engineering structural materials, such as high temperature strength, resistance to corrosion, and fabric-abil~ty, the nuclear properties of the material must be considered. In a nuclear reactor it is important to conserve neutrons, so a material which removes these neutrons from the reaction excessively is considered to have unfavorable nuclear properties. In nuclear-reactor design the engineer must have nuclear as well as other data available on alloys in order to make a wise selection of materials. Due to the fact that many of the common structural materials have undesirable nuclear properties, it is vital that new alloys of metals having more favorable nuclear properties be investigated. Columbium and vanadium are both high melting metals, both exhibit resistance to chemical attack, and no great difficulty is encountered in fabricating them into desired shapes. With proper treatment both metals can be cold rolled extensively without failure. In addition they have desirable nuclear properties for certain types of reactors. Therefore, the alloys of columbium and vanadium should be of interest in the atomic energy program. Since an alloy-development program is enhanced by a knowledge of the phase equilibria of the components, this investigation was undertaken to establish the phase diagram for the Cb-V system. According to the Hume-Rothery rules for alloying,' the chemical similarity, crystal structure, and atomic-size factor are favorable for a complete series of solid solutions for this system. Both elements are in the same family of group V of the periodic table and thus are quite similar chemically. The crystal structures of columbium and vanadium are compatible for extensive solid solubility, since both have body-centered-cubic structures. The atomic diameters of columbium and vanadium are 2.85 and 2.62Å, respectively. This difference of slightly more than 8 pct is well within the 15 pct maximum difference allowed for extensive solid solubility. Experimental Procedures Source of Materials: Columbium powder and sheet trimmings were obtained from the Fansteel Metallurgical Corp. According to the manufacturer the metal contains less than 1 pct impurity. An analysis of the metal showed approximately 1800 ppm C in the powder while the sheet trimmings contained less than 500 ppm C. Spectrographic analysis showed minor amounts of Ca, Cr, Fe, Mn, Si, Ti, V, and Zr in both forms of the columbium. No commercial source of vanadium having the ductility and purity desired was available to the authors at the beginning of this investigation. As a result, all of the vanadium used in this study was prepared by the bomb reduction of vanadium pen-toxide with calcium employing the method reported by Long.' Yields of massive vanadium normally were about 80 pct. Chemical analysis of the vanadium prepared in this manner showed the presence of 200 to 500 ppm N and 800 to 1000 ppm C. Minor amounts of Ca, Fe, Mn, Si, Zr, Cr, and Cb were detected by spectrographic analysis. This vanadium metal was ductile and was cold rolled into 5 mil sheet. Annealing was not necessary during this rolling and the metal retained its cold-rolling characteristic after are-melting. Preparation of Alloys: The Cb-V alloys were prepared by melting pieces of vanadium sheet togethel-with columbium in the form of sheet or pellets of powder. The melting was carried out under argon in conventional arc-melting equipment employing a tungsten electrode and a water-cooled copper crucible. Each alloy was remelted three or four times, inverting the alloy after each melting in order to assure complete mixing. Alloys normally were obtained as round flat disks, weighed approximately 70 grams, and had roughly the shape of a disk 1 1/2 in. in diameter and 1/4 in. thick. Half of each alloy

