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By R. A. Morse, W. W. Owens, D. R. Parrish, T. M. Geffen

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By D. R. Parrish, T. M. Geffen, R. A. Morse, W. W. Owens

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By Eliot Blackwelder

For the purposes of this paper, the boundaries of China and Siberia will be taken as they stood about 1907. Except in the Caspian region, it is doubtful if all the oil ever produced in these countries would equal one day's flow of a good Texas well. Considering the vastness of the regions and the variety of strata, it seems strange that these two countries should have made so small a showing in the petroleum industry. No doubt the condition is caused partly by lack of prospecting and of modern methods of development; in larger measure, however, it is evidently because of unfavorable geological conditions over nearly all of east-central and northern Asia. China The known oil occurrences in China are very few. For many years, perhaps a barrel a day has been obtained by primitive methods from wells near the city of Yenchang in the northwestern province of Shensi. A like amount was obtained from wells bored for salt water in the vicinity of Kiating in southwestern Szechwan. The little oil was separated from salt water by allowing it to stand in jars. The salt wells yield also considerable natural gas, which is used to evaporate the salt and also for domestic purposes. There is evidence that wells were bored in this part of China before the third century. It is said that more than 1200 wells have been sunk in that district to depths of 1600 to 2000 ft. (485 to 610 m.) in connection with the salt industry. The scarcity of petroleum in China may be ascribed to three general geologic conditions: First, China contains practically no marine sediments of Mesozoic or Cenozoic age; second, the Paleozoic sediments are not for the most part of the types that generally contribute petroleum; third, the rocks of nearly all ages have been strongly folded, faulted, and more or less intruded by igneous rocks in all parts of China except certain areas in the west and northwest. The mountainous eastern peninsula of Shantung and the similar district of Liaotung in Manchuria to the northeast have the general

Jan 1, 1923

By Eliot Blackwelder

For the purposes of this paper, the boundaries of China and Siberia will be taken as they stood about 1907. Except in the Caspian region, it is doubtful if all the oil ever produced in these countries would equal one day's flow of a good Texas well. Considering the vastness of the regions and the variety of strata, it seems strange that these two countries should have made so small a showing in the petroleum industry. No doubt the condition is caused partly by lack of prospecting and of modern methods of development; in larger measure, however, it is evidently because of unfavorable geological conditions over nearly all of east-central and northern Asia. China The known oil occurrences in China are very few. For many years, perhaps a barrel a day has been obtained by primitive methods from wells near the city of Yenchang in the northwestern province of Shensi. A like amount was obtained from wells bored for salt water in the vicinity of Kiating in southwestern Szechwan. The little oil was separated from salt water by allowing it to stand in jars. The salt wells yield also considerable natural gas, which is used to evaporate the salt and also for domestic purposes. There is evidence that wells were bored in this part of China before the third century. It is said that more than 1200 wells have been sunk in that district to depths of 1600 to 2000 ft. (485 to 610 m.) in connection with the salt industry. The scarcity of petroleum in China may be ascribed to three general geologic conditions: First, China contains practically no marine sediments of Mesozoic or Cenozoic age; second, the Paleozoic sediments are not for the most part of the types that generally contribute petroleum; third, the rocks of nearly all ages have been strongly folded, faulted, and more or less intruded by igneous rocks in all parts of China except certain areas in the west and northwest. The mountainous eastern peninsula of Shantung and the similar district of Liaotung in Manchuria to the northeast have the general

Jan 1, 1923

During the past 20 years the Westinghouse Electric & Manufacturing Co. and the General Electric Co. have collected a valuable library of some 9000 volumes on electricity. The collection was intended especially for use in patent searches and is particularly rich in patent material. Files of all the principal patents relating to electric light acid power issued by America, England, France and Germany, are present, together with copies of the patents owned or controlled by the two companies. Another feature, and one of unusual value, is a series of volumes containing the records of the important adjudicated patent cases of these companies and their predecessors during the past 25 years, and forming a storehouse of electrical history. There are also files of about 100 electrical periodicals. It is a pleasure to announce that this collection has now been presented by the owners to the Engineering Societies Library. This gift, which was arranged through Mr. Charles A. Terry, Vice-president, Westinghouse Electric & Manufacturing Co., and Mr. Charles Neave, Counsel,

