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By D. R. Irving

Prior to this time, ample supplies of high grade mineral fillers, such as clay, have been available close to consuming centers. Now depletion of these accessible deposits, coupled with other factors such as increasing demand due to population expansion and standard of living rise, has made development of upgrading techniques attractive to producers. Various investigations being carried out by the U.S. Bureau of Mines are described. Factors making the development of improved methods for upgrading clays attractive to producers include: depletion of accessible deposits of high-grade clays, rising transportation and labor costs, more exacting specifications, and increased demand resulting from an expanding population and a constantly rising standard of living. Industry recognizes the need for upgrading presently unusable materials and has cooperated with the U.S. Bureau of Mines by providing samples from submarginal deposits and by evaluating the products that USBM upgrades. Following are some examples of recent clay beneficiation work by the Bureau. FIRE CLAY BENEFICIATION At the Rolla Metallurgical Center, Rolla, Mo., the Bureau is conducting research to develop technically and economically feasible mineral-dressing methods to remove quartz, pyrite, and other impurities from submarginal fire clays. The research has been spurred by the growing shortage of high-grade bur-ley, flint, and plastic clays in the Missouri fire-clay district resulting from increased consumption and the low rate of discovery of new deposits of adequate quality. There apparently is ample tonnage of submarginal flint and plastic clays to maintain the industry for many years if such material can be upgraded to commercial quality. Samples have been submitted to USBM by several major producers of refractories, including A. P. Green Fire Brick Co.; Harbison-Walker Refractories Co.; Mexico Refractories Div., Kaiser Aluminum and Chemical Corp.; and Wellsville Fire Brick Co. Research on some samples has been completed and still is in progress on others. The Bureau has found that specimens containing quartz or pyrite in grains coarser than the accompanying clay generally can be upgraded either with a gravity table or hydraulic cyclone. The improvement in quality is notable not only in chemical analysis but in an increase in pyrometric cone equivalent (PCE) of one or more cones. As an example, consider the results attained on a sandy flint—a fine-grained mixture of kaolin and halloysite with quartz and minor quantities of iron and manganese oxides. Chemical analysis was: 35.4 pct alumina (A12O3) and 47.8 pct silica (SiO2). The sample contained 9.2 pct free silica as quartz. The PCE was 33. The sample was crushed to -10-mesh, blunged with water, and then stage-ground to -48-mesh. The ground sample was tabled to yield a clay fraction containing 37.6 pct A12O3, and 45.3 pct SiO2 of which 2.4 pct was free silica. The PCE was 34. Recovery of alumina by this process was 73.6 pct. Concentration of the same clay in the hydraulic cyclone was even more effective in respect to quartz removal. The clay fraction analyzed 38.6 pct A12O3, 45.0 pct SiO2 of which 0.5 pct was free silica as quartz, and had a PCE of 34. Recovery of alumina was 71.9 pct. The hydraulic cyclone was also effective in reducing the pyrite content of a plastic clay which likewise was a mixture of kaolin and halloysite, plus some pyrite, quartz, and carbonaceous material. It analyzed 30.6 pct Al2O3, 52.3 pct SiO2, 2.3 pct Fe2O3, and 0.76 pct S. The sample was blunged and screened through 10-mesh to remove some coarse pyrite, then ground to -65-mesh and cycloned to remove most of the remainder. The final product recovered 81.8 pct of the alumina at a grade of 32.3 pct A12O3, 50.9 pct SiO2, 1.4 pct Fe2O3, and 0.1 pct S. The PCE was 32-1/2, compared with a PCE of 31-1/2 for the crude clay. The fine beneficiated clays, of course, must be pelletized and dried or fired to meet commercial acceptance. This operation has already been solved by industry. Little progress has been made on two remaining problems. One is that of fine-grained impurities, not separable by table or cyclone. Flotation is being investigated to solve this. Although fine pyrite is readily rejected, a satisfactory quartz-clay separation has not been attained. The second problem, a stubborn one, is that of alkali. Samples containing as much as 5 pct potas-

Jan 1, 1961

By Thomas D. Henderson, Donald E. Crowell

INTRODUCTION This paper presents a "case history" of the steps taken to estimate capital and operating costs for a typical porphyry copper concentrator of ±9,070 metric tons (10,000 short tons) per day capacity. The concentrator described herein is hypothetical, but is based on experience and is, in effect, a composite of several actual projects. The numbers used are illustrative only and do not represent actual costs at any particular concentrator. These numbers are, however, representative of typical milling costs at one point in time, and. are sufficiently accurate to illustrate the cost estimating procedures described in this paper. It is not possible to publish actual, current milling costs and, in any event, actual cost figures quickly become meaningless in today's economic situation with various costs all rising at different rates. The paper is divided into three parts: (1) order-of-magnitude estimate, (2) feasibility study estimate, and (3) discussion of differences between estimated and actual costs.