Jan 1, 1955

By B. S. Butler

A. D. Mutch (Falconbridge Nickel Mines Ltd., Ona-ping, Ontario)—This contribution is prompted by the fact that the writer has recently published an article'!' which has in part the same general conclusions as B. S. Butler's, namely, the form of the standard mineral paragenesis in hypogene deposits and the parallel transition from early high temperature acid to late low temperature alkaline or neutral solutions. Since the writer also recognizes that he is not fully qualified to discuss the formation of ore deposits as a chemical problem, this discussion will be limited to summarizing other observations and will suggest how Butler's Table II might be made more effective. The form of Butler's table is not unlike that widely used by European geologists'" in which the various minerals are related to the types of ore fluids—peg-matitic, pneumatolic and hydrothermal. Thus the decrease in temperature and change in pH of the ore-bearing fluids as recognized by Butler may also be paralleled by perhaps even greater changes in composition, density, and character. W. H. Newhouse's article:" on the sequence of hypo-gene ore mineral deposition is still one of the most complete analyses of the problem. In it he makes four major observations: 1) The order of O, S, As, Sb is the same as their increasing atomic weights and the same as their melting points. 2) The order of the metallic elements is the same as the Schuermann series. 3) The general mineralogical order is paralleled by decreasing heats of formation. 4) The order is generally in decreasing hardness, higher metal content, and higher specific gravity. The order of 0, S, As, and Bi is also the same as their relative abundance. Another point worth mentioning about this series is that As, Sb, Bi, when abundant, often substitute for sulfur in the early pyrite-like minerals, whereas later in the sequence these elements appear to act more like metals. This behavior may be a further indication of the acid character of the early fluids. C. J. Sullivan"' has attempted to show that the sequence of the metallic elements is related to the order of their melting points and has discussed the interrelationship of the different types of bonding of sulfo-phile and oxiphile elements in minerals. Items 3 and 4 might best be summarized by saying that bonding of the minerals in the series appears to be from ionic to covalent to metallic, the early minerals being light in weight, hard, and near-transparent; the intermediate minerals of intermediate weight, semi-transparent, and semi-conducting; and the end minerals heavy, soft, and malleable, opaque and good conductors. A rapid fall in temperature has been assumed to be the cause of ore deposition in many deposits. Perhaps this in turn is the effect of a rapid release of energy in the form of pressure release and change of volume, the first minerals to form being those with the highest heats of formation which absorb the released energy the most rapidly. Butler's Table II could probably be streamlined and made more effective if the listed compounds were assembled as mineralogical groups as in Dana. Thus the sulfides, arsenides, antimonides, bismuthides, and sulfa salts could be arranged in AX,, AX, A2X2, etc. groups. Since these are continuous substitution series, in which the fields of stability and the heats of formation of the various individual minerals can be fairly regarded as similar, this should be accomplished with no loss of clarity. The occurrence of the individual minerals and the precise sequence of the mineral deposition in any one deposit is probably more dependent on the concentration and relative abundance of the component elements. The assembling of geological data in tabular form such as Butler's Table II will continue to be a very effective method of studying geological phenomena. The importance of this particular problem has been pointed out by C. F. Park,% who concludes that understanding of mechanisms of the standard paragenesis and interrelated problems of mineral zoning in space and time is one of the major keys to classification of ore deposits.

Jan 1, 1959

By E. L. Kamen, H. D. Kessler, M. Hansen, D. J. McPherson

The highly reactive Ti-Mo and Ti-Cb alloys were prepared and heat treated under protective conditions. Phase diagrams were established based on micrographic and X-ray diffraction analysis and detection of incipient melting. ß titanium forms a continuous series of solid solutions with both molybdenum and columbium, whereas these metals are only slightly soluble in the a titanium modification. PREVIOUS work on the Ti-Mo and Ti-Cb systems was very limited and is discussed in succeeding sections of this paper relating to the respective phase diagrams. The diagrams in the present work were determined principally by micrographic analysis, because other methods such as thermal analysis and dilatometry are not suitable, due to the low diffusion rates of these alloys in the transformation range. X-ray analysis was believed less useful than micrographic analysis because: 1—On quenching certain high titanium alloys from above their transformation range, the body-centered cubic ß phase decomposes into acicular a (hexagonal close-packed) which room temperature X-ray diffraction techniques cannot differentiate from isothermal a. 2— High temperature X-ray techniques might be used, but are difficult to apply and are subject to error because of the high reactivity of titanium with gases such as oxygen and nitrogen. Although metallo-graphic study was the basic method used, X-ray diffraction analysis was applied to a limited extent, to further substantiate the findings. The transformation ranges on the titanium side of the Ti-Cb and Ti-Mo systems were studied both with DuPont Process A (magnesium-reduced) titanium alloys and with iodide titanium alloys. The Process A metal was used chiefly to bracket the transformation range in order to reduce the number of alloys given a particular treatment for the more accurate final study with iodide titanium alloys. Experimental Procedure The analyses of the metals used in the preparation of alloys for this study are presented in Table I. Melting Practice: Early in the work, a consumable electrode, arc melting furnace was used in the preparation of the Process A Ti-base Mo and Cb alloys. This type of furnace has been described by other investigators.', ' One of the major difficulties of the consumable electrode melting process was the prep- aration of homogeneous electrodes (with the mixture of coarse titanium sponge and fine powder alloying addition) which would give homogeneous ingots. Composition gradients encountered may have been due to a tendency for powdered alloying metals to drop away from the electrode in handling. This difficulty in the preparation of homogeneous alloys was overcome by the use of a nonconsumable electrode furnace for later work. This furnace is similar to the one used by Mc-Pherson and Fontana a Ohio State University. A diagram of the nonconsumable electrode arc furnace is given elsewhere.' The source of power was a 400 amp dc welding generator. Electrode tips of tungsten (% in. in diam) were used for all columbium melts and for a limited number of molybdenum melts. Molybdenum tips were used for the majority of molybdenum alloy melts. Columbium tipped electrodes were tried, but disintegrated rapidly at currents above 300 amp. In the Process A titanium melting practice the metals were charged into the water-cooled spun copper crucible in the following forms: l—titanium: sponge (—4 + 16 mesh); 2—molybdenum: sections of 0.003 in. sheet (approximately ½ in. sq); and 3— columbium: powder compacts (? in. lumps broken from large section). After alternately evacuating and purging the furnace several times with argon or helium, the arc was struck against the metal charge,

