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By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970

By L. Leibowitz, M. G. Chasanov, L. W. Mishler

A drop calorimeter system is described for use in measuring enthalpies to 3600°K. Data are presented for tungsten between 2800" and 3600°K. The enthalpy of tungsten in cal per mole between 2000° and 3600°K can be represented by the equation HºT- Hº298 = - 1.7622 X 103 + 5.7772T + 8.9861 where T is in degrees Kelvin. A tabulation of com -puted values is presented for heat capacity, entropy, and free energy function. A drop calorimeter has been constructed to carry out enthalpy measurements at temperatures to 3600°K. Samples are heated by induction1 and dropped into a commercial adiabatic calorimeter, modified for this purpose. The experimental temperature is limited by the melting point of container materials and compatibility of the container and its contents. Several high-temperature drop calorimeters have been described in the literature1-5 but none has been used at temperatures as high as those in the present work; our measurements of the enthalpy of tungsten range from 2800" to 3600°K. DESCRIPTION OF EQUIPMENT An overall schematic view of the equipment is shown in Fig. 1. Power for the induction coil is supplied by a 25-kw 250 kHz Ther-Monic generator coupled to an iron core RF transformer. The Sample capsule is suspended in the work coil by 10-mil diam tungsten wires which are wrapped around a horizontal 5-mil diam tungsten wire. The horizontal suspension wire is clamped between two massive copper electrodes which are fixed in an x-y motion device that allows adjustment of the position of the heated capsule from outside the vacuum chamber. The copper electrodes are connected by flexible copper straps to a 1250-joule (5 kv, 100 pfarad) condenser bank. When it is desired to release the capsule, the condensers are discharged through the horizontal suspension wire causing it to vaporize rapidly. Very reliable and precise release of the capsule is achieved in this manner. Experiments have shown that no heat correction is required for this discharge energy. As part of the temperature measuring system, two prism holders have been incorporated in the apparatus. The upper prism holder is in the main vacuum chamber itself, whereas the lower one is in a side arm attached to the drop tube below the gate valve. The upper prism is mounted on a rotary vacuum feed-through, and may be moved under a protective shield when not in use. This prevents deposition of vapors on the prism surfaces when temperature measurements are not being made. Similarly, the lower prism is mounted on a push-pull vacuum feed-through, and when not in use may be pulled into its side tube. The prism mountings are fitted with guides and stops so that they may be moved precisely into the desired position. The aim throughout is to minimize the time the prisms are exposed to vapors from the hot samples. At the high temperatures reported in this paper, only the lower prism was used. The upper prism holder in these cases was fitted with an additional radiation shield. By using a prism and viewport, the lower surface of the samples can be observed by an optical pyrometer. The measurements discussed in this paper were obtained with a Leeds and Northrup 8622-C-S series manual pyrometer which is estimated to be accurate to 0.5 pct. Pyrometer calibrations and prism and window corrections were carried out in the conventional manner6 using tungsten strip lamps calibrated by the National Physical Laboratory, Teddington, England. Prism corrections were rechecked after each use. All work to date has been done in vacuum, and no measurable change has been observed in the prism correction below -2300°K for the upper prism and below -2800°K for the lower one. The total time of exposure of the prisms is about 50 sec per run. At high temperature, the final temperature reading is corrected by using the final A value for the prism; see Ref. 6 for details of this procedure. The calorimeter is a modified Parr Instrument Co. (Moline, lll.), Series 1230 adiabatic calorimeter with automatic jacket control. Other authors5 have used a similar calorimeter with good results. The calorimeter jacket cover and calorimeter cover are attached to the drop tube which contains a radiation shield. This shield is a gold-plated copper disc which can be operated manually from outside the calorimeter. The receiver is attached below the radiation shield and is lined with tungsten. In a typical experiment, the calorimeter and its jacket water temperatures were adjusted to 0.000°K temperature difference. The sample was allowed to equilibrate in the furnace at the desired temperature for about 20 min. The initial calorimeter temperature was then recorded, the sample dropped, and appropriate shutters closed. After about 3 min, the drop tube and receiver were filled with helium to 60 torr. The final calorimeter temperature was recorded after it had remained constant over a 5-min period. The equilibration time in the calorimeter was about 25 min. Thermistor probes are used to operate a hot and cold water supply system to maintain the jacket temperature equal to the calorimeter temperature. For actual measurements of the calorimeter temperatures, a quartz thermometer was used (Hewlett Packard Dymec Thermometer, Model #2801A). This thermome-

