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By H. C. Casey, M. B. Panish

The roles of the phase diagram and the diffusion and solubility analyses in the selection of sources for the diffusion of zinc into GaAs are discussed. Isothermal sections of- the phase diagram are described at 1000°, 775°, 744°, and 700°. Below 744° the three solid phases, Zn3As2, GaAs, and ZnAsz, may be in equilibrium. In the composition regions where the three solid phases are in equilibrium, the partial pressures of the components do not vary with composition and there is no liquid phase. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected to yield reproducible diffusion profiles without surface damage. The 5/50/45 ternary source Provides a significant improvement in the reproducibility and planarity of- the zinc diffusion as compared with other zinc diffusion sources that result from starting with elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. Several experimental diffision profiles for the 5/50/45 diffusion source have been determined. The profiles are very steep in the region of the junction and produce devices that exhibit step junction behavior. The junction depth varies as the square root of time. Diffusion at 700°C for 4 hr gives a 5-µ junction depth and a surface concentration of 2.4 x1020 cm-3. The surface concentration is enhanced by a factor of three and the junction depth decreased by a factor of ten as compared with diffusion with a starting source 01- elemental zinc. The differences in dijyusion behavior with these two sources are due primarily to the approximately 10' greater equilibrium As4 partial pressure for the 5/50/45 source. ThE most common technique for the preparation of GaAs p-n junctions for diverse applications ranging from switching diodes to injection lasers has been to diffuse zinc into the solid from the vapor phase. The zinc impurity has generally been provided by introducing into a diffusion ampoule elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. For the purpose of eliminating surface deterioration, zinc has been diffused into GaAs through SiO2 films1 and from zinc-doped SiO2 films.2 During a study of the injection and recombination mechanisms in GaAs junctions, we found that these diffusion techniques either resulted in nonreproducible diffusion profiles and nonplanar junction interfaces or were extremely inconvenient to use. An unpublished report by Allen and pearson3 emphasized that an understanding of diffusion requires relating the diffusion conditions and system compositions to the ternary phase diagram. Recent studies have made it possible to relate the effect of starting source composition on the GaAs sample surface and diffusion profile reproducibility and, in addition, to estimate the expected surface concentration and zinc diffusivity. These studies include the Ga-As-Zn phase diagram,415 the determination of the incorporation reaction for zinc as a substitutional impurity,6 and the analysis of the concentration dependence of the diffusion coefficient.' In this paper the role of the phase diagram in the selection of the starting diffusion source composition is illustrated, and an application of the diffusion and solubility analyses is used to demonstrate their utility in the estimation of surface concentration and diffusivity for various starting source compositions. Consideration of the isothermal sections of the ternary phase diagram shows that below about 744° C a composition region exists where the three solid phases Zn3As2, GaAs, and ZnAs2 are in equilibrium without a liquid phase. In this region the partial pressures of the components do not vary with composition, and thus the surface concentration and diffusivity depend only on temperature. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected. As will be described in detail, this diffusion source yields reproducible diffusion profiles without surface damage, planar junction interfaces, and steep profiles that result in devices with step junction behavior. Only closed diffusion systems are considered. Open or flowing vapor systems require the maintaining of constant vapor pressures in the flowing gas and represent control problems outside the scope of this discussion.

Jan 1, 1969

By Herman Garlichs

The development of the extensive Southeast Missouri deposits greatly preceded that of the Iowa and Wisconsin deposits. It began about 1720 at Mine La Motte and other localities, and has continued uninterruptedly to the present time. It is estimated that this district produced about 184,000 tons of lead in the year 1916, having a value of approximately $25,000,000. This is a new high record. The Southwest Missouri orebodies were hardly known before 1845 and were not extensively developed until 1870. Lead production in Southwest Missouri for 1916 was 38,788 tons. Oklahoma produced 14,399 tons and Kansas 2,345 tons, making a total for Southwest Missouri, and the adjoining districts in Oklahoma and Kansas, of 55,532 tons of lead. The first metallurgists in Missouri were the Indian and the hunter. The early settler learned to procure his bullets either by melting ore in his camp fire or by throwing pieces of galena on an old stump and depending on the usual roasting and reaction method to obtain the metal. A little more refined method was to arrange two flat stones in the form of a, V. Wood and galena were placed in the furnace and ignited.. As heat developed, some of the metal was extracted and molded into bullets. The next step in utilizing the lead ores was the log hearth. All lead in Missouri was smelted in this crude affair before 1820. It was built on sloping ground, and consisted of a hearth of stone, surrounded on the front and two sides by a stone wall. The wall was 7 it. high in front. The top and rear end were left open and in front an arch or opening was made, forming the eye of the furnace. In front of this a pit was dug in the ground, to receive the molten metal. Large logs were rolled in at the back and made to rest upon ledges formed inside, to raise them from the hearth and to give a draft. These logs filled the entire width of the furnace. Small split logs were then set up around the two sides and the front, and the ore was piled on until the furnace was full. Finally, the mass was covered with logs and fuel until the ore was completely surrounded. A gentle heat was started, which was raised very gradually. After 12 hr. the heat was increased and continued for 12 hr. more, 24 hr. being required for each smelting. The furnace treated about 5,000 lb. per 24 hr. and the ore yielded about 50 per cent. of its metallic lead. A considerable quantity of the ore was not desulphurized, and fell between

