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By B. H. Caudle, L. G. Loncarie

Pilot flooding is one method of evaluating a proposed secondary recovery project. However, the amount and rate of oil recovery from an unconfined pilot area is not usually the same as from an equal area in a large-scale flood. This is true because fluids are free to move across the boundary of a pilot area. The result is that some of the oil produced in a pilot flood may come from outside the designated area and some of the displaced oil may leave the pilot area completely. This paper presents the results of fluid-flow model studies on a five-spot pilot flood. Mobility ratios between 0.1 and to have been studied. The effects of changing the ratio of injection to withdrawal rates are shown. INTRODUCTION A small-scale field test, or pilot flood, is an accepted method for evaluating the applicability of a secondary recovery operation and the economic potential of that operation for a reservoir. The pilot flood is carried on in the same manner, with the same injected materials and at the same pressures as would be used were the secondary recovery program to be expanded to a larger area of the field or to the entire field. If the reservoir fluid and reservoir rock properties are the same in the pilot area as in the rest of the reservoir, the production, injection and other pertinent data associated with the pilot test will represent and measure what should be expected from a full-scale development of this secondary recovery program. There is one major exception which, unfortunately, has been overlooked by many and which has been awaiting quantitative definition. This is the sweep-out pattern the reservoir engineer must use in interpreting the pilot flood and in extrapolating it to the full-scale development. The sweep-out area in a pilot flood is not contained within the five-spot pattern. Further, there is oil flow into and/or out of the five-spot during a pilot test. Thus, production data from pilots must be interpreted with this different flow system and sweep pattern in mind. We have studied the sweep-out pattern that will exist for some conditions of operation of pilot flooding a single five-spot (four injection wells and one producer). In our study, reported here, we have assumed that the reservoir is relatively homogeneous and of uniform thickness in the pilot area. The results of this study en-able the engineer to predict the recovery, injection requirements and project life for a full-scale operation from the pilot flooding data. The effects of various injection to withdrawal-rate ratios and mobility ratios in a relatively gas-free (10 per cent pore volume or less) system are shown. Experimental Method The technique used in this study was the same as that for the X-ray shadowgraph studies of sweep-out pattern efficiencies.' The model of the pilot and surrounding area was made from a uniform packing of round-grain sand consolidated with an epoxy resin. Fig. 1 shows the relation between the model and the pilot area. Only one-eighth of the pilot area had to be represented in the model because we assumed equal injec-

By J. Gurland

A method of measuring the degree of contact between grains of 1 phase in multiphase alloys is derived. It is shown that the number and the areas of contacts between grains can be determined by metallographic analysis. Relations between the area of contact, the dihedral angle, and the mean free path of spherical grains are developed. It is often desirable to interpret the mechanical behavior of alloys in terms of structural features observed under the microscope. A quantitative description of microstructures of multi-phase alloys requires consideration of geometrical and topological factors such as the amount, size, and shape of grains and the continuity of the constituent phases. The number and dimensions of grains may be metallographically determined by applying the methods described by Smith and Guttman1 and by Fullman2 in their papers on the measurement of particle size and internal boundaries in opaque bodies. The present work intends to show that the same methods can be used to evaluate some of the parameters of phase continuity; namely, contiguity, number of contacts, and areas of contact of grains of 1 phase. Application of these concepts may be found in such problems as the calculation of electrical conductivity of 2-phase alloys, or the evaluation of the length of fracture path through grains of a brittle phase more or less dispersed in a matrix. I. DEFINITION The following definitions and derivations are based on 2-phase alloys, of which the units of the microstructure are grains. Contiguity is defined as the average fraction of surface area shared by 1 grain of a phase with all neighboring grains of the same phase. In a 2-phase alloy of constituents A and B, the contiguity of phase B is given by: where Cb is the contiguity of phase B aBß is the average area of contact between a grain of phase B and adjacent grains of phase B, aAB is the average area of contact between a grain of phase B and adjacent grains of phase A. The contiguity is a measure of the average degree of contact between grains of phase B in the 2-phase mixture. The ratio varies from 0 to 1 as the distribution of phase B changes from a completely dispersed to a fully agglomerated structure. Smith and Guttman1 have shown that the relative areas of 2 kinds of interfaces in a volume are directly proportional to the number of interfaces of each type intersected by a random line. The lines can be drawn on metallographically prepared surfaces as long as these are random sections through the sample. The contiguity ratio of phase B then becomes: Cb = 2NBB/NAB + 2N BB [2] where: NBB is the number of interfaces between grains of phase B intersected per unit length of random line. Nab is the number of interfaces between grains of phase B and grains of phase A intersected per unit length of random line. The factor 2 arises in Eq. [2] because each interface B-B is associated with 2 grains of B-phase, whereas the interface A-B involves only 1 grain of B-phase. The calculations of contiguity do not require any assumption as to volume fraction, particle size, or particle shape. Fullman2 gives an expression for the determination of the mean free path between particles. The mean free path PB between grains of phase A, i.e., through grains or agglomerates of phase B, may be found from the relationship: PB =2fB/NAB [3] where fB is the volume fraction of phase B. The calculation of the mean free path is independent of grain shape and grain size distribution. The calculation of the number of contacts and of contact area requires assumptions of grain shape, grain size, and contact shape. In the case of uni-