Jan 1, 1970

By James W. Guider

Of all the technology available to the iron blast furnace operator, raw materials preparation [(Fig. 1)] is by far the most important. Superior raw materials have been basic to the success of the Japanese steel industry, and they are just as essential to the American steel industry in winning its competitive battle against foreign government subsidized steel imports. Therefore, the mine operator and the ore beneficiation engineer must strive to produce the highest quality raw materials possible to meet the precise demands of the modem blast furnace and steel plant.

Jan 1, 1982

By Leo Horvitz

PETROLEUM and natural gas are composed principally of the saturated hydrocarbons ranging from methane, the lightest, to nonvolatile liquids and solids containing approximately thirty-five carbon atoms. A technique for locating buried accumulations of these hydrocarbons before drilling obviously requires that some of the hydrocarbons leave the deposit and migrate toward the surface of the earth where they may be detected in their original form. Earliest attempts to link near surface hydrocarbons to petroleum at depth were apparently made by Laubmeyer1 in Germany and by Sokolov2 in Russia. These investigators collected samples of soil air from boreholes one to two meters deep and analyzed them for traces of hydrocarbons. They found that soil air over producing areas is richer in these constituents than is soil air over barren areas.

Jan 12, 1954

By AIME AIME

Report of Committee 24, of the International Association for Testing Materials, presented at the Brussels Congress, 1906. Republished for use at the 94th Meeting of the American Institute of Mining Engineers, New York, N. Y., February, 1908. Discussion by letter is requested by the Secretary of the Institute. The Committee appointed for the solution of Problem 24 consisted of the following members Prof. H. M. Howe, New York, N. Y. (Chairman); L. Levy, Paris, France (Vice-Chairman) ; Prof. D. Tschernoff, St. Petersburg, Russia (Vice-Chairman) ; Prof. Albert Sauveur, Cambridge, Mass. (Secretary) ; Van Drunen, Ixelles, Belgium; Lieut.-Col. H. Tusen, Copenhagen, Denmark ; E. P. Martin, Abergavenny, England ; A. Pourcel, Paris, France ; H. Brauer, Dortmund, Germany ; Dr. Prof. H. Wedding, Berlin, Germany; P. Verole, Milan, Italy ; A. Baalsrud, Christiania, Norway ; A. R. v. Dormus, Vienna, Austria ; A. Sailler, Vienna, Austria; Bureau des Forges, St. Petersburg, Russia; Prof. N. Belelub-sky, St. Petersburg, Russia ; N. Jossa, St. Petersburg, Russia ; Maj.-Gen. M. Korobkoff, St. Petersburg, Russia ; S. Smirnoff, St. Petersburg, Russia ;.Ladislaus v. Tetmajer, Budapest, Hungary ; H. H. Campbell, Steelton, Pa. Early in February, 1905, a list of species and varieties of iron and steel, with definitions, drawn by the Chairman and Secretary of Committee 24, was sent to every member of this Committee with a request for comments and suggestions. A special request was sent to the following gentlemen . for the equivalents in their several languages of these species and varieties : A. , Pourcel, Paris, France; Prof. H. Wedding, Berlin, Germany ; J. A. Brinell, Stockholm, Sweden ; Prof. H. I. Hannover, Copenhagen, Denmark; Prof. P. Kley, Delft, Holland; P. Verole, Milan, Italy; Col. Cubillo, Trubia, Spain. This present report, which is based upon our original list and definitions, and upon the replies to these requests, consists of four parts I. A polyglot, which gives the names of the chief classes of iron and steel in English, French, German, Swedish, Danish and Dutch. We .regret that we have failed to get the Italian and Spanish names. II. English definitions of principal classes of iron and steel. III. A glossary of special sizes and shapes of iron and steel. IV. A note on the boundary between steel and cast-iron. I. POLYGLOT, IN ENGLISH, FRENCH, GERMAN, SWEDISH, DANISH AND DUTCH, OF THE CHIEF CLASSES OF IRON AND STEEL, AND OF THE APPARATUS IN WHICH THEY ARE MADE. This list is not intended to be complete, but rather to include only those varieties which are of interest to the Association.