Jan 1, 1978

By R. H. McLean

Velocity, kinetic energy and shear in crossflow beneath three-cone jet bits may influence cleaning of the bottom of the borehole and the teeth of the bit. Laboratory investigation shows that each of these parameters is a function of the diameter of the borehole and the product of the volume rate of flow and velocity through the nozzles (QVn). Increasing QV, or decreasing the diameter of the borehole increases each parameter. These functions provide means of predicting the magnitude of each parameter and of scaling the cleaning forces. INTRODUCTION In drilling operations using conventional jet-type rock bits, the impinging jels create an important flow mechanism. Called crossflow, this flow mechanism originates in the impact area of the jets, spreads across the bottom of the hole and supplies the principal source of energy to clean the teeth of the bit and most of the bottom.' Besides providing the means of cleaning cuttings from the bit and the hole bottom, crossflow may also have other, less direct, effects on the rate of penetration. The shear stress generated on the bottom by crossflow will inIluence the thickness and permeability of any filter cake of mud solids or crushed material which forms on the bottom.' These factors may affect the rate of penetration. A previous pulblication introduced some fundamental concepts of crossflow.' Crossllow was shown to occur in a thin layer adjacent to the bottom, and to cover the bottom completely. The maximum velocity in the crossflow above any position on the bottom was found to be directly proporlional to the square root of the product of the volume rate of flow and velocity through the nozzles—the jct QV,,—and inversely proportional to the diameter of the borehole. This information indicated that the effectiveness of crossllow in scavenging the bottom can be improved by maximizing the jet QV. The investigation reported herein amplifies the definition of crossflow. Complete velocity profile data above a representative position on the bottom are analyzed. These data better illustrate control of the capacity of crossflow to scavenge the bottom, and also relate shear stress on the bottom to known, controllable parameters. The conclusion reached in the previous publication that maximization of the jet QV. produces the maximunl cleaning beneath current jet bits is unchanged by these new data; rather, it is strcngthened. Data presented here show that the kinetic energy flux above a representative position on the bottom is maximized by maximizing the jet QV. The shear stress on the bottom will also be shown to be maximized in the same manner. Since the functions relating the jet QV. to velocity, shear stress and kinetic energy also involve the diameter of the borehole, means of equating, or scaling, these quantities in different sizes of boreholes will be illustrated. EXPERIMENTAL EQUIPMENT AND TECHNIQUE JET BIT MODEL Data were recorded from the same laboratory model as used in the aforementioned investigation of the flow around a jet bit.' The model consisted of a 43/4-in. three-cone, jet-type rock bit in a smooth, flat-bottomed borehole constructed of lucite. The bit had a shape and nozzle placement closely resembling larger three-cone jet bits commonly used in field operations. Fig. 1 illustrates the impact area on the bottom of a jet from this bit. Details of the orientation of the jets may be found in the previous publication. TECHNIOU'E OF MEASUREMENT Measurements of the crossflow were made by inserting a very small Pitot tube through the bottom of the simulatetl boreholc. Extreme thinness of the layer of crossflow necessitated accurate measurements of the height of the Pitot tube above the bottom to achieve close definition of the velocity profile. A cathetometer, which could be read to the nearest 0.005 cm, was used to make this measurement.

