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CHARLES H. MACDOWELL F. V. DESLOGE CHAIRMAN OF CHICAGO CHAIRMAN OF ST. Louis SECTION SECTION R. J. GRANT F. W. BRADLEY CHAIRMAN OF COLORADO CHAIRMAN OF SAN FRANCISCO SECTION SECTION

Jan 7, 1919

SINCE I have begun to tell you of the semiminerals that serve as colors, I wish to tell you of azure and green azure, so that you may know what they are. I tell you first that there are two kinds of azure, one called ultramarine blue by painters, and the other German blue. Ultra-

Jan 1, 1942

ARTICLE I: NAME AND OBJECTS Section 1: This Division shall be known as the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers. Section 2: The objects shall be to furnish a medium of cooperation between those interested in the metal-lurgy and industry of iron and steel manufacture and use; to represent the A. I. M. E. in so far as ferrous metallurgy is concerned, within the rights given by A. I. M. E. By-law XVII, Section 3, and not incon-sistent with the Constitution and By-Laws of the A. I. M. E.; to hold meetings for social intercourse and the discussion of ferrous metallurgy; to stimulate the writing, presentation and discussion of papers of high quality on ferrous metallurgy; to reject or accept such apers for publication and distribution by-the A. I. M. E. within the limits of the funds available for such purpose. ARTICLE II: MEMBERS Section 1: Any Member, Associate, or Junior Asso-ciate of the A. I. M. E. in good standing may become a Member, Associate or Junior Associate of this Divi-sion upon registering in writing a desire so to do. Section 2: But no one who has been continuously indebted to the. A. I. M. E. or to this Division for more than three months shall be entitled to vote or to receive publications to which, as a member of the Division, he would be entitled.

Jan 7, 1928

NORMAN B. PILLING (author's reply to discussion *).-The discussion by Mr, Bassett raised one or two points that deserve further discussion. The printed figure for the lead content of the copper used was 0.015 per cent. and not 0.15 per cent., upon which his comment was based. A copper having the latter figure would, of course, be quite unusual. Mr. Bassett takes exception to the writer's statement regarding the distribution of cuprous oxide in wrought copper and states that "the FIG. 1.--ROLLED AND ANNEALED SHEET. ETCHED WITH AMMONIA AND HYDROGEN PEROXIDE. X 75. eutectic of copper with cuprous oxide is usually found between the crystals of pure copper, whether in the cast or the wrought form." While it is very well known that during the solidification of cast copper the cuprous oxide is segregated completely as an envelope of cuprous oxide-copper eutectic around the crystals of copper free from oxide, it is the writer's opinion that, as a result of repeated rolling, this eutectic structure is quite destroyed and the small particles of cuprous oxide become widely scattered, and in the recrystallization following, during annealing, the rearrangement of the grain boundaries takes place with much indifference to the actual distribution of these particles. In the accompanying micrograph, taken from a rolled and annealed sheet, the random distribution of the small cuprous-oxide particles with reference to the location of the grain boundaries may be seen.

Jan 3, 1919

By W. P. Ward

I desire ho put on record a fact in relation to the effect of man ganese on pig iron which I have never seen in print, and which may, perhaps, not have been observed by anyone except myself. In 1875, while experimenting on the production of ferroman ganese in a blast furnace, I had burdened the furnace with a charge which I calculated would produce a 15-per cent. spiegel. The fur nace was very hot, having been running for a couple of days on a very light burden, and making a burnt iron, preparatory to the experiment I proposed to make to produce a high grade of spiegel. I calculated that the charge would begin to work in the fur nace in about twelve hoars after it was put on. After the -lapse of that time I commenced to watch the furnace carefully, but found little or no change in the appearance of the metal, although there was a very decided change in the cinder, showing that the man ganese ore had come in work. The iron was quite gray and very tough. The character of the cinder was good for a spiegel cinder, and 1 could not imagine where the manganese was going to, as it (lid not appear to be in either metal or cinder in anything like the quan tity indicated by the charge. The next morning things were still in the same condition. The furnace was very hot, the cinder good, and the iron very gray. I was then sorely puzzled. I had never heard of a gray iron with over 4 or 6 per cent. of manganese, and had no notion that an iron with more manganese could be gray and tough. With great difficulty a piece for chemical test was broken from a pig. Not less than a hundred blows from a heavy sledge were required to break it off, I took the specimen to the shop and directed that some borings from it should be brought to the laboratory, as soon as possible, whither I myself at once repaired to put things in readi ness for a rapid manganese determination. In about half an hour the machinist came in with the iron specimen in one hand and about a dozen blunted and broken steel drills in the other, saying that it mas impossible to drill the iron. There were several little depressions in the iron, which was malleable enough to be indented by the point of the drill, but not a chip had been cut from it. The metal was never subjected to further physical tests. A chip broken from