Jan 1, 1959

By W. C. Peters, M. W. Pullen, C. A. Bays

During the past three and a half years considerable improvement in the techniques of solution extraction of salt has been made by the use of wells which are cross-connected by hydraulic fracture at the base of the salt. Fracture is initiated by the application of hydraulic pressure. Underreaming and perforating techniques are used to control initiation. The fracture is then extended by continuous pumping until a pressure communication is obtained. Pressure communication is followed by washing-through to obtain a low-pressure connection. Well construction using non-shrinking cements that will bond with the salt and with associated strata is essential to the process. The connecting procedure described permits solution to attack the salt deposit from its base upward, thereby permitting greater recovery, fewer well repairs, better saturation of brine, and overall economy of development and operation. The fracture method of cross-connection requires special pumping of the fluid and is limited by present experience to initial well spacings up to about 1200 feet. The method has been used in bedded salts and is applicable for wells in salt domes. Since spring of 1956, new developnents in salt extraction wells have followed procedures substantially different from those in prior use. Although multiple well systems, connected either by the natural consequence of the solution process or by undercutting under protective pads, have been used previously, the past three and a half years have brought about new designs and new operation procedures based on cross-connection of the wells using hydraulic fracture. To date these techniques have been applied largely in the bedded salt deposits of Michigan, Ontario, Ohio, West Virginia, and New York. To the writers' knowledge they have not been used in salt dome wells. The methods have not yet been in use for a sufficient period to permit any statistical comparison with the older methods. It is evident from experience to date that the methods result in higher recoveries, lower capital and operating costs, better saturation of produced brine, reduced well maintenance and repair, and in considerably fewer production units to insure

