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By C. J. Frosch, J. A. May, H. G. White, C. D. Thurmond

Gallium phosphide epitaxial layers were grown from the vapor phase on undoped single-crystal galliurn arsenide substrates in silica tubes by an open-tube wet-hydrogen process. The epitaxial layers were grown over a range of water pressures at three substrate temperatures. Excess donor concentrations were determined by surface barvier capacitance measurelrzents without removing the layers from the substrates. The excess dmlor concentration, ND-NA, is fo~ind to vary approxilnately inversely with the pressure of water added to the hydrogen carrier gas. This is the relationship that would be expected for singly ionized silicon donors on gallium sites in extrinsic galliunz phosphide, with the silicon coming from the SiO generated by the reaction of hydrogen with the silica tube. An increase in the partial pressure of water in the hydrogen stream decreases the SiO pressure. The results indicate that ni, the intrinsic hole and electrmt concentration for gallium phosphide at the three substrate temperatures, is smaller than the concentration estimated from available data for the density of states effective masses and the energy gap. Mass-spectrographic measurements confirm that the dono?, introduced into gallium phosphide is silicon. The equilibrium concentrations of silicon in vapor-flown gallium Phosphide have been estimated from available thernzodynamic information that includes the solubility measurements of silicon in gallium phosphide in equilibrium with a gallium-rich liquid phase. Satisfactory agreement with the measured silicon concentrations is obtained. FROSCH1 has described an open-tube process for growing single-crystal Gap from the vapor phase by a GazO transport mechanism. The method depends upon the reaction of H20 in an H2 carrier gas with a heated source of polycrystalline Gap which provides the necessary vapor species. When the temperature of these vapor species is lowered, super saturation occurs and single-crystal Gap will deposit on a suitable substrate. Unintentionally doped single crystals of Gap grown by the wet H2 process in silica tubes are n type. Evidence is presented to show that the donor introduced is silicon, and that a qua si-equilibrium model accounts for the inverse dependence of the donor concentration on the water partial pressure and predicts the magnitude of the donor concentrations. Ainslie et al. experimentally showed a similar inverse relationship between the carrier density and oxygen pressure for GaAs. Emission-spectrographic analyses showed a decrease in the silicon concentration with increasing oxygen overpressure for GaAs. Cochran and Foster suggested the theoretical possibility of suppressing silicon contamination by using Ga20 generated by the reaction of gallium with water vapor. 1) EXPERIMENTAL The apparatus and procedures are essentially the same as those described by Frosch.' The apparatus consists of a 25-mm-ID SiO2 tube extending through a controlled high-temperature flat zone for the location of the polycrystalline Gap source and a downstream temperature gradient falling at a rate of about 14°C per cm. The latter provides the region of super saturation for the location of the single-crystal substrate. The partial pressure of water in the inflowing hydrogen stream, pA2, O was controlled by mixing me-tered proportions of dry H2 with H2 saturated with H2O vapor at 0°C. The total gas flows were about 200 cu cm per min in all experiments. The Gap sources were prepared by pulverizing boat-grown polycrystalline ingots to pass a 20-mesh sieve. The substrates were cut from an undoped single-crystal boat-grown GaAs ingot purchased from Monsanto. This ingot had a carrier concentration of about 1015 atoms per cu cm, a resistivity of about 5 ohm-cm, and a mobility of about 5000 sq cm per v sec at 25°C. Substrates with dimensions of 1 by 1 by 5 x lo-' cm were employed. The growth faces were chemically polished (111) arsenic faces. Epitaxial layers, at least 7.5 x 10-3 cm thick, were grown,. This required from 1 to 24 hr depending upon the Pii2Q values and the temperatures. In all of the runs, the source temperatures were 50°C higher than the substrate temperatures. Samples were prepared

Jan 1, 1968

By J. R. Thoenen, M. C. Malamphy, G. K. Dale

The beginning of the war and the events leading up to it precipitated a near crisis in the aluminum industry. Demands for the metal reached proportions far beyond the prewar production capacities and, in addition, the submarine menace seriously curtailed the importation of bauxite from South America, hitherto a chief source of high-grade ore. The situation required an intensive search for domestic ore to augment the reserves and in October 1941 Congress directed the Department of the Interior to investigate the extent, mode of occurrence, and quality of bauxite in the United States. In December of that year the Bureau of Mines and the Geological Survey began the search for bauxite in Arkansas, where more than go per cent of the domestic ore had been produced and where the greatest amount of bauxite was known to occur. The program involves the geophysical and geological investigation of the Arkansas bauxite region and the core drilling of areas considered favorable for the occurrence of bauxite deposits. Cores taken from the bauxite-kaolin zone are sampled and analyzed in the Bureau of Mines laboratory in Little Rock. The information from each of the deposits discovered is then assembled, the bauxite is graded with respect to its possible utility, tonnage estimates are made, and the whole is presented in the form of a war minerals report. Thirty-eight new bauxite deposits had been discovered and investigated at the end of the calendar year 1944, and the presence of several others had been indicated by the drilling. More than 5000 holes had been drilled throughout the bauxite region, and more than 60,000 chemical analyses had been made of samples taken from the bauxite-kaolin zone. A study of the chemical analyses led to certain general conclusions not only with regard to the chemical composition of Arkansas bauxite, but also with regard to its component minerals. Charts and diagrams based on these conclusions have been developed for practical use by the Bureau of Mines: (I) to serve as a check against laboratory analyses, (2) to present tonnage estimates of ore bodies based on mineral composition, (3) to illustrate the relationship of tonnages of bauxite to the alumina, silica, and iron content, and (4) to serve as a control for mining operations by providing a means for quick estimates of the value of the ore from a partial analysis of its chemical constituents. The use of charts and diagrams similar to those discussed in this paper-- is not new. The use of the trilinear diagram for studying the ultimate analyses of coals as of proposed by Ralston in Bureau of Mines Technical Paper 93 (1915) showed that the various ranks of coal fell in different areas on the diagram and that volatile matter, calorific value and other properties could also be plotted by the use of contours. A considerable subsequent literature, largely on classification of coals, has accurnulated since then, showing the utility