Jan 1, 1882

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 Tom W. Pfeifle, Paul E. Senseny

INTRODUCTION Engineered structures such as mines, shafts and tunnels, and storage caverns for hydrocarbons, chemical s and brine are being built in natural rock salt formations in increasing numbers. In addition, salt formations are being considered as potential hosts for mined, nuclear waste repositories. The popularity of these formations for engineering purposes stems from the many favorable commercial, physical, and thermal characteristics attributed to the material itself. Not only have the formations been stable and free of dissolution for hundreds of millions of years, but the salt is fairly easily mined and has very low permeability, low water content, and high thermal conductivity. Another characteristic of salt is its tendency to flow or creep when subjected to a shear stress. Although this behavior may be desirable in certain instances, it may be detrimental in other instances since the creep rate may be large enough to produce deformations that tend to reduce the volume of storage caverns or to restrict access to mining operations. In either case, the engineer is faced with the problem of accurately predicting the long-term structural deformations under various combinations of stress and temperature and is required to compare these deformations with long-term design criteria. In the laboratory, deformation-versus-time curves obtained at constant stress and temperature show that creep of salt is similar to creep of many other crystal line solids. Figure 1 shows a typical deformation-versus-time curve for salt. When a shear stress is first applied, the rate of deformation is high, but decreases monotonically. This initial behavior is called transient or primary creep. At some time, the deformation rate no longer decreases but continues at a constant rate. This behavior is called steady-state

Jan 1, 1982

(Under this heading will be published notes sent to the Secretary of the Institute by members or other persons introduced by members) Member, aged 32. Fifteen years' experience in the mining, quarrying, and manufacture of gypsum and gypsum products, as purchasing agent, designer, operating manager and managing executive. Thoroughly familiar with the business in all branches, especially the organization of efficient producing forces and machinery and the value of cost and their application to manufacturing. Desires responsible position with a financially reliable concern in the same or similar business in which an interest may be obtained at a later date. Now doing consulting work, but free for appointments after April 1. New York or Philadelphia. No. 345. Member, technical graduate. Unmarried. Aged 32. Seven and one half years' experience in mining, timbering, and mine sampling. At present, and for past two and a half years, mine sampler for well known and highly successful mining company. Desire change. Go anywhere. Prefer assisting Mining Engineer. No. 346. Member, 40 years old. 18 years' experience in examinations and operation in the United States, Mexico and South America. Especially successful with poor class of labor. Open for engagement in any part of the world, in technical, administrative or consulting work. No. 347. Member, technical graduate. Sixteen years' experience as engineer, superintendent, and manager in metal mines. Exploratory . work, developing and equipping new properties. Operation of large mines, and various systems of mining. Low costs. Specialized in iron and copper mining, but have had some experience in zinc, lead and pyrite mining. No; 348.

Jan 4, 1917

By Russell G. Haworth

Three companies, United States Potash Company, Potash Company of America, and International Minerals and Chemical Corporation, are now operating potash mines and refineries in the Carlsbad, New Mexico, area. The three mines are located approximately twenty miles east of Carlsbad. The deposits have been found ideal for mechanized mining methods. This summary has been compiled from information made available by the three operating companies.