Jan 7, 1918

The Wheeler Condenser & Engineering Co., of Carteret, N. J., is now building a line of horizontal and vertical shaft centrifugal pumps for general services, as well as for condenser work.. This company has been building centrifugal pumps for over 20 years, most of them being used, however, in connection with condensers. The new line of pumps is suited for all services. A small motor-driven unit for tank or stand pipe operation is shown in Fig. 1. Referring to the sectional illustration (Fig. 2), it will be seen that this pump conforms to the most recent advances in centrifugal pump construction, having a two-part divided casing, with the suction and discharge nozzles in the lower half. The impeller is of the closed double-suction type, protected by labyrinth wearing rings. The shaft is protected from the water by bronze sleeves, which screw on to the shaft and extend clear through into the bearing bracket boxes. Bearings are of the ring-oiled type, and in the outboard bracket, is a ring-oiled thrust bearing, which is a refinement not usually found in double-suction

Jan 4, 1916

By Valentin R. Garfias

The world's petroleum production in 1929 is estimated at 1,479,335,-000 bbl., which represents an increase of about 157,000,000 over 1928, as compared with an increase of 61,000,000 bbl. in the previous year. During the present year a more definite policy of conservation has been seriously considered by the foremost executives of the companies controlling the bulk of domestic and foreign production, and the United States Government has taken an active interest in the development of this program. Definite steps have already been taken and the industry is gradually establishing a foundation for closer and more intelligent cooperation. The entire program, however, is still in a formative or experimental stage. Among other salient constructive steps may be mentioned the establishing of tentative agreements of unification in the price of oil products exported from the United States, the putting into effect of a gas conservation law in California, and the marked tendency towards consolidatlions of the various branches of the industry into larger units. The publication of the draft of the proposed petroleum law in Colombia and of the Mexican Labor Law, on the other hand, has created papre-hension and uncertainty. It is confidently expected, however, that these perliminary drafts will be materially modified before the laws arc promulgated, or otherwise they may destroy the interest they are intended to protect. United States Production in the United States, which remained stationary during 1927 and 1928, increased about 105,000,000 bbl., or 11.6 per cent. This increase is due primarily to deeper drilling in the California fields and to the discovery of new pools in Texas and Oklahoma. The progress of the conservation program was marked by the action of the Government in stopping further permits to drill on Government lands; by putting into effect early in September the California Gas Conservation Law, and by

Jan 1, 1930

By M. J. Williams, C. P. Proctor, J. T. Crawford

The purpose of this paper is to present some data and comparisons regarding three types of Rheolaveur plants washing bituminous coal from the Pittsburgh seam. It deals only with the sections that handle coarse coal. The Rheolaveur system consists of launders or troughs in which coal and its associated impurities are conveyed by water. The impurities. being heavier than the coal, settle toward the bottoms of the launders and are drawn off through specially designed openings called Rheo boxes. Fundamentally, each plant consists of straight-sided, flat-bottomed launders of varying width and length, each launder equipped with one or more Rheo boxes for the removal of high-grauity fractions of the feed that are undesirable in the cleaned coal. Each launder has at least two longitudinal sections, the first with a slope of from 11/2 to 4 in. per foot of length, called the classification section. The single-box launder has a classification section followed by a washing section ahead of the box. A two-box launder is a single-box launder followed by a washing section and a second box. The slope of the washing section between the first and second boxes is determined to some extent by tonnage. At the end of the classification section, which may. vary from 8 to 15 ft. in length, the slope abruptly flattens out to a slope of from 92' to 1 in. per foot of length. This flatter section of the launder, called the washing section, may vary from a few feet, in a single-box launder, to 15 ft., in a two-box launder. Raw coal entering the head end of what we choose to call the "primary" launder or launders is pushed down the classification section by a stream of water entering the head end of the launder with the coal. As it strikes the washing section, of lower pitch, the velocity of flow is retarded and the heavier particles of slate, pyrite, bone, etc., take their places on the bottom and are drawn off as they pass over the Rheo boxes. The clean coal, of lighter gravity, remains on the top of the stream of