Jan 1, 1918

By E. M. Kalar, I. Iwasaki, J. D. Zetterstrom

Several methods of removing fatty acid coatings from iron ore flotation concentrates were tested both on a Mesabi oxidized iron ore and on a magnetic taconite concentrate, and their effects on the duplex flotation process and on pelletizing were compared. Either acid or alkali alone could not remove the coatings, but a combination of such reagents as lime and quebracho, calcium chloride and pyrophosphate, or sulfuric acid and an organic acid (oxalic, malonic, or citric acid) was quite effective. The use of activated carbon was found to be particularly promising. The removal of fatty acid coatings from iron ores is of much practical interest when a pelletizing process is being considered for a concentrate floated with a fatty acid collector or when a duplex flotation process is being considered for upgrading an oxidized iron ore. A duplex flotation process is a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process is being used in the Florida phosphate fields.' Although in northern Michigan mills fatty acid flotation concentrates have been pelletized successfully, at other locations fatty acid coatings on iron flotation concentrates have proved so undesirable in the agglomeration operation that other methods of concentration had to be sought.' Since fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates, a combination of reagents, such as lime and quebracho,3 lime and alkali phosphate,4 or sulfuric acid and oxalic acid,' has been proposed. It was also thought that activated carbon might be effective in removing fatty acid coatings due to its high adsorptive capacity. Activated carbon, with its enormous surface per unit of volume, is well known for its exceptional efficiency in removing organic pollutants from industrial effluents. This article presents the practical aspects of the above methods when they are applied to the duplex flotation process and to the pelletizing of iron flotation concentrates. The article also includes a preliminary investigation of the common parameters involved in the depressant activity of the reagents. EXPERIMENTAL WORK Initially, the experimental work was directed towards the optimization of each method for the removal of hydrophobic coatings from iron oxide surfaces floated with fatty acids. Subsequently, the methods thus optimized were tested in the duplex flotation process with an oxidized iron ore and in the pelletizing process with a magnetic taconite concentrate. Preliminary Flotation Tests: Although the three types of chemical treatment reported in the literature were briefly investigated for the purpose of comparison, major emphasis was placed during the preliminary flotation tests on the use of activated carbon because it was thought to have certain advantages over the chemical methods. LIME AND QUEBRACHO - To obtain a flotation concentrate for optimizing the lime and quebracho method of fatty acid removal, the magnetic taconite concentrate was used. The concentrate had a size consist of 90% passing 325 mesh and analyzed 64.5% iron. After a few preliminary tests the fatty acid flotation procedure with the magnetic taconite concentrate was standardized as follows. A 1200-g sample of the magnetic concentrate was pulped in a Fagergren laboratoy flotation cell to 40% solids, conditioned with 0.5 lb of soda ash per ton for 2 min, and then further conditioned with 1.0 lb of Acintol FA-2 per ton for 2 min. After 5 min of flotation, recovery was nearly complete, averaging 98.6% of the weight and 98.7% of the iron. The cell product, which amounted to 1.4% by weight and analyzed 63.2% iron, consisted mainly of relatively coarse middling particles. Since the repro-ducibility of the flotation concentrates produced by this procedure was vey high, the same procedure was used to prepare fatty acid concentrates for each of the six tests of the lime and quebracho method. To test the removal of the fatty acid from the magnetite surfaces by the lime and quebracho method, a fatty acid froth product was returned to the flotation cell, repulped by 30 sec of agitation, and then con-

Jan 1, 1968

By H. Furman Byars

INTRODUCTION of bottom dump hauling units into the Ray, Ariz., stripping operation of the Isbell Construction Co., was motivated by several reasons, with what appears to be debatable results. The accepted theory of truck design for use in open-pit holds that end dump vehicles are the most adaptable for the work. But, because operations of the bottom dump, under certain construction and haulage conditions, proved economically feasible, the unit was put to work in the Ray copper pit. The decision to try bottom dump was reached after considerable observation of the unit in action on construction of earth filled dams, levees, airport construction and several other similar tasks. Basic tire design also motivated the choice. All things being equal, a vehicle running on low pressure single tires will outperform another operating on dual high pressure tires, providing load carrying capacities are the same. The investment required to equip a vehicle with four single tires to handle the same load as one with dual tires mounted on two axles and single front axles is about 60 pct greater. Thus, in order to reach the break even point on tire costs, single tires must operate 60 pct longer. Comparison is made with a truck outfitted with 10 16:00x25 tires. Two other factors were considered in selecting bottom dump trucks. It was felt the bottom dump principle would work well in dumping ore into a hopper where gate design fits this particular method. Also, with the absence of hydraulic dumping, ore pollution with oil is reduced. The mechanical simplicity of the unit also lent weight to its choice. Ordinary reasoning indicated maintenance costs would be low compared with other units carrying similar loads. The bottom dumping principle is not new. It dates back to the days when horses were used to haul the same kind of rig. The unit employed at Ray holds 25 cu yd struck measure, or approximately 42 short tons. Dumping is accomplished by releasing an air cylinder opening a dog holding the doors. Doors are closed by a cable system operating off a wheel wind deriving power by friction with the trailer tire. The unit is mounted on four 27.00x33 and two 14.00x24 tires on the front axle. The power unit is a 300 hp Cummins engine. Hydraulic power boosts the steering. A straight mechanical drive and friction clutch with 10 speeds is used. Conditions Not Ideal Top performance of the truck can be expected only under the conditions for which it was designed, in particular grades under 5 pct, handling fine material, and dumping where one thin layer can be placed on top of another. The machine will handle 42 tons per haul, operating at high speed, with only seconds used for dumping. On a 2 or 3 pct grade over a one mile haul,