Mar 1, 1908

By W. J., Kroll

MOST people believe that rare metals are always, scarce in nature, expensive to make, and therefore useless despite some miraculous properties which might make them a cure-all. There are' some metals, which are quite frequent in nature, such as zirconium, which are called rare only because our present methods for making them are elaborate, thus forcing the manufacturer to sell them at a high price. There are also truly rare metals, such as gallium, which do not occur frequently in ores, but are easily reducible from their oxides. In these cases the price of the concentration operation is the decisive factor. The distribution of the elements in the earth's crust is no indication as to the availability of a metal; the concentration operation is the critical factor. Concentration is frequently obtained in the course of metallurgical operations for the extraction of other metals, and the rare metal may be enriched in by-products, flue dusts, mother liquors or precipitates from electrolyte purification as are indium, thallium, selenium, and tellurium. A periodic table of the rare elements may serve as a basis for discussion of their properties and to establish a program. (Table 1.)

Jan 1, 1946

By Hugh S. Spence

In the winter of 1941-42, muscovite mica was discovered by a young prospector, Justin Purdy, in the township of Mat-tawan, Nipissing District, Ontario, a few miles north of the small settlement of Eau Claire, which lies on the main Transcontinental Highway (No. 17) between Mattawa and North Bay. Muscovite had been known for many years to occur in the general Mattawa region, and various small efforts at production had previously been made by individuals working scattered deposits in the area. These minor activities, however, had never led to production of any consequence or the discovery of any important mica bodies. The Purdy finds were made in a heavily timbered, mountainous area lying about three miles north of the low-lying settled land along the highway, and in a section not hitherto prospected. The mica taken by Purdy and two partners from surface outcrops proved so remarkable in point of size of trimmed sheets that the find attracted considerable attention, and the area surrounding the three claims taken up by the prospectors was quickly blanket-staked by various interests. Though a number of other mica-bearing pegmatite dikes were found later on these stakings, none proved as rich as those on the original Purdy ground; very little commercial mica was obtained from them and attempts to develop them were short-lived. Purdy and his partners sold their initial production to dealers in Ottawa and Hull, where the Canadian mica industry long has centered. Young Purdy, unfortunately was killed in a motor accident in the early summer of 1942. His father continued mining operations for a few months and produced and sold a considerable amount of mica. In October 1942 the Purdy holdings were acquired by lnspiration Mining and Development Co. of Amos, Quebec, which had been active in staking in the area. This company formed a subsidiary, Purdy Mica Mines, Limited, to develop the property. Under the energetic management of Joseph R. Norrie, rapid progress was made, and production soon attained important proportions. Realizing from the outset the unusual character and potential value in the war effort of the Purdy discovery, the Metals Controller, Department of Munitions and Supply, at once arranged with the Department of Mines and Resources for an official geological report on the area, and also drew the attention of the War Production Board in Washington to what seemed likely to prove a highly important source of strategic-quality mica. Officials of WPB were sent up in the Summer of 1942 to inspect the property, and so impressed were they with the possibility that it might become of high

