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Large equipment for quarrying and for the various stages of crushing and grinding are the trend for new and existing operations. Included are large size haulage units, fast drilling equipment, impact crushers and large mills capable of high tonnage rates for metallic and nonmetallic minerals. In grinding, large-size mills continue as the choice in industries where grinding constitutes a major portion of the processing. Typical is a 10 x 34 ft two-compartment mill in closed circuit with an 18-ft diam air separator for cement. Other cement mill sizes are in the order of 12 x 36 ft, 2500 hp; 10 x 37 ft ball and rod (wet), 1400 hp; 13 x 36 ft, 3000 hp; 13 x 40 ft (wet), 3000 hp. Several installations of combination ball and rod mills have been made, and one of the largest is 12 x 45 ft. In connection with the wet grinding of raw materials, the DSM 270-degree screen has been installed in several cement plants with the intention of producing a material finer than 50 mesh. In ore processing, large autogenous mills (121/2 x 20 ft) are being installed.

Jan 2, 1964

By D. L. Wood

INTERNAL oxidation of alloys has been investigated by Rhinesl,2 and by Meijering and Druy-vesteyn. Rhines showed that dilute Cu-A1 alloys can be internally oxidized without forming an external scale by annealing in an oxygen partial pressure equal to the decomposition pressure of Cu2O. The oxygen is supplied at the outside surface at a rate sufficient to maintain saturation of the surface with respect to oxygen. Oxygen diffuses inward and, at the interface between the subscale and the alloy, oxygen meets the solute and reacts to precipitate its

Jan 1, 1957

GEO. F. COMSTOCK,* Niagara Falls, N. Y. (written discussion?).¬A study of this paper raises a question on which it is hoped Mr. Stork will throw more light; that is, why does an oxygen content generated on poor melting conditions have a deleterious effect on the properties of the iron, while an oxygen content generated by the oxidation of steel scrap in the cupola is beneficial to the strength and chilling ability? In each case the oxygen is absorbed at the same time and place in the process of melting and it is by no means clear why the superiority of semisteel should be assigned solely to its oxygen absorption, when oxygen absorbed without the steel addition is admitted to be injurious. It is not apparent why oxygen caused to be absorbed by the steel addition should not pro-duce the effects of burning, sluggishness, slag inclusions, gas occlusions, etc., the same as oxygen absorbed by the iron in the cupola for any other reason, and it would seen that other factors to which he has not given sufficient emphasis must enter into the author's results. To an impartial reader of this paper, who was most favorably inclined toward J. E. Johnson, Jr.'s theory of the improvement of cast iron by oxygen, the discrepancy in the author's reasoning or statements is difficult to accept, and it is hoped that an explanation will appear in the final discussion.

Jan 11, 1919

By Herbert Clark Hoover, Lou Henry Hoover

SINCE I have written of the varied work of pre- paring the ores, I will now write of the various methods of smelting them. Although those who bum, roast and calcinea the ore, take from it something which is mixed or combined with the metals ; and those who crush it with stamps take away much ; and those who wash, screen and sort it, take away still more; yet they cannot remove all which conceals the metal from the eye and renders it crude and unformed. Wherefore smelting is necessary, for by this means earths, solidified juices, and stones are separated from the metals so that they obtain their proper colour and become pure, and may be of great use to mankind in many ways. When the ore is smelted, those things which were mixed with the metal before it was melted are driven forth, because the metal is perfected by fire in this manner. Since metalliferous ores differ greatly amongst themselves, first as to the metals which they contain, then as to the quantity of the metal which is in them, and then by the fact that some are rapidly melted by fire and others slowly, there are, therefore, many methods of smelting. Constant practice has taught the