Jan 1, 1952

By P. A. Robbins

FAR NORTH, on the bare Arctic tundra, 11 mi. above the mouth of the Keewalik River where the latter discharges into Kotzebue Sound. several ., Eskimos garbed in parkies and muck lucks mingle with a small group of similarly clad white men. All of them shield their eyes from the white glare of the arc as a gasoline-driven arc-welding set rains molecules of metal on the break in a bull wheel, the large gear wheel which swings the boom and cab of a dragline shovel.

Jan 1, 1937

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.' Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2'4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy's equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.' were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By D. D. Smith, D. P. Squier, E. L. Dougherty

A system of differential equations describing the temperature behavior of fluid injected at constant surface temperature in a well is derived and .solved analytically. A formula for the fluid temperature at any time and depth is given, as well us a special formula valid for very large times. These formulas are used to calculate temperatures for several typical cases. The results indicate that, initially, the temperature of the water entering the formation is considerably lower than the injection temperature. This condition lasts for only a short period— less than three days for most cases of practical interest. Following this highly transient period, during which the temperature of the fluid entering the formation builds up to about 50 to 75 per cent of the injection temperature. the system enters a quasi-steady state in which the temperature changes are very slow. After severl years, the bottom-hole temperature will still be 50" to 100°F lower than the injection temperature, hilt the heat losses may he tolerable. INTRODUCTION Predicting the behavior of a hot-water flood requires that the temperature of the water entering the injection interval be estimated. This report describes the development and solution of a system of equations which describes the temperature behavior of the injected water in the wellbore with certain simplifying assumptions. The only previous means known to the authors for describing such a process is that of Moss and White.' Their results appear to be close to those obtained by our method in the practical cases which were compared; this agreement is largely due to the fact that in our method temperature soon approaches a quasi-steady state, as was assumed in their method throughout. However, our model covers all times, is continuous (whereas the Moss-White model depends on breaking the depth into discrete intervals) and. we feel. more closely describes the physical problem. FORMULATION OF THE PROBLEM PHYSICAL SYSTEM AND ASSUMPTIONS The injection procedure consists of pumping water at a fixed surface temperature T., down an infinitely long cylindrical well or tubing of inner radius Any material exterior to the water column such as mud, casing, or cement is regarded as part of the formation. The general behavior of the system may be described qualitatively as follows. When the hot water is first introduced into the system, the temperature difference between the formation and the water is large, resulting in a high rate of heat transfer. As a result, the temperature adjacent to the wellbore rises very quickly. Because the segment of the formation adjacent to the wellbore largely controls the heat transfer rate, the heat transfer rate will become relatively constant when this portion has reached a temperature close to that of the water opposite it. The temperature of the water and formation then increase very slowly with time. The length of the initial highly transient period and the temperature of the water at its conclusion will be functions of depth, injection rate, injection-string radius, surface injection temperature and the physical properties associated with the water-formation system. The following additional assumptions were made. 1. There is no heat transfer by radiation in the system. 2. There is no heat transfer by conduction in the vertical direction in either the injection stream or the formation. 3. The linear volumetric and mass flow rate of the water is constant throughout the injection stream. 4. No horizontal temperature gradient exists in the injection stream. 5. The product of density and heat capacity is constant for both the water and the formation, and the formation thermal conductivity is constant. 6. Initially, both the water in the wellbore and the reservoir are at a temperature given by the (constant) ambient surface temperature plus the product of depth and geothermal gradient (assumed constant). At large distances for the wellbore (r m), the formation will remain at this temperature. 7. The water temperature and the formation temperature at r — r,, are equal for all depths D. DERIVATION OF EQUATIONS The differential equation satisfied by the fluid temperature T,(D, t), which is obtained by writing a heat balance on a cylindrical differential of volume dV of the injection string between the depths D and D i dD, is

By R. A. Flinn, John T. Norton

A CONSIDERABLE number of experiments in recent years have definitely established the fact that the internal friction or mechanical hysteresis of a metal under cyclic stress is a property that is highly "structure sensitive." Because of this fact, it has been suggested that an observation of this property, which often is referred to as "damping. capacity," might be a useful indicator of structural. changes taking place when a metal or alloy is subjected to any of a number of metallurgical treatments. Damping capacity is of interest to both engineer and metallurgist, but from a rather different point of view, and the information that each desires from such observations is of a different nature. The metallurgist is in search of various external indications of changes taking place in the interior of a metal; changes which are in themselves not directly observable. Even if the observed phenomenon cannot be explained in fundamental terms, it may be empirically related to certain characteristics of the material and prove of real value in research. Internal friction os mechanical hysteresis occupies such a position, and, although it is nor well understood in terms of basic metallic theory, an observation of itt changes can serve in a very useful capacity. Of course, there is nothing new in the measurement of damping, but the use of this property in metallurgical research constitutes a vast field, which has received all too little attention: The present work is essentially of an exploratory nature in this field and is an attempt to evaluate the process as a research tool. The phenomenon of age-hardening was chosen as a typical example of a structural change and one method of measuring damping was examined in considerable detail.