Jan 1, 1966

By C. D. Stahl, R. Sandrea

This investigation was made to evaluate the comparative effects of the viscosity and the phase behavior of the buffer fluid in the composite solvent displacement of Bradford crude from waterflooded sandstone cores. Buffer slugs of propane, naphtha and other refined hydrocarbons exbihiting increasingly favorable viscosity ratios and decreasing solubility relationships, respectively, with Bradford crude, were used in long Berea sandstone cores. The secondary slug was isopropyl alcohol. The results indicate that higher oil recoveries are obtained for increasingly favorable phase relationships even when these are accompanied by unfavorable viscosity ratios within the range studied. Moreover, when propane is used as a buffer slug with an adverse viscosity ratio of 36, it gives higher oil recoveries than at a similar size slug of an any1 alcohol having a viscosity ratio of 1.09. The investigation was extended to the study of the effect of flooding rate on oil recovery. Residual Bradford crude was displaced from a 6-ft Berea sandstone core at rates varying from 0.3 to 30 ft/ day. The results show that as flooding rates were increased above or decreased below a minimum range of 1 to 2 ft /day, displacement efficiency increased considerably. INTRODUCTION In recent years, the alcohol slug process as a means of tertiary recovery has been the subject of many investigations. Gatlin and Slobod showed the advantages of the combination solvent slugs over the previous single-slug process.1 The combination slugs require less total slug material to obtain similar oil recoveries. The basic combination process involves injecting a primary or buffer solvent which is preferentially oleophilic, followed in turn by a water-driven slug of isopropyl alcohol. This procedure ensures that the buffer slug, which is miscible only with the reservoir oil, displaces and replaces the oil and is in turn displaced, together with the water, by the isopropyl alcohol slug miscible with both fluids. Likewise, for those reservoir oils that show some degree of phase incompatibility with isopropyl alcohol, as does Bradford crude, a proper buffer solvent can artificially make the alcohol process technically feasible. From an economic standpoint, propane or LPG would be the most appropriate primary solvent to be used in the field; however, Taber, et a12 have indicated that the alcohol process becomes highly inefficient in the displacement of light hydrocarbons because of the entrapment of these hydrocarbons during the stabilized bank formation. Moreover, since materials such as propane have such low viscosities, adverse viscosity ratios with most reservoir oils would be penerated, thereby possibly further reducing the efficiency of the buffer solvent. This paper presents the results of an experimental study of the comparative effects of viscosity ratio and phase relationships on the displacement efficiency of Bradford crude by means of dual solvents. The work was extended to include the effect of flooding rate on oil recovery. Rates within the range of field and laboratory values were used. EXPERIMENTAL PROCEDURE APPARATUS The porous media used in this study consisted of two 10-ft and one 6-ft Berea sandstone cores, 3-in. in diameter. These were cast in galvanized steel pipe of 31/2-in. ID and the annulus was filled with Armstrong cement. The 10-ft cores were assembled by connecting two 5-ft units, which were joined together by 8-in. steel flanges fitted to the pipe. Intimate contact between the two sections was obtained by inserting a thin disk of the same sandstone between the core faces. The outlet and inlet ends of the cores were covered with threaded pipe caps. The injected fluid was gravity fed to two variable-rate positive-displacement pumps. The fluids were filtered before entering the core and the effluent was collected in an automatic fraction collector and

Jan 1, 1966

By Lester Uren

The fluid level maintained in wells pumped for oil is an important factor in deter-mining their productivity but one that has received little attention in the literature relating to petroleum-production technology. In the present paper the writer undertakes to show how and to what extent fluid level influences productivity and suggests the use of a fluid level indicator as an aid to the oil producer in maintaining the fluid surface within the well at the proper position. IT is realized that the depth of fluid maintained in a pumping well is sometimes influenced by other considerations than the quantity of fluid that will enter the well: the prevention of sand incursion, prevention of waste of natural gas, and the maintenance of a suitable submergence for the pump, for example. These latter factors have an important influence on the productivity of the well, so that otherwise unwarranted fluid levels must sometimes be maintained to offset them; but where the handling of unconsolidated sands is not a problem of consequence and where water has been properly excluded, the principles developed here and the practices recommended, should apply. The principal objective of the producer should be to produce the maximum quantity of oil in the shortest possible time. Any method or equipment that will increase the rate of production during the early years of the life of the well, when gas pressure is high, will greatly augment the .ultimate production. The maintenance of a proper fluid level in the well at all times will go far toward accomplishing this desired result. For a given set of conditions surrounding the flow of oil into a particular well, in which the viscosity of the oil, the porosity and grain size, of the sand, and the diameter of the well appear as constants, two variables determine the quantity of oil that will flow from the sand into the well. These are: the effective pressure behind or within the oil in the reservoir sand, and the fluid level maintained within the well.. The former is the expulsive force that causes movement of oil from the sand into the well, while the latter determines the magnitude of a resisting force opposing such movement. The first of these factors is largely beyond the control of the oil producer, but it is in his interest to reduce the opposing force to the lowest economic limit.