Jan 1, 1950

By L. D. Jaffe, J. H. Hollomon

THE effect of tempering temperature and time upon the properties of quenched steel is clearly a subject of great practical importance, as well as of considerable theoretical interest. It would be very desirable to be able to predict the properties of a quenched steel when given any selected tempering cycle, with a minimum of experimental work upon that heat or even type of steel. Two problems are involved: one consists of relating the structure obtained to the physical properties, and will not be discussed here; the other, with which this paper deals, involves the relations of time, temperature and composition with the structure obtained on tempering. Indentation hardness is perhaps the most convenient quantitative measure of the tempered structure, or of what might be called the "degree of tempering." Undoubtedly, it is not an exact measure, and in some cases (as when temper-brittleness occurs) pieces of the same quenched and tempered steel may have widely differing properties at the same hardness. However, hardness has the advantage of being simple to determine and is certainly the most widely used indication of the degree of tempering. Moreover, for fully quenched steels that are not temper-brittle and do not contain retained austenite when quenched, it appears that, in general, if the hardness of the steel is the same, the tensile and impact properties will also be identical, whether a high or a low tempering temperature is used. The tempering charts available in the metallurgical literature usually give the hardness as a function of tempering temperature for only one tempering time. However, in practice, tempering times frequently vary, and a method of converting tempering curves for one time to tempering curves for some other time would be very valuable. It is also advantageous, in determining the tempering treatment necessary for a given part, not to have to temper samples at several temperatures for the time used for the commercial tempering operation. A more satisfactory procedure would be to employ times of the order of 10 to 30 min., rather than 5 or 10 hr., and if possible to use only one temperature. Furthermore, it is frequently desirable, for reasons such as temper-brittleness,* to obtain a given hardness with short times at relatively high temperatures, and it would be convenient to be able to compute without tests the time required to produce this hardness. Remarkably few quantitative studies of the hardness of quenched steel tempered over wide ranges of temperature and time

Jan 1, 1945

By William M. Bowron

Thirty years ago, when I stood on the cliff of red fossil iron-ore, on Red mountain, Jefferson county, Ala., I asked what were the geological relations of this remarkable deposit. In reply I was told that it was a limestone, colored and saturated by some unknown but wholly external influences, and that at a reasonable distance from the surface the color would disappear. I could find no satisfactory explanation, either of the nature of this wonderful external permeating influence, or of the cause of such a ferrous impregnation selecting this one particular bed of limestone, to the exclusion of the higher and lower beds of the same material which are not even stained. I. The Present Theory. Referring to this subject, Dana says :' "The clays, clayey sandstones and limestones of the Clinton epoch, through New York and the Appalachians, show that the mud-flats and sand-banks, and hence the shallow seas of the coast region, still continued.... The beds of argillaceous iron-ore, which spread so widely through New York and some of the other States, west and south, could not have been formed in an open sea; for clayey iron-deposits do not accumulate under such circumstances. They are proof of extensive marshes, and, therefore, of land near the sea-level. The fragments of crinoids and shells found in these beds are evidence that they were, in part at least, salt-water marshes, and that the tides sometimes reached them." At first, this explanation seemed satisfactory, but the more I studied the ore the less satisfying the explanation became. 1. In the ore itself, I found associated with the small particles of rounded matter (now consisting of iron oxide in which organic structure, if ever present, has become lost, though the

