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By M. R. Lorenz

Efficient visible light emission from p-n junctions in semiconductors is currently achieved in the four materials, Sic, GaP, ]Ga1-xAs and GaAs1-x,. Recent advances in materials preparation and p-n junction formation are briefly reviewed. The radiative recombination processes in the different materials depend largely on the band structure and the impurity states of each material. The spectral distribution of the emission ranges from the blue in Sic, to green in Gap, yellow in Sic and red in Gap, Ga1-x AlxAs and GaAs1-x Px. The origin of the various processes are discussed. The conversion of the electrical power into optical power and the measurement of the conversion efficiency are reviewed. The currently maximum quantum efficiencies at 300°K are: 3 pct in GaP(red), 1 pct in SiC(yellow), 0.1 pct in GaP(green), 0.2 pct in Ga1-x AlxAs at 66001, and 0.1 pct in GaAs1-x Px at 6800. The brightness and the interplay of the quantum efficiency and the luminous efficiency are given detailed consideration. VISIBLE light generated by the application of a direct current to a semiconductor crystal was first observed by Lossev1 in 1923. Light emission came from naturally occurring junctions in Sic crystals but little was known then with regard to the mechanism of charge transport and light emission. Some nearly 30 years later and with a vastly increased understanding of semiconductors the phenomenon of electroluminescence was studied in more detail, for example in p-n junctions of germanium.2 In these early studies, the efficiency of converting the electron current into a photon current was very low and therefore aroused little interest toward practical application. More recently it became apparent that in certain materials, for instance GaAs, and under certain conditions, the conversion efficiency was not low at all.3 The subsequent discovery of the p-n junction laser4-6 provided the impetus for increased studies of electroluminescence. Light emitted from GaAs occurs in the infrared region of the electromagnetic spectrum and is not visible to the eye. At nearly the same time the use of GaAs1-xPx led to laser action at low temperatures which was visible to the eye.7 Later a red light emitting diode, made from Gap, was reportedS which emitted incoherent radiation at 300°K with an external quantum efficiency of about 1.5 pct. The fact that such efficient devices were obtainable led to a more concentrated effort in the search for highly efficient room-temperature semiconductor light sources. It is some of this later work on p-n junction luminescence with which we will be concerned here. Since our aim is centered on visible light, with hv =1.8 ev ( ?=7000?), only the wider band gap semiconductors are of interest, i.e., Eg 1 1.8 ev. Although many compounds meet this criterion, only a limited number of those are also good semiconductors, i.e. contain low resistance n and p regions. Some of the more promising candidates are listed in Table I. We will only be concerned with light generation from a p-n junction. This limitation excludes essentially the group II-VI binary compounds, although we will briefly review the case of ZnTe and the solid solution ZnTe1-xSex. As we will show they may contain a p-n junction but only of a special kind. Most of the discussion will deal with the four materials, Sic, Gap, Gal-xAlxAs, and GaAs1-xPx. These appear to be at the present time the best visible light emitting semiconductors. In the following sections we will briefly consider: 1) the electrical properties of p-n junctions; 2) some recent advances in materials preparation; 3) the formation of p-n junctions; and then in somewhat greater detail we will consider: 4) the various radiative recombination processes; 5) the measurement and observation of the external quantum efficiency; 6) the luminous efficiency; 7) the brightness of light emitting diodes (LED'S). THE P-N JUNCTION The p-n junction in a semiconductor crystal is the interface between two differently doped regions. More specifically the p region is doped predominantly with acceptor impurities and the n region contains predominantly donor impurities. The energy band structure of a degenerate p-n junction at thermal equilibrium is shown in Fig. l(a). The excess electrons on the n side of the junction are confined to this region by the barrier potential Eg. Similarly the excess holes on the p-side of the junction are confined to the p-region by a similar potential barrier. If we now apply a dc voltage V such that the p region is made positive and the n region negative, the barrier potential EB is reduced by the applied voltage, V and the junction is said to be forward biased. With the barrier potential lowered, electrons and holes can drift toward the p region and n region, respectively, see Fig. l(b). The current voltage characteristics of p-n junctions in most wide band gap materials can be described by the relation: J = Joexp(eV/BkT) [1] where the functional form of Jo is determined by the recombination mechanism. Jo is generally a complicated parameter which depends on a number of different factors including temperature, junction width, bias voltage, and carrier lifetimes. The parameter B also depends on the recombination mechanism but