Jan 1, 1938

By M. J. Williams, C. P. Proctor, J. T. Crawford

The purpose of this paper is to present some data and comparisons regarding three types of Rheolaveur plants washing bituminous coal from the Pittsburgh seam. It deals only with the sections that handle coarse coal. The Rheolaveur system consists of launders or troughs in which coal and its associated impurities are conveyed by water. The impurities. being heavier than the coal, settle toward the bottoms of the launders and are drawn off through specially designed openings called Rheo boxes. Fundamentally, each plant consists of straight-sided, flat-bottomed launders of varying width and length, each launder equipped with one or more Rheo boxes for the removal of high-grauity fractions of the feed that are undesirable in the cleaned coal. Each launder has at least two longitudinal sections, the first with a slope of from 11/2 to 4 in. per foot of length, called the classification section. The single-box launder has a classification section followed by a washing section ahead of the box. A two-box launder is a single-box launder followed by a washing section and a second box. The slope of the washing section between the first and second boxes is determined to some extent by tonnage. At the end of the classification section, which may. vary from 8 to 15 ft. in length, the slope abruptly flattens out to a slope of from 92' to 1 in. per foot of length. This flatter section of the launder, called the washing section, may vary from a few feet, in a single-box launder, to 15 ft., in a two-box launder. Raw coal entering the head end of what we choose to call the "primary" launder or launders is pushed down the classification section by a stream of water entering the head end of the launder with the coal. As it strikes the washing section, of lower pitch, the velocity of flow is retarded and the heavier particles of slate, pyrite, bone, etc., take their places on the bottom and are drawn off as they pass over the Rheo boxes. The clean coal, of lighter gravity, remains on the top of the stream of

Jan 1, 1938

By T. H. Alden

A correlation has been found in rock-salt structure single crystals between the latent hardening, measured by the direct stress activation of oblique slip systems, and the stress-strain behavior in simple compression. Materials with high latent hardening, like LiF, strain-harden at a low rate (Stage I) even when severely constrained. KCl, in contrast, shows low latent hardening and a tendency to strain-harden at a high rate (Stage 11). This correlation suggests that oblique slip is essential for Stage II hardening of these materials. THE role of secondary slip in the strain hardening of metal single crystals is a topic of lively controversy. On the one hand are theories in which secondary dislocations participate directly in Stage II hardening in the fcc metals, for example through the production of sessile dislocations,1 forest intersections, or jog formation. Much of the experimental evidence on which these theories are based has been reviewed by Clarebrough and Hargreaves.~ On the other hand, a recent theory5 denies that secondary slip has an essential role in Stage II hardening or in the transition from Stage I to Stage 11. In the latter view, Stage I is not terminated by an increase in the activity of secondary systems but by the exhaustion of undeformed material.6 The experiments reported in this paper will not resolve this controversy since the materials being studied are cubic ionic crystals rather than metals. However, the results do show in an unusual way a direct connection between "secondary" (nonortho-gonal or oblique) slip and strain hardening in these materials. Specifically, a correlation has been found between two independently measured properties, first the latent hardening of oblique (110)(1i0) slip systems as measured by direct stress activation of these systems, and second the stress-strain behavior at small strains. From prior work, it was known that in most cubi-cally oriented rock-salt structure crystals, two orthogonal slip systems operate and exclude the other equally stressed pair, oblique to the first pair.7'8 This observation apparently indicates that a significant interference exists between slip on oblique (110) planes and a relatively small interference between orthogonal (110) planes. The present experiments were begun with the intent of obtaining a quantitative measure of this difference by means of a study of latent hardening in these crystals. I) EXPERIMENTAL METHODS The experiments were basically of two types, first the determination of stress-strain curves by compression along a single (100) axis, and second the measurement of latent hardening by compressive prestrain along one cube axis followed by the determination of the yield stress in a second (latent) cube direction. All tests were done at room temperature in an Instron machine by compression between lapped, parallel steel faces. Three specimen shapes were used. For long crystals (nominal dimensions, 1/8 in. square by 1/2 in. long) the ends were lubricated with an oil-graphite mixture. Superior results with short crystals (about 1/8 in. cube) were obtained using 0.003-in. teflon film.' Thin crystals (1/4 in. square by 3/32 in.) were used for latent-hardening measurements and similar results were obtained with either lubricant. Test specimens were cleaved from Harshaw single crystals which had been irradiated to a dose of lo8 roentgen using a cobalt-60 source. The irradiation raises the yield stress and tends to prevent plastic deformation during sample preparation.10 Prior to testing, the irradiation hardening was removed by an anneal at 400°C. Ideal compression specimens have flat, parallel faces. In short specimens particularly, satisfactory results demand a close approximation to this ideal. In the present work, cleaved surfaces were often used directly as compression faces. The degree of success using this method depends on two factors: 1) the smoothness of cleavage faces, and 2) the extent to which the crystal is deformed or crushed by the chisel during the cutting of a long crystal into short pieces. Unfortunately, only one material of those studied, LiF, was completely satisfactory. NaF, NaC1, KC1, and KBr behaved less well so that