Jan 1, 1948

By Hugh S. Spence

In the winter of 1941-42, muscovite mica was discovered by a young prospector, Justin Purdy, in the township of Mat-tawan, Nipissing District, Ontario, a few miles north of the small settlement of Eau Claire, which lies on the main Transcontinental Highway (No. 17) between Mattawa and North Bay. Muscovite had been known for many years to occur in the general Mattawa region, and various small efforts at production had previously been made by individuals working scattered deposits in the area. These minor activities, however, had never led to production of any consequence or the discovery of any important mica bodies. The Purdy finds were made in a heavily timbered, mountainous area lying about three miles north of the low-lying settled land along the highway, and in a section not hitherto prospected. The mica taken by Purdy and two partners from surface outcrops proved so remarkable in point of size of trimmed sheets that the find attracted considerable attention, and the area surrounding the three claims taken up by the prospectors was quickly blanket-staked by various interests. Though a number of other mica-bearing pegmatite dikes were found later on these stakings, none proved as rich as those on the original Purdy ground; very little commercial mica was obtained from them and attempts to develop them were short-lived. Purdy and his partners sold their initial production to dealers in Ottawa and Hull, where the Canadian mica industry long has centered. Young Purdy, unfortunately was killed in a motor accident in the early summer of 1942. His father continued mining operations for a few months and produced and sold a considerable amount of mica. In October 1942 the Purdy holdings were acquired by lnspiration Mining and Development Co. of Amos, Quebec, which had been active in staking in the area. This company formed a subsidiary, Purdy Mica Mines, Limited, to develop the property. Under the energetic management of Joseph R. Norrie, rapid progress was made, and production soon attained important proportions. Realizing from the outset the unusual character and potential value in the war effort of the Purdy discovery, the Metals Controller, Department of Munitions and Supply, at once arranged with the Department of Mines and Resources for an official geological report on the area, and also drew the attention of the War Production Board in Washington to what seemed likely to prove a highly important source of strategic-quality mica. Officials of WPB were sent up in the Summer of 1942 to inspect the property, and so impressed were they with the possibility that it might become of high

Jan 1, 1948

By F. L. Ruhlman, Max C. Eastman

The termination of the recent war marked a major changc in the oil-field operations at. Elk Hills. Production was greatly curtailed, various experimental production projects were started, and a long-range exploratory program was inaugurated. Production was reduced from the wartime peak of 65,000 bbl per day to the current rate of about 8ooo bbl per day in order to maintain an available source of crude that can be drawn upon during a national emergency. The existing production rate is deemed essential to carry on the experimental production projects. These projects are being conducted to determine the best methods and means of maintaining the Reserve, shut in, but in a state of readiness to produce the maximum quantity of oil in the most expeditious manner. Projects now being investigated include: (I) protection of surface equipmerit; (2) repair of wells that might damage the reservoir; (3) gas injection; (4) water eneroachment, (5) gravity drainage. An exploratory program is being carried on to determine the amount of recoverable oil in the unexplored portions of the Reserve. The Shallow-zone exploration is practically completed, but owing to the complexity of the Stevens structure and the magnitude of the oil discoveries in the Stevens, exploration will probably continue in that zone for another two years. Introduction Summary of Development History of Elk Hills Although a detailed history of Elk Hills oil field is presented in various publications,1,2 a summary of its unusual development and production history will be given in order that the present problems may be more readily understood. The first development that resulted in commercial production was in the central part of the Reserve. The first well, Hay No. I, in sec 36-R,* was completed in January I9I9, and was soon followed by 37 Others in the same general area. It is commonly referred to as the Hay-Carman area and was shut in in stages from 1925 to 1934 as a result of litigation regarding the title to the land. Not being highly producti,, only about 6½ million barrels of oil with a large volume of gas was produced from the area prior to the shutdown. Shortly after the start of the development of the Hay-Carman area, drilling was started 6 miles east in sec 36-S' Tupman NO. I came in for 5000 bbl per day early in I92o, It was followed by more than 200 others in the next few years, and the field became one of major importance. Produc-