Jan 1, 1970

By Byron B. Morton

NICKEL-BEARING alloys are associated with petroleum in the fields of exploration, production, and refining. In the first- named field the geologist of today makes use of such instruments as the seismograph, torsion balance, and magnetometer, the selection of proper alloys and metals for the manufacture of which is an important matter. Nickel-bearing alloys are useful for parts that require resistance to corrosion or that must have non-magnetic properties. Where special co- efficient of thermal expansion are de- sired, they are obtained by using alloys high in nickel (20 to 60 per cent), since, by varying the nickel contents, alloys can be obtained ranging fro111 "Invar", with a low expansion between -40 and 175 cleg. F., to those with coefficients of expansion exceeding that of steels. The latter are obtained by additions of chromiurn to the alloys. Alloys containing 50 to 80 per cent of nickel, which possess high magnetic permeability, find application in certain instruments where this property is important.

Jan 1, 1935

Robert T. Hill, Washington, D. C.: Having studied very minutely the geology of the district referred to by Prof. Branner, I beg to state that his quotation of my classification of the Cretaceous deposits of Arkansas is not the one which I originally gave,* nor is it the one which has since been published and is now generally accepted.? I did not assign ally of the Cretaceous formations of Arkansas to the " middle Cretaceous,"

Jan 1, 1898

By G. Stuart Jenkins

Conditions at the properties of the Consolidated Coal Co. had reached a point where improvements were almost impractical. The mines, sunk years ago, had shafts and entries so small as to preclude the use of large mine cars. A radical change was necessary in the type of mining and also in the type of mine to accommodate such haulage units. After due consideration, the company decided to enter the field of trackless mining, utilizing belt conveyors and chain-flight conveyors, the belt conveyors to take the long haul, and the chain-flight conveyors to be used for gathering. It was decided not to sink a shaft, hut to drive a slope on an inclination of 17½°, which the company believes to be about the limit on which coal can be carried on a belt without rolling back unduly. Sinking the Slope It was decided, in sinking the slope, to make an opencut until rock was reached, which was some 65 ft. below the surface, and then to drive the slope through an inclined tunnel from that point. In making the open-cut, the schedule called for the removal of about 25,000 cu. yd. of clay, holding the banks on an inclination of one and a half to one, the thought being to make this cut in a minimum of time, put in a reinforced concrete slope, and then back-fill. Difficulty was experienced because the clay was of a sort that was called "subsiding base" material by contractors visiting the job. In other words, a "squeeze" occurred, the pressure causing the floor of the cut to move up just as it does in many mines where the coal is underlain by thick fire clay and inadequate pillars have been left. It was necessary to move the waste banks back from the edge of the cut 700 or 800 ft., and even then the floor could not be controlled, the result being that almost 100,000 cu. yd. of clay was handled before the rock was reached. A concrete slope was then rapidly constructed, using 95 tons of special-shaped reinforcing iron. The floor of this slope was made 30 in. thick at the bottom, and 17 in. thick at the top, the sidewalls being 18 in.

Jan 1, 1940

By G. Stuart Jenkins

Conditions at the properties of the Consolidated Coal Co. had reached a point where improvements were almost impractical. The mines, sunk years ago, had shafts and entries so small as to preclude the use of large mine cars. A radical change was necessary in the type of mining and also in the type of mine to accommodate such haulage units. After due consideration, the company decided to enter the field of trackless mining, utilizing belt conveyors and chain-flight conveyors, the belt conveyors to take the long haul, and the chain-flight conveyors to be used for gathering. It was decided not to sink a shaft, hut to drive a slope on an inclination of 17½°, which the company believes to be about the limit on which coal can be carried on a belt without rolling back unduly. Sinking the Slope It was decided, in sinking the slope, to make an opencut until rock was reached, which was some 65 ft. below the surface, and then to drive the slope through an inclined tunnel from that point. In making the open-cut, the schedule called for the removal of about 25,000 cu. yd. of clay, holding the banks on an inclination of one and a half to one, the thought being to make this cut in a minimum of time, put in a reinforced concrete slope, and then back-fill. Difficulty was experienced because the clay was of a sort that was called "subsiding base" material by contractors visiting the job. In other words, a "squeeze" occurred, the pressure causing the floor of the cut to move up just as it does in many mines where the coal is underlain by thick fire clay and inadequate pillars have been left. It was necessary to move the waste banks back from the edge of the cut 700 or 800 ft., and even then the floor could not be controlled, the result being that almost 100,000 cu. yd. of clay was handled before the rock was reached. A concrete slope was then rapidly constructed, using 95 tons of special-shaped reinforcing iron. The floor of this slope was made 30 in. thick at the bottom, and 17 in. thick at the top, the sidewalls being 18 in.