Jan 2, 1925

By Alexander Squire

ONE of the principal factors that have contributed to the hesitancy of design engineers to use metal-powder parts is the difficulty experienced in the determination of the mechanical properties of compacted components. Because standard test: methods cannot usually be applied in the inspection of such parts, and because adequate special test methods have not been developed, it has been considered desirable to investigate the methods that are applicable. These may then be included in specifications for metal-powder materials' and components in order that the design engineer may be assured that the subject parts possess the desired mechanical properties for satisfactory performance. It is known that direct relationships exist between usually nonmeasurable properties as tensile strength and elongation and shear strength and the angle through which compacts may be plastically deformed before fracturing. These correlations are valuable in the inspection of specific parts, but it is necessary to set up standards before they may be satisfactorily employed. Apart from the use of correlations, the number and character of the inspection methods that are applicable to almost all powder parts is limited to three-chemical analysis, density, and hardness. The last of these may or may' not be a pertinent characteristic, since the indentation hardness of many powdered-metal materials is so low as to have little significance. It is, however, occasionally desirable to use hardness measurements as an indication of the uniformity of the structure of pieces of a given type. Chemical analysis reveals very little about the physical properties of metal-powder compacts, since the unpressed powder is usually of a composition almost identical with that of the finished pieces. Density determinations are simple, to perform and have the advantage of being nondestructive in character. If the dimensions of a machine part are known (and usually they are), the average density may be determined by weighing a given number of pieces and dividing by the calculated volume of the parts. More accurate measurements may be made by the water-displacement method. , It. is recognized that mechanical properties of metal-powder materials are related to their density, but usually these relations are determined for only one type of powder, processed under a given set of conditions. Comparisons of the properties of compacts formed from different types of powders are made on the basis of compacting... pressures instead of density, and for. this reason the results obtained by using powders of different types appear widely variant.

Jan 1, 1947

By Dorsey Hager

The information given in the accompanying table is submitted as evidence confirming the application of the anticlinal theory and the value of geology in the Kansas and Oklahoma oil fields. The term anticline has been used to define a particular type of arched fold. The anticlinal theory of oil accumulation should, however, be broadened to include any structural fold of an arched type even if not a distinct anticline. A terrace may very properly come under the heading of the anticlinal theory of accumulation, as the folding is closely related to that of the anticline; in fact, in many cases is an arrested anticline, though not completely closed in all directions. Stratigraphic forms due to lensing or irregular cementation of the sands certainly cannot be considered to fall within the anticlinal theory, though the laws of accumulation may be similar. A dome is similar to an anticline and belongs to the same class. A dome is broader in proportion to its length than an anticline. Many anticlines undulate along their axes to form domes. The anticlinal theory in this discussion will then be applied to anticlines, domes and terraces. In the following list, the writer has tabulated the main oil fields of Oklahoma, and a few recently discovered fields in Kansas. The fields discovered within the past 4 years are listed with the date of their discovery. Under "How found," the writer puts "Wildcat" where a geologist has not been employed, "Geology" where it has been used, and "7" where there is doubt. In some places the geologists have claimed pools that may rightly belong to them, but their claims have been questioned, so that they belong in an unsettled category. Unless one has mapped all the old pools, it is not possible to say just how far they are dominated by structure, but from our own work, and from discussions with others, it is safe to venture that nearly all the "shallow-pool" districts, Nowata, Bartlesville, and the Eastern Osage, are controlled by structure; domes, noses, and terraces are the main structural features. The "shallow pools" of Kansas show the same relation. At Peru and at Sedan, domes are evident, though gas occurs high on the domes, and oil well down the flanks, leading some to believe

Jan 1, 1917

By C. M. Nickerson

It is apparent that repressuring of the oil measures is becoming increasingly important to the oil industry, and is a matter that warrants the best efforts of the petroleum engineer charged with applying this method of operation to a producing property. Considerable attention has been directed to repressuring in various California oil fields, such as Dominguez and Seal Beach, which have served to sell the more progressive operator on this idea and also to keep him sold. The projects that have received most attention are in comparatively young fields where the fluid levels are high, the wells, perhaps, still flowing, where the wet gas production is of considerable volume, and where there is vital need of immediate conservation of gas, which otherwise would be blown to the air. The new State of California Gas Law, which prohibits the waste of gas, has served to interest the oil industry in means of conserving the gas that is now being blown to the air because of lack of markets. This vitally affects the operator in the older, well-depleted oil fields of the state, because in many cases he has a limited market for gas, on account of the flush production from the more active oil fields. While the waste of gas is relatively small in these older fields, such as the Midway-Sunset area, it now attains considerable importance, since under the new State Gas Law it must be put to some bcneficial use. Repressuring in the older fields of California has not received the attention of the petroleum engineers that is warranted by the present situation. This paper was prepared with the view of presenting the salient features connected with repressuring in the well-depleted oil measures of the older fields, and to show what results have already been obtained in these fields by injecting the unmarketable gas into the sands, particularly in the Midway-Sunset field in the San Joaquin Valley of California. Other projects in the older fields of the state offer some supporting data in this connection, such as the Shields Canyon and the Brea Canyon fields. Gas Storage and RepressuRing On account of the lack of market for a large portion of the dry gas produced in certain of the older, well-depleted oil fields of California, the