Jan 1, 1949

By Floyd E. Bliven

A century ago, Thomas Carlyle sketched the Emblem of the Wasting Candle in one of his papers. "Terar Dum Prosim" he wrote under the candle-" May I be wasted so that I be of use." The application of his reasoning is an excellent guide for a discussion of the scrap problems of today. The General Electric Co. has addressed itself to the need of proper and careful preparation of scrap metals for many years. A supervisor of salvage directs this work in each of the works. Generally he is an engineer and has had broad factory training. He gives general direction to the collection, preparation and disposition of scrap materials. He operates the extensive facilities which each works has provided for the centralization and control of scrap accumulations, and also initiates studies leading to the reduction of scrap accruing from machining and assembly operations. r We recognize that each industry, each factory, each locality faces a different set of conditions. Irrespective of size, in a plant employing 20 men or a large works with 15,00 employees-certain fundamental principles can be applied for organization and the collection of scrap. The manufacture of electrical apparatus is a highly complicated intricate business. In one area we make electronic tube and adjacent buildings house the manufacture of steam turbines. Both are instruments for power-different in size and in many cases serving different fields of application. Unlike the great industries that build automobiles, trucks, or engines where repetitive operations, once solved, set the stage, electrical manufacturers' plants are large jobbing shops. Therefore, we must carefully plan every step in handling the scrap that "in so wasting to produce the finished motor or locomotive-we can return this product to reprocessing and ultimate use." ESSENTIALS FOR SALVAGE EFFICIENCY The essential steps for an efficient salvage department are: I. Selection of Personnel.-An able foreman would be a man of broad experience and understanding-one who commands the respect of the entire foreman group as well as that of his own men. In the interest of clean scrap, it is necessary to acquaint the foremen in the separate manufacturing units with the need of careful segregation in the shop and the best methods of obtaining it. At least 40 per cent contact time should be devoted for this purpose. 2. The physical equipment of the salvage department should be devised and selected to handle complete, at one point, all scrap operations. Bulky materials as produced by some large shops can be economically placed in salable shape at the divisional point. Because salvage

Jan 1, 1943

By Howard N. Eavenson

One who has been trained in belief in the law of supply and demand and its effect upon prices finds it difficult to adjust himself to the minute regulations imposed by the New Deal, and also to the bewildering changes of government policy as expressed within a short period of time between the antitrust laws and the N.R.A., and later by the Bituminous Coal Conservation Act of 1935. A survey of the coal industry since the World War, both in this country and Great Britain, however, shows that regulation of some sort is needed if any stabilization is to be achieved and if the wage structure and economic welfare of the many communities dependent solely upon coal are to be maintained. Let us look at what has happened to the industry since 1920, which can be considered as the end of the period affected by the war influence. This discussion will be confined solely to bituminous coal, although many of the general conditions are equally applicable to anthracite, the position of which now is at least as bad as that of the softer variety. Since 1920—to the end of 1934—the production of coal has decreased from 568.7 million to 358.4 million tons, or 37 per cent; the number of mines from 14,766 to 6,258, or 58 per cent; the average annual production per mine has changed from 38,512 to 57,425 tons, or 50 per cent. The number of large mines has increased considerably, and the number of men employed has decreased from 639,547 to 458,011, a reduction of 28 per cent, while the average output per employee has changed from 4.0 to 4.4 tons, or an increase of 10 per cent. The average price per ton of coal at the mine has varied from $3.75 to $1.75. During that time wages decreased largely until 1933 and since that time have increased, until now the rates paid are considerably above those in other occupations, although the actual yearly earnings are low, because of part-time work. From 1920 to the signing of the Jacksonville wage agreement in 1924, about two-thirds of the men were union members and practically all of the nonunion mines were south of the Ohio River; with the fixing of the high wage scale of that agreement, which soon proved to be an uneconomic one, many of the mines found that they could not retain their business, so gradually changed to nonunion. By 1928 the proportion

Jan 1, 1936

By Howard N. Eavenson

One who has been trained in belief in the law of supply and demand and its effect upon prices finds it difficult to adjust himself to the minute regulations imposed by the New Deal, and also to the bewildering changes of government policy as expressed within a short period of time between the antitrust laws and the N.R.A., and later by the Bituminous Coal Conservation Act of 1935. A survey of the coal industry since the World War, both in this country and Great Britain, however, shows that regulation of some sort is needed if any stabilization is to be achieved and if the wage structure and economic welfare of the many communities dependent solely upon coal are to be maintained. Let us look at what has happened to the industry since 1920, which can be considered as the end of the period affected by the war influence. This discussion will be confined solely to bituminous coal, although many of the general conditions are equally applicable to anthracite, the position of which now is at least as bad as that of the softer variety. Since 1920—to the end of 1934—the production of coal has decreased from 568.7 million to 358.4 million tons, or 37 per cent; the number of mines from 14,766 to 6,258, or 58 per cent; the average annual production per mine has changed from 38,512 to 57,425 tons, or 50 per cent. The number of large mines has increased considerably, and the number of men employed has decreased from 639,547 to 458,011, a reduction of 28 per cent, while the average output per employee has changed from 4.0 to 4.4 tons, or an increase of 10 per cent. The average price per ton of coal at the mine has varied from $3.75 to $1.75. During that time wages decreased largely until 1933 and since that time have increased, until now the rates paid are considerably above those in other occupations, although the actual yearly earnings are low, because of part-time work. From 1920 to the signing of the Jacksonville wage agreement in 1924, about two-thirds of the men were union members and practically all of the nonunion mines were south of the Ohio River; with the fixing of the high wage scale of that agreement, which soon proved to be an uneconomic one, many of the mines found that they could not retain their business, so gradually changed to nonunion. By 1928 the proportion