Jan 1, 1938

By C. A. Mitke

(Butte Meeting, August, 1913.) 1. Character of Gases which Caused Helmets to Get Out of Order. DURING September, 1911, the fire area, in the Lowell mine continually increased. and gases resulting from the fire came through the upcast shaft. These gases contained such a large percentage of sulphur dioxide that the men were unable to go up and down on cages, and, within a comparatively short time, repairs in the shaft were found to be necessary. Since the fire was in sulphide ores and extended into certain timbered sections, the gases contained varying amounts of SO2, CO2, and perhaps, at times, CO. The temperature in the shaft was generally about 97°, and the relative humidity from 97 to 99.5 per cent. The corrosive action of the fumes became apparent when the cables had to be changed more often than usual, the heads of lag screws in the guides of the shaft disappeared, and the cages needed frequent repairs. It also became necessary to repair two compartments of the shaft by putting in 150 ft. of new guides between the 600 and 800 levels and lag screws in nearly all the old guides from the surface to the 800 level. 2 Ordinary Methods of Testing Helmets which were Unsatisfactory. These conditions required all work to be done by men wearing oxygen helmets. The Draeger type was tried, and was used until all repairs were completed. At first the helmets were tested for air circulation and air tightness .and the injector was tested by water gauge according to the methods recommended by the Draeger Oxygen Apparatus Co. Six arrangements, covering these different tests, are illustrated in the catalogue and circulars of the company.

Jan 7, 1913

By L. J. W. JONES, B. H. Bennetts

THE removal and disposition of large quantities of slag from blast-furnaces is a question of great importance in the design of works, and various methods have been devised, from time to time, in order to take the best advantage of local conditions. In blast-furnaces treating copper-ores or lead-ores, it is necessary to use a fore-hearth, or matte-settler, in order to collect, if possible, every particle of valuable matte which, otherwise, would be carried away with the out-flowing slag. In all of these cases, the slag overflowing from the fore-hearth is caught in pots and then conveyed to the dump. If the slag is of no value and the necessary water-supply, grade and dumping-space be available, the disposal of the slag by granulation is by far the cheapest and best method. It involves a minimum of labor, both at the furnace and at the dump; and it permits a continuous outflow of slag from the furnace- or settling-pot, thereby avoiding frequent tapping and plugging. When the conditions of water-supply, grade and dump-area will not permit slag-granulation, there are three other methods in common use. Large steel or cast-iron pots, or ladles, supported by trunnions on heavy cars which are moved by steam-, air-, or electric locomotives; some type of mechanical conveyor; and small pots or buggies moved by hand. The pots on the slag-cars are generally circular or oval in shape, and each one contains from 15 to 40 or more en. ft. of molten material. The mechanism for tipping them is more or less elaborate; and, as a general rule, the slag is dumped alongside, and quite close to, the track. They are more or less costly to construct and to keep in repair, and, in order to use them to best advantage, it is necessary to have a good elevation of track above the dumping-ground; furthermore, the rails must be of heavy weight, and well-supported on heavy ties. Other disadvantages of the slag-pots are-1, that the slag cannot be removed continuously

Mar 1, 1905

By R. W. Young, Arthur F. Taggart

The tests herein described are part of an extended series of expel<ments, performed by the authors together with J. F. McClelland and L. W. Bahney, on the reclamation of metallics from foundry and manufacturing-plant scrap. The most obstinate problem encountered was the proper cleaning of the metal. Introduction In the manufacture of brass and brass products the weight of the finished product leaving the plant is much less than the total weight of. copper and zinc entering. A small part of this discrepancy is due to the unavoidable oxidation of the metals in melting, but by far the largest part of the loss is in the form of metallic particles of copper,. zinc, and brass. These losses occur principally at three points in the process: (a) in the casting-shop ashes; (b) in the slags from furnaces melting scrap brass; (c) in material spilled on the floor throughout the manufacturing process. The amount of these products in some plants is nearly 100 tons per 24 hours. Casting-shop ashes contain the metal spilled from the crucibles during melting and pouring, and the metal included in the slags formed in the melting process. The ashes also contain pieces of broken crucibles with adhering metal; 20 to 30 per cent. of unburned coal is also present. The metal in casting-shop ashes contains clean pieces of zinc or copper ingots weighing 1 to 2 lb., jagged pieces of metal of all shapes ranging in size from several inches down to the finest dust, and shot and botryoidal shapes ranging in size from 2 or 3 in. down to 0.01 mm. or less in diameter. Slags from furnaces melting scrap brass contain metal in the form of small shot. Floor sweepings occur in all shapes: spirals, thin shavings, pins and pin-like pieces, wire, rods, and buffing-wheel dust are the commonest.