Jan 1, 1949

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 D. W. Brunton

Discussion of the paper of D. W. Brunton, presented at the Spokane meeting, September, 1909, and published in Bulletin No. 33, September, 1909, pp. 837 to 855. WILLIAM' KENT, New York, N. Y.:-The Institute may congratulate itself on the opportunity of reading the splendid address of President Brunton. It is au admirable summary of the progress that has been made in the mining and metallurgical arts in recent years. The paper rightly give's the chief credit for this progress to the aid which has been rendered to these arts by the advances in mechanics, chemistry, and electricity. It is notable that most of the headings in Mr. Brunton's address refer to the work of the mechanical engineer, the electrical engineer, and the chemist, rather than to that of the specialist in mining-operations. It seems that. the most successful mining engineer of the present day is the one who makes the most intelligent application of the inventions and designs of engineers and others who are not directly engaged in mining. A tabulation' of the headings of the address, grouped as below, shows this most clearly. Work of the Mechanical Engineer-Rock-drills, hoisting-machinery, tramming, pumping, ventilation, dredging, sampling, concentration, briquetting, fume-recovery. Work of the Electrical Engineer-Electric machinery for hoisting, pumping, tramming, lighting and signaling, electric . transmission, electric smelting. Work of the Chemist and Metallurgist-Explosives, chlorination, cyanidation, roasting, lead-smelting, and copper-smelting. Work of the Geologist-Economic geology. Work of the Mining Engineer-Mine-mapping, surface-mining, timbering, tunneling; and planning and supervision of the work in general. The mining engineer of the present day, who is in responsible charge of a large plant, finds his chief work not in doing

Jan 1, 1910

By L. A. Wilson, P. J. Root

The relative costs of heating a reservoir by steam injection and by combustion have been examined. The comparison was based on a model similar to that proposed by Chu.' The cost of boiler feed water, the price of fuel, pressure and plant capacity were parameters in determin-ing the costs of air compression and steam generation. The analyses compare the cost of heating to the same radius by the two methods. Results suggest that the two primary factors for comparison are the price of fuel and the amount of crude burned during underground combustion. The cost of fuel has a greater effect on the cost of heat from steam than it does on its cost by combustion. As a result, analyses indicate that when the price of fuel is low, steam may be unequivocally cheaper than air. The influence of heat loss is such, however, that as the heated radius increases combustion becomes relatively more competitive depending upon the amount of crude burned. This implies that steam may be cheaper for small stimulation jobs (huff and puff) but combustion may be more economically attractive for heating large areas (flooding). INTRODUCTION Use of thermal methods of recovery is an accepted fact today. After an induction period of several years, processes are being widely used that involve reservoir heating to augment recovery. Of the several techniques, steam injection and forward combustion appear to be destined to dominate the field. Although the objectives of both are the same, the basic differences between generating heat in situ and injecting heat after surface generation influence the cost in different ways. This study compares the cost of heating a reservoir either by steam injection or by forward combustion. There has been no consideration of recovery. Presumably, recovery from the swept region would be high in either case. The sole consideration was the cost of heating to the same radial distance by either process. PROCEDURE THE MODEL The basis for comparison was a mathematical model similar to that used by Chu' for combustion. The model simulates a radial heat wave in two-dimensional cylindricaI coordinates. It includes heat generation, conduction and convection within the reservoir and conduction in the bounding formations. Thus, heat losses from the formation are considered. Three significant modifications were made. 1. Equal logarithmic increments rather than equal increments were used for the mesh spacing in the r direction. By this technique large distances were simulated with relatively few mesh spaces. 2. A backward difference approximation to the convection term was used to avoid troublesome oscillations which result from a central difference approximation when the convection term is large. 3. The radial increments of the combustion zone motion were not necessarily uniquely related to the mesh configuration. The cumbersome step function introduced by the heat of vaporization of steam was circumvented by assuming the enthalpy of the steam to be a linear function of temperature between reservoir temperature and steam temperature. This is equivalent to assuming an average heat capacity numerically equal to the difference between the enthalpy of saturated steam and the enthalpy of water at reservoir temperature divided by the difference between the two temperatures. Heat losses obtained by this model are in essential agreement with those obtained by the analytical solution of Rubenshtein.' A detailed description of the model is presented in the Appendix. Using the model, the times required to heat to particular radial distances were obtained as a function of injection rate and other physical parameters. For the steam case, injected fluid was assumed to be saturated steam at pressures of either 500, 1,000 or 1,500 psia. The corresponding temperatures are 467, 544 and 596F, respectively. Thickness ranged from 10 to 50 ft and injection rate ranged from 100,000 to 1 million Ib/D. Reservoir and overburden temperatures at the injection well were assumed to be that of saturated steam at the injection pressure. The effect of maintaining the overburden temperature at the well at a different temperature (initial reservoir temperature) was examined with no significant change in behavior. The influence of wellbore heat losses for the steam case was determined in the following manner. The rates of heat loss as a function of time were estimated using an approach similar to that suggested by Ramey." he data were based on injection through 2%-in. tubing in 7-in. casing. Integration of these data over the entire iniection period yielded the total heat loss. Total heat losses were then corrected to their equivalents in steam (this number resulted from dividing the total heat loss by the latent heat). This was considered additional steam required to accomplish the reservoir heating and the total cost was increased accordingly.

