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By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By George J. Bancroft

At the New York meeting of the Institute, April, 1907, I presented a paper entitled, The Formation and Enrichment of Ore-Bearing Veins,' in which paper I advanced the following propositions: (1) That the majority of mineralized veins are the product of expiring vulcanism; (2) that most of these veins were primarily mineralized by comparatively rich solutions in comparatively short periods of time; (3) that the solutions gained their metal-values from a comparatively rich source; (4) that there is a bary-sphere containing large amounts of the useful metals; (5) that eruptions spring from various depths and bring various kinds of magmas towards the surface; and (6) that only those eruptions which disturb the barysphere and bring a magma rich in metals sufficiently near the surface to be leached by vein-making solutions are productive of valuable ore-deposits, other eruptions producing barren veins. Ore-deposits due to magmatic segregation were not included in this general survey. As a result of considerable further study I have modified my views in some respects, while in others I feel more sure than ever of the ground taken at that time. That ore-bodies are infrequent occurrences and born of extraordinary conditions I think is now generally accepted. The theory that persisted for a time—namely, that ore-bodies were formed by the ordinary ground-water, which consists of extremely dilute solutions, derived from leaching extremely lean surface-rocks, and which must occupy enormously long periods of time in concentrating the values so leached, is, I think, now pretty generally regarded as not applicable to the great majority

Jan 1, 1910

By R. S. Dean

AMONG naturally occurring inorganic compounds, magnetite has many unusual and interesting properties, and it is the purpose of this paper to call attention to these properties and review possible uses of magnetite that might be based on them; in other words, to see what uses may be found for magnetite as a physical rather than as a chemical entity, as a mineral rather than as an iron ore. The Mineral Physics Studies initiated in the Metallurgical Division of the U. S. Bureau of Mines a few years ago gathered together much information on mineral properties, and they are therefore the principal source of material for this paper.

Jan 1, 1937

By Frank Clemes Smith

In describing a certain class of ores, of ever-increasing importance in the Black Hills, they are variously called " refractory,)' "siliceous," or Potsdam;" the first name serving to distinguish them from the other important class—the free mill-

Jan 1, 1898

By R. A. Breitrick, J. N. Swinderman, J. J. Cooper, H. L. Bauer Jr.