Jan 1, 1948

By J. R. Thoenen, M. C. Malamphy, G. K. Dale

The beginning of the war and the events leading up to it precipitated a near crisis in the aluminum industry. Demands for the metal reached proportions far beyond the prewar production capacities and, in addition, the submarine menace seriously curtailed the importation of bauxite from South America, hitherto a chief source of high-grade ore. The situation required an intensive search for domestic ore to augment the reserves and in October 1941 Congress directed the Department of the Interior to investigate the extent, mode of occurrence, and quality of bauxite in the United States. In December of that year the Bureau of Mines and the Geological Survey began the search for bauxite in Arkansas, where more than go per cent of the domestic ore had been produced and where the greatest amount of bauxite was known to occur. The program involves the geophysical and geological investigation of the Arkansas bauxite region and the core drilling of areas considered favorable for the occurrence of bauxite deposits. Cores taken from the bauxite-kaolin zone are sampled and analyzed in the Bureau of Mines laboratory in Little Rock. The information from each of the deposits discovered is then assembled, the bauxite is graded with respect to its possible utility, tonnage estimates are made, and the whole is presented in the form of a war minerals report. Thirty-eight new bauxite deposits had been discovered and investigated at the end of the calendar year 1944, and the presence of several others had been indicated by the drilling. More than 5000 holes had been drilled throughout the bauxite region, and more than 60,000 chemical analyses had been made of samples taken from the bauxite-kaolin zone. A study of the chemical analyses led to certain general conclusions not only with regard to the chemical composition of Arkansas bauxite, but also with regard to its component minerals. Charts and diagrams based on these conclusions have been developed for practical use by the Bureau of Mines: (I) to serve as a check against laboratory analyses, (2) to present tonnage estimates of ore bodies based on mineral composition, (3) to illustrate the relationship of tonnages of bauxite to the alumina, silica, and iron content, and (4) to serve as a control for mining operations by providing a means for quick estimates of the value of the ore from a partial analysis of its chemical constituents. The use of charts and diagrams similar to those discussed in this paper-- is not new. The use of the trilinear diagram for studying the ultimate analyses of coals as of proposed by Ralston in Bureau of Mines Technical Paper 93 (1915) showed that the various ranks of coal fell in different areas on the diagram and that volatile matter, calorific value and other properties could also be plotted by the use of contours. A considerable subsequent literature, largely on classification of coals, has accurnulated since then, showing the utility

Jan 1, 1948

By M. G. Corson

UNTIL recently, the characteristics of cast copper have seldom been studied and such study as has been made has been inadequate. The prevailing idea seems to be that since pure copper is infrequently used in the cast state, there is no reason for trying to establish precise data regarding the properties of the metal in that condition. On the other hand, wrought copper either in the shape of sheets or wire rarely fails in service, except as a result of the action of reducing gases at the annealing temperatures, so there is little incentive to study the properties of the cast shapes -cakes, bars, ingots and billets-for the sake of tracing the causes of failures of the wrought metal to the cast stock. However, about a decade ago, wirebars of American origin often cracked badly while being hot-rolled in mills in Germany. This led to four investigations: by E. Seidl and E. Schiebold,1 by P. Siebe,2 by 0. Bauer and G. Sachs,3 and by G. Welter.4 These authors came to the conclusion that failures in hot-rolling were due essentially to the presence of a' wide zone of columnar crystals between the thin layer of fine crystals near the surfaces of the bars and the large but more nearly: equiaxed grains of the central core. This macrostructural defect was explained in turn by the probable upward deviation in the temperature of the metal while it was being poured into the molds of the casting machine. More recently, cast shapes of copper were investigated by N. P. Allen5 and by C. Blazey.6 Allen examined vertically cast wirebars and horizontally cast wedge cakes of electrolytic tough-pitch copper, but only for the distribution of densities; i.e., porosity. Blazey was interested mainly in the mechanism of the variations in electrical conductivity due to cold-work and anneal, but gave introductively an account of the composition and average densities of the tough-pitch horizontally cast wirebars used. As far as the present writer can tell, no investigation was undertaken for the sake of presenting a picture of the distribution of mechanical characteristics in the wirebars of copper, tough-pitch or otherwise.