Jan 1, 1961

By J. F. Shea, O. F. Tangel

Battelle Memorial Institute participated in a program for the General Services Administration aimed at developing a nickel-cobalt separation process that could be integrated in the Nicaro nickel plant. At the time the programwas being carried out, the Nicaro process was a straight-through operation, in which the ore was reduced and leached, after which the pregnant solution was boiled to produce a so-called "bulk precipitate" which contained virtually all of the nickel and cobalt which had been dissolved in the leaching step. The weight ratio of nickel to cobalt in Nicaro ore is approximately 15 to 20:l. The weight ratio of nickel to cobalt in the finished product had to be 100:l or higher to meet specifications. Because the Nicaro process embodied no nickel-cobalt separation step, the only way that a bulk precipitate of the specified nicke1:cobalt ratio could be produced was to so adjust roasting and leaching conditions that nickel would be selectively leached and most of the cobalt would be rejected with the tailings. The required selectivity, however, was achieved at the expense of nickel recovery, which was 5 or more per cent less than might have been obtained with the existing equipment, utilities, man power, etc., had selectivity been no object. The over-all purpose of the program was to develop a separation step that could be fitted into or onto the Nicaro facilities and which would permit the manufacture of a product that would meet the desired specifications and still permit the recovery of a maximum amount of nickel. Battelle suggested that this might be accomplished by reprocessing off-specification bulk precipitate and specifically suggested the process based on ammonium sulphate leaching followed by hydrogen reduction of the leach solution according to techniques developed commercially by Sherritt Gordon Mines Limited. Such a process would not only satisfy the objectives of the research but would present two additional advantages. (1) It would produce a separate cobalt product which could be further processed into metal, alloys, oxides, or salts. (2) It would yield nickel in metallic form which might be more generally marketable and command a slightly higher price per unit of nickel than the Nicaro oxide product. DESCRIPTION OF THE PROCESS Figure 1 is a flowsheet of the process. The essential features are: (1) Extraction of about 97 per cent of the nickel and about 85 per cent of the cobalt from bulk precipitate by a principal leach with ainmonium sulphate solution (Step A). Extraction of virtually all of

Jan 1, 1961

By W. G. Davenport, M. Paneni

Experiments in sheets of mercury and water have confirmed that the dynamics of bubble rise are simi-lur in Liquid metal and aqueous systems. RECOGNITION that bubble/metal interactions are important in pyrometallurgical refining processes (e.g., steelmaking, vacuum degassing, deoxidation of copper) has led to a number of investigations into the dynamic behavior of bubbles rising in liquid metals. Terminal velocities of bubbles rising in mercury (20°C)' and silver (1000" to 1050"c)1,2 have been measured. Good agreement between aqueous and liquid metal systems has been obtained. Shapes of air bubbles rising in mercury have been determined experimentally by Davenport, Bradshaw, and Richardsonl who used a system of electric probes to measure maximum horizontal and vertical dimensions, Fig. 5. In the present work the motion and shape of nitrogen bubbles rising in a thin sheet of mercury (i.e., a "two-dimensional" environment) have been studied with the view of confirming dynamic similarity between aqueous and metallic systems. The use of thin sheets of liquid permitted direct visual and photographic comparisons of bubble behavior in clear liquids and in mercury. EXPERIMENTAL METHOD The thin sheets of mercury or water were held in a clear acrylic plastic container, Fig. 1. The sheets of liquid were 80 cm high by 30 cm wide and 0.47 cm thick. Single bubbles were formed by injecting the desired volume of nitrogen into an inverted semicircular cup (stainless steel). The cup was then rotated into the upright position using an external handle thus releasing a single bubble of measured volume. Nitrogen was injected into the cup from a nitrogen cylinder through the external handle and a hollow rotating axle. The volume of a bubble (volume range 0.01 to 10 cu cm) at any instant was obtained by connecting a soap film meter to a small gas space above the liquid. By this technique any change in the volume of a gas bubble in the liquid (i.e., during cup filling or during rise) produces an equivalent displacement from gas space A into the buret B. This displacement is determined by measuring the movement of a horizontal soap film in the buret. Bubble shapes were determined using single-frame photography. Rising velocities were determined by cinephotography with a 1/100-sec stopwatch in the field of view. In both cases dimensions were referenced to a rule attached to the container surface, also in the field of view. Linear dimensions were measured on projections of the single-frame negatives. Rising velocities were calculated from measured heights of rise (10 to 20 cm) and times of rise. The effects of disturbances caused by cup rotation and by bubble release were minimized by photographing bubbles at a point not less than 25 cm above the cup. MATERIALS Mercury: Technical-grade purified: minimum 99 pct Hg; Johnson Matthey and Mallory Limited, Toronto. Nitrogen: Technical-grade purified nitrogen: 99.99 pct Nz, 0.01 pct 02, trace argon; Air Liquide Canada Limitee, Montreal.