Jan 1, 1967

By G. L. Craig

COPPER containing a small amount of arsenic has been used extensively abroad, and a number of reports, particularly those by English workers, have indicated that such copper is better suited for certain uses than high-conductivity copper. Inasmuch as a large percentage of the copper fabricated is used for nonelectrical purposes where high conductivity is not at all essential, it has been suggested that arsenical copper might be at least as suitable as high-conductivity copper for many purposes. An investigation spon-sored by the Calumet & Hecla Consolidated Copper Co. at Battelle Memorial Institute was therefore undertaken with the object of determin-ing the effect of small amounts of arsenic (up to 0.75 per cent) on the properties of copper. In this work the effect of arsenic on the basic properties of tough-pitch and of phosphorized copper have been critically studied and many data collected from laboratory experiments which have been supplemented by mill-scale tests. The results of these tests, with coppers of the type referred to, in the annealed condition and after various degrees of reduction, show that the basic properties of copper are not greatly affected by small amounts of arsenic, an increase in strength being observed with increasing arsenic with no corresponding decrease in ductility. It is well known that the evaluation of material for plastic deforma-tion, on the basis of laboratory tests, may not be directly comparable with its performance in commercial operations. In order, therefore, to substantiate the data obtained at the Institute, the cooperation of the Wolverine Tube Co. was obtained for a series of production tests on the fabrication characteristics of phosphorized arsenical copper in the manu-facture of seamless copper tubing. In these tests the behavior of the arsenical coppers was carefully observed in comparison with that of representative types of phosphorized arsenic-free copper, which were fabricated under the same conditions.

Jan 1, 1933

The opening session* was held in the hall of the Franklin Institute, on Tuesday evening, June 20th, President Holley in the chair. The President introduced Mr. Franklin B. Gowen, who addressed the Institute as follows: Mr. President and Gentlemen : It has been made my pleasant duty to welcome you to the city of Philadelphia, but in so doing I shrink, with some natural reluctance, from appearing before an audience so much better fitted than I am to cope with the subjects which are usually presented to your association, and I can assure you that no trembling neophyte, first venturing within the groves of the Academy, or walking, with sacred reverence, in the gardens of Plato, felt more natural dread at the consequence of his own temerity than I do in appearing before an audience composed of geutlenlen belonging to a scientific society of which I am but too sensible that until now I have been a member only in name. In olden times, upon entering a temple sacred to the worship of any deity, it was customary to lay some offering upon the altar, and, in following this custom, it will be my duty, before entering upon the more pleasant part of the task which is assigned me, to call your attention to a subject with which I have been somewhat familiar, and which is entirely within the scope of your investigations, in the belief that I may throw out some hints or some suggestions of a process that may be fully developed by some of you, and eventually lead to the introduction of that which may be of service to the human race. The satirist who described the philosopher whom he met, as engaged in the process of extracting sunbeams from cucumbers,