The Robinson Mining District, near Ely, Nev., is one of the major porphyry copper districts in the world. Within the district is an eight mile long east-trending zone of altered porphyry, metamorphosed sedimentary rocks, and sulphide mineralization surrounded by Paleozoic limestone, dolomite, shale and sandstone, Tertiary volcanics, and Quaternary alluvium. Six major disseminated ore deposits have been exploited in this zone. About 20% of the district production has come from disseminated ore in metamorphosed sedimentary rocks found adjacent to altered quartz-monzonite porphyry. The following brief statements summarize some of the relations between porphyry alteration, metamor-phism, and mineralization: 1) Disseminated copper ore does not occur in unaltered porphyry or in m-metamorphosed sedimentary rocks. 2) Sedimentary rocks have been only weakly metamorphosed where intruded by unaltered porphyry. 3) Intensely metamorphosed sedimentary rocks are found only adjacent to altered porphyry. 4) Many hydrothermal minerals are common to both altered porphyry and adjacent metamorphosed sediments. 5) Disseminated ore is found in altered porphyry and adjacent metamorphosed sedimentary rocks. 6) In general, there is a direct correlation between grade of ore in porphyry and copper content in the adjacent rocks. 7) Chemical changes in the altered porphyry and metamorphosed rocks appear to be related. The foregoing relations support a hypothesis that the porphyry alteration, the metamorphism of the sedimentary rocks, and the ore deposition were all part of a continuous hydrothermal process which probably closely attended the porphyry intrusion. The Robinson Mining District, most often referred to as the Ruth or Ely District, is located in eastern Nev. and is one of the major porphyry copper districts of the world. Production from 1908 through 1962 was nearly 250 million tons of ore averaging a little over one percent copper with a total metal value of nearly one billion dollars. The ore has been produced from six major disseminated-type deposits with the Liberty Pit deposit accounting for 70% of the total district production. Less than one million tons of base metal and gold ores have been produced from the replacement-type deposits of the district. Approximately 20% of the district production has come from underground mining operations; the pit ore has been mined with shovels and removed by train haulage, truck-train haulage combinations, truck haulage, and presently by a combination truck-skip system. Many of the ore deposits formerly worked by underground methods have been and are being exploited by open pit methods. (See Fig. I.) Two co.'s have accounted for virtually the entire production from the district. In 1958 Kennecott Copper Corp. acquired the district assets of Consolidated Coppermines Corp. and is now the sole ore producer in the district. Present operations are confined to the Liberty Pit where 22,500 tons of ore averaging a little less than 0.8% copper is mined per day. Cutoff grade is 0.4% copper, and the stripping ratio is three to one. The ore is hauled by rail 23 miles to the McGill Reduction Plant where it is concentrated to about 20% copper. Molybdenite is recovered as a by-product in the mill. The copper concentrates are smelted in McGill, and the blister copper is shipped for refining to Balt. where gold, silver, platinum and palladium are recovered. The Robinson Mining District has been well known as a porphyry copper district for the past fifty years, but many geologists are unaware of the fact that a large portion of the production has come from disseminated ore found in metamorphosed sedimentary rocks. The scope of this paper describes the occurrences of disseminated ore in the various metamorphosed sedimentary rocks, and presents evidence for the hypothesis that these ores are genetically, spacially, and coevally related to the disseminated ore in the porphyry rocks. Publication of this paper was granted by the management of Kennecott Copper Corp. A. H. James suggested and encouraged the writing of the manuscript. Special mineralogical and spectrographic analyses were performed by the Kennecott Research Center. The deposits of the district have been studied by many geologists since the turn of the century, and

Jan 1, 1964

By W. D. Robertson

A considerable quantity of experimental data is available on the effect of time, temperature, work-hardening and composition on the mechanical properties and corrosion resistance of aluminum alloys. There is, however, little unity of purpose or generality in most of the studies and, because the number of variables is large, the results often are not applicable to the problems that arise in practice. Furthermore, the customary expression of the effect of different variables as separate curves or as three-dimensional diagrams with time, temperature and the dependent variables as coordinates, renders the task of selecting the optimum time and temperature of precipitation treatment, with respect to their simultaneous but unequal effect on the various properties, exceedingly difficult. The introduction of precipitation treatments to raise the yield strength of 24S-type alloys has created a need for a method of correlating and summarizing the effect of time and temperature on the mechanical properties and susceptibility to intercrystalline corrosion. Correlation is particularly desirable because the choice of time and temperature is of necessity a compromise to achieve the best possible combination of properties, and the optimum conditions cannot be accurately specified unless the data are in a form in which the alternatives can be readily compared. Therefore, the work described here was undertaken to find a common relationship that would be capable of expressing the effect of precipitation time and temperature on the various properties and by means of which the relative effects could be correlated and their interpretation facilitated. REVIEW OF PREVIOUS WORK In connection with an investigation of the interrelation of age-hardening and creep performance of nickel-silicon-copper alloys, Jenkins and Bucknall1 demonstrated that the time required to attain maximum hardness and tensile strength could be expressed by a relationship of the form: t = K. 10m/T (I) where t is the time in hours and T the temperature of aging, expressed in degrees absolute, and m and K are constants. They also pointed out that this expression is analogous to that which describes the change of the diffusion coefficient D with temperature; namely, D = Ae-Q/RT (2) Later, Cohen used this relationship in studies of the mechanism of age-hardening of a silver- rich copper alloy2 and of duralumin. 3