Jan 1, 1916

By J. B. Warriner

Stripping is the name given to the process of removing clay, rock, or other cover from deposits of coal or ore. In this paper it is intended to cover the methods used in carrying on this operation in the anthracite coal regions of Pennsylvania. In doing this, attention will be chiefly devoted to those methods wherein practice in different sections of the region differs, or is susceptible to change or improvement, though it is intended to give as complete data as possible concerning all stages of the operation. The data from which this paper has been prepared have been collected and submitted by a committee† representing the larger users of stripping methods, of which committee the writer has acted as chairman. Data and assistance have also been obtained from various mining men, engineers, contractors and manufacturers of stripping equipment, to all of whom our appreciation is due. Early History and Statistics The earliest mining operation on a commercial scale in the anthracite region was a stripping operation. This was the famous Quarry mine at Summit Hill, where this method was used only because no other method of mining a deposit of the nature found there seemed feasible to the early operators. A description of this stripping from a report published in 1821 is as follows: "The coal mine at present worked by the company lies on the top of a mountain, and appears to extend over some hundred acres of land covered by about 12 ft,. of loose black dirt resembling moist gunpowder, which can be removed by cattle with scrapers, and thrown into the valley below so as never to impede the work. The thickness of the coal is not known, but a shaft has been sunk in it 35 ft. without penetrating through. More than an acre of mine has been uncovered and presents a huge rock of coal, which is easily quarried without blasting."

Jan 1, 1918

By A. C. D. Chaklader, Ashok K. Kakar

The basic density equation originally dericed &apos; to predict the increase in density of a compact of spherical particles with the progressive deformation at the points of contact has been further modified to include the yield strength of the material. This has been done by assuming that the contact areas grow to stable sizes under a fixed stress which is equal to three times the yield strength. The final equation has the form: where Do and D me the initial and final bulk densities of the compact, u is the applied pressure, and Y is the yield strength of the material. This equation was tested with the data obtained on spheres of lead, K-Monel, and sapphire. The calculated yield strength t~alues for lead and sapphire are within the range of values reported in the literature. A few of the earliest hot pressing models proposed to explain the mechanism by Murray, Livey, and williams2 and then by McClelland3 are based on a plastic flow mechanism. However, more recent investigations suggest that the overall densification process is a combination of several mechanisms, such as particle rearrangement, fragmentation, plastic flow, and stress-enhanced diffusional creep. While fragmentation and particle rearrangement are considered to be responsible for the densification in the early stages,"475 it has been concluded that the final stages of hot pressing are controlled by stress-enhanced diffusional creep.516 The manner in which the densification takes place, i.e., by fragmentation, particle rearrangement, plastic flow, or stress-enhanced diffusional creep, would depend upon the type of material, the temperature, and the stress level used during the hot-pressing experiments. Metal compacts can be expected to have a much greater contribution from plastic flow than ceramic oxides. Also, plastic flow would be a significant contributing factor to densification at high temperatures and high stresses. Most of these works, directed towards elucidation of densification mechanism, have dealt with kinetics of the process. The results of most of the authors vary from one another and they have proposed either new empirical or semiempirical equations to fit their data. The densification rate was found to vary with the type of the powder, shape and size of the powder, initial packing density of the compact, and a few other factors such as rate of heating, pressure, and so forth. Beyond the initial stages, the densification process has been considered to be as time-dependent flow, controlled by a diffusional process, e.g., Nabarro-Herring creep. Palm our, Bradley, and johnson&apos; have attempted to use modified creep rate equations to interpret the data of densification under hot-pressing conditions. Beyond the initial stages, however, the densification would be controlled by a process depending upon the temperature, pressure, and size of the powders. It is the authors&apos; belief that such densification cannot be exclusively controlled by a single process and so attempts should be made to study some observable phenomenon like microstructure, yield strength, and so forth. The emphasis of this work has been toward studying the densification problem from a more fundamental point of view. Some of the principal variables, like initial packing density, mode of packing, and size of the powders, have been controlled to a great extent. The total strain produced on pressure application (instantaneous) in such a case can be considered to be due to plastic and elastic deformation. The elastic component of the strain can be determined by decreasing the load to the initial value. The strain remaining then can be correlated with the contact areas produced by deformation and the corresponding applied load. In a previous paper,&apos; the possible deformation behavior of spheres in a compact has been theoretically analyzed and experimentally tested. The change in contact area radius a relative to the particle radius R was related to the bulk density and the bulk strain for simple and systematic modes of packing. Tt was found that a density equation relating the above parameters can be represented by: where D and Do are the bulk densities of the compact at any value of a/R and a/R = 0, respectively. This basic equation should hold for any material as it was derived from geometrical considerations alone. An attempt has been made in this work to include the yield strength in the above density equation, so that a knowledge of the properties of any material can be used in predicting the densification behavior during the hot-pressing process. THEORETICAL CONSIDERATTONS The deformation of two spheres in contact under a static load can be compared to the deformation occurring between a hard spherical indentor and the flat face of a softer metal. Tt has been shown theoretically by both ~encky~ and lshlinskyg and experimentally by ~abor" that, for a material incapable of appreciable work hardening, the mean pressure required to produce plastic yielding (for deformation occurring between flat face and a hemispherical indentor) is approximately equal to three times the elastic limit, Y, of the material (in tension or compression experiments). Tabor has further observed that the same relationship is valid in the case of work-hardening materials, if the elastic limit at the edge of the indenta-