Jan 1, 1952

By R. J. Weege, A. W. Schillinger

Conventional underground mapping methods and diamond drilling are being applied in a study to determine the nature of the copper ore occurrences near the footwall of the Osceola lava flow top, commonly referred to as the Osceola Amygdaloid. The work to date suggests that structures formed by relatively impermeable barriers, created by flowage and injection of still-molten lava from the interior of the flow into the solidified, brecciated crust, acted as the ore receptacles. Ascending hydrothermal fluids traveling near the footwall contact were trapped and confined in these barriers which retarded the direct upward movement of the ore fluids and caused deposition of copper. Oreshoots located near the footwall appear to have been formed spatially independently from the hanging-wall oreshoots by fluids traveling simultaneously, but along different channelways. The barrier concept, as advanced by earlier writers to explain the concentration of the ore-bearing fluids into broad shoots constituting entire ore bodies, is found to be equally as applicable for the localization of smaller oreshoots within the Osceola ore body. Recently, the Calumet Division of Calumet and Hecla, Inc. completed the unwatering of the old mine workings on the Osceola amygdaloid. Two shafts were subsequently reactivated and mining commenced on the Osceola lode after an idle period of over 20 years. Early in 1961, the Calumet and Hecla Geological Dept. was assigned the task of locating additional reserves. Accordingly, an intensive mapping and underground diamond drilling program was initiated. Except for a very few years following the first mining on the amygdaloid, the Osceola lode had never been a high grade producer. It was, therefore, recognized from the onset that a concentrated effort would have to be made by the mining, milling, and geological departments to insure success of the project. Company reports contained many references to ore that had been located near the footwall of the Osceola amygdaloid. Information concerning the grade of this ore was meager, but it was known that at least some was very rich. In contrast to ore that occurred near the hanging-wall, however, the footwall copper did not appear to have a systematic distribution and a large amount of poor rock had to be removed in developing this ore. This, of course, resulted in high development costs and discouraged any extensive mining of footwall ore. The possibility of more continuity than had previously been suspected was recognized by other workers, in particular Dr. T. M. Broderick, formerly Chief Geologist of Calumet and Hecla, who suggested attempts be made on a trial basis to follow the footwall contact with the main development drift. As most mining was done on the Osceola lode before a geological department had been established by the company, and almost all of these openings are now caved, very little information concerning the geology of footwall ore was available. It was, therefore, decided that the first step in the exploration program would be to become familiar with footwall ore occurrences by mapping the geology as the openings were driven. It was possible that a mapping program would reveal the features that controlled the localization of the ore. Furthermore, if it could be shown that footwall ore was more continuous, or if its distribution was more systematic than generally believed, it would be possible to produce a high grade ore that could be blended with the lower grade hanging-wall ore. In connection with the geological program, the Michigan College of Mining and Technology Geophysical Dept. under the direction of Professor Lloyal Bacon, is making a geophysical study of the problems of locating footwall ore by electrical methods. GENERAL GEOLOGY OF MICHIGAN NATIVE COPPER DEPOSITS The native copper deposits of Michigan are located in Keweenaw, Houghton, and Ontonagon Counties. The host rocks are Keweenawan in age and are comprised of interbedded sediments and lava flows which form a belt two to four miles wide and over one hundred miles long. These rocks form part of the south limb