Jan 1, 1945

By Douglas Bunting

THE first presentation of this paper was before the Pennsylvania Anthracite Section of the Institute in May, 1914, after which a committee was selected to verify and add to the data contained in the original paper. The author is indebted to G. W. Engel, H. W. Montz, R. V. Norris, and H. H. Otto, of this committee, for additional information. I also wish to acknowledge the courtesies extended me by a number of the mining companies for information relative to accidents, systems of proving, and mining practice. The paper should bring forth additional criticism and recommendations, which will be of value in establishing future practice relative to this subject. Throughout the northern anthracite field of Pennsylvania glacial and alluvial deposits of sand, gravel, and clay exist in varying quantities. The extent and character of these deposits are described by N. H. Darton in Bulletin 45 of the U. S. Bureau of Mines, entitled, Sand Available for Filling Mine Workings in the Northern Anthracite Basin. It is estimated that the northern field contains 10,000,000,000 tons of these deposits, or a sufficient quantity to cover the 176 square miles of coal area to a depth of about 25 ft. These deposits of sand, etc., overlying the coal measures attain a maximum depth of more than 300 ft., and are usually saturated to such an extent as to render them semi-fluid. It is .this condition of fluidity that limits the mining of coal seams cropping in or in close proximity to these deposits, and it is in the interest of safer and more efficient mining methods under these conditions that the study of this -subject is here presented. The dangers incident to mining under deep deposits of sand have long been realized by operators in the northern anthracite field, and much has been done to prove the contour of the rock and vein croppings underlying these water-bearing deposits of sand and gravel.

Jan 1, 1915

By Donald F. Taylor

TANTALUM and columbium are newcomers in the world of metals. Many of the metals described in this volume had been known and used for centuries before either tantalum or columbium was known to exist. The scarcity of the ores and the comparative difficulty of extraction delayed their technology until specialized methods of processing could be developed. HISTORY Early in the nineteenth century, 1801, Hatchett discovered a new oxide, which he called columbium oxide, and a year later, Ekeberg announced that he had found a new element, which he named tantalum. The preparation of the metal tantalum in impure form was first announced by Berzelius in 1824, but the actual production of ductile metal did not occur until 1903, when von Bolton, of Siemens and Halske, developed a process for the production of tantalum pure enough to be drawn into electric-lamp filament wire. The use of tantalum as a filament wire began to decline when ductile tungsten was introduced in 1909. In 1921, C. W. sake, of Fansteel Metallurgical Corporation, produced the first ingot of tantalum metal in America. The first ingot of columbium was produced in 1927 in the laboratory of the same company. There are several good reasons why tantalum and columbium are often mentioned together. They occur together in their important minerals, are similar in many of their properties, and are

Jan 1, 1953

By P. A. Boeck

(San Francisco Meeting, September, 1915) THE thermal insulation of high-temperature equipment for industrial purposes is a subject that has not received from engineers and designers the attention its importance deserves. This may be attributed to a number of causes: In the first place, heat flow is a rather difficult factor to measure under the working conditions of an industrial furnace, and until the comparatively recent introduction into certain operations of the heat balance sheet, with a systematic attempt to account for the discrepancies in the totals, the various causes of heat losses and the reasons for their existence were not brought to light. Moreover, such rapid advancement and radical changes in the design of equipment, especially in metallurgical lines, have occurred that practice has apparently outdistanced the theory of design. In the modern tendency toward greatly increased size of units, effort has seemingly been made to utilize the heat of fuel gases without proper. attention having been paid to conserving heat energy and confining it strictly to the points of maximum activity. The systematic study of the thermal properties of structural materials, which is being carried out by various government bureaus and also by a number of technical societies, is forming the basis for more intelligent and consistent work in the economically important subject of prevention of fuel waste.