Jan 1, 1906

By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

By Guillermo V. Borquez

INTRODUCTION The basic factors that influence the selection of a mining method are the geometry of the ore deposit and the strength of the ore and surrounding rock. These factors usually determine the ore recovery and dilution of the deposit under analysis. For the purpose of this paper we will consider a generalized case of a block caving system and the sequence of the analysis needed to optimize ore recovery. The analysis presented is intended for the preliminary planning stage. The critical factors involved in the caving process are identified and the methods for evaluating the suitability of a particular deposit to the caving method of mining are outlined. The mine design is approached by identifying the two most important, dimensions: the size and spacing of the draw points. These dimensions are estimated from a simulation model which takes into account the ore recovery, the incremental value of the ore recovered, and the safety conditions of the operations. The model estimates the number of draw points required to extract efficiently and safely the broken ore from the caving area. This number is found in the range where the net incremental value of the ore is maximized and the probability of pillar failure does not exceed the limit which is acceptable for a safe mining operation. A mining method and its design are in a continuous process of optimization. This process is unique for each deposit because of the many parameters involved; therefore, a back analysis of the operations should be performed when possible. These analyses will indicate if the ore body responds in a predictable manner to the parameters contained in the geological, fragmentation, and draw point models. SELECTION OF ALTERNATIVE MINING METHODS The selection of a mining method best suited to define the minable ore reserves of a given deposit involves consideration of the geometry of the ore deposit and the strength of the ore and surrounding rock. These two factors are usually sufficient to determine the ore recovery and dilution of the deposit. After analyzing the geological reserves and defining the limits of the deposit, either an open pit or an underground mining method can be selected to define the minable ore reserves. The sequence of steps to follow in the selection of a mining method is presented in Figure I. From an economic point of view, the strip- ping ratio is the determining factor for the selection between an underground or open pit method. In turn, the stripping ratio is a function of the grade distribution and con- figuration of the ore body. In order to obtain a preliminary estimation of the stripping ratio, a parametric analysis could be applied, such as the approach used by Professor E. P. Pfleider (1972) and summarized in Table 1.

Jan 1, 1981

By J. C. Purcupile, R. L. Morris

Present methods of roof support require that first a hole must be drilled, and then a toggle belt or grouted resin bolt be set. Automating this system is very difficult. Therefore, we decided to develop a system which would insert pins into the roof in one step. We think that this type of system can be automated much easier. It would then speed up the roof bolting operation and eliminate the need for a man to work under unsupported roof, making roof bolting a much safer job. There are two ways that a pin can be inserted in a mine roof without drilling a hole. It can either be pushed in, using a very high, constant axial force; or it can be hammered in like a nail. The former method involves very high compressive stresses in the pin, and requires complicated machinery to prevent buckling. Since hammering the pin does not require high axial forces buckling is not as likely. Also, experiments have shown that there are no problems associated with getting the pin to go in straight. We chose to develop the second method. While investigating methods for hammering a pin into a mine roof, we learned that piles were being driven 10 times faster than by conventional methods with a method called "orboresonance." We decided to turn the pile driver upside down, and drive pins up into the mine roof. Sonic Pin Setting Machine The machine consists of a steel bar supported at the nodal points of its first mode of transverse vibration (Fig. 1). A mechanical oscillator, driven by a hydraulic motor, is attached to one end of the bar. This provides the forcing function for the vibrations in the bar. The hydraulic power is supplied by a portable unit. When the forcing function is near the natural frequency of the bar, large amplitudes of vibration occur and require little power input. An anvil is attached to the bar at a point of maximum deflection, providing a means for striking the pin. Since the bar is being driven near its natural frequency, it takes little energy to accelerate the bar back and forth between each hit. This means that most of the power being put into the bar is going into driving the pin. This is unlike conventional pile drivers which use most of their power to accelerate the hammer back and forth between hits. The resonant frequency of the bar we used is about 250 Hz, which is in the audible range, hence the term "sonic pin setting machine." The system benefits are: (1) elimination of the two-step drilling and pin-setting roof bolt operation, (2) increased speed, (3) more intimate contact between the formation and bolts, (4) less expensive roof bolts, (5) higher integrity, (6) potential for automatic operation. Modifications During the months from Oct. to Dec. 12, 1974, under U.S. Bureau of Mines grant No. 00144104, "Projects on Coal Extraction," six members of the senior class at Carnegie Mellon University designed and built the experimental machine. They drove three pins into the Safety Research coal mine at Bruceton, Pa., and determined that the project was worth continuing. In January 1975 we began making modifications and repairs in preparation for a more extensive program of testing at Bruceton. The major items were: 1) Design and build a collapsible pin guide to keep the pin parallel with the line of travel of the lift table. 2) Move the anvil to the center of the bar. 3) Refinish the nodal holes and install new node pins and bushings. 4) Realign the bar in its frame. 5) Install a relief valve on the lift unit to control the upward force. The upward force that we exert on the pin is relatively small, so there is no tendency for it to buckle. This means that all we need to do is hold the pin straight during its initial penetration. This allows the bushing to travel up and down in a straight line. At the beginning of penetration, the bushing