Jan 1, 1930

By Irving A. Palmer

During the past 15 years in this country there have been few additions to the literature of lead smelting. After the consolidation of the principal smelting companies at the beginning of this period it became the policy of the larger company not to permit the publication of details in regard to many of its metallurgical processes. This led to similar action on the part of some of its competitors. The result, of course, was a decided decrease in the number of papers written upon the practical side of the subject. Even upon the theoretical side the contributions have been few. It would seem that the industry as a whole has suffered from this general unwillingness to exchange information. While it is true that a given company is entitled to the reward that may come from its own development of a new process, it is also true that a still greater reward might be the result of a free exchange of ideas with other plants. This principle has been recognized for a long time in other metallurgical industries, notably those engaged in the smelting of iron and the manufacture of steel. It is pleasing to note that the leading lead-smelting company has very recently decided to modify its policy of secrecy, and to permit the publication of papers covering some details of its metallurgical methods. The statement has been made that there has been but little progress in lead smelting during the period just referred to. This impression is due in part, no doubt, to the scarcity of papers written on the subject. 'There has been, it is true, some discussion of the new sintering processes, but with little reference to detail, and to the effect that blast roasting has had upon the industry as a whole. In spite of the prevailing belief, it may be said that lead smelting, in common with other metallurgical industries, has made steady and substantial progress. It is the purpose of the present paper to discuss briefly some features of the industry as it is now conducted, with special reference to the blast-furnace practice in the larger silver-lead smelting plants of the United States and Mexico.

Jan 1, 1915

By A. L. Holley

THERE is a growing demand for pure and cheap material for fine open-hearth steel ; a material not only very free from phosphorus, but from carbon and silicon; so that it may he rapidly converted into steel. Iron and steel scrap are not trustworthy as to quality, and they are often dear. There are three methods of purifying cheap materials for the open hearth. 1. Mechanical puddling, as done at Creusot, which removes 90' per cent. of the phosphorus from the pig iron. 2. Krupp's washing process (the conduct and results of which I fully described in a former paper*), which eliminates 70 to 80 per cent. of the phosphorus and most of the sulphur and silicon from pig iron. Neither of these processes would sufficiently purify, for very fine steel, those very impure pigs which are cheapest in many parts of the United States: 3. The process of producing directly from the ore an iron which is practically pure chemically, although mechanically mixed with the impurities of the ore. This is the oldest of iron processes ; one form of it, the Catalan forge, employed to produce charcoal blooms, is still in use, but its great cost is rapidly throwing it out of competition. Among the modern attempts to produce iron direct from the one, on a large scale and at a cheap rate, several have been in various respects successful. Dr. Siemens's process of treating a ton and a half or more of ore and the coal to deoxidize it, in a rotating gas furnace, and bringing out, in some four hours, a ball of chemically pure iron so soft that the fluid and impure slag may be squeezed out of it, is the most attractive and the most highly developed of all the modern direct processes. I have watched it, from time to time, since 1874, and have noted a steady improvement. It may now be said to have passed the experimental stage, although, like older processes, it must be adapted by practice to special materials. The cause which has been more potent than all others, including the defects of the best direct processes, to bring these processes into disrepute, is the waste-ful treatment of the direct product. With one or two exceptions (when failure was due to other and obvious causes), the direct product has been made into wrought iron (weld iron). Even Dr. Siemens has, at Towcester, in England, and at Park, Bro. & Co.'s, in Pittsburg, set up his apparatus for this purpose. Is it likely that

Jan 1, 1880

By Geo. H. Ashley

The following paper is intended to be suggestive only, and to open the way for discussion and further observation. Its preparation was requested only two days before the time limit set for the submission of the papers comprising this symposium. Thus no time existed for detailed studies, so it is largely a memorandum of such facts as have come incidentally to the notice of the writer in the study of coal in the field. The field study of sulfur in coal has received very little special attention or description from coal student's. The presence of sulfur concretions is noted in hundreds of descriptions, and certain benches of a coal bed may be described as "sulfury" or the presence and position of sulfur bands may be noted in coal sections in connection with sampling. It may be accepted that some sulfur is present in all coal. The amount varies greatly in different regions, in different beds, and in the same bed in different areas. The anthracite of Rhode Island comes the nearest of any coal known to the writer of being free from sulfur, several analyses of that coal showing less than 0.1 per cent. Subbitumi-nous coals in Colorado in a few places have close to 0.2 per cent. of sulfur on the dry-coal basis and in other states subbituminous coals approach this lower limit. Bituminous coals seldom run under 0.4 per cent. of sulfur on the dry basis, though in a few places dry bituminous coals in Colorado and Washington have between 0.3 and 0.4 per cent. The better known bituminous coals have almost everywhere over 0.4 per cent. The best of the Pocahontas and New River coals run close to 0.4 per cent., but there is very little commercial coal in Pennsylvania, Ohio, Indiana, Illinois, Kentucky, or the other states, that runs under 0.5 per cent. on the dry basis. From these minimum figures, the amount will range up to 5 or 6 per cent. or higher if visible sulfur is not excluded. It must be remembered that the usual analysis of a coal bed is not intended to give the total proportion of sulfur in the bed but the amount in the coal after the removal of the more obvious and larger sulfur masses. Professor Parr has already pointed out that, chemically, sulfur occurs in several forms: as pyrite, organic sulfur, sulfates, and possibly as un-combined sulfur. Sulfur in the form of sulfates is commonly the obvious result of the weathering of pyrite and may be found in the coal within .