Jan 8, 1915

By Ralph H. Sweetser

AT the end of 1943 the charcoal pig iron capacity of the United States was at the lowest point in over 1110 years, with only one strictly charcoal blast furnace in operation, and all others permanently out of blast except one in Tennessee d reported to he running on part charcoal and part coke. Such a decrease in production has taken place in spite of the O.P A.'s high-premium price on charcoal pig iron of +34 per ton f.o.b. furnace in Michigan. Depletion of the hardwood supply within fifty mlles or inure of the blast furnace is the reason why; the deplorable lack of reforesting is the cause.

Jan 1, 1944

By J. W. Halley, G. L. Plimpton

Because of the two distinct stages in the solidification of rimmed steel, segregation in the rimmed ingot is more complex than that in the killed or semikilled ingot. In the earlier stage, chemical reactions, resulting in evolution of gas and vigorous stirring of the metal, effect a degree of negative segregation unique to rimmed steel. The composition of this zone constitutes the principal quality advantage of this type of steel. In the later stage of solidification, after the evolution of gas has ceased, the segregation follows the general pattern of a more completely deoxidized steel. However, the composition of the liquid remaining after the first solidification stage varies markedly from that of the original melt, some constituents having been partially removed as reaction products while the concentration of others has been intensified by rejection from the metal solidifying in the first zone. The aim, from the standpoint of segregation, in rimmed steel of high quality is to effect a maximum negative segregation in the rim zone without excessive concentration of undesirable elements at the center of the ingot. To achieve this aim, the composition of the melt may be varied and the furnace and pouring practice may be adjusted within certain limits. It is the purpose of this study to discuss segregation in rimmed steel from the standpoint of the mechanisms that produce it and to survey the phases of open-hearth practice that influence those mechanisms. Mechanisms Producing Segregation The mechanisms that determine the degree of segregation in the rimmed ingot are closely interrelated, making it difficult to select the primary factors and to determine a satisfactory order for presenting them. For instance, the question of sulphur segregation is relatively simple, since sulphur is not directly involved in chemical reactions in the ingot; but its concentration in the rim zone is dependent not only on its original analysis in the melt, its segregation coefficient, and the freezing rate, but also on the rate of its removal from the impure film on the solidifying surface. This washing action involves all the factors (such as freezing rate, the carbon-oxygen product, pressure, etc.) that determine the rate of gas evolution and hence the efficiency of film removal. Sulphur distribution between the rim and core is affected by the volumetric ratio between the two zones, and its segregation in the core is a function not only of the freezing rate of the core but also of all the foregoing factors that determine its concentration in the metal when solidification of the core starts. To simplify the presentation, it is proposed to treat the mechanisms affecting segregation independently in this section, reserving a discussion of their over-all effects for the section in which actual segregation data are given. The factors affecting segregation will be treated in the following order: (I) differential solidification, (2) removal of constituents as

Jan 1, 1945

By Gordon M. Yocom

A pRopeR consideration of the subject of this paper should include economic aspects as well as the technical phases of the metallurgy, production, and properties of the product. The metallurgical phases of the processing and properties of the product will be considered only from practical aspects and within the scope of the writer's experience with tonnage production. The Bessemer process was invented 85 years ago and became important because it put steel manufacture upon a larger and less costly basis. In America the Bessemer production has declined for many years and has not maintained its proportionate place with the rapid advances of the open hearth. The achievements in the open-hearth field were attained by the greater number of technical people attracted to that branch of the industry. The antipathy of technical students for the older and less popular Bessemer field gradually weakened the forces defending it and retarded the development of new and better methods. In Europe the economic advantage of the basic Bessemer process has not been overlooked and the tonnage usually is greater than that of the open hearth. The acid process has been the subject of renewed attention in America during the past few years and those who are more familiar with it are striving to show that the method is too valuable to abandon. A considerable tonnage of Bessemer-blown metal, in both molten and ingot forms, used in connection with the open-hearth practice makes it an important auxiliary unit to the industry. This practice aids in modifying the price level of heavy remelting scrap in addition to speeding up the open-hearth operation. The use of Bessemer steel has continued not only because of periodic economic advantages but also because of certain inherent qualities of machinability, weldability and stiffness, which are valuable for many applications. The properties of stiffness and rather high reaction to cold-work require some modification in order to meet the demands of modem methods of processing, which involve cold-reduction and cold-forming. At least one factor contributing to the stiffness of this steel is the relatively high phosphorus content of the acid product. The phosphorus content of the Thomas or basic Bessemer steel of Europe is considerably lower than the normal acid product in America. The American industry has continued the use of the acid process chiefly for the reason that the available ores are more easily adapted to this process from both metallurgical and economic standpoints. In European practice the basic process is necessary with the highly phosphoric ores available and it is sustained to some degree by the sale of the rich phosphate slag as a by-product. The basic process was used in this country at several plants many years ago, but was abandoned for economic reasons. A part of the past history of these trials is given here because the author believes it has not been published and it has some bearing on the subject of this paper. The information is authentic to the extent that he possesses chemical laboratory notebooks