Jan 1, 1970

By TSUYEE PEI

I FEEL greatly honored and appreciate this opportunity to be able to say a few words about that rather perplexing subject, silver. The constant decline in the price of this metal has now reached the stage where it is of much concern and the cause of serious discussion among the leading financiers, economists, and statesmen of the world. Further- more, it is significant that this subject is so important that almost every day one can read articles pertaining to it in the newspapers and trade publications. Being essentially a banker, and not an economist, I do not claim to be an authority on the silver question. These remarks are merely some of my observations in, regard to the many puzzles which-I came across in my recent studies of this very important question.

Jan 1, 1931

By E. H. Herron, J. H. Perry

Mathematical simulation of reservoir behavior may be used to help understand reservoir processes and to predict reservoir behavior, thereby leading to the most economically desirable form of exploitation. In addition, simulation can be used as a tool for reservoir description to learn more about the physical nature of the reservoir and the mode of primary recovery. This use is essential in most reservoir studies and represents one of the more significant applications of simulation. Prediction of reservoir behavior provides information concerning displacement efficiency, optimum well locations, and the comparison of alternative producing processes. Since oil, water and gas all commonly occur in many reservoirs, a simulation that takes into account the simultaneous flow of three immiscible phases is a prerequisite for obtaining such information. Furthermore, a simulation that describes this flow in two dimensions provides the capability of evaluating combination gas- and water-drive reservoirs with either an areal or a cross-sectional description. Many reservoir problems require such a simulation. The objective of the research described here was to develop a mathematical model and associated computer program for accurate, efficient, and economical prediction of the reservoir flow of three phases in two-dimensional geometry. Several authors have discussed multidimensional reservoir simulation of two phases.l-3 Gottfried et al.' presented an analy- sis of three-phase simulation in one dimension. Fagin and Stewart" and Garrett6 have discussed the simulation of three-phase flow in two dimensions, but their solution techniques were different from the method discussed in this paper. In particular, previous models and computer programs have usually involved either fewer capabilities or inefficient and less rigorous descriptions resulting in limited applicability. In the following sections, we present a description of the model, an evaluation of the method, and the application to reservoir problems. Additional and supporting material is presented in the Appendix. The Three-Phase Model General Description The three-phase model consists of the mathematical description of the flow of oil, water and gas in a reservoir. Conceptually this description considers flow in all three space dimensions, but in the subject simulator it is assumed that no flow occurs in the third dimension. The model includes the effects on reservoir behavior of fluid and rock compressibility, viscosity, gravity, capillary pressure, relative permeability and gas solubility. Within the two-dimensional restriction, the reservoir considered may be completely heterogeneous and anisotropic. The differential equations governing multiphase, multidimensional flow in a reservoir are too complex to be solved analytically, so they are approximated by a system of finite difference equations and solved

Jan 1, 1970

By R. N. Edmondson, L. Mair, M. Tenenbaum

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhord Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chipmon, Vice President; T. D. Jones, Treosurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. w. Thornton, Chairman; Dennis Carney, John Chipman, J. C. Fulton I. H. Hollomon H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supenision of the following Publications Committees: Extractive Metallurgy Division: T. 0. King Chairman; S. J. Dickenson, R. P. Hermsdorf R. Schuhmann. Jr.. and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman F. Lincoln Vogel Jr., Vice-chairman, W. A. Baikofen, R. W. Boliuffi J. H. Bechtold M. B. Beyer. R S. Busk, C. G. Gaetzel, Paul Gordon C. D. Groham, Jr., Robert F. Hehe-mann,' R. I. Joffee, F. c. Joumot Jr lrving R. Kramer A. J. Lena Harold Morglin, C. J. McHargue, Russell A: Meussner, J. B. Newkirk H. W. Paxton, G. E. Pellissier, I. S, Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B King, F. C. Langenberg, W. 0.. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining Metallurgical and Petroleum Engineers Inc., 29 West 39th Street, New York 18, N. Y. Telephon: pEnnsvlvanio 6-9220. Subscription 522 Per year for non-AIME members in United States and North South and Central America; $25 foreign;, $5 for AIME members. Single copies, 54.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed In its publications . . . Copyright 1958 by the American lnstltute of Mining Metallurgical and Petroleum Engineers Inc. . . . Registered cable address AIME New York , . . lndexed in Engineering Index Industrial Arts Index and Chemical Abstrats . . . Application for second class mail privileges ii pending at New York, N. Y. Volume 212, Number 4.