Jan 1, 1940

By Thomas L. Kesler

Essentially all of the barite produced in Georgia has come from the Cartersville district in the northwest part of the state. The earliest recorded shipment of ore, 60 tons, was made in 1894.1 With the exception of the four-year period 1931 to 1934, the separate yearly output has been recorded and published since 1915, whereas the total yearly output of the United States has been published since 1880. The separately recorded production of Georgia (Cartersville) through 1947 is 2,232,544 short tons valued at $14,900,746,2 but unpublished data on the period 1931 to 1934, plus the estimated unrecorded output prior to 1915, make the actual total about 2,400,000 short tons. This is about 21 pct of the total production of the United States, which, through 1947, is 11,328,440 short tons valued at $71,683,386.2

Jan 1, 1949

By John Gjers

Being on a visit to your great and prosperous country, and having been favored with an invitation to attend this meeting of your Institute, the author has been requested by your Secretary to give a short account of his invention of the " soaking-pit," which he has great pleasure in doing. The object of the soaking-pit is the rolling of steel ingots with their own initial heat, that is, to supply the missing link in that chain of metallurgical operations which Sir Henry Bessemer began in 1857, when he proved how it was possible to produce malleable iron or steel direct from the fluid cast-iron out of the blast-furnace, without any further direct use of fuel. The great Bessemer invention has revolutionized iron and steelmaking throughout the world; but it stopped short at producing the ingot, which, it was found, had afterwards to be heated in a furnace to enable it to be rolled or hammered; and it is only lately, twenty-five years after Mr. Bessemer's announcement, that the author of this paper has been able to show that furnacing can be dispensed with, and that it is practicable to roll a steel ingot into say a bloom, a rail, or a billet, with its own initial heat. It has no doubt suggested itself to many that there ought to be heat enough in the ingot just cast, for the purpose of rolling; and from time to time attempts have been made to utilize this heat; but such attempts always ending in failure, it became a settled opinion in the trade that it could not be done—an opinion which the author is aware that your late lamented countryman, Mr. Holley, than whom there was none more conversant with Bessemer steel-making, also entertained. But settled opinions sometimes prove to be great fallacies. As an instance, it is not many years since the opinion prevailed in the trade that steel ingots could not be rolled successfully, that is, so as to make good rails, unless they were first allowed to get quite cold, and afterwards heated. No greater boon was ever conferred on the

Jan 1, 1885

By R. S. Newlin

IN reality, the Butte district is the birthplace of the Anaconda Copper Mining Co., for it was here that strength was gathered and means provided for later expansions of the Company. The Butte district was organized at a miners' meeting on Aug. 20, 1866, primarily for gold placer-mining operations. Substantial amounts of placer gold were recovered from gulch gravels during the period 1862 to 1868. The earliest lode claim locations in the district were recorded in July and August 1864. Copper ore was first shipped, to Swansea, Wales, in 1866. In November 1866, according to the Montana Post, construction of a smelter was started to treat the silver

Jan 1, 1948

By Robert S. Shoemaker

At this Symposium on Gold which is sponsored by The Metallurgical Society of AIME and the International Precious Metals Institute many distinguished authors will present the latest developments in the metallurgy of gold and in operating practices at mines and in refineries. It seems appropriate then, as the introduction to this volume to recall some of the history of gold and the metallurgical developments which have been accomplished, especially during the past 100 years and some of the people who have contributed so much to the metallurgy of gold. Of all the elements gold has been the most sought after since the earliest times. Perhaps the quotation from Virgil's Aeneid best describes man's desire for gold but Pliny the Elder also put it very well when he wrote in 79 A.D. that "Gold is the first of man's follies, silver the second". This quest for gold has markedly influenced man's history and through the efforts of the early philosophers and alchemists to turn base metals into gold the foundations for modern chemistry were laid. The pages of history literally teem with references to gold. Gold is the first metal mentioned in the Bible and was the source of Croesus wealth as well as the death of King Midas whose touch turned everything into gold. And of course almost everyone has heard of Jason's Argonauts and the golden fleece. They are the subject of one of the many drawings in Agricola's De Re Metallica published in 1556. The Argonauts were probably prospectors seeking the source of the placers in the region near-the Black Sea. The time was about 1200 B.C. and the placer miners recovered gold by trapping the particles in sheep's fleeces placed in sluices. After drying, the fleeces were shaken to recover the gold. Gold is not hydrophilic, or wetted by water and thus the oils in the wool aided in collecting the particles. Here we have perhaps the earliest reference to surface chemistry and the basis for concentration of gold by flotation.