Jan 1, 1977

THIS chapter and Chapter 19 deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the first two laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only: 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the heat balance of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced. The cause probably lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities in flow distribution and air leakage present in any real open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot- metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million Btu per net ton of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million Btu and the sensible heat in the preheated air at the port ends is 117 million Btu, so that the total heat input at the ports is 477 million Btu. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million Btu, but 120 million of this is supplied by the heat in the hot metal and by various heat-evolving reactions in the bath,

Jan 1, 1964

By W. N. Best

Crude oil attracted attention because of its excellence as a fuel for openhearth furnaoes; for making crucible steel and brass; for melting copper, lead, tin, zinc, nickel, silver, malleable iron, gray iron; and for the production of steam in all sizes and types of boilers. For heating furnaces, mold-drying ovens, core ovens, ore roasters, calciners, hotair furnaces, sand drying, asphalt road work, etc., its superiority over other fuels is due to the fact that the heat is at all times under perfect control, so that a constant temperature may be attained and maintained at the will of the operator. This mcans a maximum amount and uniform quality of work. Crude oil is of two kinds, paraffine base and asphaltum base, and varies from 11 to 46 gravity BaumB. The light-gravity oil does not require heating before use; but oil of less than 20 gravity Baumé should be heated to just below its vaporizing point, in order to reduce its viscosity and to obtain the highest efficiency of combustion. Heavy California oil vaporizes at 230". F., Mexican crude oil at from 175" to 210" F., and Beaumont, Texas, oil at 142" F. Fuel oil vaporizes at 130" F. Scientific Installation Essential The burning of oil is an art based on science, and the "rule of thumb" should never be employed, especially in heating heavy crude oil. Thermometers should be used on both suction and supply pipes so that the fireman or smith will at all times know the temperature of the fuel. The indicators on such thermometers should be large enough to be readily seen by the operator, night or day. It is necessary to have an unvarying pressure of steam or air through the burner, to atomize the fuel. Also, the air used to support combustion should be delivered through a nozzle under the burner at a constant pressure. The oil pressure must not fluctuate; under no eircumstances should it vary more than 1 1b. The oil pump, which should be brass-lined, with the aid of the pulsometer and superheater, will insure a constant

Jan 1, 1916

By Benny Langston, Frank M. Jr. Stephens

IN recent years much attention has been given to recovery, treatment, and disposal of dusts discharged into the atmosphere from operations of industry. Considerable data has been accumulated on both operational1-4 and design5,6 of dust-collector equipment for commercial installations. On the other hand, there is almost no published data on design and construction of small-scale equipment to handle dust problems that arise in the ore-dressing laboratory. Dust-collection equipment such as multiclones, single-cyclones, scrubbers, chemical and mechanical filters, settling chambers, and electrostatic separators has proved its efficiency for collecting dust in industry. In the laboratory, however, the engineer is faced with the problem of collecting small quantities of dust, inexpensively, without diverting the major effort from the metallurgical problem to the problem of collecting dust produced by the process.

Jan 8, 1954

Jan 1, 1966

By Eduardo Martinez Baca

Although Mexico has always been justly considered by the whole world essentially a mining country, this reputation is due principally to the richness of the deposits which have been worked. In reality, the majority of the States have been little