Jan 1, 1941

By Gordon M. Yocom

A pRopeR consideration of the subject of this paper should include economic aspects as well as the technical phases of the metallurgy, production, and properties of the product. The metallurgical phases of the processing and properties of the product will be considered only from practical aspects and within the scope of the writer's experience with tonnage production. The Bessemer process was invented 85 years ago and became important because it put steel manufacture upon a larger and less costly basis. In America the Bessemer production has declined for many years and has not maintained its proportionate place with the rapid advances of the open hearth. The achievements in the open-hearth field were attained by the greater number of technical people attracted to that branch of the industry. The antipathy of technical students for the older and less popular Bessemer field gradually weakened the forces defending it and retarded the development of new and better methods. In Europe the economic advantage of the basic Bessemer process has not been overlooked and the tonnage usually is greater than that of the open hearth. The acid process has been the subject of renewed attention in America during the past few years and those who are more familiar with it are striving to show that the method is too valuable to abandon. A considerable tonnage of Bessemer-blown metal, in both molten and ingot forms, used in connection with the open-hearth practice makes it an important auxiliary unit to the industry. This practice aids in modifying the price level of heavy remelting scrap in addition to speeding up the open-hearth operation. The use of Bessemer steel has continued not only because of periodic economic advantages but also because of certain inherent qualities of machinability, weldability and stiffness, which are valuable for many applications. The properties of stiffness and rather high reaction to cold-work require some modification in order to meet the demands of modem methods of processing, which involve cold-reduction and cold-forming. At least one factor contributing to the stiffness of this steel is the relatively high phosphorus content of the acid product. The phosphorus content of the Thomas or basic Bessemer steel of Europe is considerably lower than the normal acid product in America. The American industry has continued the use of the acid process chiefly for the reason that the available ores are more easily adapted to this process from both metallurgical and economic standpoints. In European practice the basic process is necessary with the highly phosphoric ores available and it is sustained to some degree by the sale of the rich phosphate slag as a by-product. The basic process was used in this country at several plants many years ago, but was abandoned for economic reasons. A part of the past history of these trials is given here because the author believes it has not been published and it has some bearing on the subject of this paper. The information is authentic to the extent that he possesses chemical laboratory notebooks