Jan 1, 1962

By R. D. Mollison, C. F. Fogarty

Sulfur is widely distributed in nature. It is present in the earth's crust, the ocean, the meteorites that come to us from cosmic space and in practically all animal and plant life. According to Clarke,9 the earth's crust contains 0.06 pct sulfur. Large quantities of free or combined sulfur are found in coal, natural gas and petroleum. Mineral waters contain sulfates and hydrogen sulfide. Sulfur is rather plentiful in the crust of the earth; however, only under special circumstances can it be produced profitably. Sulfur is one of the cheapest raw materials used by industry; and, therefore, the economic feasibility of a given deposit is strongly dictated by the law of supply and demand on local as well as world-wide levels. The forms which are commercially important are elemental sulfur or brimstone, and the sulfides such as pyrite (FeS2), pyrrhotite (FenSn+1), chalcocite (Cu2S), sphalerite (ZnS), and galena (PbS); the sulfates such as gypsum (CaSO4,2H2O), anhydrite (CaSO4), and kieserite (MgSO4,H2O). Elemental Sulfur Elemental sulfur is found in many localities, generally in solfataras and gypsum type deposits. The solfatara deposits are found commonly in the neighborhood of active or extinct volcanoes as in Italy, Japan and Chile, or fumaroles associated with mineral springs such as the Mammoth Hot Springs in Yellowstone Park. Here the sulfur is deposited in tufas or other porous host rocks. This type of sulfur deposit probably results from the oxidation of hydrogen sulfide or the reaction of hydrogen sulfide with sulfur dioxide. Most of the world's supply of elemental sulfur comes from the gypsum-type deposits. Here the mineral occurs as either crystalline or amorphous sulfur in sedimentary rocks in close association with gypsum and limestone. This association is characteristic and occurs in almost all the great gypsum beds of the world, although sulfur is not always present in quantities of economic importance. Various theories have been advanced to account for this association. Bischof5 suggested that the sulfur came from hydrogen sulfide which resulted from the reduction of calcium sulfate by carbon or methane in accordance with the following reactions: CaSO4 + 2C= CaS + 2CO2 CaS + C02+ H2O = CaCO3 + H2S CaSO4 + CH4= CaS + C02+ 2H20 2H2S + 02= 2H20 + 2S All of the sulfur-bearing domes on the Gulf Coast have calcium sulfate in great quantity in the cap. They all show the presence of hydrocarbons. The oxygen for the final reaction could have been supplied by circulating ground waters. The principal objection to this theory is that temperatures of 700° to 1000°C are needed to reduce the sulfate to sulfide with carbon compounds. The geologic evidence is that the temperature of the sulfur-bearing domes of Texas did not exceed 100°C. Proponents of the theory say that geologic time or a catalyst replaced temperature. According to another theory the sulfur in the salt domes is the result of bacterial action. Sulfate reducing bacteria have been detected in sulfur cores and in the formation water issuing from salt domes. It has, therefore, been suggested that these bacteria converted the sulfate to sulfide which subsequently was converted to elemental sulfur.