Jan 1, 1936

By M. Cohen, S. A. Kulin

AT a recent symposium on thermodynamics in physical metallurgy1 two opposing theories of the austenite-martensite transformation were presented. Both theories agreed that this type of reaction involves a nucleation process which requires activation and that the activated nuclei develop into the well-known martensite plates with tremendous speed. However, there were essential differences in the two points of view concerning the nature of the nucleus and the mechanism by which the nucleus propagates. According to Cohen, Machlin, and Paranjpe,' the nucleus is a strain center with sufficient elastic energy to initiate a cooperative displacement among the atoms of the parent phase when a sufficiently low temperature is reached. This displacement propagates as a wave in shear-like fashion to transform the austenite into martensite without benefit of diffusion. On the other hand, Fisher, Hollomon, and Turnbull3 regard the nucleus as a solute-poor region (in the austenite) of a size which becomes supercritical relative to coherent growth into martensite when an appropriately low temperature is reached. This growth process is taken to be an atom-by- atom transfer from the receding austenite lattice to the advancing martensite lattice through the coherent interface that exists between the two phases. The present paper is not conceded with the divergent views as to the nature of the nucleus but describes some critical experiments which differentiate between the two proposed mechanisms of propagation. Fisher' has summarized the latter issue in the following way: According to the cooperative displacement theory, the speed of formation of mar-tensite plates should not be decreased by lowering the temperature, and martensite should form with extreme rapidity at very low temperatures; whereas with the alternate growth process, the speed of the martensite transformation should be retarded at very low temperatures, decreasing to zero at the absolute zero. The atom-by-atom growth mechanism predicts a marked slowing down of the reaction rate with decreasing temperature because the rate of self-diffusion in the austenite is involved in this picture. For example, Fisher, Hollomon and Turn-bull5 estimate that the activation energy for this growth process in steel is (0.34)2(0.36)* times the activation energy for self-diffusion in y-iron. The two most recent determinations of the latter quantity are 67,900" and 74,2007 cal/mol, which may be averaged as 71,000 cal/mol. This, in turn, gives a value of 3000 cal/mol for the activation energy of the atom-by-atom process, and hence the rate of growth should vary as e 8,000/RT where R is the gas constant

Jan 1, 1951

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,' who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C'. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,' who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C'. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By R. F. Mehl, B. Lustman

THE formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.1 It is necessary here only to enumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type-i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained-the isothermal growth of the phase follows a simple parabolic equation: [1 = ki [I]] where X is the thickness of the alloy layer, k the reaction rate constant, and [t] the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.3 In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varies with temperature according to the Arrhenius equation: [k = Ae-QIRT [2]] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By Keith Leonard Sutherland