Jan 1, 1984

By Charles H. Fulton

THE Engineering Education group began its sessions Tuesday morning, Feb. 16, as a Committee and wound up the day as the Institute's fifth " Division." C.II. Fulton presided. The first paper for discussion was entitled "Teaching Management in Engineering Schools,"' by Eugene McAuliffe, president of the Union Pacific Coal Co., space for which may be found later in these pages. In it, Mr. McAuliffe argued that an engineering student should be taught the knowledge of men, much as a medical school teaches surgery. He then went on to indicate, out of the wealth of his administrative experience, the problems an executive needs to be equipped to handle, and said that every student engineer should look on himself as a potential manager.

Jan 1, 1932

By Lucius W. Mayer

The iron-mines of the Ilsede Hütte Co. are at a town called Peine, about 20 miles east of the city of Hanover, on the railroad to Brunswick (Braunschweig). Hanover, the capital of the province, is a military city, of approximately 250,000 inhabitants, and Brunswick, 33 miles to the westward, has half this number. The mines here described are located in a hamlet called Bülten. The Ilsede Hütte Co. operates two mines, 1.5 miles apart, in this district, Gruber Bülten Adenstadt and Gruber Lengede Bodenstadt. It also operates an iron-mine north of Hanover, known as Eiserhaven, and one in the Harz mountains, the Georg Friedrich, at Grauhof. At Bülten a coarse conglomerate, a, Figs. 1 and 2, contains nodules of limonite, cemented together by calcium phosphate. The ore contains Fe, 25 to 45; Mn, 3 to 4; P, 0.6 to 1.4; S, 0.02 to 0.09; and CaCO3, 40 per cent. Directly above the conglomerate is limestone, b, followed by a mixture of clay and sand, c. Below the conglomerate is a hard clay floor, d. The ore-body, from 10 to, 12 km. long, and from 3 to 4 km. wide, has a maximum thickness of 20 m. It clips approximately 10° S.E., and strikes N. 45° E. Diamond-drill prospecting shows that the thickness diminishes to 1 m. as the end of the deposit is approached to the northward. At this point the deposit is 250 m. below the surface. In Fig. 2, the arrow, A, indicates the general direction of the work along the face, a, which is carried forward in a straight line for its entire length. At B, a train is approaching, which has come from the bench-track, shown at G, by a circuitous route, and is dumping the overburden behind the face, in the space left by the excavated rock. Formerly the work at this mine was essentially open-cut, the deposit having a very strong outcrop. Figs. 1 and 2 show also

Sep 1, 1908

By R. S. Craig, W. E. Wallace, G. S. Kamath

The destruction of long-range order in Mg-Cd, has previously been thought to occur as a second order process. In the present work a variety of X-ray diffraction techniques are employed to show that in this case and in Mg-Cd alloys containing frorn 20 to 33 1/3 at. pct Mg the process more nearly resembles an ordinary first order phase transformation. It is found that the ordered alloy, which occurs as a single phase at lgw temperatures, transforms with increasing temperature into a Cd-enriched disordered (P) phase and an Mg-enriched ordered (a) phase. The interval over which these two phases coexist under apparently equilibrium conditiovs extends from 25" to 87°C content. At 33 1/3 at. pct Mg the two-phase region has disappeared. Measurement of the long range order parameter, s, for the ordered phase in MgCd, (from superlattice line intensities) shows that it disorders only very slightly before it is transformed into the p form. Kinetic experiments reveal that when the a phase is formed frorn the p phase by suitably quenching so as to suppress phase segregation, the transformation is essentially complete and the a phase has acquired its equilibrium value of S in less than 1 min. In an earlier investigation carried out in this Laboratory1 the rate of disordering of the MgCd3 superlattice was determined over an extensive range of temperature. The process was found to be first order and the rate constant, k, was established. At the lowest temperatures studied k was found to increase exponentially with temperature. At higher temperatures, however, it passed through a maximum and for the 100 deg interval below the point at which the superlattice was destroyed k was observed to decrease with increasing temperature. The various theoretical treatments1-3 of order-disorder phenomena lead to a negative temperature coefficient for k near the superlattice critical temperature but this region for MgCdB seemed unusually wide. Detailed analysis of the point indicated' that either the long-range order parameter, S, for MgCda varied with temperature in an anomalous way or the disordering in this instance is more complex than in the cases which have been treated theoretically. The original objective in the present work was simply to determine S vs temperature for MgCda to ascertain whether the disordering was in conformity with theoretical expectations.2° In an early stage of the work it was noted, however, that under equilibrium conditions ordered (a) and disordered (0) phases coexist in MgCd, over a considerable range of temperature. Since on thermo- dynamic grounds the coexisting phases must differ in composition, the investigation was enlarged to permit the compositions of the two phases in MgCd3 to be determined and to establish the extent of the two phase regions for alloys containing from 20 to 33 1/3 at. pct Cd.