Jan 1, 1941

R.. B. T. KILIANI, New York, N. Y.-I do not care to discuss Mr. Taggart's paper in the light of theory, as that has been very well done by Prof. Bell,1 but I should like to criticize some of his conclusions, in the light of actual operating practice at plants all over the country. 1. Mr. Taggart's first conclusion is that in crushing average ore, the character of the gangue has little effect on the efficiency of the mill. This, I believe, is not in accordance with the usual practice, since in crushing a hard ore the capacity will be much reduced below what it would be with a softer ore, while the power consumed will be practically independent of the character of the ore, being proportional only, to the load of ore and balls in the mill. 2. Mr. Taggart's second criticism is that the Hardinge mill is not suitable for grinding soft, tough material. In answer to this I might mention that the mill is being used for grinding tough, dnctile material, such as metallic aluminum, and also for grinding licorice root. 3. He says that the ball-mill works more efficiently on material of intermediate size, say 1/2 to 3/4 in., than on either coarser or finer feed.. This is true as to coarser feed. For the most efficient work, I believe that a ball-mill should be fed with material not coarser than 1 1/2 in.; it' will handle material up to 3 and even 4 in., but the reduction from 3 or 4 in. to 1 1/2 in. can be done much more cheaply and efficiently by rolls or disk crushers than in the ball-mill. 4. As to Mr. Taggart's fourth conclusion, that a greater ratio of reduction can be expected with feed of an intermediate size than with a coarse feed, I have not enough information to express an opinion. 5. His next conclusion is that steel balls are much more efficient crushing media than pebbles. Steel balls are undoubtedly more efficient for crushing coarse feed. On fine material they are also more efficient as to tons per horsepower crushed to 10-mesh, but on fine material I think it will be found that flint pebbles are cheaper than cast-iron balls, per ton of ore, although there will be a saving in power per ton by using cast iron instead of flint. The increased cost of crushing with cast iron will be due to the higher cost of iron at the present time. 6. Mr. Taggart's sixth conclusion coincides with present practice, that steel balls will grind as fine or finer than pebbles when working on the same feed.

Jan 1, 1918

By Donald L. Katz, Leslie J. Noaker

Experimental data are presented for hydrate formation conditions for mixtures of hydrogen sulfide and methane. Vapor-solid equilibrium constants for hydrogen sulfide are also presented. Equilibrium constants, defined here as the ratio of the mole fraction of hydrogen sulfide in the vapor phase (dry basis) to the mole fraction of hydrogen sulfide in the solid phase (dry basis), were calculated using the vapor-solid equilibrium constants for methane presented in an earlier paper. The conditions at which a natural gas will form gas hydrates with water may be computed from its composition, when hydrogen sulfide is present in addition to carbon dioxide and the paraffin hydrocarbons. INTRODUCTION Many gases are known to form solid hydrates in the presence of liquid water at temperatures above 32°F. This hydrate formation is of importance to the natural gas industry inasmuch as most of the constituents found in natural gases will form hydrates. The attention of the industry was called to hydrates by Hammer-schmidtl0 in 1934. A number of papers have been written giving the temperatures and pressures at which these hydrates will form3,4,5,6,7,8,9,10,13,14,15,18,19 and a bibliography on the subject has been compiled13. Deaton and Frost4,5,6,7,8 report work for various pure gases and for some natural gases. Katz and co-workers3,4,13,14,18,19 have reported data for various gases at high pressure. They developed a method of predicting conditions for hydrate formation from equilibrium constants3,19 and from gab gravity." The effects of anti-freeze agents on the formation of hydrogen sulfide hydrate were reported by Bond and Nelson.' The hydrogen sulfide-water system, including hydrate, has been the subject of recent investigation by Sage and co-workers." Mixtures of hydrates behave as solid solutions and an equilibrium exists between the vapor phase and the solid phase that appears to be comparable to the equilibrium between vapor and liquid phases.3,10 By means of the vapor-solid equilibrium constants which have been published for methane, ethane, propane, iso-butane, and carbon dioxidel6 it is possible to determine the temperature and pressure at which hydrates will form for a specific gas mixture when water is present. Hydrogen sulfide which is frequently found in natural gases has a very strong tendency to form hydrate and must enter the solid solution when present in a natural gas forming a hydrate. To determine the effect of hydrogen sulfide when computing the conditions for gas hydrate formation, it is necessary to have the equilibrium constant giving the ratio of the concentration of hydrogen sulfide in the gas phase to the concentration in the solid phase. This paper presents data on hydrate formation for mixtures of hydrogen sulfide and methane and presents the equilibrium constants which were calculated from these data. EXPERIMENTAL PROCEDURE The apparatus used to determine the conditions of hydrate formation for the methane-hydrogen sulfide system was similar to that employed by previous investigators.3,18,19 A charge gas cylinder was used to supply the hydrogen sulfide-methane mixtures, called the charge gas, and to supply the pressure up to 1.000 psia. This