Jan 1, 1920

By C. S. Smith

The solubility of tantalum at 1100°C is 0.025 pct in pure copper, 1.2 pct with 20 pct Ni, and 2.7 pct with -30 pct Ni. The solubility decreases with temperature, and the alloys are precipitation hardenable. A 79/20/1 Cu-Ni-Ta alloy reaches maximum hardness after aging at about 750°C and, if cold worked, does not recrystal-lize below that temperature. The alloys have good tensile properties at moderately elevated temperatures and, since they can be hot and cold worked nearly as easily as cupronickel, they are suggested for service at temperatures above the usual limits for copper alloys. MASSIVE tantalum dissolves extremely slowly in copper-rich alloys, and tantalum powder forms refractory surface layers which prevent its solution unless special precautions are taken. After many trials, an 80 pit recovery was consistently obtained by using a mixture of a finely divided tantalum powder with two or three times its volume of potassium tantalum fluoride (K2TaF1,-melting point about 750°C) poured in a slow stream directly on to the surface of the molten copper alloy, so that each particle would remain coated with flux and be immediately and individually wetted by the molten metal. A 50-50 nickel-tantalum alloy has a melting point of about 1400°C and small lumps of it slowly but satisfactorily dissolve in molten copper-nickel alloys as does commerical "ferro-tantalum." The high affinity of tantalum for carbon makes it necessary to avoid carbonaceous crucibles. COPPER-TANTALUM ALLOYS Castings with good shrinkage resulted when 0.1 pct Ta or more was added to copper melted under charcoal and cast in air. Copper in two-pound melts to which 0.1, 0.15, and 0.2 pct Ta had been added retained residual amounts, by analysis, of 0.025, 0.023 and 0.026 pct, respectively. The solubility of tantalum in molten copper at about 1200 °C is therefore about 0.025 pct. The electrical conductivity of these three samples was 100.48, 100.00 and 100.20 pct IACS in the annealed condition, and 98.24, 97.98 and 98.08 in the cold-drawn condition. Wires 0.080 in. in diam withstood from thirteen to nineteen reversed bends after annealing for 30 min in hydrogen at 850°C and the metal was therefore completely deoxidized. The annealing temperature corresponding to 50 pct loss of work hardness in 1 hr in a strip cold rolled 77 pct reduction was 175C, compared to 230°C for equivalent undeoxidized material. It is unusual for a decrease of recrystallization temperature to result from an alloying addition, and the tantalum probably combines with and removes some minor impurity in the original copper that restrained its recrystalliza- tion. No difficulty whatever was encountered in hot or cold rolling or drawing these ingots, and were tantalum not so expensive it would make an excellent deoxidizer for copper. COPPER-NIcKEL-TANTALUM ALLOYS Studies were made of the solubility of tantalum in a large number of copper-rich alloys, but of these significant solubilities were found only in the case of an iron alloy (which, however, separated into two immiscible liquid layers) and alloys of copper and nickel, in which tantalum is freely soluble and which were found to have interesting properties. The latter alloys are the subject of U. S. Patent No. 2,430,306 (1947). They are not at present available commercially. The Ternary Constitution Diagram—The copper-rich corner of the constitution diagram was constructed on the basis of microscopic examination of samples of various composition and treatments. The alloys were hot rolled to 0.25 in. from castings 0.625 in. thick, then annealed for 1 hr at 1000°C, quenched, cold rolled to 0.10 in. and finally annealed for various periods of time at temperatures between 800" and 1100°C in a nonoxidizing atmosphere and quenched. When the solid-solubility limit had been transgressed, particles of a compound believed to be Ni2Ta*were