Jan 1, 1963

By G. W. Preckshot, J. W. Gorman

MOLTEN metals offer an excellent medium for the study of molecular diffusion and interphase transfer. In the absence of intermetallic compound formation, solutions of molten metals are solutions of elements. Therefore, complicating factors such as molecular structure, dissociation, association, polarization, and so on, are generally absent. Further, metals remain in the liquid state over a wide range of temperature. Thus, the effect of temperature on transport processes can be studied in more detail. Although some data are available for the diffusion of metals in the molten state at high temperatures,"""".'!' the most useful and accurate data are those for the diffusion of various elements in mercury at room temperature. The effective radius of diffusion for the various elements in mercury may be calculated from the Stokes-Einstein relation.'-These calculated radii are compared with the atomic and ionic radii calculated from X-ray data on crystals." The effective radii of diffusion of the alkali and alkali-earth metals correspond to those of the neutral atom; those of cadmium, silver, lead, zinc, thallium, bismuth, and tin correspond to ionic radii; and those of copper and gold indicate larger radii due to association with mercury or more likely, faulty diffusion data. Independent evidence"' supports the notion that alkali metals are uncharged in amalgams. The concept of metals moving free of their conductance electrons in the liquid state has been discussed by Eyring, et al,'" in connection with studies on the viscosity of pure molten metals. Considering the approximate nature of the tabulated atomic and ionic radii and the variance in the diffusion measurements, the application of the Stokes-Einstein equation to the diffusion of metals in mercury gives gratifying results. It is noted that a number of these metals have article radii eaual to or less than those of the solvent mercury.".'*,"' Soba1,'" sing the inaccurate Roberts-Austin20 data, indicated that the effective radius of diffusion might well be a function of temperature. Additionally in studies of mass transfer between phases, many conflicting opinions have been expressed concerning the assumption of equilibrium at the interface." ,","," The results of the present work on the diffusion of solid copper in molten lead throws light on the tempera- ture variation of the diffusion radius as well as the extent of the interfacial resistance. The theoretical background and experimental procedure are presented here in detail. Results on other systems will be presented in subsequent papers. Nomenclature The following nomenclature is used in the paper: A—cross-sectional area of diffusion column, sq cm C, C,—concentration of solution and saturated solution respectively, g per cc D,D'—-diffusivity, sq cm per sec e—Naperian base h—ratio, k/D k—mass-transfer coefficient, cm per sec L—diffusion column length, cm n—series index q—flux, g per sq cm-sec r—radius, cm or A R—-gas constant t—time, sec T—temperature, K V—volume, cc w—weight of copper-lead alloy on copper cylinder WT—-total copper transferred to lead diffusion, column, g Z—distance from top of diffusion column, cm 2'—distance from copper-lead interface, cm (2' = L-2) u,,—roots of diffusion equation Mathematical Apparatus The model shown in Fig. 1 applies to the diffusion of solid copper into molten lead. Here Fick's first law may be written where all terms are defined in the nomenclature. It is assumed that the volume of the lead column is constant. This is justified since experimental densities compared favorably with calculated densities based on perfect interstitial mixing. Thus there is no counter diffusion of lead. It is clear that 2 in Equation [I] should be measured relative to the interface which moves relative to the diffusion cell but not to the liquid phase. Hence, the frame of reference is the plane of the copper-lead interface. The diffusivity calculated at constant volume, D", is that defined by Hartly and Crank" and is designated herein as D. No Interfacial Resistance—The two situations of the presence and absence of interfacial resistance will be treated. The simplest is the latter which re-