Jan 1, 1955

By Charles H. Behre

This paper discusses education and training for economic geologists other than petroleum geologists. Candidates enter economic geology through liberal arts colleges, engineering schools and university graduate study. Whatever their backgrounds, rigorous courses are desirable-now conceded in theory, but not adequately recognized in practice. Besides basic sciences (each studied long enough to give a fair comprehension of its basic tenets), a functional command of English and two modern foreign languages is needed, as well as a broad understanding of mining, milling and metallurgy. A year of economics and finance is recommended. Surveying and drafting are essential skills. Yet geology should be represented in each term; otherwise the initial enthusiasm for the science, once contact is broken, may never be regained. A five-year curriculum is thus designed to take care of all major requirements and culminate in the M. S. degree. This curriculum reduces "cultural" courses below the average liberal arts requirements, but this is regarded as necessary. The pursuit of "culture" is assigned, as in most engineering and medical curricula, to extra college years or extracurricular time. To avoid the danger of over-crowding the schooling, the Doctorate in geology is preferred wherever possible. Its two added years should permit wider professional education; more browsing in "cultural" pastures; due attention to broader social implications; and some training in the research now increasingly required of the mineral industry. "In-course" training through cooperation between school and industry is especially advocated. The Institute should take the initiative in stimulating this practice.

Jan 1, 1947

By J. Jones-Parra, J. C. Calhoun

INTRODUCTION The purpose of this paper is to present the results obtained by solving the fractional flow' and frontal advance' equations to obtain oil recovery at water breakthrough as a function of the length of the system being flooded, the linear velocity of injection and the displacing phase viscosity. The method of solution makes use of the stabilized zone concept first presented by Terwilliger, et al3 when calculating saturation distributions in a gravity drainage system. In order to check the calculated results, the equations and method of solution were applied to the system on which Rapoport and Leas' reported experimental data. METHOD OF SOLUTION The solution of the fractional flow equation and the frontal advance equation is obtained by assuming that a water front forms to sweep the oil out ahead of it. There is ample evidence that under the proper conditions a water 'front does form. If this water front is not to dissipate, the water saturations which comprise it must have equal linear velocities. These water saturations are said to comprise the stabilized zone. Equation (2) indicates that for all these saturations and hence fw must plot as a straight line against saturation for those water saturations comprising the stabilized zone. The water saturations lying between the highest in the stabilized zone and the highest that can be achieved in the porous medium comprise the variable zone. Regardless of the numerical value of the length of the system, the variable zone must eventually span all of it, so that for long enough systems in Equation (1) will be small enough to be neglected. Hence, for the saturations in the variable zone Equation (1) can be simplified to In order to determine the composite fw function applicable to the entire range of saturations in the porous medium, it is necessary to find the water saturation which separates the stabilized zone from the variable zone. This dividing saturation must be on the curve defined by Equation (4), and a tangent curve at that point must pass through the initial water saturation to satisfy Equation (3). Hence, the valid fw curve is given by a straight line starting at the initial water saturation, tangent to the curve of Equation (4): and along the curve of Equation (4) from the point of tangency on. The point of tangency determines the water saturation dividing the zones. The length and shape of the stabilized zone can be found by solving Equation (1) for Integrating this expression numerically between any two saturations in the stabilized zone gives the distance separating these two saturations. By repeated integration, the saturation distribution of the stabilized zone can be determined. The total length of the stabilized zone is given by The integral appearing in Equation (5) is a function of the viscosity ratio, the capillary properties of the rockfluid system, the relative permeabilities, and the initial water saturation. Considering these variables fixed and designating the value of the integral by writing caw for and v/60 for q/A; Equation (5) becomes The saturation distribution of the stabilized zone can be integrated over its length and divided by the length to obtain the average water saturation The volume of water in the stabilized zone is then given by The average water saturation in the variable zone can be found by extending the straight line segment of (the segment joining Sw and Sw) until it intersects fw = 1.00. The saturation at the intersection is. This method of finding is nothing more than the graphical solution of the equation The volume of water in the variable zone at breakthrough is then given by Assuming no initial water saturation, the recovery at breakthrough expressed as percent pore volume is given by