Jan 1, 1938

By A. Dubé, G. Letendre, C. E. Beaulieu

An experimental study has been made of the time dependence of internal .friction and modulus of rigidity in- freshly quenched steels at room temperature. The effects of frequency, composition, and various thermal treatments are given. The kinetic 1aws observed cannot be fully explained by the so-called first stage of tempering and the transformation of retained austenite. It is suggested that the observed phenomena are due to the progressive immobilization of dislocations introduced by the martensitic transformation. It is generally agreed that the conversion of tetraginal martensite into cubic ferrite and ce-mentite occurs in three stages which at moderate rates of heating take place in the following temperature ranges:'-3 a) The first stage involves mainly a partial loss of tetragonality of martensite and the formation of ?-carbide between 95" and 175oC. b) The second stage consists of the decomposition of retained austenite between 230 and 290' C. c) The third stage covers the formation of ce-mentite between 290o and 400' C. The kinetic laws of these heterogeneous reactions have also been the subject of isothermal studies. Thus, Roberts, Averbach. and cohen3 report a very low reaction rate with a eutectoid steel at room temperature. For example, less than 10 pet of the contraction associated with the first stage is observed after 50 hr at room temperature. Hollonlon, Jaffe, and Buffum4 show that under the same conditions less than 10 pet of the tetragonality is lost. These results have led to the belief that martensite is a relatively stable phase at room temperature. On the other hand, it is well known that important structural changes occur in martensitic steels during the first few minutes at room temperature after quenching. This pretempering has at least two important consequences. In the first place, freshly quenched steels have a tendency to crack at room temperature, a fact which leads to the necessity of tempering as soon as possible after the quench. Another important consequence of pretempering a steel for short periods of time at room temperature is the stabilization of the retained austenite. Thus, as shown by Cohen,5 a very pronounced stabilization is effected with holding periods of 30 min at room temperature. Since these two effects are apparently not caused by the heterogeneous reactions mentioned above, they must be related to the rearrangement of structural defects within the martensite and retained austenite. According to the modern theory of dislocations, the shears required to effect the austenite-marten-site transformation may be realized through the motion of dislocations at the austenite-martensite interface and within the martensite plates.6 In this way, a martensitic transformation closely resembles a plastic deformation. In cold-worked solids, high concentrations of dislocations are left immediately after the plastic deformation and it seems reasonable to assume that appreciable densities of dislocations should also appear in the wake of a martensitic transformation. A considerable part of the high hardness of martensite would then originate in the obstruction of dislocations in analogy

Jan 1, 1961

By T. Fraser, F. F. Giese, R. L. Sutherland

Under a cooperative agreement between United States Bureau of Mines and the Truax-Traer Coal Company, some operating-scale experiments have been made with the cyclone thickener in the preparation plant of the Shamrock No. 1 mine at Kayford, West Virginia. These tests were made with a 14-in. cyclone of the type developed by the Dutch State Mines in Limburg. It was applied experimentally to the thickening of solids in washery water to obtain performance data to show the range of sizes that may be recovered and other operating characteristics that would indicate the field of usefulness of this device in coal preparation practice. This is a progress report only. It covers results obtained in a series of 17 tests of the operation of what has been considered a unit of commercial size operating on suspensions of fine coal mixed with a relatively small amount of free impurities. The underflow material, after further dewatering in centrifuges, is a marketable grade of coal. The coal at Shamrock No. 1 is mined from the No. 2 Gas seam. It is made up essentially of a low ash coal suitable for byproduct use with one or more bands of splint coal of higher ash content suitable for industrial fuel. The washing plant was installed for the two-fold purpose of removing the free impurities incident to mechanized mining and to separate the run of mine coal into the two types. To accomplish these results it is necessary to make a separation at a specific gravity of about 1.4 to recover the byproduct coal and to separate the splint coal from refuse at a higher gravity. The coarse coal section of the washing plant was put into service about 10 months before the fine coal section was completed. Inadequate screening capacity in the raw coal preparation plant resulted in a portion of the fine coal being fed to the jigs. No provision for preliminary dedusting of the raw coal feed was incorporated in the design. Under the conditions in the initial operating period, separation at the desired lower gravity was not realized, apparently because of the presence of an excessive amount of fine solids in suspension in the wash water. Difficulty in wetting the fine coal may also have been a contributing factor. Additional facilities for the removal of the fine solids from the wash water was indicated. Information then available on the Driessen cone for this purpose was studied and a cooperative agreement with the Bureau of Mines for experimental work with a unit of standard size as developed by the Dutch State Mines was arranged. During the time required for construction of the cone it was found the addition of a small amount of wetting