Jan 1, 1959

By H. Le Chatelier

An evident connection exists between chemical and calorific phenomena: the most important, of our sources of heat, the combustion of coal, is nothing else than a chemical reaction. Not satisfied with this indefinite statement, investigators have attempted to establish a more precise correlation between these two orders of phenomena, and have questioned whether there be not a necessary connection between the possibility of a chemical reaction and the algebraic sign of the quantity of heat which it would call into play (i.e., liberate or absorb). This question possesses the highest interest for metallurgical chemists. But the study of it by experimental methods only could not completely elucidate it. To arrive at a definite solution, it was necessary to appeal to a science much more general than chemistry,—namely, that of energetics, which embraces all the physical sciences. We can place absolute confidence in its conclusions, because they rest upon a proposition which can scarcely be denied, namely, the impossibility of The main facts in the history of the development o‡ this field of Triassic coals have been already set before the Institute in the papers of Mr. Oswald J. Heinrich, a former member of the Institute and the superintendent of the mines at Midlothian. † From these and other references to the field, it appears that coal was known to exist here as early as 1701; for on the 10th of May that year Colonel Byrd reported to the Colonial Council of Virginia the discovery of coal. Coal was mined from 1770 to 1780; but the amount shipped is unknown. It was much used in Richmond at this early date for gratefires. In 1789 shipments were made to northern ports. During the first half of the century just passed, mining operations attained in this field their greatest development, the number and extent of the collieries and the tonnage of coal raised per annum being greater for that period than for any similar period since. The maximum annual output exceeded 100,000 tons, while in two years only since the Civil War has the amount of coal raised exceeded 50,000 tons. This field covers about 150 sq. in. Its outline and the position of the strata in which the coal-outcrops occur are shown on the accompanying map, reproduced from the latest survey by the U. S. Geological Survey. Mining has been carried on along the margins of the area, often in the primitive manner in vogue at the beginning of operations, by means of shafts and slopes, usually too small in cross-section to permit the proper working of the beds. Most of the output has been won from

Jan 1, 1902

By Kenneth Robertson

ALL, strangers visiting this district are struck with the peculiar manner in which the pig-iron is graded. There are eleven regular grades, besides which, when gray forge is ordered, one-half of Nos. 1 and 2 Mill are shipped. Occasionally there is another grade Known as Silver Mill, which is made so seldom that I cannot describe it, and have no sample to exhibit. Most of you have found it difficult to grade properly and uniformly under the simpler system which obtains elsewhere, and can consequently readily imagine the increased difficulty with us. Each furnace employs an " expert," and even with this precaution, the system is not conducive, at all times, to amicable relations between buyers and sellers. I am told that it was adopted at the time Southern irons were seeking a market; but it still remains, although the time has come when our iron is sought for and has obtained for itself a place in the markets of the country. The grades are as follows:

Jan 1, 1889

By G. W. Tracy, R. D. Carter

Numerical calculations were made to determine the behavior of reservoirs with high-pressure drawdown and wide well spacing where the initial productivity is low and the wells are completed by hydraulic fracturing. The two-phase flow equations were solved for the flow into a single well. This well was assumed to be producing from a reservoir with hydraulically created horizontal fractures (four different systems with fractures were studied). For comparison purposes, additional two-phase flow calculations were made assuming a reservoir with uniform rock properties. The two-phase flow results were also compared with the conventional calculation methods, which do not include the effect of saturation gradients resulting from a simultaneous flow of oil and gas which are normal to this type reservoir. It was found that the conventional methods predict (1) a high and too optimistic value of ultimate recovery, (2) a high producing rate and a high reservoir pressure at a given oil recovery and (3) a low trend of gas-oil ratio with oil recovery. Included in the two-phase flow calculations were provisions to control the oil production rate by an allowable rate and, also, by a gas-oil ratio penalty rule. For the systems with hydraulic fractures, the producing rate was controlled by the gas-oil ratio penalty rule for most of the life. This is in contrast to the system with uniform rock properties which went "on decline" almost immediately. An unexpected characteristic of the systems which included fractures was the early rise in producing gas-oil ratio from 730 cu ft/bbl to approximately 1,200 cu ft/bbl, followed by a "leveling off" before the normally expected gas-oil ratio rise began. Additional features which are a result of hydraulic fracturing are (I) greater ultimate recovery, (2) higher average producing rates and (3) a lower average reservoir pressure at a given oil recovery. INTRODUCTION Some oil fields discovered during the past few years are producing from certain volumetric ally controlled reservoirs (often referred to as solution or internal gas- drive reservoirs) which are characterized by high-pressure drawdown at the wells. Since the available pressure drawdown at a well is limited by the static reservoir pressure and the producing rate is controlled by the available drawdown, wells completed in this type of reservoir usually produce at a rate less than the allowable from the time of completion. Because of this, this type of reservoir is referred to as a low productivity reservoir. Economic considerations require the use of wide well spacing and well stimulation by hydraulic fracturing to make commercial wells in this type of reservoir. Performance predictions for volumetrically controlled reservoirs have been made using a combination of two standard equations. 1. The "Schilthuis" or "Muskat" type material balance equation is used to relate the average reservoir pressure and the cumulative oil recovery. 2. The results from the material balance equation and the productivity factor as described by Pirson' are used to relate the cumulative recovery with producing rate and time. The material balance equation assumed uniform pressure and liquid saturation conditions throughout a reservoir. The steady-state radial flow formula allows for a pressure gradient toward a well but assumes uniform liquid saturation. These calculation methods are adequate for application to reservoirs wherein the drawdown at the well to realize satisfactory producing rates is small compared to the total pressure. In low productivity, volumetrically controlled reservoirs, the pressure drawdown at the well is large cornpared to the total pressure. Although a precise number cannot be given for the magnitude of a large pressure drawdown, values in excess of 1,000 psi would definitely be included. For practical considerations, this usually occurs when the formation flow capacity is less than about 100 md-ft. However, this limit of formation flow capacity will vary with the well producing rate. The low pressure in the neighborhood of the well which results from a high drawdown causes evolution of large volumes of gas. This causes the gas saturation to be higher near the well than at a greater distance—-hence, a non-uniform gas saturation. Also, the relationship between the relative permeability to oil (K/K) and gas saturation is nonlinear but decreases approximately in an exponential way with increases in gas saturation. Because of this, the following chain reaction is established.