Jan 1, 1902

By Y. Shimomura, M. Serizawa, Y. Takahashi, K. Miyagawa

The "semi-pellet" sintering method developed and currently being used at the Fuji Iron & Steel's Hirohata Works is discusssd. It is shown that the method makes fine-sized material easily sinterable and increases sinter production. The operation can be incorporated readily into conventional sintering plants. Sintering plant raw materials currently being used in the Hirohata Works consist of 40 pct pyrite cinder, 40 pct fines resulting from crushing and screening of imported ores, and 20 pct others, such as mill scale and iron sands. Pyrite cinder, a major component in the sinter feed, has been getting finer since 1952, due to the increased grinding required for the improvement of the results in the iron sulfide flotation and to the adoption of FluoSolid roasters in sul-furic acid plants; some fines pass 100-mesh sieve almost completely. Increased use of the fine-sized pyrite cinders in the sinter raw mix resulted in such difficulties as decreased bed permeability, uneven firing conditions, and low yield. In an attempt to study the cause and to find a remedy for this problem, a series of experiments were made, using an 80-kg experimental sintering pan. As a result it was established that, by rolling the fine-sized pyrite cinders into small balls of 10 to 3 mm diam (hereafter called semi-pellets) and mixing them into the sinter raw mix, the bed permeability was improved, the sintering time shortened, and the yield and production rate increased. It is proposed that this new method be called the semi-pellet sintem'ng. In recent years the pelletizing process has taken the spotlight in the agglomeration field for treating fine-sized ores here in Japan as well as in the U.S. and Europe. This process produces pellets suitable for the blast furnace charge as such, and consists of three major operations: fine grinding, balling, and firing. With regard to the firing technique, some problems still appear unsolved. In the semi-pellet sintering, however, several ad- vantages can be claimed: the balling operation is relatively simple because only small-sized balls are shown to be acceptable and the operation can be readily incorporated into the conventional sintering plant, since only balling, not grinding or firing, equipment is needed. Basic test work on the process was initiated in 1954 and favorable results were obtained. Accordingly a pilot plant was built in 1955 and the test work was continued. The semi-pellets thus prepared in the pilot plant were tested further by USing them in the actual sintering pan and their beneficial effects ascertained. In late 1956 a drum-type balling machine (2.4X4 m) was installed and it went into operation in April 1957 in conjunction with the Greenawalt sintering plant (8 pans having dimensions of 7.2 m in length, 3 m in width, and 0.3 m in depth). In October 1958 a cone-type pelletizer, with a 2.2 m diam, and later a disk-type pelletizer were further added in the plant. In the DL sintering plant (2000 tpd), newly built in July, 1960, four disk-type pelletizers (3.2 m diam, 10 tph capacity) were installed. By mixing the semi-pellets thus prepared with the feed, the sintering operation was found to be greatly improved. The results of the basic test work, and the equipment and operation of the semi-pellet sintering operation at the Hirohata Works will be described. ON THE SINTERING CHARACTERISTICS OF FINE SIZED PYRITE CINDERS To ascertain the effect of addition of fine-sized pyrite cinders on the sintering characteristics, a series of measurements on bed permeability was carried out by varying the size distribution of pyrite cinders. The composition of the raw mix used in the tests was fixed at 50 pct pyrite cinder, 20 pct Larap magnetite fines, 30 pct sinter return, and 5 pct coke; only the size distribution of the pyrite cinder was varied. Also the moisture content was changed at each size distribution. The results are given in Fig. 1. For all pyrite cinders tested the bed

Jan 1, 1961

By Karl Cohen

The question of attainment of competitive nuclear electric power is of interest to uranium producers because the rate of attainment of this goal determines the date when there will be a solid, non-political, domestic uranium market. It is a burning question to those of us in the civilian nuclear power business, because our entire business future hinges on how well, and how soon, we can make electricity from nuclear reactions at prices comparable to electricity from coal. For an idea of the magnitudes involved, consider that the first fuel load of the Dresden (Illinois) nuclear power station, plus spares, will be about 90 tons of 1.5 pct UO2. This requires about two-and- a-half times as much natural uranium oxide feed to the diffusion plant, or 225 tons. This, in turn, represents about a month's production from the nearby Uranium Reduction Co. mill. Note also that the 180,000 kw electric output of the Dresden station will be about 0.1 pct of the national electric generating capacity in 1960.