Jan 1, 1969

By G. St. J. Perrott

During the past year, the Bureau of Mines has carried on an investigation of liquid-oxygen explosives (L.O.X.) to supplement the work described in previous publications.&apos; The present paper gives results of the first part of this work, which was a laboratory investigation of the properties of typical combustibles used in L.O.X., and the relation of these properties to the absorption and retention of oxygen by the explosives and their explosive characteristics. No attempt will be made to describe the development of liquid-oxygen explosives, because this phase of the subject has been well covered.2 The L.O.X. cartridge consists of a paper wrapper filled with an absorbent combustible material that is saturated with liquid oxygen by soaking it therein. After saturation, the cartridge is removed from the liquid and fired with fuse and cap, or electric detonator, in a manner similar to other explosives. Certain types of cartridge may be detonated with fuse alone, requiring no cap to initiate the detonation. &apos; By suitable variation of the nature and density of the combustible, cartridges having a wide variety of explosive characteristics may be made.

Jan 1, 1925

By R. W. Regehr, R. A. Burmeister

Epitaxial growth of GaAs 1-xPx on germanium substrates was achieved using an open tube vapor transport system. The compositional range of 0.3 < x < 0.4 was examined. The best results were obtained with (311) orientation of the germanium substrate. The physical and chemical properties of the resulting layers were investigated using several techniques. Spectrographic analyses of the layers indicate substantial incorporation of germanium into the GaAs t-X Px layer. Evidence is presented which indicates that this incorporation occurs via a vapor phase transport process rather than by solid phase dijfu-sion. Electrical measurements suggest that the germanium thus incorporated behaves predominantly as a deep donor in the compositional range of 0.33 < x * 0.40 and has a deleterious effect upon the luminescent properties of GaAs1-x Px. The increasing technological importance of GaAs1-xPx for use in light-emitting devices has led to an evaluation of several aspects of existing growth processes. The method most commonly used to prepare GaAs1-xPx for electroluminescent device applications is vapor phase epitaxial growth on GaAs substrates.&apos;-4 In a typical electroluminescent diode structure the active region of the diode is entirely within the epitaxial layer and thus the electrical properties of the substrate are relatively unimportant since it is effectively a simple series resistance (assuming hetero-junction effects to be negligible). The use of germanium rather than GaAs as the substrate material is of interest for several reasons. First, GaAs of reasonable structural quality has been epitaxially grown on germanium4-2 and it is reasonable to expect that GaAs1-xPx could subsequently be deposited on the GaAs layer. Second, germanium substrates are readily available with both lower dislocation densities and larger areas than GaAs. Finally, single crystals of germanium are more economical than GaAs single crystals. The principal objective of the present investigation was to test the feasibility of growing GaAs1-xPx epi-taxially on germanium substrates, and to evaluate the properties of such layers with regard to electroluminescent device requirements. The approach used was to a) demonstrate epitaxial growth of GaAs1-xPx on germanium, and b) characterize the relevant structural, electrical, and optical properties of the GaAs1-xPx layers. The possibility of germanium incorporation into the grown layers was of special interest since there was some indication of this in previous studies of GaAs growth on germanium.5&apos;11,12 Although a study of the electrical properties of germanium in GaAs1-xPx was not an intent of this investigation, several features of the electrical properties of the layers grown in the present study which appear to be due to germanium are described. EXPERIMENTAL PROCEDURE The open-tube vapor transport system used for the epitaxial growth of GaAs1-xPx is illustrated in Fig. 1. This system utilizes the GaC1-GaC13 transport reaction and is similar in most respects to the larger system described elsewhere.&apos; The germanium substrates were n-type, with a resistivity of 40 ohm-cm (Eagle-Picher Co.). These were cut to the orientations of {100), {111), and (3111, and were mechanically polished and chemically etched in CP-4 (5 min at 0°C) prior to growth. In some cases, a GaAs substrate was employed in addition to the germanium. The orientation of the latter was {loo}, and they were also mechanically polished and chemically etched prior to growth. The initial composition of the deposited layer was pure GaAs. After approximately 10 microns of GaAs was deposited on the germanium substrate, the phosphorus content of the layer was gradually increased over a distance of approximately 15 microns to the desired concentration and maintained at this value throughout the remainder of the growth. Typical operating parameters used during growth are given in Table I. Selenium was used as a n-type dopant in several runs to facilitate comparison of the electrical properties of the layers grown on germanium with those of layers grown on GaAs substrates, which are usually doped with selenium. The concentration of H2Se in the gas phase was adjusted to a value which would normally yield a carrier density of 1 to 5 x 101 7 at room temperature in layers grown on GaAs substrates. The terminal surfaces of the epitaxial layers were examined by optical microscopy for structural characteristics. Laue back-reflection photographs (Cu radi-ation) were also made on the terminal surface to verify the epitaxial nature of the deposit. After these steps