EXECUTIVE COMMITTEE OF THE BOARD OF DIRECTORS W M Peirce, Chairman Philip Kraft, Vice-Chairman Francis B Foley Hjalmar W Johnson Thomas G Moore ENDOWMENT Cleveland E Dodge, Chairman C F Kelley John D Bradley Harvey S Mudd J Coulter W A Sinsheimer N Eavenson Wilfred Sykes C Jackling Clyde E Weed

Jan 1, 1951

By Charles M. Rolker

It is now three years ago that I wrote a paper on the fire which broke out in October, 1880, at the Chrysolite mine, Leadville, Col orado, of which I was at that time manager. The paper was read by title at the Harrisburg meeting in 1881, and was accompanied by plans and sections fully illustrating it. It was written to invite a general discussion of the course pursued in the management of that fire, since the various fragmentary and sometimes prejudiced or inaccurate newspaper accounts were not suitable to base judg ment on. The paper I offered, gave the facts as they appeared in the contemporaneous record which I had kept. At that time, a dif ference of opinion had arisen with an adjoining mine, as to possible damages entailed through the fire; and a law suit was talked of. In view of these circumstances, the President of the Chrysolite Company advised a temporary withdrawal of my paper. Somewhat later, I withdrew it entirely, because of the unlooked-for delay in * arranging the controversy referred to. It. has now, indeed, been amicably settled; but the lapse of time has deprived the matter of much of its immediate professional interest. To the urgent request of some of the members, that I should, at least, give a description of the fire- and gas-proof bulkheads employed, I yield with some hesitation, since I lay no claim whatsoever to orig inality in these devices, and therefore question the value of such a paper. The fire originated by accident, in the Chrysolite, a mine comprising extensive and more or less irregular workings, containing immense quantities of timbering, but partially packed with waste rock or earth. This class of mines is numerously represented at