Jan 1, 1959

By V. J. Parks, Leonard Obert, A. J. Durelli

The state of stress in the region where core discing initiates has been investigated through the use of three-dimensional photoelastic models and the results of this study have been compared with those of a previous investigation of rock models. This comparison showed that discing initiates at a point of maximum shear stress, but that the magnitude of the shear stress, as determined photoelastically, is much larger than the shear strength of the rock as deter-mined from conventional triaxial testing. Moreover the shear stress required to produce discing is not constant, but depends on the applied stress field. Possible explanations for these effects are included in this article. In both exploration core drilling and overcore drilling to determine the stress in rock, occasional sections of the core obtained are broken into a series of discs.I* This discing phenomenon has been investigated in the laboratory to ascertain the state of stress required to produce it. The objective of the study was to obtain information that would make it possible to approximate the state of stress in subsurface rock from which disced cores are obtained. Referred to as the discing test, this laboratory study was conducted to determine the applied axial and radial loads required to produce discing in cylinders of rock from several sources. The dimensions of these cylinders are given in Fig. 1. Discing was produced by first applying an axial load to the cylinder and then diamond drilling the core along its axis. The radial load was then incrementally increased until discing initiated. The discs fractured or ruptured* on surfaces approximately normal to the axis of the core (planes A, B, C, D, E, Fig. 2). In many instances, the bottommost disc fractured before the drill had advanced past the points F and F', cre- ating a mush room-shaped fracture surface FEF'. Alternatively, it was also found that the same shaped fracture surface could be created by first drilling in an unloaded core to some point, say F and F', and then triaxially loading the core until fracture occurred on the plane FEF'. Jaeger and cook4 produced similar fracture surfaces in specimens subjected only to a radial biaxial load. From these laboratory studies and observations made in the field, it can be inferred that fracture or rupture initiates in the proximity of the lowest point in the kerf area, (at F and F', Fig. 2) and that the fracture or rupture surface progresses inward from this point. The experiments described above, however, do not provide any information as to the state of stress at the point at which fracture or rupture initiates. In the investigation discussed in the following sections, a three-dimensional photoelastic analysis was conducted to determine the stress distribution in the proximity of the kerf area of a triaxially loaded plastic (epoxy) cylinder containing a short section of core.