Jan 1, 1960

By J. O. Brittain, N. R. Adsit

A number of zinc bicrystal specimens with the grain boundary loaded in simple shear were plustically deformed in creep in a vacuum at 200°C and under an argon atmosphere at 350°C. The results indicated that the amount of grain boundary sliding at a given time was controlled by the slip in the grains and was proportional to the resolved shear stress on the slip plane. Curves of grain boundary sliding vs time were found to be cyclic with no regular periodicity. ALTHOUGH grain boundary sliding (G.B.S.) has been investigated in a number of different types of tests on various materials there is substantial disagreement on the interpretation of the various observations. Gifkins1 has presented a comprehensive review of the subject of G.B.S. and fracture. He reports that the activation energy for high-temperature creep is equal to that for volume self-diffusion and that pure metals show less tendency towards intercrystalline fracture than alloys. Pure metals show appreciably greater grain boundary migration than alloys, and both grain boundary migration and grain boundary sliding follow the same general trend in time as plastic deformation during creep.' While there have been a number of different mechanisms proposed to account for G.B.S., none of the models explains all the results. Since zinc has only one prominent slip system, it was hoped that experiments on G.B.S. in zinc bicrystals might enable us to separate the effect of grain boundary angle and the effect of matrix slip and thereby resolve at least one part of this complex phenomenon. EXPERIMENTAL PROCEDURE Bicrystals of pure zinc (99.99 pct) were grown by a Bridgeman technique in a furnace having a gradient of 20°C per in. The bicrystals were seeded to a desired orientation and grown in a split graphite mold which was 3/4 by 5/8 by 8 in. The mold was enclosed in a Pyrex tube and the tube was evacuated and then filled with a small amount of argon before it was placed in the furnace. The growth rates were 1/2 to I in. per hr for the bicrystals and 1/2 to 3 in. per hr for the single-crystal seeds. The longitudinal V notches served to hold the grain boundary in position during the growth process. A schematic rep- resentation of a specimen which had been cut with a jewelers saw from the bicrystals is shown in Fig. 1. All specimens of a series were cut from the same crystal, some of which were 7 in. in length. After specimen preparation the boundary was approximately 5/16 in. long and the V notches had a radius of 1/16 in. The boundaries were straight at a magnification of X100 with the exception of a few which had a gradual radius of curvature of greater than 3.2 in.-1. Laue back-reflection photograms were taken on the specimens to check the orientation of grains in the bicrystals. The method of relating the orientation of the two lattices is shown in Fig. 1, where 0 is the angle between normal to the boundary and the trace of the basal plane, is the angle in the boundary between the trace of the basal plane and a line parallel to the V notch, and x is the angle in the basal plane between the Burgers vector and the perpendicular to the grain boundary. After mechanical polishing the specimens were chemically polished.2 Subsequent to the polishing operation the specimens were encapsuled under a vacuum of better than 25 annealed at 340°C for 1 hr to remove the effects of this handling, and again chemically polished. Finally, fiduciary marks were scribed on the specimen using a micromanipulator. Creep tests, which were conducted in a modified Bausch apparatusS with the boundary loaded in simple shear, were run at a constant load (since the boundary area remained essentially constant this is approximately constant grain boundary stress). The temperature was controlled to ±1/4°C as measured on a semiprecision potentiometer with a calibrated thermocouple. The specimens were tested in a vacuum of better than 0.5 at 200°C and in purified argon at a pressure of 1/2 atm at 350°C. The op-