Jan 1, 1950

By Henry D. Hibbard

At the beginning of a Henry M. Howe lecture it seems fitting to refer to Howe's great contributions to steel metallurgy, and particularly to the literature thereof. Most of my predecessors in this role have been able, from their association with him, to give direct testimony as to his great services; but although connected with him for years in a business way, I am less familiar with what might be called his academic side, except as it is embodied in his utterances, written and oral. Howe was adept in his genial way in extracting information in any line which, at the time, was of interest to him. In a technical lecture one expects as a rule new knowledge—something about recent advances relating to the subject. On this occasion, however, I will ask you to go back with me to the primary department of steel lore, as the title of my lecture shows, to review the more fundamental features in that field for the purpose of seeking some gaps which we can fill and so give the subject renewed interest. In thus going back one must inevitably repeat many familiar facts, but that seems to be necessary in order to reach a clear understanding of the unrecorded matters. The full interpretation of a steel analysis is at present unattainable, though much progress toward that end has been made. The ultimate analysis, giving the percentages of the five commonly determined elements, does indeed usually give a fair idea of what the steel is, and is ordinarily enough, with knowledge of its history and physical condition, to enable it to be assigned to some purpose or use for which it is reasonably suitable. But discrepancies arise. Every maker and every user of steel knows, from at least occasional examples in his own experience, that the ultimate analysis is insufficient by itself to enable one to tell positively, from its interpretation, either the mechanical properties of the steel or its adaptability to the purpose for which it was made. Further, if, while having the specified composition, it is abnormal or unsatisfactory, why it is so. Good, bad and indifferent steels may have substantially the same ultimate analysis.

By H. W. Gillett

WE hear much in these days about "tailor-made" steels. Farseeing executives have sensed the demand for metals of improved and special properties, with those properties deliberately built into the steel in order to fit it for a particular use or group of uses. They have set their metal-lurgists at work to produce what the customer needs, even though the tonnage required may not, at least at first, be great. As the metal-lurgists bring out such metals, the products are advertised and the customer becomes increasingly conscious that he no longer has to take "ready-made" steel as the only thing available, whether it fits his needs or not, but that there are plenty of steelmakers ready to serve his specific needs with a tailor-made steel. Of course this is nothing new in the realm of rather highly alloyed steels to be heat-treated. The automotive industry demanded and got such steels long ago. Indeed, one could not design a modern car using only non-heat-treated carbon steel, since an engine of present horsepower would be so heavy that the gasoline required merely to lug the engine itself around would be absurd. Many different alloy steels and many different heat-treatments are required to produce the fine gradations of properties and the strength per unit weight that are needed in each particular part. Aircraft designers, of course, count a high strength-weight ratio in the materials used as Article I in their constitution, and they too, and in outstanding degree, require tailor-made alloys. Aircraft and automobiles may be considered as the tail coats and Tuxes of the metallurgical tailors. Nowadays there is also a demand for business suits, in the form of high-strength alloys to reduce dead load and so increase payload, all through the transportation industry. We hear most about weight-saving design and materials in respect to the railroads, with the spectacular new high-speed passenger trains and the prosaic freight car. The latter sounds especially sweet to steel-mill ears, because it means tonnage. While most of us think of these developments, and of the engineering acceptance of high-strength materials as "new," the fundamentals are of almost hoary antiquity. It is the widespread availability of a variety of materials and their general acceptance that are new.

Jan 1, 1936

By William M. Bowron

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

Jan 1, 1906

By Howard I. Smith

POTASH is of prime importance as a plant food and is also widely used in industry. The term "potash was applied to a crude pearlash obtained by evaporating, in iron pots, solutions leached from plant ashes. Later it included caustic potash obtained by treating pot ashes with lime, and now it is applied generally to various compounds of potassium used by agriculture and industry. Herein it applies to the theoretical equivalent in potassium oxide (K20)--a compound never found in nature or manufactured in commerce but generally used as a common denominator for comparison of all potassium compounds. Potash was made from plant ashes at an early date, but potassium in mineral form was not noted until 1797, when it was identified in leucite.3 The importance to plant life of potash in the soil was first recognized by von Liebig3 and his published reference thereto appeared in 1840. In 1843, potash was discovered in the brine of a well drilled for salt near Stassfurt. HISTORY OF THE AMERICAN POTASH INDUSTRY Among the colonists reaching Virginia in 1608 were men from Poland skilled in making potash from wood ashes19 and records show that the production of potash was begun in other colonies also, soon after their establishment. The American product entered the trade in 1635, and at various times since that date the production of potash for industry has been subsidized by the Government or protected by tariffs. The production of potash from wood ashes reached its peak in 1825. Beginning in 1823, a cheaper product, sodium carbonate, made by the Leblanc process, was substituted for much of the potash used in industry. Production rapidly declined after the Civil War, when the forests most productive of potash had become depleted and labor had become