Jan 1, 1964

By AIME AIME

THE best meeting ever held, was the opinion expressed by a number of those who attended the annual meeting of the Institute in New York, Feb. 18 to 21, and there was an atmosphere of friendliness and good fellowship about it that fully justified the feeling. In numbers it was not quite so large as last year and unless the Engineering Societies should build for themselves a new building it is probable that no meeting can be larger, in respect to numbers, than that held in 1928, which was only made possible by the circumstance that the eighth floor of the building happened to be, temporarily vacant at the time. The number of rooms available for -sessions that were provided when the building was built long ago proved inadequate, and it is only by the expedient of obtaining the temporary use of the board and committee rooms of other societies that it is possible to arrange for the over 40 sessions that must be spread over the four days of the meeting. The-fifth floor, where. a buffet lunch is served each-day, has reached its full capacity and it seems quite evident that any future development of Institute meetings must be along the lines of quality, not size.

Jan 1, 1929

By Frank Firmstone

The piece of spiegeleisen, the analysis of which is given below, was collected by my father, together with various other specimens, while he was manager of the Glendon Iron Works. It bears a label stating that it was taken from a building in the town of Newton, New Jersey, erected in 1765 and torn down in 1863. The building belonged, in 1863, to T. N. McCarter, Esq. The label is in the hand-writing of Mr. McCarter, now deceased, well known as a member of the bar of northern New Jersey. The specimen was, no doubt, given by him to illy father, with whom he had business in 1863 and 1864. It is now in the metallurgical collection of Lehigh University. I know nothing further as to the history of the specimen, but there is no reasonable doubt that it was made from ore from the Andover mine, at the old charcoal-furnace which once stood at the village of Andover, about 5 miles south of Newton, on the Sussex railroad. It was probably broken from one end of a bearer over an open fire-place, is about 6 in. wide by 2.5 in. thick, has been cast in open sand and shows the charcteristic fracture of spiegeleisen rather low in manganese, as shown in Table I. One edge has been white-washed. Table I.—Analyses of Spiegeleisen Made from Andover Ore. 1. 11. Per Cent. Per Cent Graphite,.0.101 0.005 Combined carbon,... 4.529 4.212 Silicon,..0.037 0.294 Manganese,..... 5.760 3.750 Sulphur,.0.003 0.031 Phosphorus,.0.060 0.072 Iron,........ 89.440 91.570 99.920 99.934 I. Spiegeleisen made at Andorer (charcoal) furnace not later than 1765. IT. Spiegeleisen made from Andover ore at Phillipsburg, N. J., anthracire-furnwe, 185-. Both analyses were made by Dr. P. W. Shimer.