Jan 1, 1970

By R. K. Dann, L. W. Roberts, R. B. Benson

The mechanical properties of 300-series stainless steels were investigated in both high-pressure hydrogen and helium environments at ambient temperatures. An auslenitic steel which is unstable with respect to formation of strain-induced a (bee) and € (hcp) mar-tensile is embrittled when plastically strained in a hydrogen environment. A stable austenitic steel is not embriltled when tested under the same conditions. The presence of hydrogen causes embrittlement at the mar-lensitic structure and a definite change in the general fracture mode from a ductile to a quasicleavage type. The embrittled martensitic facets are surrounded by a more ductile type fracture which suggests that the presence of hydrogen initiates microcracks at the martensitic structure. If a steel is unstable with respecl to fortnation of strain induced martensile, plastic deformation in a hydrogen environment will produce rapid embrittlement of a notched specimen in comparison to an unnotched one. FERRITIC and martensitic steels can be embrittled by hydrogen that has been introduced into the alloys, either by thermal or cathodic charging prior to testing.1-5 However, conflicting reports exist as to whether austenitic steels that are stable or unstable with respect to formation of strain-induced martensite can be embrittled by hydrogen.8-12 A recent investigation has shown that cathodically-charged thin foils of a stable austenitic steel can be embrittled.13 An earlier investigation of a thermally charged 18-10 stainless steel revealed a significant decrease in the ductility only at the lowest test temperature of -78°C, although strain-induced bee martensite was shown to be present in one specimen tested at ambient temperatures.&apos; When martensitic steels are tested in a hydrogen atmosphere, they are embrittled.&apos;4-&apos;7 It has been observed in this Laboratory that 304L steel, which is unstable with respect to formation of strain induced martensite, forms surface cracks when plastically strained in a high-pressure hydrogen environment. Work in progress elsewhere concurrent with this investigation has also established that 304L is embrittled when tested in a high-pressure hydrogen atmosphere." The objective of this investigation was to study the effect of a high-pressure hydrogen environment on the tensile properties of a stainless steel that contained strain-induced martensite (304L) and one that did not (310). EXPERIMENTAL TECHNIQUES Notched and unnotched cylindrical specimens were machined from 304L* and 310 rods that were heat- treated at 1000°C in argon for 1 hr followed by a water quench. The chemical analyses of these steels are given in Table I. The unnotched specimens had a reduced section diameter of 0.184 & 0.001 in., a gage length of 0.7 in., and were threaded with a 0.5-in.-diam. thread on each end. The notched specimens had a reduced section diameter of 0.260 * 0.001 in. and a 0.75-in. gage length, with a 30 pct 60 deg v-notch at the center. The notch had a maximum root radius of 0.002 in. The tensile bars were fractured in a hydrogen or helium atmosphere of 104 psi at ambient temperatures. The system used for mechanically testing the specimens is to be described in detail elsewhere.19 Several specimens of each type were tested in air using an Instron testing machine. The same yield strength and ultimate tensile strength were obtained in 104 psi helium with the above system as with the conventional testing machine. Magnetic analysis was employed to determine that there was a (bee) martensite in plastically deformed 304L and that it was not present in plastically deformed 310. The magnetic technique depended on allowing the material being studied to serve as the core between a primary and secondary coil. Thus, any change in the amount of magnetic material present between the annealed and plastically deformed steels will be indicated by corresponding changes in the induced voltage in the secondary circuit." The ratio of the output signal of a nonmagnetic stainless steel to a completely magnetic maraging steel was 2000 to I. Several unnotched 304L bars tested in hydrogen were analyzed for hydrogen by vacuum fusion analysis. There was an increase in the hydrogen content to approximately 2 ppm for the specimens tested in hydrogen, as compared to less than 1 ppm for the as-received material. Several thin sections cut from notched areas of 304L specimens tested in hydrogen and containing the fracture surface contained approximately 1.5 ppm H. The accuracy of these determinations was estimated to be ± 50 pct.

Jan 1, 1969

By Heihachi Kamura

The reduction of iron oxide, such as Fe203, to iron in the blast furnace is performed principally by carbon monoxide, but partly by solid carbon by the two following reactions: Fe2O3 + 3CO = 2Fe 4- 3CO2 2Fe2O3 + 3C = 4Fe + 3CO2 It is known that reduction by carbon monoxide takes place at a much lower temperature than reduction by carbon and that the reducing action of earbon monoxide progresses to the inside of the ore in lump form by gaseous diffusion. In the reduction by carbon, however, the reducing action takes place only at the contact surface of the ore and carbon, so that the more complete the reduction by carbon monoxide, the more efficient is the operation. However, the reduction does not progress as shown in the foregoing equation, because carbon dioxide acts oxidizingly on the metallic iron to such a degree that when the gaseous composition reaches a certain proportion of carbon dioxide to carbon monoxide, the reduction practically stops, even though the gases are moving slowly through the heated ore. The proportions of carbon monoxide and carbon dioxide in the gas depend on the kind of iron oxide and the temperature of reduction, also on the duration of time in the reaction. The longer the time of the reaction, the higher the proportion of carbon dioxide obtained in the gas, but finally it will attain to a condition of equilibrium. Chemical Equilibrium of Iron, Oxygen, and Carbon Investigations concerning the equilibrium between iron, oxygen, and carbon have been carried out by E. Baur and A. Glaessner,1 who deter-