Jan 1, 1885

By J. W. Cuthbertson, R. A. Cresswell

THE constitution of Cu-rich alloys with 1.5 to 13.5 pct Sn and 0.25 to 3.0 pct Be and the precipitation-hardening characteristics of alloys with 1.5 to 13.5 pct Sn and 0.25 to 1.0 pct Be have been examined. The hardness and tensile strength of the alloys examined increase markedly after solution treatment at 700°C followed by heat treatment at temperatures between 200" and 450°C. By a combination of cold work and heat treatment, hardness values similar to those exhibited by commercial Be-Cu alloys containing 2.25 pct Be can be obtained with ternary alloys containing 9 pct Sn and 0.75 pct Be and containing 10 pct Sn and 0.5 pct Be. Marked hardening effects occur with alloys containing even less beryllium. By heat treatment alone, a hardness value of 310 diamond pyramid hardness can be obtained from an alloy containing 10 pct Sn and 0.75 pct Be. Preliminary tensile tests have shown that an ultimate tensile strength of 110,000 psi with an elongation of 23 pct is obtainable by precipitation hardening an alloy with 8 pct Sn and 0.75 pct Be. The precipitation-hardening process has been followed microscopically for certain alloys and the inference is that, while the initial hardening effect is probably explained by the precipitation of the ß phase of the Cu-Be system, further hardening, proceeding at a much slower rate, also occurs, apparently as a result of precipitation of phases of the Cu-Sn system, particularly precipitation of the 6 phase at temperatures below 350". The presence of the e phase of the Cu-Sn system in certain alloys at temperatures below 350°C has been confirmed. Tin-bronzes are widely used in engineering applications where a combination of high strength and good resistance to corrosion is wanted. The maximum strength is induced in these alloys by cold working, and it would be an advantage for many purposes if high strength could be achieved alternatively by an age-hardening process. While Cu-Sn alloys have a good fatigue resistance they can be surpassed in this respect by Cu-Be, but the use of the latter alloy is limited by its high cost. If, by adding beryllium to tin-bronze, the properties of the respective binary alloys could to some extent be combined, a most attractive alloy should result. As pointed out by Raynor,¹ beryllium is on the borderline of the zone of favorable size factors for copper, and the solid solubility of beryllium in copper is consequently much more restricted than if the size factor were strongly favorable. The size factor is sufficiently favorable, however, to permit an increase in solid solubility with rise in temperature, and there is thus a composition range in which CU- Be alloys are susceptible to hardening by precipitation heat treatment. Although the a phase of the Cu-Sn system is similarly susceptible to precipitation treatment, the time necessary to establish equilibrium in commercial alloys of this type is usually so great that age hardening becomes impracticable. The addition of beryllium to Cu-Sn alloys would appear to offer a means of conferring on the latter useful age-hardening properties. Masing and Dahl² and others have, in fact, shown that the addition of beryllium to Cu-Sn a solid solutions renders these alloys susceptible to precipitation hardening and after such hardening confers on them an encouraging improvement in physical properties. If this improvement could be achieved by the addition of substantially smaller amounts of beryllium than are customarily found in binary Cu-Be alloys, the ternary alloys should possess economic advantages which might make them more attractive than the binary alloy for some applications. Binary Systems Copper-Tin: The constitution of these alloys is now reasonably well known and is summarized in the equilibrium diagram published by Raynor.³ The following observations, due to Raynor,¹ on the structure of those phases of the Cu-Sn system that are likely to be found in the ternary alloy system will facilitate the subsequent discussion on the examination of that system. The ß phase is an electron compound at the electron-atom ratio 3:2 and has a body-centered cubic crystal structure. This phase is stable only down to 586°C, at which temperature it decomposes eutectoidally into the a and y phases. The y phase has a structure that is also based on the cubic system. This phase is stable down to 520°C, at which temperature it decomposes eutectoidally into the a and d phases. The d phase is an electron compound (Cu³¹Sn8) which has a crystal structure analogous to that of 7 brass. This phase is stable from 590" to 350°C; on prolonged annealing at the latter temperature it breaks down into a mixture of the a and E phases. The e phase is an electron compound (Cu³Sn) having the electron-atom ratio 7:4. Its structure may be regarded as a superlattice based on the close-packed hexagonal system. This phase is stable from 676°C to room temperature. The primary solid solubility of tin in copper increases to a maximum of 15.8 pct as the temperature falls from that of the peritectic reaction to 586°C. The solid solubility remains constant from 586" to 520°C. At lower temperatures the solubility decreases progressively. Below 350°C the fall in solubility is pronounced and is associated with the precipitation of the e phase. This precipitation is very sluggish and does not normally occur under service conditions. Copper-Beryllium: The Cu-Be system has been investigated by Borchers' and others. Raynor5 summarized the present state of information on it.