Jan 1, 1965

By T. M. Morris

A SEARCH of the literature reveals that no measurements have been made of the forces acting between a small solid particle whose surface is hydrophobic, and an air bubble to which the solid adheres, both immersed in water. Analyses have been made of the forces acting to support a greased solid on the surface of water, and the forces acting to cause a solid, whose surface is hydrophobic, to adhere to an air bubble in water. The latter analysis T. M. MORRIS, Junior Member AIME, is in the Department of Metallurgical Engineering and Mineral Dressing, School of Mines and Metallurgy, Rolla, Mo. New York Meeting, February 1950. TP 2734 B. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received May 16, 1949. This paper is the result of work done for part of a doctor's thesis at the Missouri School of Mines and Metallurgy. is often incomplete, however, because the internal pressure of the bubble has been neglected. It will be demonstrated that the internal gas pressure is not a negligible factor when dealing with bubbles of the size encountered in flotation. A study of the forces acting between an air bubble attached to a large flat surface is informative. It must be borne in mind, however, that this is not the condition present in a flotation cell, where the particle is small compared to the size of the bubble. The bubble is allowed to spread to its maximum contact angle on a large flat surface in the first case, whereas in the second case, the spread of the bubble is limited to the surface of the small particle which is presented to the bubble. Kabanov and Frumkinl studied the forces acting to cause adhesion of bubbles of hydrogen to a large surface of mercury, which served as an electrode in a dilute sulphuric acid solution. The force acting to hold the bubble to the mercury surface was found to be the vertical component of the surface tension between hydrogen and the sulphuric acid solution. The forces tending to cause the bubble to separate from the mercury surface were found to be: (1) the force exerted due to the internal pressure of the bubble acting upon the area of contact between the bubble and the mercury surface, and (2) the buoyant force of the bubble minus the hydrostatic force acting at the base of the bubble. These investigators photographed bubbles that were just on the verge of separating from the mercury surface. From these photographs, they measured the contact angle between the mercury surface and the tangent to the hydrogen-solution interface at the point of contact between bubble and mercury surface. They calculated the volume of the bubble and the internal pressure of the bubble. The equivalence between the upward acting and downward acting forces was remarkable. Wark2 pursued an investigation similar to that of Kabanov and Frumkin, and at the same time. His deductions verified those of Kabanov and Frumkin. He also considered the conditions present in flotation and was aware of the effect of the internal pressure of the bubble. Further, he proposed several conditions under which a small solid particle would adhere to an air bubble in water. In 1922, Edser," an English physicist, made the following statement. "It must be remembered that no particle could float stably, but for the possibility of variation of the contact angle, for if this were a constant, a slight tilt would inevitably cause the particle to sink." Wark criticized this statement, maintaining that the contact angle does not vary. The experimental data to be presented indicates that Edser was correct. Experimental Procedure: Briefly, the experimental procedure was as follows. A bubble of air was generated in distilled water. A rod of known diameter, one end of which was water repellent, was attached to this bubble. The weight of the 'rod was measured. The internal pressure of the bubble was measured with a manometer. The hydrostatic head from the surface of the water to the bottom of the rod was measured. The angle between the horizontal projection of the end of the rod and the tangent to the bubble at the circle of contact be-

Jan 1, 1951

By N. K. Chen, R. Maddin

In the extension of molybdenum single crystals at room temperature, the slip planes were found to be of the type (1101; the slip direction <111>. Theories of plasticity of body-centered cubic metals have been examined, and an explanation based upon planes of highest atomic density seems plausible to explain the plastic behavior of molybdenum single crystals. IN body-centered cubic metals, slip has been reported to occur on several planes; these are of the type {110), {112), and (123). Andrade has correlated&apos; the operative slip planes in body-centered cubic metals with the testing temperature relative to the melting point. In this correlation, if T is the absolute temperature at which slip takes place and Tm the absolute melting point, then the acting slip planes in body-centered cubic metals may be arranged as shown in Table I. However, deviations from this correlation have been reported in iron and iron-silicon alloys2 and also in molybdenum deformed at a temperature around 2400°C." In the case of iron and other body-centered cubic metals or alloys in which all three slip planes have been reported to be active at any one temperature, the crystallographic mechanism of slip is not well understood. Numerous investigators in this field have assumed that the resolved shear stress is a deciding factor. Such considerations were given by Gough in his experiments with repeated torsion of iron single crystals4 and recently by Opinsky and Smoluchowski in their study of iron-silicon alloys," and will be dealt with later in this report. A third possibility is that slip lines in body-centered cubic metals may be formed by alternate slip on nonparallel (110) planes and not by slip on any plane of higher indices. This was advanced by Elam in the case of ß brass." Since (1101 planes are planes of highest atomic density in the body-centered cubic structure, this hypothesis would be in accordance with the plastic behavior of metals in other systems, namely, face-centered cubic and hexagonal close-packed. Experimental evidence in support of this hypothesis is lacking. Nevertheless the work of Barrett, Ansel, and Meh12 has definitely demonstrated that the slip resistance on {110} planes in iron is very much smaller compared with that on (112) and (123) planes. In the present investigation, molybdenum single crystals were carefully documented as to the operative slip planes and lattice reorientations after plastic extension at room temperature. In three crystals studied, (110) planes were found to be active invariably rather than the (112) planes, which were previously reported for molybdenum at this temperature&apos; and predicted by Andrade&apos;s theory.&apos; In two other cases (112) and (123) planes seemed to operate together with (110) planes as active slip planes. However, it is believed, after careful analysis of crystallite and lattice rotations, that slip on (112) and (123) planes may be spurious. Particular reference will be made to the formation of asterism, lattice rotation, and crystallite rotation in an attempt to show that slip apparently observed on {1121} and (123) planes is actually slip on nonparallel {110} planes. Materials and Treatment Sintered molybdenum rods ? in. in diam, obtained from the Fansteel Metallurgical Co., were reported to have a purity of 99.9 pct.* One specimen, Mo-13, ¼ in. in diam, was supplied by Westinghouse Electric Corp. Single crystals were prepared, using the technique devised by Chen, Maddin, and Pond." Mo-13 was ¼ in. in diam x 7 in. long with a reduced gage section of 0.200 in. in diam x 3 in. long. The center of