Jan 1, 1925

By Chi-shing Wang

The late Professor P. B. Bucky of Columbia University introduced the principles and techniques of barodynamic experimentation in early 1931 by the application of centrifugal loading to achieve dynamic similitude between models and prototypes of mine structures.1 Later, he and his associates introduced the combined experimental technique of photo- elasticity and the centrifuge to determine the stress distribution in civil engineering structures and mine workings by the use of transparent bakelite models.2,3 The photostress technique, also known as the birefringent-coating method of photoelastic stress analysis, dates back to 1930, when Mesnager published its principles.4 Since then it has been widely applied to experimental stress analyses in many industries. A practical method of observing the dynamic behavior of opaque mine models, which are made of prototype materials, by means of a combination of the centrifugal and the photostress techniques is a new experimental approach under development at the Henry Krumb School of Mines, Columbia University.5 This paper summarizes the development of the barodynamic photostress technique and presents the information obtained from a recent series of experiments in the study of the behavior of rock beams loaded by their own weight. THEORETICAL BACKGROUND Theory of Pure Bending In the general theory of strength of materials, the flexure stress at any point in a beam of any type of cross section which has a longitudinal

Jan 1, 1968

By Marion Rice

The copper-mining district of Jerome, Ariz., is of such economic importance that the following brief notes may be of interest. The ore deposits are said by Ransome1 to be pre-Cambrian, and are contained in the pre-Cambrian schists of the region. In the vicinity of the mine (the United Verde) the schist stands nearly vertical and strikes a little west of north. At least three varieties are distinguishable—(1) a green rock, schistose on its margins but grading into massive material, which is evidently an altered dioritic intrusive; (2) a rough gray schist with abundant pheno-crysts of quartz, apparently an altered rhyolite; and (3) a satiny, greenish gray, very fissile sericitic schist that may be a metamorphosed sediment. The ore occurs in varieties (2) and (3), the main belt of dioritic rock (1) lying just west of the orebodies. The ore is said to follow as a rule the layers of fine sericitic schist. T. A. Rickard2 Says that the ore at the United Verde Extension mine is found at the contact of diorite and schist, that both diorite and ore are earlier than the regional metamorphism, and that the quartz porphyry ("rhyolite" of Ransome) is of post-Cambrian age. The material considered here, a part of which was gathered by the writer, came from four of the mines of the district, and its study was undertaken at the suggestion of Dr. Berkey of Columbia University. The field relations and exact locations of the different specimens are not known, but a microscopic study of the thin sections gave some evidence as to the origin of the ore, which will be discussed below. The indications are that both ore and porphyry were introduced at the closing stages of the metamorphism, this being in accord with Ransome&apos;s view of the genetic relation of porphyry and ore rather than with the opinion that the ore is related to the diorite. Certain field occurrences mentioned in the literature also support this theory. Rickard, in the same article to which reference has been made, speaks of a vein of chalcocite several inches wide at the contact of one of the porphyry dikes, and Provot,3 although he regards the porphyry as subsequent to the ore, says: "Acid dikes encountered underground should be followed as they have been found in practice to lead to orebodies."

Jan 1, 1920

By Walter A. English, Ralph Arnold

Though production began in Canada only a short time after the discovery of oil in the United States, it has never attained large proportions, and if we were to judge entirely by the past the reserves of Canada would be put at a very low figure. There are only two areas from which oil is marketed at the present time; one, the old district around Petrolia in southern Ontario, and the other is the small Sheep Creek field near Calgary in Alberta. The former district has produced between 200,000 and 800,000 bbl. annually for the past 40 years, recent figures being near the minimum amount. Sheep Creek has produced about 12,000 bbl. annually for the past five years. The known reserves in proved territory in each of these fields are exceedingly small, when considered in terms of world reserves. The chief hope of Canada for reserves of considerable magnitude lies in the western provinces. Sedimentary rocks similar to those in the productive fields of the United States occupy thousands of square miles in the western provinces, so that it seems likely that somewhere within this great area the peculiar conditions necessary for the presence of oil pools will be found. Prospecting is being carried on energetically by several large companies, as well as by many independents. The Dominion Government, which controls most of the public lands, is pursuing a fairly liberal policy toward the prospector, which should stimulate wild-catting, although the province of British Columbia, which controls public lands within t.hat province, is at present unwilling to give adequate encouragement to make wildcatting attractive. As there is really no assurance that any productive pools will be found in western Canada, the estimates of reserves are subject to a wide possibility of error. In making estimates, the various areas within which geologic conditions are more or less uniform are discussed separately; the estimates given for each area are not given with the idea that there is a reasonable probability of their eventually proving to be correct. It is hoped that an average of these estimates, taken together with those made for other undeveloped countries, will give a correct total of reserves

Jan 1, 1923