Jan 1, 1960

By H. S. Jerabek, Charles S. Barrett, Robert F. Mehl

The precipitation of the nitride Fe4N from the solid solution of nitrogen in a Fe and of the phosphide Fe3P from the solid solution of phosphorus in a Fe both lead to the formation of structures that may be easily identified as Widmanstatten figures, within the meaning of the term as used in this series of papers. A complete solution has been obtained for the figure formed by Fe4N. The structure of Fe3P, however, is not fully known and a complete solution of this figure thus cannot be obtained; nevertheless, a study of this figure has furnished some new information. Precipitation of Fe4N from Alpha Solid Solution of N in Alpha Fe Constitution of System Iron-nitrogen A knowledge of the constitution of the whole of the Fe-N system is unnecessary for this work, though the recent studies by Eisenhut and Kauppl and by Lehrerz have clarified most of the moot points; it is sufficient for our purpose to state that a Fe of high purity dissolves 0.42 per cent of nitrogen in solid solution at the eutectoid temperature, 591' C., and that this solubility decreases at first rapidly and then more slowly until at room temperature the solid solubility amounts to approximately 0.1 per cent nitrogen.3

Jan 1, 1934

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neilll observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in inter-granular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle3 in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1942

By Charles R. L. Oder, Howard W. Miller

Approximately 5000 tons of zinc ore a day was mined during 1943 in the Mascot-Jefferson City district in East Tennessee. This ore came from the Kingsport formation, a part of the Knox dolomite, of Ordovician age. The Kings-port is composed of 350 to 400 ft. of limestone and dolomite. Thin cherts, sandy layers and shales are numerous. Frequently, the limestones are altered to crystalline dolomite. The Kingsport is divisible into four main lithologic zones. These divisions are illustrated in an accompanying table, which gives detailed sections of the ore-bearing beds as found in the mines and shows the exact positions of the various ore zones within the formation. Key beds are described and the practical applications of stratigraphy in mapping, prospecting and mining are discussed. Introduction The Mascot-Jefferson City zinc district is in Knox and Jefferson Counties, in the Great Valley of East Tennessee. It extends from Mascot, I3 miles northeast of Knoxville, to Jefferson City, about 30 miles northeast of that city. The American Zinc Company of Tennessee is producing from five mines in the district, in which it has operated for more than 30 years. The only other important producer is the Universal Exploration Co. The approximate daily production of the district in 1943 was 5000 tons of sulphide ore, grading from 2.5 to 6 per cent zinc. Small amounts of oxidized ore are mined intermittently. The Knox dolomite has been described by various geologists,'-' but no detailed descriptions of the rock sections revealed by mining have been published. Rock units are not conspicuously different and careful study is required to distinguish them. Nevertheless, familiarity with the stratigraphy of the mineralized zones is essential to successful exploration and extraction of the ores; therefore the purpose of this paper is to give detailed stratigraphic sections as measured in the mines, to discuss their important features and to show their relationship to the stratigraphy of the district. Generalized Section Table I gives the most characteristic general features of the major stratigraphic units. The formation names given in parenthesis are locally and widely used terms, the correlations of which are not necessarily established. For this reason they are put in quotation marks and are replaced by more restricted terms. The names "Mascot" and "Kingsport" were adopted from local towns. They were chosen jointly by Josiah Bridge, of the Federal Geological Survey, and the senior author for use in their separate unpublished manuscripts describing the Knox dolomite in East Tennessee. Descriptions of the type sections may soon be published. The name "Longview" was first applied by Butts6 in Alabama.

Jan 1, 1949

By Howard W. Miller, Charles R. L. Oder

Approximately 5000 tons of zinc ore a day was mined during 1943 in the Mascot-Jefferson City district in East Tennessee. This ore came from the Kingsport formation, a part of the Knox dolomite, of Ordovician age. The Kings-port is composed of 350 to 400 ft. of limestone and dolomite. Thin cherts, sandy layers and shales are numerous. Frequently, the limestones are altered to crystalline dolomite. The Kingsport is divisible into four main lithologic zones. These divisions are illustrated in an accompanying table, which gives detailed sections of the ore-bearing beds as found in the mines and shows the exact positions of the various ore zones within the formation. Key beds are described and the practical applications of stratigraphy in mapping, prospecting and mining are discussed. Introduction The Mascot-Jefferson City zinc district is in Knox and Jefferson Counties, in the Great Valley of East Tennessee. It extends from Mascot, I3 miles northeast of Knoxville, to Jefferson City, about 30 miles northeast of that city. The American Zinc Company of Tennessee is producing from five mines in the district, in which it has operated for more than 30 years. The only other important producer is the Universal Exploration Co. The approximate daily production of the district in 1943 was 5000 tons of sulphide ore, grading from 2.5 to 6 per cent zinc. Small amounts of oxidized ore are mined intermittently. The Knox dolomite has been described by various geologists,'-' but no detailed descriptions of the rock sections revealed by mining have been published. Rock units are not conspicuously different and careful study is required to distinguish them. Nevertheless, familiarity with the stratigraphy of the mineralized zones is essential to successful exploration and extraction of the ores; therefore the purpose of this paper is to give detailed stratigraphic sections as measured in the mines, to discuss their important features and to show their relationship to the stratigraphy of the district. Generalized Section Table I gives the most characteristic general features of the major stratigraphic units. The formation names given in parenthesis are locally and widely used terms, the correlations of which are not necessarily established. For this reason they are put in quotation marks and are replaced by more restricted terms. The names "Mascot" and "Kingsport" were adopted from local towns. They were chosen jointly by Josiah Bridge, of the Federal Geological Survey, and the senior author for use in their separate unpublished manuscripts describing the Knox dolomite in East Tennessee. Descriptions of the type sections may soon be published. The name "Longview" was first applied by Butts6 in Alabama.