Jan 1, 1907

By C. D. Stahl, S. M. Farouq Ali, W. E. Culham

One- and two-dimensional mathematical models have been developed that simulate transient, two-phase flow of hydrocarbon mixtures in porous media in a manner that accounts for interphase mass transfer. Numerical simulations of one-dimensional depletion-drive experiments using a two-component hydrucarbon fluid were used to establish the validity of the mathematical models. In addition, the experimental and numerical data were used to demonstrate that production rate had a relatively insignificant effect on the recovery of individual hydrocarbon components from the experimental system, and that attainment of equilibrium between phases is possible for a wide range of liquid and vapor velocities in reservoirs containing light hydrocarbon fluids. Results of some two-dimensional numerical simulations are also presented. INTRODUCTION This study was undertaken to develop a mathematical model that would simulate transient, two-phase flow of hydrocarbon mixtures in porous media under conditions that result in interphase mass transfer and to test the validity of the assumptions used to set up the model. In addition, the study was designed to determine if production rate influences the recovery of individual hydrocarbon components from reservoirs producing by depletion drive. Two-phase flow in porous media, with interchange of components between the two phases, is important in many petroleum recovery processes. Studiesl-5 conducted within the last 3 years have outlined methods of solving multiphase flow problems incorporating mass transfer. Some of these studies have also indicated the importance of accounting for mass transfer under various producing conditions. An earlier work6 first demonstrated the importance of combining relative permeability data with equilibrium ratios in compositional balance methods. The mathematical model presented in this paper is formulated so that a phase behavior package, as described in previous papers,5,17 is not required as an integral part of the routine employed to solve for the primary dependent variables. The finite difference formulation is designed so that all the primary variables can be solved for simultaneously. This is accomplished by utilizing one basic set of equations. These innovations, which are in contrast to other models2,3,5 but are similar in some respects to the approach used by Taylor,l render the total problem computationally simpler than any of the previously referenced formulations. The mathematical model was developed by combining Darcy's law with a continuity equation for each hydrocarbon component. The principal assumptions invoked in the formulation were (1) that capillary forces and diffusional effects are negligible, and (2) that thermodynamic equilibrium exists in the reservoir at all times. No assumption as to the type of vaporization process was made in formulating this model. Experimental data were required to complete this study. These were generated by conducting several depletion drive experiments. The experimental apparatus consisted of a sandstone core enclosed in a pressurized casing. The apparatus was designed in such a manner that the core could be charged with a liquid hydrocarbon mixture and depleted at different production rates. The experimental tests were designed to determine the effect of production rate on component recovery. In addition, direct comparison of experimental and mathematically predicted

Jan 1, 1970

By J. W. Rutter, K. T. Aust

The migration of individual, large-angle grain boundaries has been studied as a function of tempereature and solute concentration in specimens of zone i.e filled lead containig very small additions of silver and of gold. Tile results are compared with various the-ories of grain boundary migration and with observations made prev.iorlsly of grain boundary migration in similar specimens of zone-refined lead containing tin additions. A previous investigation by the authors dealt with [he temperature dependence of grain boundary migration in bicrystals of zone-refined lead containing small additions of tin.' It was shown that tin additions as low as a few parts per million cause a large decrease in the grain boundary migration rate at any given temperature, as well as a marked increase in the temperature dependence of the migration rate. It was found that existing theories of grain boundary migration. based on the motion of dislocations. or upon the concept of atom transfer in groups across the boundary (group process theory). or upon the control of grain boundary motion by volume diffusion of impurity atonls along with the boundary. are incapable of accounting for the observations. The single process theory of grain boundary migration. which is an absolute reaction rate calculation based on the transfer ui atoms singly across the moving boundary, was found to predict the migration rate reasonably well for a number of boundaries whose motion was shown to be very little influenced by impurities, but not for boundaries whose illation was influenced markedly by impurities. It was concluded that the elementary process of grain boundary migration involves the activation of single atoms during transfer across the boundary. and that inadequate knowledge is available to permit the influence of impurities to be properly taken into account. The present study was initiated to check the validity of the above conclusions with other alloy systems, namely high-purity lead with small additions of silver and of gold. Both silver and gold diffuse faster. and with a lower activation energy of volume diffusion. than does tin in lead;' consequently, a study of the effects of silver and gold on grain boundary migration in high-purity lead offered a means of testing theories of boundary migration based on bulk diffusion of the solute (eg. ref. 3). In addition. it was hoped that the present work, in comparison with the results for tin in lead, would provide information concerning which factors are important in determin- ing the interaction between solute atoms and a grain boundary. EXPERIMENTAL PROCEDURE The preparation of bicrystals of zone-refined lead, with various silver or gold additions, was identical to that previously described for the lead-tin alloys.''4 Each bicrystal consisted of a striated crystal which was grown from the melt. and an adjacent striation-free crystal which was introduced by artificial nucleation and growth.''4 The striation or lineage substructure in the melt-grown crystal provided the driving force for grain boundary migration. During the preparation of striated single crystals by growth from the melt, it was found that silver or gold concentrations as low as 2 or 3 ppm by atoms were sufficient to cause formation of the hexagonal cell structure. which is due to the presence of impurity, during freezing. This structure is revealed on the solid-liquid interface by decanting the liquid during freezing. The hexagonal cell structure was observed previously4 in zone-refined lead crystals with tin contents above approximately 200 ppm by atoms. These concentrations of silver, gold, or tin are in agreement with the predicted amounts required for cell formation in lead,5'6 under the present conditions of freezing.4 The absence of cell structure at decanted interfaces, therefore, served as a useful indication that the silver or gold contents were less than 2 or 3 ppm by atoms in the specimens as grown. It was found that grain boundary migration occurred only very slowly when the solute content approached that necessary for cell formation. As a result, the present experiments were conducted with silver or gold additions less than 1 ppm by atoms. This impurity level is well within the solid solubility limits for silver and gold in lead.7 The annealing treatments, measurements of grain boundary velocities, and orientation determinations were carried out as described previously.' However. each bicrystal was also chemically polished in a solution consisting of 8 parts glacial acetic acid and 2