Jan 12, 1958

Joseph HartshoRnE, Pottstown, Pa.: I have read Professor Akerman's valuable paper with great interest. Few of the present generation of American steel metallurgists are aware of the very important part taken by Swedish engineers in the successful development of the Bessemer proeess, and I am afraid some of the older ones have forgotten it. Certainly, I think, most of us would have said that Terre Noire was the first to introduce the use of metal direct from the blast-furnace. It is very well, therefore, that honor should be given to whom honor is due. I can speak from personal experience upon one part only of Prof. Akerman's paper; namely, the effect of the temperature at which the molten metal is cast upon the quality of the finished steel. In a general way I have, of course, known for a long time that the

Jan 1, 1894

By C. D. Young

IN an effort to employ cast steel of a stronger structure than that found in the annealed steel castings, the possibilities of heat treatment which will increase the strength without materially decreasing the ductility may be resorted to. The following abstracted report (which is a brief outline of what has already been clone by the Pennsylvania Railroad Co. at its shops and Test Laboratories at Altoona, Pa.) is of material interest, as it indicates what may be done with steel castings when properly treated, thereby permitting in railway service greater strength of cast steel parts without any increase in weight or space. The question of the heat treatment of alloy steel castings is not taken up in this paper. The obscurity formerly surrounding the heat treatment of steel has been for the most part removed by the development of our knowledge of the critical points of steel, pyrometers, furnace construction, and the testing of the finished product. The operations of the heat treatment proper will be taken up under the heads of (1) heating for quenching; (2) quenching; (3) drawing. (1) Heating for Quenching.-Heating for quenching is best conducted slowly, especially in the case of castings of variable thickness. Cracks may occur either in heating or in cooling, clue to different temperatures at different points of the casting. The castings should be thoroughly soaked at the maximum temperature (generally 1,500° to 1,600° F.), 1 hr. being sufficient for sections 1 ft. in thickness. The minimum temperature which will produce the desired hardening effect will, in all cases, be found to be the most satisfactory, as the grain coarsens when the critical range is exceeded to too great an extent. All temperatures should be governed by a checked pyrometer with the hot junction to the heated object, and with several couples in a large furnace to insure a uniform temperature.