Jan 1, 1949

In 1820, the Board of Public Works was considering some improvements to the canal, in order to reduce the cost of transportation, and in its annual report for that year gives a description of the method of loading the coal from the pit to the boat, and also from the boat to the dealer's yard, which is illuminating in showing how coal of this type should not be handled. It follows:- "It will be seen by the estimates, that the improving the present canal, forming a canal of large dimensions, from the head of the present lower canal to Sabbot Island; erecting locks of large capacity, and making a communication with the river, so as to completely accommodate the coal trade, (except it should hereafter be found necessary to make another communication with the river,) will not cost more than 126,000 dollars. But as there is some doubt whether the streams that may be received into the canal between Sabbot Island and the upper arch, will at all times be competent to supply the locks on that portion, we will extend our calculation to a point nearly half a mile above Pleasants' Island; where, by erecting a dam, any desired quantity may be thrown into the canal. This extension of the canal with one lock, and the dam across the river, is estimated at 34,000 dollars, making in the whole a little over 160,000 dollars. There will then remain a surplus of 40,000 dollars after completing the works to the point last mentioned. "In order to discover what effect the improvement of this first section will have on the tolls, it will be necessary to take a view of the present state of the coal trade, and endeavor to ascertain what change will result from the increased facility of transportation. "That part of the business which is carried on by water, is conducted nearly in this way. When the coal is drawn out of the mines, it is thrown in a heap near the mouth of the mine, or shaft; it is then loaded into carts, and carried to the river bank, where, in some instances, it is discharged from the cart at the brow of the bank, and runs down to the beach near the water's edge; then shovelled into wheel-barrows, and wheeled aboard of the boat, and discharged from the barrows by upsetting. In other instances, the carts are driven on to a kind of scaffold, furnished with a wide spout or director at the edge; by which the coal is conveyed immediately into the boats. These boats are the common James river poplar batteaux, and require three men to each. The up-stream navigation being laborious, the boats are built of light materials, and continue fit for service but a short time, (say) from two to three years; their cost, when new, from fifty to one hundred dollars. "When the river is tolerably flush of water, one of these boats will carry about two hundred bushels; but in low water their load is sometimes diminished to one hundred, and even as low as eighty bushels. They pay for passing the canals and locks to the Basin, one dollar per load; so that when full loads are taken, it will amount to half a

Jan 1, 1942

By W. M. Weigel

Salt production in Louisiana and Texas at the present time is entirely from salt domes of the interior and coastal groups. Before and during the Civil War salt was recovered from numerous salines and salt springs by evaporation in open kettles. The location of these in nearly every instance was near what is now known to be a salt dome, and the source of the salt in the salines and spring waters was that in the salt core. The tops of many of the shallower domes have been subjected to erosion1. The discovery that the salt occurred as large masses of rock salt in the form of domes was made in May, 1802, at Avery Island, La., by John Marsh Avery, grandson of the original owner, John C. Marsh, who built the old salt works in 18122. The first shaft for mining was sunk on the Avery dome in 1867 by Chouteau and Price. It was 90 ft. deep, about 58 ft. being in solid salt. It was abandoned in 1870. There are three general groups or fields of salt domes; interior Louisiana in northern Louisiana, interior Texas in northeastern Texas, and the coastal domes nearer the Gulf Coast and extending from the Mississippi River to the Rio Grande. This last group contains by far the greatest number of domes. As many of the coastal domes especially are prolific producers of petroleum and a few of sulfur, their geology has been intensively studied and fully covered in the literature. The depth to the top of the salt varies from near the surface, where shallow ground waters have dissolved the salt to just below recent deposits, to several thousand feet, where the depth has been cstimated only by geophysical methods. The diameter of the salt core varies from less than 1/2 mile to over 2 miles. Only domes where the salt is comparatively near the surface have been developed for commercial salt. Three deeper domes, which will be described later, have recently been developed or are in process of development, as a source of brine for chemical use. Fig. 1 shows the location of the domes so far developed for commercial salt and brine. Nos. 1, 2, 4, 7, 8, 9 and 10 are in the Gulf Coastal field,

Jan 1, 1938

By H. K. Work

The Bessemer process is one of the most interesting methods of making steel. At one time it was by far the most important. In recent years, however, it has steadily lost ground to the open-hearth process. The forces working against this method of stccl-making are partly economic and partly metallurgical.1 In this paper, dealing as it does with the control of the process, the metallurgical factors alone will be considered, although it is obvious that economic factors must play a part in determining the ultimate status of the Bessemer process. This discussion has been limited in another respect—it deals primarily with the acid Bessemer process in bottom-blown converters, although much of the information is applicable to basic and side-blown converters. The fact that open-hearth steel has superseded Ressemer steel to a large extent has tended to create an impression that Bessemer steel is inferior. As a matter of fact, Bessemer steel is actually superior to open-hearth for many applications.2 There are, however, definite metallurgical limitations to the use of Bessemer steel, resulting largely from two factors: (1) the physical properties conferred by nitrogen and phosphorus, and (2) the variability from blow to blow. These, of course, are not entirely independent, since some of the variability covered in the second item is undoubtedly due to nitrogen. But the variability is also caused by other factors. One of these is the relatively small size of the Bessemer heats. Because of this, a given shipment of Bessemer steel is more likely than a shipment of open-hearth steel to contain the product of several heats, each with its own distinctive and slightly different characteristics. Added to this is the fact that the refining of Bessemer steel proceeds so rapidly that the timing of the end point is limited to a matter of seconds, whereas the finishing period in the open hearth extends over a period of one or two hours and the timing of the end point may vary by several minutes without seriously affecting the product. There is no doubt that this has contributed to the variability of Bessemer steel and has led to the use of open-hearth steel in many optional applications. That Bessemer steel may vary is not necessarily objectionable, and it may even prove an advantage, providing a precise control is available to secure the desired qualities for any specific application. With this in mind, a comprehensive research program was undertaken, one phase of which was directed toward securing more accurate control of the blow. The results have been encouraging, and it is the purpose of this paper to describe a method in which modern scientific instruments, based on photocells, are currently being employed to assist the blower. The Control Problem In this day of scientific control of technical processes, where the operating