This paper is a study of the differential flotation of the sulphide minerals in the presence of salts of silver, lead and zinc. In practice, accidental activation due to these salts is more important than their use as reagents to replace copper sulphate. The general method of investigation has been based upon contact tests, the temperature of 35°C being chosen in conformity with earlier work. Potassium ethyl xanthate and potassium amyl xanthate were selected as collectors and pure sulphide minerals were used. The experimental procedure has been outlined in earlier papers and all solutions were kept carbonate-free.14 Contact, or spreading of an air bubble, at a mineral surface indicates the presence of an adsorbed collector film. Purity of Reagents The xanthates were purified in the usual manner.' Neither the cyanide nor the sodium hydroxide solutions contained sufficient carbonate to give a precipitate with barium chloride solution. The silver sulphate was prepared from pure silver nitrate by evaporation with concentrated sulphuric acid until there was no evidence of brown fumes, This solution was diluted and the difficultly soluble sulphate washed with water so that unchanged nitrate was dissolved. The resultant crystalline powder was pure white. The lead and zinc salts were prepared by dissolving especially pure lead and zinc in C.P. nitric and sulphuric acid solution and the crystals drained. The standard solutions were checked by titration. It was felt desirable to use the sulphate radical wherever possible, but since lead sulphate was insufficiently soluble for the purpose of the experiments, it was necessary to use some other lead salt. A.R. copper sulphate was used without further purification. Results The results are presented in the accompanying figures; the areas of noncontact (nonflotation) are shaded in Figs. 8, 9, 10 and 11; in the remainder they lie to the right of the curve. Zinc Sulphate The curves in Fig. I are to be compared with those for Fig. 2, for which zinc sulphate is absent. This comparison shows that the influence of the zinc ion is usually small. Its influence is more marked, however, for chalcopyrite in the absence of cyanide. The influence of zinc sulphate is also marked for copper-activated sphalerite, for which tests were made only in the "absence of cyanide. The results are of importance in the separation of pyrite from copper-activated sphalerite when zinc sulphate is added in the lead flotation section (p. 204 of ref. I). Sphalerite does not adsorb the collector (i.e., become floatable) under the conditions chosen.

Jan 1, 1943

By Shiou-Chuan Sun, R. E. Zimmerman

An evaluation of the mechanism surrounding the froth flotation of coarse coal and mineral particles as a result of experiments conducted at The Pennsylvania State College. Maximum size ranges for both bituminous and anthracite coals were established as well as the factors affecting the floating of coarse particles. CONSIDERABLE interest is developing in the froth flotation of coal and the maximum particle sizes which can be treated by such method. The economic necessity of recovering extreme coal fines and slurries plus the restrictions being placed upon stream pollution have brought about many new and prospective installations of flotation plants. Most coal slurries or silts have a wide size range, some sizes of which may be unsuitable for effective froth flotation. This fact also enters into the froth flotation of other minerals and the principles that SHIOU-CHUAN SUN and R. E. ZIMMERMAN, Members AIME, are Assistant Professor and Division Chief, respectively, Division of Mineral Preparation, The Pennsylvania State College, State College, Pa. Joint AIME-ASME Fuels Conference, French Lick, October 1949. TP 2843 F. Disccussion (2 copies) may be sent to Transactions AIME before June 30, 1950. Manuscript received Sept. 12, 1949. apply to coal would also apply to minerals in general. A series of experiments were made by the authors for the purpose of investigating factors influencing the froth flotation of coarse mineral particles and an attempt has been made to evaluate those factors. This paper presents the results of a study of the froth flotation of coal particles in the size range greater than 35 mesh. During the study a "multi-bubble" hypothesis has been developed to explain the various phenomena observed in the behavior of coarse particles in froth flotation of coal. The terms coarse, intermediate, and fine particles as used in this paper are arbitrary and differ for various minerals. For coal alone the term intermediate particles means that the particle size is within the range of 35 and 200 mesh of Tyler sieve sizes. Sizes of coal particles coarser and finer than this size range are termed respectively as coarse and fine particles. Methods of Conducting Flotation Experiments: All of the flotation tests, except those shown in table 1, were carried out in a laboratory Fagergren flotation machine, using 300-a samples of solids for each test. All mineral samples we; prepared from selected lumps of high purity by crushing, grinding, and screening to the desired sizes. Except coals, all the other samples were cleaned through magnetic