Jan 1, 1969

By W. J. Kroll

Jan 1, 1960

By H. B. Charmbury, D. R. Mitchell

Everyone in the coal industry from top management to the preparation engineer is vitally interterested in recovering as much salable coal as possible from the run-of-mine product. Coal losses from a preparation plant occur in the solid refuse material being discharged from the plant and in the bleed-off slurry from the water circuit. The refuse is generally hauled from the plant in solid form by trucks, conveyors, or aerial trams to the refuse or culm banks or it may be crushed and transported by hydraulic methods to refuse ponds or dams. The loss of coal in refuse material and the extent of this problem has been covered in another paver.' The loss of salable coal in the plant bleed-off slurry is one of the water circuit problems in coal preparation plants. Slurries originate at various places in the processing circuits and are usually disposed of by transportation to waste ponds known as slurry ponds. Even though the combustible material discharged as slurry and refuse from the plant is labeled a loss, the loss must only be considered temporary. There is a tendency at the present time to examine refuse and slurry losses and to reprocess these materials to recover valuable coal. Slurries from eight bituminous coal preparation plants in central and western Pennsylvania have been sampled and examined to determine the amount of recoverable coal in each. Examinations of the samples were made to determine the tons per hour of solids and the gallons per minute of water in the slurry; the size, ash, and sulfur analyses of the solids; and the sink-float characteristics of the larger solids. The extreme fines (—325 mesh material) from one of the samples has been examined further to determine the micron size fractions as well as the ash and sulfur content of the micron sizes. Collection of the Samples: Field trips were made to each of the plants where samples were obtained and discussions held with the preparation engineer prior to sampling. The flowsheet of the plant operation was studied and a time-period selected to obtain a representative sample. At least 20 1-gal samples of total plant bleed-off suspensions were collected at each plant in increments over designated periods belived to be typical of the plant flow Three of the samples were obtained from plants in the Pittsburgh area. Each plant supplied information on the capacity, operating time, type of cleaning equipment used, water and material balances, and auxiliary equipment. From the time required to collect given amounts of slurry and from the amount of solids in the slurry, total solids discharges from the plant were calculated and compared with the plant flow. Ash and sulfur analyses of the total solids were also checked, at some plants, with company figures. In all cases where checks could be made there was reasonable agreement between company figures and those reported here. Analysis of the Slurries: Representative fractions of properly agitated samples were examined in the laboratory to determine the specific gravities of the slurries. The solids and water were separated by filtration to check the weight of each so that the percent of solids in the pulp could be determined. From the resulting data, presented in Table I, it may be seen that the percent solids in the slurries ranges from 2.8 to 39.0 and the amount of solids from 2.61 to 45.61 tph. Size Analysis of Solids: Representative fractions of the slurries were permitted to settle and the clear water was removed by siphoning. The solids were then wet-screened at 28, 35, 48, 65, 100, 150, 200 and 325 mesh. Results of the size analyses are presented in Table 11. These results indicate the extreme variation of sizes and in most cases the degree of fineness of the solids. The amount of —325 mesh ranges from 22.5 to 84.5 pct and the amount of+200 mesh from 8.3 to 69.1 pct.

Jan 1, 1961

By D. W. Smith, Robert F. Mehl

It has been shown by numerous studies that the orientations of new metal crystals are determined by the orientations of the crystals in the original matrix, whether these new crystals are formed by recrystalliza-tion, by precipitation from solid solutions, or by transitions in the solid state. The orientations of crystals formed by recrystallization of cold-worked metals that bear preferred orientations are occasionally simply related to the initial preferred orientation; often, however, the relationship is not simple, but complicated and obscure in origin.1 The orientations of crystals formed by precipitation from solid solutions have been shown by many studies in this and other countries to be determined by the orientation of the crystals of the solid solution stable at the higher temperatures, though here again complicated cases have been found and no general theory is available.2 Related to this latter class are the relationships found in crystals formed by suppressed transforma-

Jan 1, 1935

By D. W. Smith, Robert F. Mehl

It has been shown by numerous studies that the orientations of new metal crystals are determined by the orientations of the crystals in the original matrix, whether these new crystals are formed by recrystalliza-tion, by precipitation from solid solutions, or by transitions in the solid state. The orientations of crystals formed by recrystallization of cold-worked metals that bear preferred orientations are occasionally simply related to the initial preferred orientation; often, however, the relationship is not simple, but complicated and obscure in origin.1 The orientations of crystals formed by precipitation from solid solutions have been shown by many studies in this and other countries to be determined by the orientation of the crystals of the solid solution stable at the higher temperatures, though here again complicated cases have been found and no general theory is available.2 Related to this latter class are the relationships found in crystals formed by suppressed transforma-

Jan 1, 1935

By Sherwin F. Kelly

One of the most succinct and illuminating perspectives of the field of geophysical exploration to appear in recent years is an article by E. A. Eckhardt, in the magazine Geophysics for October 1949. Although his review covers the year 1948, many of the data presented are apropos to a review of 1949, and form a pertinent background for a consideration of current progress. He presents charts of the world-wide distribution of gravimeter and seismograph activity in oil exploration, which show that surveys in the United States accounted for practically 68%; of all gravity work and 80%; of all seismic activity. Canada ranked second, with a proportion of roughly 6%, in each case; South America accounted for about the same percentage of seismic work, and double that amount for gravity surveys. Within the United States, Texas and Louisiana were the scenes of the greatest activity, both claiming about 60% of all surveys by each method.