Jan 1, 1941

By Raymond S. Weimer

Of the several characteristics of a coal that influence its suitability for use in a given piece of burning equipment, the clinkering and slagging characteristics of the ash of the coal are highly important. They determine the maximum rate at which the coal may be burned on a stoker or in pulverized form without difficulty from damage to metal parts, from erosion of refractory walls, or from stoppage of gas passages by accumulation on the tubes. They also determine the minimum rate at which a slag-tap furnace may be operated without difficulty in removal of the ash in fluid form. Need for a Better Criterion In common with other producers and users of coal, the Northern Illinois Coal Corporation has long used the available methods for the measurement of the clinkering characteristics of coal ash, chemical composition and fusion temperature of the ash, as criteria for the selection of coal that would suit the particular requirements of its customers. These two available criteria have greatly helped in the problem of selection but it is unnecessary to dwell upon the fact that they are not completely adequate for the purpose. The composition of the ash and its clinkering tendency vary widely over the company's mining area. In a certain period, some years ago, an unusual amount of severe clinkering of the ash of coal shipped made extremely acute the need for a better criterion of the clinkering that might be expected. It was also desirable that the criterion result from a reasonably rapid method, so that the clinkering characteristics of the coal would be known before shipment. Complaints on the severe clinkering of the ash came from only a fraction of the output of the mine but the occurrence of the clinkering seemed quite unpredictable. Attempts to relate the chemical composition of the ash and the fusion temperatures to the clinkering were unsuccessful. Coal from the area of the mine in which the fusion temperature of the ash was the lowest gave the least trouble from clinker-ing. Chemical analysis of the ash from that section giving the most trouble showed high contents of iron and low contents of silica, but frequently these were not greatly different from those of coals that gave little trouble from clinker. Aside from the clinkering difficulty, the coal was quite satisfactory. The ash content was normal and high rates of burning could be obtained, but again and again such severe clinkering would occur that the furnace would be shut down because of the accumulation of clinker. Examination of the clinker from the customers' plants showed that the clinkers that adhered to the grates and fouled the fuel beds were hard, flat, dense, and usually dark in color. Coal that was satisfactory gave clinkers that were softer, bulky rather than flat, of low density, and usually lighter in color.

Jan 1, 1944

By W. H. Brandt

ThEre has been much progress in the last two decades in understanding the hardenability of steel. Roughly, the progress has been along two lines, which may be designated as empirical and fundamental. This empirical work has progressed to the point where steels may be manufactured to the desired characteristics quite closely and heat-treatment and application problems can be approached with considerable confidcnce. Particularly noteworthy among the empirical work is that of Grossmann,12. who has given formulas for calculating hardenability as a function of composition, and the establishment of the isothermal transformation curve by Davenport and Bain.13 The latter does not fall entirely in the class of an empirical study, for while it provides a means of presenting a tremendous amount of empirical data in the form of a single curve, it also outlines clearly the problems that face the fundamental investigator. The isothermal transformation curve shows clearly that the phenomena occurring in the neighborhood of the knee of the curve are those that limit the hardenability of steel. Above the knee of the curve, the product of decomposition of austenite is lamellar pearlite and fundamental progress has consisted chiefly of a detailed study of structure and formation of pearlite, largely at the hands of Mehl and his collaborators.'-5 They have shown that formation of pearlite proceeds by a process of nuclea-tion and growth and they measured both the nucleation and growth rate. However, there is still a wide gap between our empirical knowledge and fundamental knowledge, owing largely to the fact that there is no satisfactory theory of nucleation rate or of growth rate. This paper is being written in an attempt to Hl in a small part of the gap. A method was prcsented recently1' for calculating the velocity of edgewise growth of pearlite using an expression for the carbon concentration that satisfies the diffusion equation. The edgewise velocity of pearlite growth in a plain carbon eu-tectoid steel was calculated, using linear extrapolations of the ferrite and comentite solubilities. While the results are in fairly good agreement with the experimental facts, the calculated velocity of edgewise growth is smaller at 600°C. than G, the radial growth velocity of pearlite nodules, whereas one would expect it to be larger. In this paper the calculation will be repeated using a new extrapolation for the ferrite solubility, which gives better agreement between G and T', the calculated velocity of edgewise growth. A calculation will also be made of the effect of carbon content on velocity of edgewise growth, and the problems of calculating the effects of other alloying elements on growth rates will be discussed. It will be assumed that the mechanism of pearlite growth, established by Mehl and