Jan 1, 1961

By J. O. Betterton, W. M. Spicer

The solubilities of antimony in the a and ß-forms of zirconium were determined between 750" and 1300°C. The a-phase forms by a peritectoid reaction, and the a/(a + ß) and ß/(a + ß) phase boundaries rise in temperature with in- ' creasing antimony. Impurities in the 99.95 pct zirconium were sufficient to influence the phase boundaries and the variation reported is approximate. The restricted solid solubility of the terminal zirconium phases, which is especially characteristic of this system, is thought to result from the low free energy of the Zr2Sb phase. ZIRCONIUM-antimony alloys are important in zirconium alloying studies since antimony is one of the highest valent elements which can be used to make zirconium alloys. The dilute alloys are of further interest as they have somewhat better corrosion resistance' than pure zirconium. The first investigation of the phase diagram was made by Russi and wilhelm2 who found a eutectic reaction, liquid (- 17.5 at. pct Sb) = ß zirconium (- 11 at. pct Sb) + Zr2Sb, at 1430°C'. The Zr2Sb phase was of complicated hexagonal structure, and by thermal analyses of the relatively impure alloys then available, Russi and Wilhelm found evidence for the peritectoid formation of the a-phase. EXPERIMENTAL In the present work, the phase diagram was re-investigated in the region 0 to 5 at. pct Sb and 750" to 1300°C using iodide-zirconium alloys. Details of the procedure have been described earlier. Essentially the alloys were prepared by arc casting and were then examined by the annealing and quenching method. The times of annealing varied from 1 hr at 1300°C to 30 days at 760°C. As in other zirconium phase-diagram studies1"5 the impurities in the zirconium were still sufficient to affect the results, and the experiments will therefore be described in 3 parts. The results from the first 2 parts of the work are shown in Fig. 1. Here the ß/(ß + Zr2Sb) and a/(a + ZrzSb) phase boundaries were determined with alloys made from 99.9 pct zirconium,* and cast under such conditions that the Vickers hardness of a alloys extrapolated to 95 to 110 VPN at 0 at. pct Sb. Such alloys were not suitable for investigations of the (a + ß) region, and the results shown in Fig. 1 near the (a+ ß) and (a +ß + Zr2Sb) regions were determined with purer alloys. These alloys had an extrapolated hardness range of 75 to 85 VPN and were made from 99.95 pct zirconium. A deviation from binary equilibrium occurs in Fig. 1 as indicated by the (a + ß) region of pure