Jan 1, 1950

By David H. Browne

(Pittsburg Meeting, March, 1910.) NICKEL has always been a fruitful mother of problems. Previous to the year 1906 nickel was regarded as an element replacing iron in copper-mattes, and it was believed that the same laws which governed the elimination of iron could be applied-to nickel. This conception has lately undergone a complete change, and nickel in all its stages is now regarded as an element replacing copper; in other words, copper-nickel is considered now as two elements, but as one metal. When we commenced our investigations on Monel metal we made a great many experiments on the conversion of mattes, both high copper and high nickel. We studied closely the composition of the mattes and the changes produced by the blow. We found in all cases certain agreements which we believe are due to some law. Briefly stated, our conclusions are as follows 1. Nickel is not an element replacing iron in matte. 2. Nickel-copper alloys act in the matte-blow like one metal. 3. Nickel-copper alloys follow, during the matte-blow, exactly the same laws as govern. the behavior of copper alone. This brings up the question : What are the laws governing the production of metallic copper, and what are the relations copper to sulphur and iron during the Bessemer blow ?

Apr 1, 1910

By K. J. Gill, P. Chiotti

Thermal, metallographic, and vapor pressure data were obtained to establish the phase diagram for the thorium-zinc system. Four compounds corresponding to the stoichiometric formulas Th2Zn, ThZn2, ThZn4, and Th2Zn17 were observed. The melting points of these compounds under constrained vapor conditions were found to be 1055°, 1105°, 1095°, and 1015°C respectively. Four eutectics exist in this system with the following eutectic temperatures and thorium contents in wt pct: 1040°C, 89 Th; 945°C, 79 Th; 1045°C, 55 Th; and 995°C, 35 Th. The standard free energy, enthalpy, and entropy of formation for the compounds were determined from zinc vapor pressure data. ALTHOUGH the thorium-zinc system has been of technical importance in the commercial production of thorium and more recently of interest to some proposed pyrometallurgical separations processes for reactor fuels or blanket materials no detailed investigation of this system has been made in the past. Some previous work has been reviewed by Hanssen.1 The existence of four compounds, Th2Zn17, ThZn4, ThZn2, and Th2Zn has been established and their crystal structures have been studied by X-ray diffraction techniques.2-4 Smirnov et al.,5 determined the solubility of thorium in zinc and investigated the two-phase region between Th2Zn17 and zinc. They calculated some of the thermodynamic properties for these alloys from emf measurements on the cells Th/ThCl4(fused)/Cl2, C and Th2Zn17(s)+ Zn (l)/ThCl4(fused)/Cl2, C. The possibility of reaction between the anode materials and fused thorium tetrachloride to produce a lower valent thorium salt would have to be resolved in order to evaluate the results obtained. The purpose of the present investigation is to establish the phase diagram for the thorium-zinc system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure and Ames Lalboratory thorium. The major impurities in the thorium in parts per million were oxygen—1250, carbon—350, iron—100, nitrogen-75, and silicon—70. The metals in the form of several small massive pieces, total weight about 30 g, were cleaned with acid, washed with water and acetone, and dried just prior to their use for alloy preparation. Tantalum containers were found to be suitable for all the alloys studied and were used throughout this investigation. The metals were sealed inside of small 1-in.-diam tantalum crucibles by welding on preformed tantalum covers. A small thermocouple well made from 1/8-in.-diam tantalum tubing was welded in the bottom of each crucible. These crucibles were enclosed in