By E. Gybbon Spilsbury

It is not my purpose in this paper to describe all the different contrivances which have been devised, during the last quarter of a century, for the purpose of Iessening the expense of mining and tunnelling operations; I wish merely to call your attention to the crying want of the Western miners for some cheap and effective machine, capable of economizing on the heavy item of hand-drilling, and to enumerate a few of the latest improvements which have been made in machines of this class. This necessity for the introduction of some kind of labor-saving machinery in mining, especially in the West, begins to make itself felt more imperatively every day. No branch of industry has remained so conservative to the old customs and systems of working, as has mining; and yet no branch is so entirely dependent on economical working for a successful issue; and in very few is the proportion of cost of hand-labor to profits obtained so preponderantly heavy. Perhaps the chief reason for this seeming apathy towards progress in this direction arises from the fact that nearly all mining operations, especially in this country, are carried on in regions more or less remote from the great centres of civilization, thereby rendering the carriage and erection of machinery extremely difficult and expensive. Another reason, however, exists in the fact that a large number of men in charge of mining operations are greatly prejudiced against the introduction of machinery underground, from the idea that it cannot be made to adapt itself to the various positions and

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The microhardness of single crystals of tungsten disilicide has been investigated by the Knoop method. The average random room-temperature hardness of the WSi, matrix was 1350 kg per sq mm. Hardness crnisotropy was noted with respect to plane and indenter orientation as determined by single-crq.stal X-rny studies. Annealing at 1600" and 1800°C decreased the average hardness to 1310 and 1230 kg per sq tnm, respectively, and produced a second phase identified by X-ray diffraction and electron-microprobe analysis to be wSio.7. Ball-impact experiwzents produced rosettes at 850°C. Optical and electron microscopy showed evidence of slip and cross slip and twinning produced by microhardness indentations. Prismatic (100), [001] slip was found and cor~elated with hardness data. THE present study was undertaken to investigate the hardness anisotropy of as-grown and annealed single crystals of tungsten disilicide. The existence of the silicide WSiz in the W-Si system has been well-established and its structure thoroughly investigated zachariasen2 found WSi, to have a tetragonal C type of structure, similar to that of MoSi, with lattice parameters a = 3.212A, Kieffer et al. studied the W-Si system and measured the density and microhardness (at a 100-g load) of both polycrystalline WSi, and WSi,.,. The values found were 9.25 g per cu cm and 1090 kg per sq mm for WSi,, and 12.21 per cu cm and 770 kg per sq mm for WSi0.7, respectively. According to Samsonov et a1.5 the microhardness of polycrystalline WSi2 is 1430 kg per sq mm (at a 120-g load). EXPERIMENTAL The WSi, single-crystal boules investigated in this paper were grown by a Verneuil-type process using an electric arc by the Linde Division of the Union Carbide Corp.6 The largest specimens were 8 mm in diameter by 16 mm long. The crystals had an average density of 9.01 g per cu cm with a tungsten • silicon content of 99.9 wt pct. The major impurities were: 87 ppm O, 41 ppm N. 54 pprn C, 500 ppm Zr, 50 ppm Na, and 50 ppm Mn. The crystals were silicon-poor, the average silicon content being 22.20 pct (stoichiometric value is 23.40 pct), and tungsten-rich, the average tungsten content being 77.70 pct (stoichiometric value is 76.60 pct). As-received single crystals were ground and analyzed by powder X-ray diffraction technique using Cu Ka radiation. Laue and layer line rotation patterns were obtained on cleaved sections of WSi, single crystals. Electron-microprobe traverses of representative crystals were done using a Phillips-AMR electron microanalyzer. Carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to the metallographic examination, the specimens were mounted in Lucite and then polished for short times on polishing wheels using 9-, 3-, and 1-p diamond-grade pastes. Finally they were fine-polished with Linde A powder for 24 hr on a Syntron vibratory polisher. The samples