Jan 1, 1959

By W. A. Griffith

The fundamental principles and modern techniques of experimental planning and data analysis, applicable to any type of research, are particularly important in flotation experimentation. Since they constitute the modern science of experimentation, they should be among the working tools of any scientist, research engineer, or plant operator engaged in flotation investigates. This chapter is a review of these principles and techniques. Equipment and procedures for the actual conduct of experiments will not be discussed here since these subjects are well covered elsewhere in this volume. Neither will any attempt be made to impart a working knowledge of statistical methods of data analysis since this would be impossible in the space allotted, and many excellent texts are available to the diligent inestigator.1-4 The objective here is simply to interest the reader in the application of statistical techniques to flotation experimentation by illustrating their utility in situations frequently encountered, and to point out the principles of experimental planning necessary for their proper use. Any conscientious metallurgist engaged in flotation experimentation or operations is well aware of the inherent complexity of the flotation process, and of the often frustrating difficulties this introduces into experimentation. The raw materials normally treated by the process are complex both physi- cally and chemically, and often highly variable even when from the same source. The flotation process itself is characterized by a very large number of potentially important process variables. Many of these are beyond the con- trol of the metallurgist, and some cannot even be measured quantitatively with available instruments. Those which can be measured and controlled with reasonable precision often produce effects which are intricately interrelated. Not only are the variables many, but the physical and chemical mechanisms by which they function are imperfectly under stood. To compound the difficulty, experimental techniques are relatively crude. Controls are not very precise, and the human factor looms large in most flotation experiments. These situations lead inevitably to experimental data of a relatively low degree of precision or reproducibility. Some are inclined to think that these conditions are unique to flotation experimentation. They are not. The experimental problems met by the agronomist, the biologist, the social scientist, and others are equally complex. Investigators in these fields pioneered in the development of methods for handling just such situations by proper experimental planning and the application of statistical methods in the analysis of data. Their pioneering work has grown into a well established modern science of experimentation which has spread into every field of science. This science is based upon statistical

Jan 1, 1962

By W. Joseph Schlitt, Kenneth J. Richards, John D. Prater

Kennecott Minerals Company has developed a leach-hydrolysis route for treating flue dusts from copper smelters The flue dusts are acid leached in an oxygen atmosphere to solubilize copper and fix the arsenic, antimony, and bismuth as stable compounds Copper is recovered by cementation with Iron and the barren solution is recycled Molybdenum and other values may be recovered by modification of the basic flow sheet Results of bench scale and pilot plant tests are discussed in terms of the effect of operating parameters.

Jan 1, 1981

BEFORE an audience which included many notable members of the engineering profession, the John Fritz Medal was presented to Senator Guglielmo Marconi on July 6, 1922, in the auditorium of the Engineering Societies Building, in New York. The medal was awarded for achievements in the development of wireless telegraphy, but all of the speakers emphasized the inventor's service to mankind, in saving life at sea, especially, as well as his remarkable scientific attainments. SIGNIFICANCE OF THE JOHN FRITZ MEDAL The John Fritz Medal is presented from time to time for notable achievements in applied science, as a memorial to the engineer and metallurgist whose name it bears, one of the charter members of the American Institute of Mining and Metallurgical Engineers. The medal fund, contributed by friends of Mr. Fritz, is administered by representatives of the four national engineering societies. Seventeen awards have been made to men of eminent distinction in the various branches of the profession of engineering, whose names are more familiar to the civilized world than are the names of most of the presidents of the United States. Four of the medallists were present on the evening of July 6: Dr. Elihu Thomson, the dean of the electrical engineers, General Goethals, Orville Wright, and J: Waldo Smith, who developed the New York City water supply, system. In opening the meeting, Dr. Comfort A. Adams, president of the Board of Award, said in part: The profession of engineering knows no national boundaries. That the engineers of this country sense this fact deeply is evi-denced by the absence of any limitations as to nationality in the award of the John Fritz Medal. The engineer is seeking for the truth wherever it may be found, and it frequently happens that the most helpful sugges-tions for the solution of a particular problem are the results of the work of men of other nationalities on the other side of the world, whom we have never seen. Thus through this long range interchange of information and of ideas, there has grown up a feeling of real kinship among the engineers of the civilized world, a sense of interdependence and of the need and value of cooperation, in wide contrast with the all too prevalent sense of conflicting interests, of racial and national antagonisms of bitterness and misunderstanding. We often think of the nations of the earth as separated by walls or barriers, of various kinds and of various heights. Some of these are the natural results of evolution, for example, differences of language, customs and traditions; while others are more artificial, being maintained by law and dictated by fear, greed, and shortsightedness or ignorance. There is deep conviction that the degree in which we can abolish these barriers is a true measure of our progress towards real civilization, and that the destruction of these barriers is the only method of attaining that world-wide peace for which every