Jan 1, 1962

Jan 1, 1969

[Executive J. V. W. REYNDERS, Chairman WILLIAM H. BASSETT E. DEGOLYER I-I. C. BELLINGER RICHARD PETERS, JR. Finance GEORGE OTIS SMITH, Chairman H. A. GUESS F. JULIUS FOHS Admissions GEORGE D. BARRON, Chairman DAVID LEVINGER P. A. MOSMAN H. K. MASTERS J. A, SINGMASTER Alternates F. G. BREYER C. W. HAMILTON F. E. PIERCE]

Jan 1, 1928

By Jack L. Taylor

As expected from similar crystal structures and favorable atomic size factors, titanium, vanadium, and molybdenum are completely soluble in one another above the transformation temperature of titanium. The fl phase parameters of the continuous solid solution are shown graphically. Limiting compositions for retained fl phase have been determined. VANADIUM and molybdenum both have body-centered-cubic structures at all temperatures and, from the atomic diameter comparison factor, 3.9 pct, would be expected to form a complete series of solid solutions. The existence of complete solubility has been confirmed by work' at the Jet Propulsion Laboratory. Furthermore, vanadium and molybdenum have favorable atomic size factors to form complete binary solid solutions with the B phase, high temperature form of titanium, which also has body-centered-cubic structure. Pietro-kowsky and Duwez' and Hansen et al." have established the existence of the complete series of solutions in these binary systems. It would be logical, therefore, to expect that p-titanium, vanadium, and molybdenum would be completely soluble in one

Jan 1, 1957

By Robert Bakish, William D. Robertson

AFTER more than fifty years of investigation and continuing failure in service, a satisfactory mechanism to explain stress corrosion cracking in homogeneous alloys is still lacking. The relative chemical activity of grain boundaries and adjacent grains, inferred from the boundary structure, has been used to explain intergranular cracking in a brass.' This concept is probably correct as a general hypothesis, but it requires much more extensive development in order to explain satisfactorily the observed phenomena. For example, the specific function of the solute in an alloy must be considered, because intergranular failure does not occur in pure metals,' which are structurally similar to homogeneous alloys. Also, in this connection, an inter crystalline fracture path in binary copper alloys can be changed to a transcrystalline path by relatively small ternary additions.' The fracture path in ß brass is predominantly transcrystalline,' in contrast with an inter crystalline path in a brass. Whether the two different fracture paths are the result of a difference in composition, crystal structure, or the state of long range order is unknown and cannot be determined with ß brass, because only the ordered state can be obtained at room temperature. The study of chemical activity at structural sites in the Cu-Zn system is restricted by the formation of opaque films in an ammonia environment in which stress corrosion cracking is generally observed. Furthermore, both components of the alloy are chemically active and the interpretation of observations is therefore relatively complicated. The Cu-Au system is a better choice for the purpose of studying structural factors. In particular, CuAu is very susceptible to cracking in ferric chloride and opaque films are not formed in this solution; it may be obtained in different states of long and short range order; and, finally, only copper is oxidized in dilute ferric chloride, which considerably simplifies the chemical problem. To provide information necessary for a more general explanation of stress corrosion cracking in homogeneous solid solutions, the following structural factors have been investigated in a Cu-Au alloy having a composition corresponding to Cu,Au: 1) the effect of long and short range order; 2) the structural sites from which copper is removed from the annealed and cold worked polycrystalline alloy; and 3) the effect of annealing time and temperature on structural reactions in the cold worked alloy. Experimental Procedure A Cu-Au alloy of nominal Cu3Au composition was cast from cathode copper and high purity gold and fabricated into sheet and wire. Chemical analysis for copper and gold indicated 48.92 wt pct Cu and 51.01 pct Au. Quantitative spectrographic analysis indicated 0.01 pct Ag, 0.002 pct Pd, 0.001 pct Pb, and 0.002 pct Fe, with traces of magnesium, silicon, and zinc. Presumably most of the remaining 0.055 pct corresponds to the limits of analytical precision. Heat treatments of wire and sheet were conducted in argon or vacuum. Wire specimens, 0.064 in. diam, were heated for 1 hr at 850 °C to establish a definite

Jan 1, 1957