Jan 1, 1949

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neilll observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in inter-granular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle3 in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1942

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

By G. W. Crane

When ore was discovered on the Tintic Standard property in the spring of 1916, new developments were immediately started both north and south of that property, on the supposition that in East Tintic the ore would be found to occur in northerly trending channels, similar to those so characteristic of the older camp. But 9 years of developments have failed to establish the existence of such a channel. This is due undoubtedly to important differences in the geology of the two camps, that were not recognized, and is indicative of the danger in the general tendency toward interpreting the geology of East Tintic too strictly in terms of that of the older camp. It should not be forgotten that while the two sections have had practically the same geological history, the net results of a long series of geologic processes have developed in them conditions that differ so widely and in so many particulars that the necessity of regarding them as essentially different districts seems apparent. In an effort to emphasize this fact, this paper is devoted chiefly to a comparison of the geological conditions as found in the two camps and is addressed more particularly to those familiar with the geology of the Tintic district. Following a short description of the several ore discoveries and of the Tintic Standard mine is a brief discussion of the evidence of ore channels in East Tintic. For my information regarding the Tintic Standard mine, I am indebted to the courtesy and generous assistance of Messrs. Wade and Snow of the Tintic Standard Mining Co. East Tintic District The Term East Tintic district is here used to represent that eastern part of the Tintic mining district lying between the productive portion of the old camp of Tintic on the west, the foot hills of Goshen Slope, on the east, the Denver and Rio Grande Railroad on the north, and Silver Pass on the south, all in Utah County. As represented by the geological map, Fig. 1, it includes an area about 4 miles wide, east and west, and 5 miles long, north and south, within which the Tintic Standard mine is about centrally located. The map is a compilation of data supplied, for the most part, by the Chief Consolidated Mining Co. and represents the

Jan 1, 1927

By Daniel D. Pollock

The il'lott and Jones theory of thermoelectricity predicts that the absolute thermoelectric power of alloys of transition and noble metals should be a maximum when the concentration of the noble metal is approximately 55 to 60 at. pct. An examination of the emf of a series of relatively pure alloys of copper and nickel shows that the predicted maximum occurs at about 57 at. pct Cu. This excellent agreement with the theory is considered to substantiate the Mott and Jones theory of thermoelectricity for binary alloys of transition elements. This theory is extended to show that the emf behavior of dilute, ternary copper-nickel base alloys, which contain approsimately 60 pct Cu and 40 pct Ni, may be described in terms of a scattering mechanism. The scattering effect of a third element is demonstrated to be a function of its valence and its period in the periodic table. Small amounts of solute elements have additive scattering effects upon the emf of the Cu-Ni base. The Mott and Jones equation is modified to include this scattering parameter. This adaptation accurately describes the thermoelectric behavior of ternary and quaternary CLL-Ni base alloys. An empirical form of the modified Mott and Jones equation is derived which permits the calculation of thermoelectric power with an average error of less than 0.4 pct at 500 "C. CONSTANTAN has long been used as a thermocouple element. Its approximate composition varies from 50 pct Cu, 50 pct Ni to 65 pct Cu, 35 pct Ni. Small amounts of manganese, iron, and other elements have been used to modify the composition in order that the resultant emf vs platinum conforms to nationally accepted table. Adjustments of this type are made on a purely empirical basis. Constantan was originally made in Germany and was imported into this country for thermoelectric and electrical resistance purposes. During World War I, the supply of this material became seriously depleted. The work of Bash4 was done in this period in order to develop a satisfactory substitute for the imported material. Bash's empirical work on Cu-Ni alloys is still the basis for all commercial constantans made in this country. No reexamination of the electrical properties of this system has been made, despite the fact that it is now well known that Bash's alloys contained impurities which strongly affected their thermoelectric behavior.

Jan 1, 1962