were etched with 4H 2 O:1HF:2HNO3, which is a medium fast-acting etchant. The combination 1HF:2HNO3:5 lactic acid is also a satisfactory etchant. Annealing runs for selected specimens were made at 1600" and 1800°C for 3 hr at 1.0 to 3.0 x 10-5 mm Hg. A Brew tantalum resistance furnace with WSi2 powder for setters was used. The WSi2 powder was the same as that used for the crystal growth. Temperatures were measured with a calibrated W, W-26 pct Re thermocouple and a microoptical pyrometer. Powder X-ray diffraction, emission spectrographic, and electron-microprobe analyses were done after the annealing runs. For microhardness measurements a Tukon Microhardness Tester Type FB with a Knoop indenter was used. Although measurements were taken at loads ranging from 25 to 1000 g, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Only indentations of cracking classes 1 and 2 were considered.' DISCUSSION OF RESULTS Powder X-ray diffraction analysis showed the as-received crystals to be single-phase WSi2. Laue and layer line rotation patterns obtained on cleaved sections of WSi2 single crystals proved them to be tetragonal WS 2 2 The results also indicated that the c axis of the crystal was oriented parallel to the boule or growth axis. Electron-microprobe traverses across the matrix of the as-grown crystals showed them to be homogeneous WSi,. Optical and electron microscopy of etched crystals, however, revealed that they contained minute amounts of the "golden" and the "blue" second phases as opposed to the "white" or WSi2 phase. These two second phases were concentrated in inclusion and etch-pit

Jan 1, 1965

By Lyall Zickrick

As a result of the studies on recrystallization and crystal growth made in this laboratory, certain theories have been developed. These are expressed briefly in a paper by Dean and Hudson.1 One of the principal points brought out in that paper is that in the deformation of a crystal, the energy supplied is distributed to the atoms of the lattice, probably by the forced formation of molecules. It is found that a Maxwellian distribution of the energy among these atoms will account for the grain growth at various temperatures. According to such a distribution the number of atoms with energy above a certain critical value, E, necessary for recrystallization at the absolute temperature T is given by n Ne(-E/kT) where N is the total number of atoms. It is apparent that if this line of reasoning is correct, a metal which has been cold-worked and reheated to a temperature below that of complete annealing will have the atoms with the higher energy recrystallized, that is, reduced to normal energy and there will remain only atoms below a certain energy. If this metal is again cold-worked the peak in the number-energy distribution curve will be displaced toward the regions of lower energies, that is, higher temperature of recrystallization. By a repetition of this process the position of this maximum and hence the recrystallization temperature of the metal could be raised considerably. In order to' check this theory, experiments have been made on copper wire. The wire was drawn from 1/4-in. rod to 22 B & S gage and then sample lots were annealed at 400 and 220° C., respectively. The wire annealed at 400° C. gave an elongation of 34 per cent., whereas that annealed at 220° C. gave only 23 per cent. These wires were then drawn by identical practice to 34 B & S gage and the elongation determined after an anneal of 3 mm. in an oil bath held at various temperatures.

Jan 1, 1927

"The reduction works of the Boston & Montana Reduction department, near the north end of this dam is one of the reduction plants belonging to the Anaconda Copper Mining Company, the other being at Anaconda. These works employ about 1,100 men and have a capacity of about 3,800 tons of crude ore per day. This plant is now being remodeled to embody results of experiments and investigations which have been made with a view to more economic.al treatment of ores. A brief description of the plant as it will be after the remodelling is as follows:Concentrator Department: Consists of six units or sections, each section treating from 550 to 600 tons of crude ore per day. This department is not being. remodelled at the present time. A concentrating process, however, has been developed and partially installed in the old mill, and an experimental section embodying this concentration process has also been installed at the concentrator at Anaconda."

Jan 1, 1913