Jan 1, 1953

By T. A. El-Bassyouni, Paul Gordon

Grain-gvowth data in zone-refined aluminum and in dilute alloys of copper with this aluminum have been obtained. The amounts of copper added were from 4 to 400 at. ppm. It was found that in both the unalloyed aluminum and the alloys grain growth was characterized by a high value of n in the isothermal growth equation 6n = Kt The inadvertent presence of 1 at. ppm Fe in the alloys was found to he more potent in slowing growth than the purposely added copper. Possible rationalizations of these observations and their general relevance to the theoretical use of gvain-grozvth data have been discussed. Grain growth data of Winegard and his co-workers' on zone-refined tin and dilute tin alloys were analyzed with some success2 in terms of approximate theoretical equations for boundary migration.2-4 In view of this success, experiments were carried out in an effort to obtain similar data on zone-refined aluminum and on dilute copper-in-aluminum alloys. The results obtained were anomalous in several respects and could not be used to test theory. A discussion of these anomalies is presented here; they have been attributed to impurity effects and serve to emphasize the sensitivity of grain growth in general—and the particularly high sensitivity in aluminum—to impurities. The resulting difficulties in the theoretical use of grain-growth data are also discussed. EXPERIMENTAL DETAILS An aluminum bar was zone-refined and leveled by methods similar to those described previously.' The degree of purity obtained is indicated in Table The data in Table I were determined by mass-spectrographic methods through the courtesy of Mr. Thomas A. Johnson of AIAG Metals, Inc.* Three dilute copper alloys with this aluminum were prepared also by methods described previously.' The alloys contained nominally 4, 40, and 400 at. ppm of Cu, respectively (0.001, 0.01, and 0.1 wt pct). Each material was fabricated by swaging and rolling into a round bar about 1/4 in. in diameter with an annealed penultimate grain size of approximately 0.003 to 0.007 cm. In order to minimize preferred orientation the fabrication was carried out in several steps, each consisting of a reduction of about 40 pct followed by a recrystallization anneal. Annealing temperatures for the grain-growth studies were attained by the use of boiling liquids up to 213°C and molten metal baths at higher temperatures. Temperatures were controlled to within 1°C. Samples for measurements were cylinders about 3/4 in. long and 1/4 in. in diameter cut from the fabricated rods. In the interests of sample economy a single sample was used for the grain-growth measurements at each temperature. Each sample was, thus, annealed for several successive periods of time, the grain size being measured at each annealing period on a transverse surface exposed by

Jan 1, 1965

By R. W. Raymond

The death of Professor Blake removes the oldest of American economic geologists and mining engineers, and deprives this Institute of one of its earliest and most illustrious members. To many of us it brings a personal loss also, the loss of a friend. William Phipps Blake was born June 21, 1826, in New York City. His father, Elihu Blake, was a surgeon-dentist of eminence, a direct descendant of William -Blake, who settled in the Massachusetts Bay Colony about 1630. He was prs pared for college at private schools in New York, and entered the Sheffield School of Yale, where he was graduated as Ph.B. in the chemical course, class of 1852, the first graduating-class of the institution. In the same year he became chemist and mineralogist of the New Jersey Zinc Co., and chemist of chemical works at Baltimore, Md. In 1853, he started the Department of Mineralogy of the World's Fair at New York City. In 1854, 1855 and 1856, he was mineralogist and geologist of the United States Pacific Railroad Surveys of Willianlson, Pope, and Whipple, and for the War Department at

Jan 1, 1911