Jan 8, 1922

By R. M. Rose, D. P. Ferriss, J. Wulff

Single crystals of tantalum, tungsten, and the binary alloys thereof were grown by electron-beam zone melting and tested in tension between 77° and 373°K. The ductile-to-brittle transition temperature increased sharply with solute concentration, for both tungsten-rich and tantalum-rich alloys; apparently, the maximum transition temperature exists near the 50 pet concentration. Twinning was observed to be a consequence of cleavage-crack propagation. Cleavage occurred on(100)planes, and extensive tearing and "river markings" were present. The onset of brittleness could not be associated with any change in deformation mode, the yield point phenomenon, or the large rise in yield stress with decreasing temperature. Cleavage was observed to initiate at either the specimen surface, or subgrain boundaries. The observation was made that the grain boundaries of Polycrystalline materials are probably even better as nucleation sites for fracture, and are responsible for brittleness at high temperatures and lower solute concentrations than those of the corresponding single crystals. TUNGSTEN and tantalum, the two high-melting neighbors in the third transition period of the periodic table, present striking contrasts. Although both are bee, tungsten has far higher elastic moduli, and the highest ductile-to-brittle transition (DBT) of all the pure metals.' Tantalum, however, is ductile at liquid helium temperatures. Large strain aging and yield point phenomena are observed in tantalum,2,3 but only to a lesser extent in tungsten.4 Tungsten work-hardens at a high rate,5 whereas this effect is negligible in tantalum.' Since the mutual solid solubility of these two metals is complete,7 and no ordering has yet been reported in the binary system, the possibility of depressing tungsten's DBT by tantalum additions was considered. Also, tungsten additions to tantalum could produce hard, high-melting alloys which might be ductile at room temperature. Such alloys offered excellent bases for complex alloy development, particularly with regard to the effect of rhenium on Group VI metals.8"10 In addition, there was the opportunity to examine flow and fracture modes in the vicinity of the DBT, with particular emphasis on the correlation between brittleness and fundamental deformation mechanisms. Myers11 has reported that recrystallized alloys with up to 10 pet W in tantalum are ductile at room temperature, but alloys with 20 pct W could not be swaged at temperatures as high as 500°C. The whole spectrum of Ta-W alloys has been surveyed by Braun, Sedlatschek, and Kiefferl2 using sintered powder compacts. In addition to some physical properties they reported a maximum hardness at about 50 at. pet W, dropping to much lower hardness levels for the pure components. They were able to cold work tantalum-base alloys with as much as 30 pet W and to warm work tungsten-base alloys with up to 20 pet Ta by procedures similar to those used for pure tungsten. EXPERIMENTAL In order to study deformation modes and to keep the impurity concentrations at a minimum, electron-beam zone melting was used to prepare single crystals of high purity. The electron-beam zone melting apparatus is similar to that described by Calverley, Davis, and ever" and incorporates a grid control rectifier to maintain control of emission current. Pure metals were refined by making three zone passes at 4 mm per min up the rod. Alloys were prepared by melting together wire of one constituent on a previously melted rod of the major constituent. Subsequently, two zone passes were made in opposite directions to level the composition after the manner suggested by pfann.14 Purification of the starting materials was accomplished by evaporation of the several impurities, and the degree to which this was accomplished is indicated in the chemical analyses of Table I. The uniformity of composition along a zone levelled rod was within the i 1 pet accuracy of the fluorescent X-ray technique used to determine composition. Crystallographic orientation of the

Jan 1, 1962

By H. A. J. Wilkens, H. B. C. Nitze

At the Atlanta meeting of the Institute in October,' 1895, some brief remarks were made by Mr. Wilkens on the above subject. It is the object of this paper to set forth the substance of these previous statements, embodying therewith additional information gained since that time, and a brief illustrated description of the method and means of the separation.* Lack of time will unfortunately not allow as complete a resume of the subject in all its phases, especially those relating to the scientific side of the question, as its novelty and importance would warrant, so that even this paper must be considered a preliminary one. It is hoped that at some future meeting of the Institute we may find an opportunity of presenting supplementary data of interest. The paradoxical title above used requires some explanation. The term " non-magnetic material " is applied to such substances as have heretofore been considered non-magnetic in the arts, more especially in the practice of ore-concentration. Scientifically, it has been shown by Faraday, Plucker, Wiedemann and other physicists that magnetism is an inherent property common to all substances, solid, liquid and gaseous, i.e., all suhstances are either attracted or repelled by the poles of a magnet, although ill the great majority of cases the manifestation of this

Jan 1, 1897