Jan 1, 1947

By George A. Morrison

THE Columbia Chemical Division of the Pittsburgh Plate Glass Co. is at Barberton, Ohio, 35 miles south of Cleveland. For many years large tonnages of limestone have been brought to the Barberton plant from distant points. The stone is here burnt in vertical kilns, the resultant product then hydrated and the hydrated lime used in chemical processing. To eliminate the expense of these shipments, the company decided to investigate a limestone bed known to exist on company property at Barberton, where the stone is used. The bed lay at a depth of more than 2000 ft. and was known locally as the "Deep Lime." Chemical analyses of sludge from churn-drill holes made some years ago proved that the limestone was of sufficient purity to warrant diamond-drill exploration. Four diamond-drill holes were put down at well-spaced intervals, to represent fairly an area of four miles by one mile. Cores logged as to chemical and physical conditions were found to compare closely, and to corroborate the earlier evidence that the limestone was of superior quality for chemical use. A plant of 300 tons per hour was subsequently decided upon. SITE The yard at the chemical plant was already so congested that location of the projected mine within its area could not be considered. Eventually a site was selected 2 miles northwest of the plant, near the main line of the Erie Railroad. Here 412 acres were owned outright by the company and stone rights were obtained on 250 additional acres. This location required a transportation line of nearly 2 miles (8800 ft.), crossing two major highways, and to avoid interruption of deliveries to the plant, overpasses were planned. GEOLOGY The limestone in the immediate vicinity lies about 2200 ft. below the surface. Geologists* identify this stone as Delaware of Devonian age. It is overlain by 18 ft. of unconsolidated (sand and gravel), 100 ft. of water-bearing sandstone, and finally 2080 ft. of shale into which sandstone in thin layers is interbedded. The contact of shale and limestone is abrupt, flat-lying and very pronounced. Berea sandstone, often found at 520 ft., is absent, but Euclid sandstone was encountered, together with a seepage of oil and a small amount of methane gas. The limestone bed itself is 345 ft. thick, and overlies 200 ft. of gypsum. The lower part becomes dolomitic as it approaches the gypsum. A detailed study of the drill cores indicates that the upper 50 ft, are highest in lime and reasonably low in silica. The physical make-up shows several separating cherty layers. These occur at definite horizons and cause distinct partings, which become horizontal planes of

Jan 1, 1943

By C. S. Brooks

Several of the commonly used methods for deter-mination of effective grain densities of minerals have been evaluated for accuracy and precision, and their applicability to various types of petroleum reservoir minerals tested. Consideration was given to the effect of consolidation, swelling clay, and wettability on these grain-density determinations. Procedures with helium displacement, a modified low-pressure Boyle's law porosimeter, and liquid displacement (water, n-decane, and n-octanol) were tested. The helium-displacement procedure was used primarily as an independent reference for which the effects of fluid-solid interaction, e.g., adsorption and wettability, were negligible. The procedures with the Boyle's law porosimeter and with liquid displacement are the methods in common use. Minerals investigated included calcite, West Texas limestone core samples, California sandstone core samples, and Wyoming bentonite. The number of samples tested, while not large, was adequate to permit application of statistical methods. Grain-density measurements on calcite (Iceland spar) provided a basis of comparison for the accuracy and precision of the procedures under investigation for a material with a high degree of chemical and physical homogeneity and for which fluid-solid interactions were at a minimum. Liquid-displacement procedures (water or n-decane) provided the greatest reliability and precision for measurement of the grain densities of the limestone tested. Gas-displacement procedures (helium or Boyle's law porosimeter) provided the greatest reliability and experimental convenience, if not the greatest precision, for the measurement of the grain densities of the swell- ing clay, Wyoming bentonite, and the shah sandstones which -contained appreciable amounts of swelling, in-terstitial clays. These experiments were designed to evaluate the applicability of the grain-density procedures in common we to some of the less tractable minerals—tight limestones, shaly sandstones, and swelling clays. The results should provide a useful basis for a selection of the method most suitable for application to the various petroleum reservoir minerals encountered and especially for use in the estimation of formation porosity. INTRODUCTION These experiments were undertaken to evaluate the accuracy and precision of several commonly used methods for determination of effective grain densities of minerals, and to test their applicability to various types of petroleum reservoir minerals. Consideration was also given to the effect of consolidation, clay, and wettability on these grain-density determinations. Procedures used included measurements with helium displacement, with a modified low-pressure Boyle's law porosimeter, and with liquid displacement (water, n-decane, and n-octanol). The minerals investigated included calcite, West Texas limestone core samples, California sandstone core samples, and Wyoming bentonite. The accurate determination of the porosity of petroleum reservoir formations, in particular those of low porosity, has received much attention. Both bulk-volume and grain-volume measurements necessary in the evaluation of porosity have been examined by many investigators with the objectives of improving both the accuracy and the precision of these determinations. In this investigation statistical criteria for selection of the most reliable and suitable procedure for use with a given type of mineral are demonstrated. The grain-volume measurement procedures appear to be the most susceptible to improvement.

Jan 1, 1958

By Earl Bardwell

THE structural relations existing between cuprous oxide and copper -were first systematically studied by Heyn1', who suggested that a study of the microstructure of refined copper might be substituted for the analytical methods in vogue for determining the oxygen content of copper coming from the refining furnace. Hofman, Green and Yerxa,2 in their paper A Laboratory Study of the Stages in the Refining of Copper, working along the lines suggested by Heyn, showed that a study of the microstructure could be made to yield a correct estimate of the oxygen content of the specimen of refined copper under examination. In order to determine the oxygen content of the specimen of refined copper under. examination a photomicrograph was first made. From the relative areas of copper and eutectic, the percentage of cuprous oxide and the corresponding percentage of oxygen were then readily calculated. It was found that the values for oxygen thus obtained corresponded closely with the analytical results. With the idea of utilizing this method of determining the oxygen content of each charge dipped from the refining furnaces at the Boston & Montana Reduction Plant, the physical testing laboratory was equipped with suitable apparatus for carrying out the work. It may be of interest to describe certain of the methods which have been worked out in this connection and give such data as have been obtained bearing on the effect of the oxygen content of refined copper upon its conductivity. Apparatus.-For the benefit of those who may be unfamiliar with metallographical apparatus and methods and may be interested to know what equipment is required, a few words with regard to the apparatus is in place at this point.