Jan 1, 1952

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 S. J. McCarroll

Fig. 1—The belt shown at right carries filter cake to mixing station over calciner. Crude ore conveyors appear in right background. THE Three Kids mine, some six miles east of Henderson, Nev., is in a typical southwest desert area, with high dry summer heat and cool to cold winter seasons. The manganese deposit was located during World War I.' During this period 15,000 to 20,000 tons of ore assaying up to 41 pct manganese were shipped. Interest in the deposit was not revived until the middle thirties, when experiments on the ore were initiated. Test work indicated possible recovery of only 70 pct by flotation, but in 1941 additional work was done at the Boulder City pilot plant of the U. S. Bureau of Mines and also by M. A. Hanna Co. As a result, the Manganese Ore Co. was formed and a plant utilizing the SO2 process was constructed. Numerous operation difficulties ensued, and the plant. was closed when the manganese situation in the country eased. In 1949 Hewitt S. West initiated negotiations to acquire the plant. In 1951 Manganese, Inc., was formed and contract entered into with the General Services Administration to supply 27 million units of metallurgical grade manganese in the form of nodules to the national stockpile. A second contract was made to upgrade 285,000 tons of stockpile ore. Test work was undertaken by the Southwestern Engineering Co. and likewise by the Boulder City pilot plant at the U. S. Bureau of Mines. Results obtained indicated the commercial feasibility of the flotation process. Construction of the plant, which is shown in Figs. 1 and 2, was started in June 1951, and operations on a break-in basis began in September 1952. Apart from the usual starting difficulties two major disasters caused serious setbacks, one a kiln failure in February 1953, and the other a fire that destroyed the flotation building in June of the same year. The nodulizing section of the plant resumed operation in November, and the flotation section in January 1954. The ore minerals are chiefly wad,* with minor amounts of psilomelane, and occur in sedimentary beds of volcanic tuff. The ore is overlain with beds of gypsum which outcrop or may be covered with surface gravel. Intermediate beds of red and white tuff occur frequently with lenses of red and green jasper and stringers of gypsum and calcite. Small amounts of iron are present; lead content averages about 1.0 pct and minute amounts of copper and zinc are found. Barite, celestite, and bentonite are present. Since these are made up of minute asicular crystals, moisture content is very high, averaging about 18 pct. Ore reserves have been estimated at 3 million tons averaging 18 pct Mn2 and up to 5 million tons after grade is dropped to 10 pct Mn. A good part of the orebody was stripped of overburden by the previous operating company . Approximately 50 pct of the ore, representing more than 60 pct of the manganese, can be mined by open-cut methods. A system for underground min- . ing has not yet been decided on. Open-cut mining with benches of 20 ft has proved satisfactory. Although the ore is soft and appears dry and dusty it has a certain resilience, probably due to the porosity and moisture which makes drilling and fragmentation difficult. Wagon drills have been abandoned in favor of the Joy 225-A rotary drill which will put down a 43/4 -in. hole at the rate of 2 ft per min. Holes are spaced in a pattern with 8 to 9-ft centers. Forty percent powder has been used, but better breaking to 2-ft size is obtained with low velocity bag powder of 30 pct strength. Loading is done with one 21/2-yd shovel, and cleanup follows with one D-7 bulldozer. The ore is hauled with Euclid trucks about 1000 ft from the pit to a blending pile, where the daily mine production is spread in layers by bulldozing until approximately one month's mill feed is accumulated. A new pile is then started and mill feed is drawn from the first pile by one 13/4-yd shovel and Euclid trucks, with a haul of approximately 500 ft. Mining is performed by an independent contractor with engineering and supervision by the company staff. Early test work indicated that the manganese could be floated with soap, a wetting agent, and fuel oil to give a recovery of better than 75 pct with a grade of 43 pct Mn. The concentrate when nodulized with coke would upgrade to 46 pct Mn or over, and the lead volatilized to 0.6 pct residual.