Jan 1, 1952

By J. T. Norton, A. L. Mowry

The monocarbides of the A subgroup elements in the fourth and fifth group of the periodic table in addition to being hard and refractory are of special interest in that they are isomorphous in crystalline structure. They are cubic with a sodium chloride type structure in which the metal atoms are essentially close packed in a face-centered cubic arrangement with the carbon atoms placed in the interstices between. Interstitial structures of this close packed type were first investigated systematically by Egg1 and he gave the rule for their formation, stating that the radius ratio of the nonmetal to the metal atom should not exceed the value of 0.59. The carbides of interest are those of titanium and zirconium of the fourth group and vanadium, columbium and tantalum of the fifth group. Table 1 shows the radius ratio using the Goldschmidt radii for 12 coordination for the metal atoms and the diamond radius for the carbon atom. It will be noted that while there is considerable variation in the size of the metal atom, in all cases the ratio is smaller than the limit of 0.59 placed by Hägg. It has been known for some time that these cubic carbides are soluble in one another, at least to some extent or, in other words, the metal atoms can be replaced, one by another without destroying the stability of the structure. Since the stability of these close packed interstitial substances appears to depend more upon geometry than upon the exact chemical nature of the atoms involved, it is of interest to examine the possibilities of replacement in these carbides in some detail. Hume-Rothery2 has pointed out the importance of the difference in size of solute and solvent atom as a factor in limiting the solubility in simple binary solid solutions. Largely on an empirical basis, he states that if the difference in size between solvent and solute atom is more than 14-15 pct of the solvent atom, the range of solubility is very restricted. The atom size was based on the distance of closest approach in the elements involved. While there is some question as to how one should calculate the size of the metal atom in the carbide structures, reference to Table 1 will show that zirconium is the largest and vanadium the smallest of the group and that the difference is about 15 pct. The Ti-Zr difference is about 9 pct and the others are smaller. Thus one would predict that if the size factor controls the solubility, all of the pairs except VC-ZrC would have wide or complete solubility whereas this latter pair is on the border line and might have restricted solubility. The purpose of the present investi- gation was to examine the solubility of the several pairs of carbides by heating them together until equilibrium was established and then examining the product by X rays. Previous Work Agte3 and his associates prepared various transition metal carbides and determined the melting points of binary mixtures. He concluded from the shapes of the melting point curves that there was extensive solubility in the case of the cubic carbides. Umanskii and his colleagues made an investigation of a number of pairs of the cubic carbides, using X rays and plotted lattice parameter vs. composition curves for the systems TaC-Tic, CbC-Tic, TaC-ZrC and CbC-ZrC. All pairs showed a continuous series of solid solutions. The first two pairs gave a linear relation while the latter two showed a negative deviation from Vegard&apos;s law. Kiefer and Nowotny, in a paper which became available after the present work was well advanced, investigated the binary pairs of the five cubic carbides by means of X rays. Relatively few points were obtained and results indicated that in some cases, at least, equilibrium was not reached at the temperatures used. The results indicated that solubility in the VC-ZrC system was not complete. All of the results of previous investigations indicated the desirability of a more detailed study. Materials The raw materials used were mono-carbides of titanium, zirconium, vanadium, columbium and tantalum and were the purest which could readily be obtained commercially. Spectrographic qualitative analysis showed that the CbC and TaC contained less than 1 pct

Jan 1, 1950