Jan 7, 1913

By Charles Law McCabe, Lyndon H. Everett, Edna A. Dancy

It has been found that the carbide phase present at equilibrium in the system M-H2-CH4, at about 600°C, is MC for the rare-earth metals Ce and Pr. X-ray diffraction analysis showed that the monocarbides have fcc structures with lattice constants of 5.036 + 0.009Å and 5.131 + 0.001Å for CeC and PrC respectively. Gaseous equilibrium measurements were used to calculate the standard free energy of formation of the monocarbides from the elements. for the formation of (+ 1300) for the formation of PrC. THE rare-earthdicarbides, and their crystal structures, have been known for some years,l but only more recently were the carbides CeC,2,3 Ce2C3 2 and CeCS3 reported. In 1958 to 1959, Spedding et al. published work on the lanthanum-carbon system4 and other rare-earth metal-carbon systems,5 proving the existence of M2C3 and MC2, and measuring the lattice constants. They also demonstrated that tri-rare earth carbides, M3C, exist for the rare-earth metals samarium through ytterbium. However, they concluded that the cerium monocarbide reported by Brewer and Krikorian2 and by Warf,3 and given a fcc structure with a lattice constant of 5.130Å bythe former workers, was, in fact, cerium metal with carbon dissolved in it. They were also unable to find any evidence for the existence of Warf's CeC3, for which no structural details had been given. Even more recently, Palenik22 reported the existence of only M2C3 and MC2, having been unable to find any evidence for the existence of any other rare-earth carbides. There are no published experimentally derived thermodynamic data for the formation of any of these carbides, although Brewer and Krikorian6 have estimated values of for CeC, Ce2C3 and CeC2. The objective of the present investigation was; to determine experimentally the free energy of formation of any of the reported carbides of cerium and praseodymium, through a study of the rare-earth metal-hydrogen equilibrium. EXPERIMENTAL A methane-hydrogen mixture was circulated, in a closed system over previously prepared cerium or praseodymium hydride, and when equilibrium had been attained, the gas mixture was analyzed by selectively oxidizing the hydrogen and condensing out the water formed. The metal hydrides were used as starting material for convenience because, otherwise, the hydrogen in the gas mixture would immediately dissolve in the metals; in addition, the metals would not react with methane alone at the experimental temperature (around 600°C). The circulating system was based on that used by Browning, DeWitt, and Emmett7 for similar studies on iron carbides. It consisted of a quartz reaction vessel, all-glass circulating pump, analysis tube containing copper oxide that could be heated to 300" C by means of a small furnace, a solid CO2-methanol trap, and a double limb absolute manometer, Fig. 1. A cathetometer, capable of reading to 0.005 cm, was used to measure the difference in height between the two columns of mercury. In its final form, the reaction vessel was enclosed in an outer jacket, containing approximately the same pressure of hydrogen as that within, to reduce errors due to diffusion of hydrogen out through the fused silica of the reaction vessel., The circulating system was supplied with

Jan 1, 1962

By H. K. Work

The Bessemer process is one of the most interesting methods of making steel. At one time it was by far the most important. In recent years, however, it has steadily lost ground to the open-hearth process. The forces working against this method of stccl-making are partly economic and partly metallurgical.1 In this paper, dealing as it does with the control of the process, the metallurgical factors alone will be considered, although it is obvious that economic factors must play a part in determining the ultimate status of the Bessemer process. This discussion has been limited in another respect—it deals primarily with the acid Bessemer process in bottom-blown converters, although much of the information is applicable to basic and side-blown converters. The fact that open-hearth steel has superseded Ressemer steel to a large extent has tended to create an impression that Bessemer steel is inferior. As a matter of fact, Bessemer steel is actually superior to open-hearth for many applications.2 There are, however, definite metallurgical limitations to the use of Bessemer steel, resulting largely from two factors: (1) the physical properties conferred by nitrogen and phosphorus, and (2) the variability from blow to blow. These, of course, are not entirely independent, since some of the variability covered in the second item is undoubtedly due to nitrogen. But the variability is also caused by other factors. One of these is the relatively small size of the Bessemer heats. Because of this, a given shipment of Bessemer steel is more likely than a shipment of open-hearth steel to contain the product of several heats, each with its own distinctive and slightly different characteristics. Added to this is the fact that the refining of Bessemer steel proceeds so rapidly that the timing of the end point is limited to a matter of seconds, whereas the finishing period in the open hearth extends over a period of one or two hours and the timing of the end point may vary by several minutes without seriously affecting the product. There is no doubt that this has contributed to the variability of Bessemer steel and has led to the use of open-hearth steel in many optional applications. That Bessemer steel may vary is not necessarily objectionable, and it may even prove an advantage, providing a precise control is available to secure the desired qualities for any specific application. With this in mind, a comprehensive research program was undertaken, one phase of which was directed toward securing more accurate control of the blow. The results have been encouraging, and it is the purpose of this paper to describe a method in which modern scientific instruments, based on photocells, are currently being employed to assist the blower. The Control Problem In this day of scientific control of technical processes, where the operating

Jan 1, 1941