Jan 1, 1955

By Garth M. Crosby, F. McIntosh Galbraith, Bronson Stringham

THE Hercules mine is located in the northeastern section of the Coeur d'Alene district, approximately 1 1/2 miles north of the town of Burke, Idaho. Surface indications of the ore deposit were first discovered in 1886, but regular mine production was not started until 1902 and was continuous until April 1925, when the known ore had been extracted. Incomplete records show that from 1912 until operations were suspended the mine produced 2 1/2 million tons of ore containing 9.4 pct lead and 7.7 oz of silver per ton, together with an estimated 2 pct zinc, 0.3 pct copper, and 20 pct iron. This operation was the first in. a series of mining enterprises culminating in October 1947 with the consolidation of Day Mines, Inc. In the same year it was decided to unwater the levels below the collar of the Hercules shaft in the hope of finding some indication of a recurrence of ore. The unwatering operation has been described in a. previous paper.' The initial exploration, following recapture of the workings, showed sufficient promise to warrant a detailed study of the mineralogy with modern techniques. The general geo1ogy of the Coeur d'Alene district, including a detailed description of the rock types encountered, has been comprehensively treated by Ransome and Calkins' in their classic paper, and only local background description, therefore, is felt to be appropriate here. The Hercules deposit transects a portion of the trough of a broad south-trending synclinorium which has been greatly complicated by faulting. More locally, it lies within a block of ground bounded on the east; by the O'Neil Gulch fault, a steep north-south overthrust of considerable magnitude, and on the west by a monzonite stock, the outcrop of which is 1/2 mile or more wide and 5 miles long. The country rock is composed of thin to medium-bedded argillites and argillaceous quartz-ites of the Prichard and Burke formations, the oldest members of the Pre-cambrian Belt Series of sediments in the area, believed to be of Algonkian age. The contact between them is a conformable gradation. The argillite is colored gray to tannish-gray and is fine-grained, compact, and generally massive in structure. Under the microscope the unaltered argillite is seen to be composed principally of anhedral quartz and a few feldspar grains which were at one time presumably partly rounded sand grains, but as a result of recrystallization and cementation by silica, the interstices are now almost obliterated and quartz grains show crenulate boundaries. The sizes of these crystals vary from 0.5 mm down to 0.1 mm in greatest dimension. In all specimens sericite comprises 10 to 20 pct of the rock and is present abundantly between most of the grains as flakes or shreds which vary considerably in size. Sometimes they form a fine felt-like mat or aggregate, and sometimes flakes are seen which appear to be good muscovite. In some specimens, separated rhombic-shaped carbonate grains are abundant, and in some instances these have been changed to sericite. Mining operations to date have explored the Hercules vein to a maximum vertical depth of 3600 ft below its outcrop, and along a maximum strike-length of 3600 ft on certain of the lower mine levels. The main orebody is irregular in outline, extending over a variable strike-length of 400 to 1500 ft; and it is intersected by a strong transverse fault that has been traced from the surface to the bottom level. This has been named the Hercules fault, and apart from the vein itself, it is the most prominent structural feature in the mine. There is good evidence that it existed prior to the introduction of ore solutions and may have influenced ore deposition, but it was also the locus of important post-ore displacement and shows a progressive right-handed horizontal component reaching 200 ft on the deeper levels. Its vertical component is not definitely known but may be considerably greater. The fault strikes 20° N to 50° E and dips westerly at angles of 70" to 45", flattening in dip where it crosses the original orebody from east to west between 1000 and 1600 ft below the surface. At about 3000 ft in depth the Hercules fault is joined by a vertical fault of similar strike, and the major post-ore dis-placement below their junction is taken up along this vertical branch of the structure, now called the Mercury fault. Recent work has been concentrated in this vicinity. Another structural feature of special geologic interest, though of little economic importance, is the occurrence of a porphyritic dike in this area. This lies a short distance above the Hercules fault, essentially parallel to it, and is 5 to 15 ft in thickness. It appears at first glance to cut the mineralization, suggesting push-apart relationship, but small stringers of the vein minerals have been observed to penetrate the dike for a matter of inches at several points. The dike is thought to be related to the monzonite intrusion. A vertical longitudinal projection of the mine is shown in Fig. 1, which illustrates most of the features discussed above. The Hercules vein was deposited along the course of a strong, persistent shear zone that now appears as a braided network of gouge seams running through more or less crushed and shattered country rock. It strikes 70° N to 80° W and dips southerly at an average of 75". Barren parts of the structure vary in width from less than 1 ft to more than 15 ft. The width of mineralized segments may be double that. Although the evidence is not conclusive, pre-mineral, normal movement along the zone may be 1000 or 1500 ft. The horizontal component is unknown. Post-ore movement appears to have been

Jan 1, 1954