Jan 2, 1914

By S. Sumski, M. B. Panish, R. T. Lynch

The liquidus isotherms in the gallium-rich corner of the Ga-Al-P phase diagram have been determined from 1000" to 1200°C and at I100°C the corresponding solidus isotherm was obtained. A simple thermody-namic treatment which permits calculation of the solidus and liquidus isotherms is discussed. A technique which was previously used for the growth of GaxAl1-xAs was used for the preparation of solution epitaxial layers of GaxAl1-xP and ALP. An approximate value of 2.49 i 0.05 ev for the band gap of Alp at 300°K was obtained and the ternary phase data were used to estimate a value of 36 kcal per mole for the heat of formation 0f Alp at that temperature. The Gap-A1P crystalline solid solution is one in which there exists the possibility of obtaining crystals with selected energy gaps, within the limits imposed by the energy gaps of Gap and Alp. Such crystals are of considerable interest because of their potential value for optoelectronic and other solid-state devices. Furthermore, it has been amply demonstrated for GaAs and GaP,'-7 that device, or bulk materials grown from gallium solution generally have more efficient radiative recombination than materials prepared in other ways. This presumably due to the lower gallium vacancy concentration in such material.= Small crystals of GaXAl1-xP and A1P have been grown from solution,8-10 and A1P has been grown from the vapor," but neither have previously been grown by liquid epitaxy. In this paper we present the ternary liquidus-solidus phase diagram of the Ga-A1-P system in the region of primary interest for solution epitaxy, and discuss the thermodynamic implications of that phase diagram with particular reference to the liquidus and solidus isotherms in the gallium-rich corner of the GaxAl1-xP primary phase field and to the A1-P system. Several measurements of the absorption edge of GaxAl1-xP crystals have been made and the width of the forbidden gap of A1P has been estimated from these measurements. EXPERIMENTAL The differential thermal analysis technique used to determine the liquidus isotherms and the optical measurements used in this work are similar to those described previously12 for the Ga-Al-As system, ex- thermocouples in the thermopile for added sensitivity. The materials used were semiconductor grade Ga, Gap, and Al+ The composition and temperature range at which DTA studies could be done was quite restricted. The upper temperature was limited by the chrome l-alumel thermopile to about 1200°C, and the highest aluminum concentration to about 5 at. pct by low sensitivity caused by the reduced solubility of Gap with increasing aluminum concentration in the liquid. DTA studies were not possible at 1000°C and below because of the low sensitivity caused by low solubility of Gap in the Ga-A1-P system. The cooling rate for these studies was about 1°C per min. No heating studies were done because of limited sensitivity. Supercooling probably does occur, but our experience with other 111-V systems indicates that it is no greater than about 10 to 15.c. Solid solubilities were determined by analyzing epitaxial layers of GaxAl1-xP grown from the liquid, with an electron beam microprobe. The layers were grown on Gap seeds by a tipping technique in which the layer is grown over a short-temperature range (20" to 50°C) on the seed from a solution of known composition. The tipping technique reported by Nelsson1 for GaAs could not be used, particularly for solutions containing appreciable amounts of aluminum, because of the formation of an A1203 scum on the liquid surface. A system was therefore designed, which would effectively remove the oxides mechanically, so that uniform wetting and crystal growth could occur. This tipping technique has already been described in detail." The best control over the composition of the re-grown layer was obtained when the tipping was done at a temperature which corresponded to the temperature of first formation of solid for the solution being used. Generally, therefore, a solution was prepared by adding the amounts of Ga, Gap, and A1 required to yield a solution which would be completely liquid above the tipping temperature with solid precipitating below that temperature. For most of the work reported here, the 1100°C isotherm of the ternary was used. It was generally necessary to heat the solution to 50" to l00. C above the tipping temperature to dissolve all of the Gap in a reasonable length of time. The epitaxially grown layers were used both for optical transmission measurements to aid in the estimation of the way in which the absorption edge changed with aluminum concentration, and for the electron beam microprobe analyses to provide data for the determination of the solid solubility isotherm. RESULTS AND DISCUSSION Liquidus Isotherms in the Ga-A1-P Ternary Phase Diagram: Thermodynamic properties of the system. The only thermal effect studied in this work was that

Jan 1, 1970

By E. P. Haqyes, J. K. Butler

011, and gas development has continued unabated on the Texas Gulf Coast during 1937. Although the number of important new discoveries has not been great, the extensions in older fields, owing to discovery of new sands and the lateral extension of known sands, has been extensive. Twenty-four new producing fields were added during the year, and many of these areas give promise of developing into important producing districts in the future. Alta Mesa, Amelia, Aransas, Clara Driscoll, Five Corners, Hamman, Heyser, Old Ocean, Premont, Seabreeae, Segno and West Columbia have all had major extensions during 1937. The 1937 production for the Texas Gulf Coast was 120,141,429 bbl., or 32f per cent increase over the 1936 production of 90,865,293 bb1. t The total number of producing wells has increased from 6727 to 8968. Well abandonments have becn few and indications are that they will continue to be so. Rigid proration has been and continues to be in effect, and, as a result, wells in the Gulf Coast will have prolonged life. New Fields Tables 1 and 2 contain general information on all fields in this district. The following named fields were discovered in 1937: Aransas County.—Barnsdall Oil Company's No. 1-A Edwards was the discovery well for the Lamar field. It was drilled to a total depth of 9785 ft., plugged back and completed at 7530 ft. in the Frio as a gas and distillate well. Present indications are not very promising for a major field. Bee County.—The McMurray (Strauch) field was discovered by Dirks Bros. No. 1 Strauch at a total depth of 4577 ft. This is a Yegua producer, and had an initial production of 230 bbl. on a 3/16-in. choke. Brazoria County.—The Sandy Point field was discovered by Henry DeArmanls No. 1 Fite, which was completed as a producer at 6501 ft. in the Marginulina-Frio series. Galveston County.—Although the Hitchcock field was discovered in 1936, the first commercial oil producer was completed in 1937 when

Jan 1, 1938