Jan 1, 1951

By W. B. Humes

The use of high vacuum on a large industrial scale in the ferrosilicon process for the production of magnesium marks the coming of age of an important new metallurgical technique. The economical production of reactive metals, such as magnesium, which combine with all the well-known furnace atmospheres, has until recently been successfully carried out only by electrolytic methods. It is now apparent that, through the use of high vacuum, the distillation or sublimation of many metals can be done industrially at much lower temperatures, and hence in much simpler equipment, than heretofore has been thought possible. At the beginning of the present emergency, when the ferrosilicon process of producing magnesium was brought to the fore, little was generally known about vacuum engineering, practices, and techniques. In a comparatively short time, the available equipment has been adapted, new equipment designed and built, and a fund of know-how evolved to make possible the production of thousands of pounds of magnesium per day at pressures less than 1/ r0,000 of an atmosphere. Pilot-plant operations have been consistently maintained at pressures even as low 2s one micron (0.001 mm.). These low pressures, which previously were regarded as prohibitively costly or impossible to attain, have been demonstrated as economically feasible on an industrial scale. Necessity for Vacuum The main function of vacuum in the ferrosilicon process, and hence in most vacuum smelting processes, is to lower the temperature at which the metal may be distilled or sublimed from the reduction mixture. A secondary function is to protect the distilled metal from attack by the furnace atmosphere and to permit the formation of a dense condensate. In the ferrosilicon process, magnesium is formed by the reaction between dolomite and ferrosilicon: 2(Mg0-Ca0) -\- HFeSU / t=> aMg + MFe + (CaO)2-SiO2 The metal is distilled from the pelleted charge at a free air pressure of about 0.100 mm. of mercury (100 microns). This low pressure is not needed for the reaction, but rather serves to protect the metal vapor from the oxygen or nitrogen of the atmosphere and permits the formation of a condensate free of pyrophoric material. The reaction proceeds at air pressures as high as several millimeters of mercury, and evidence has been offered to show that the actual equilibrium pressure of magnesium at operating temperatures of 2I50°F. is somewhat higher. Experimentation indicates that the yield begins to decrease at pressures above 500 microns. While no real operating data are yet available on the relationship between

Jan 1, 1944

By R. E. Zimmerman, Shiou-Chuan Sun

An evaluation of the mechanism surrounding the froth flotation of coarse coal and mineral particles as a result of experiments conducted at The Pennsylvania State College. Maximum size ranges for both bituminous and anthracite coals were established as well as the factors affecting the floating of coarse particles. CONSIDERABLE interest is developing in the froth flotation of coal and the maximum particle sizes which can be treated by such method. The economic necessity of recovering extreme coal fines and slurries plus the restrictions being placed upon stream pollution have brought about many new and prospective installations of flotation plants. Most coal slurries or silts have a wide size range, some sizes of which may be unsuitable for effective froth flotation. This fact also enters into the froth flotation of other minerals and the principles that SHIOU-CHUAN SUN and R. E. ZIMMERMAN, Members AIME, are Assistant Professor and Division Chief, respectively, Division of Mineral Preparation, The Pennsylvania State College, State College, Pa. Joint AIME-ASME Fuels Conference, French Lick, October 1949. TP 2843 F. Disccussion (2 copies) may be sent to Transactions AIME before June 30, 1950. Manuscript received Sept. 12, 1949. apply to coal would also apply to minerals in general. A series of experiments were made by the authors for the purpose of investigating factors influencing the froth flotation of coarse mineral particles and an attempt has been made to evaluate those factors. This paper presents the results of a study of the froth flotation of coal particles in the size range greater than 35 mesh. During the study a "multi-bubble" hypothesis has been developed to explain the various phenomena observed in the behavior of coarse particles in froth flotation of coal. The terms coarse, intermediate, and fine particles as used in this paper are arbitrary and differ for various minerals. For coal alone the term intermediate particles means that the particle size is within the range of 35 and 200 mesh of Tyler sieve sizes. Sizes of coal particles coarser and finer than this size range are termed respectively as coarse and fine particles. Methods of Conducting Flotation Experiments: All of the flotation tests, except those shown in table 1, were carried out in a laboratory Fagergren flotation machine, using 300-a samples of solids for each test. All mineral samples we; prepared from selected lumps of high purity by crushing, grinding, and screening to the desired sizes. Except coals, all the other samples were cleaned through magnetic

Jan 1, 1951