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Jan 1, 1968

By W. H. Eatock

In its infancy, the potash refining industry in Saskatchewan was heavily influenced by practices developed in Carlsbad, NM, resulting in modern, highly productive plants. The first 15 years has been a period of reduced production, due to excessive capacity, when improvements tended to be emphasized in the mining rather than the refining functions. However, some innovations have been developed and applied in Saskatchewan and the industry is entering a period of massive expansion which will produce further advances. This paper discusses, in general terms, some of the different approaches and recent trends.

Jan 1, 1983

By N. J. Grant, C. C. Wang

The Ti-Cr-O ternary system has been studied in detail near the titanium-rich corner within the limits of 10 wt pct 0, and 20 wt pct Cr. Studies were extended, but not in detail, to the region beyond 25 wt pct 0, (50 atomic pct) and 62 wt pct Cr (60 atomic pct). Four isothermal sections at 1400°, 1200°, 1000°, and 800°C are presented as well as two vertical sections at 1 and 2 wt pct 02. DURING the last decade much interest has been shown in the development of high strength titanium alloys for high temperature and corrosion resistant applications. Extensive research is being carried out at present, as the current literature indicates, in order to study the properties of titanium and to develop improved alloys. Two of the important alloying elements in commercial titanium alloys are chromium and oxygen and it would be desirable to know their combined influence upon titanium. For this purpose the present work was carried out to investigate the titanium-rich corner of the ternary system TiICr-0. The binary systems Ti-Cr and Ti-0 have been published recently. The Ti-Cr system was studied by several investigators " and their results are in close agreement. The eutectoid decomposition of the B phase has been shown to be extremely sluggish. TiCr, was the only intermetallic compound found in this binary system and was formed at 1350°C by a transformation from the p phase. TiCr? was established as the cubic C 15 (MgCu,) type of structure with 24 atoms per unit cell and was designated as the y phase. This terminology will be adopted in the present work. There was disagreement about the actual composition of this compound among the several investigators, although it is evident from their data that the compound probably has a solubility range of about 2 to 3 pct and is in the vicinity of 65 pct Cr. It has been indicated recently that a high temperature modification of this y phase (TiCr,) existed at a temperature above 1300°C." ' This high temperature modification was identified as a hexagonal C 14 (MgZn,) type of structure with 12 atoms per unit cell. The exact transformation temperature from the high temperature phase to the low temperature phase has not been established. A considerable hysteresis was observed and, due to the sluggishness of this transformation, the high temperature phase often co-existed with the low temperature phase at temperatures below 1300°C. A preliminary study of several Ti-0 compounds and the Ti-0 system had been carried out by Ehr-1ich."-"' The most complete binary Ti-0 system was the one reported recently by Bumps, Kessler, and Hansen." The first intermediate phase found in the system was the 8 phase which formed by a peritec-toid reaction of the phases a and Ti0 at temperatures below 925 °C. This reaction is extremely sluggish. The structure of this 8 phase was tentatively identified by these authors as being tetragonal and the lattice constants were found as c,, - 6.645A, a,, = 5.333A and c/a = 1.246A. Experimental Procedure The raw materials used for this investigation were TiO,, electrolytic chromium, iodide titanium, and sponge titanium. The TiO, was in the form of powder of chemically pure grade (99.8 pct pure). The chemical analysis of the electrolytic chromium was: 0, 0.50 pct; Fe, 0.07; Cu, N, and C, 0.01; and Pb, 0.001. The oxygen in the chromium was calculated as part of the final oxygen content of the alloys. The alloys were prepared by the cold crucible method using a tungsten arc. The entire system was evacuated and flushed with purified helium three times and then filled with helium. Each alloy was melted, turned over, and remelted at least four times to insure homogeneity. The total melting time was generally from 6 to 10 min. A master alloy of 25 pct 0,-75 pct Ti was prepared to facilitate alloying by melting compacts of TiOl powder with either iodide or sponge titanium, yielding the compound TiO. It was found necessary to bake the TiO, powder compact at about 150°C to remove adsorbed moisture. This was done to prevent the disintegration and spattering of the compact when the arc was struck. TiO, powder dissolved quite readily into the melt and no other trouble was encountered.

Jan 1, 1955

Jan 12, 1951

By Ralph A. Sherman, E. R. Kaiser

The remarkable increase in the distribution of the small underfeed stoker for use in furnaces and boilers in small industrial plants, apartment houses and homes has brought producers and distributors of bituminous coal to consider the problem of which coals and which sizes are best suited to this market. Many papers have also appeared, mostly in the trade journals, discussing the problem of the combustion of various coals and various sizes of coal in small stokers. Much difference of opinion has been apparent in these articles; due often, it would appear, to a misunderstanding of the fundamentals of the process of combustion in the stoker fuel bed. During the past year and a half, a program of research has been conducted at Battelle Memorial Institute: (1) On the process of combustion in the fuel bed of the small stoker, sponsored by Battelle Memorial Institute, and (2) on the relation of the characteristics of bituminous coals to their performance on small underfeed stokers, sponsored by Bituminous Coal Research, Inc. As a result of this program of research, two publications have been made, one1 dealing with the problem of clinker formation, and the other2 with the relation of the size of the coal fed to the stoker hopper to that of the coal that reaches the retort to be burned. The experimental research on the relation of size to the performance of the coal is being actively continued. A publication of Bituminous Coal Research, Inc. presenting the data obtained on the performance of several sizes of four typical bituminous coals will appear shortly. Because of the early appearance of that publication, the present paper includes few numerical data. The purpose of this paper is to follow the coal from the hopper through the furnace with a discussion of the various actions that occur, in the hope that it will lead to a clearer understanding of the relation of the type of coal, the size of coal, and other characteristics, to the performance. The authors do not pretend to have obtained the answers to all the complex questions involved; many unanswered questions will be proposed on which future research work is planned.

Jan 1, 1938

By E. R. Kaiser, Ralph A. Sherman

The remarkable increase in the distribution of the small underfeed stoker for use in furnaces and boilers in small industrial plants, apartment houses and homes has brought producers and distributors of bituminous coal to consider the problem of which coals and which sizes are best suited to this market. Many papers have also appeared, mostly in the trade journals, discussing the problem of the combustion of various coals and various sizes of coal in small stokers. Much difference of opinion has been apparent in these articles; due often, it would appear, to a misunderstanding of the fundamentals of the process of combustion in the stoker fuel bed. During the past year and a half, a program of research has been conducted at Battelle Memorial Institute: (1) On the process of combustion in the fuel bed of the small stoker, sponsored by Battelle Memorial Institute, and (2) on the relation of the characteristics of bituminous coals to their performance on small underfeed stokers, sponsored by Bituminous Coal Research, Inc. As a result of this program of research, two publications have been made, one1 dealing with the problem of clinker formation, and the other2 with the relation of the size of the coal fed to the stoker hopper to that of the coal that reaches the retort to be burned. The experimental research on the relation of size to the performance of the coal is being actively continued. A publication of Bituminous Coal Research, Inc. presenting the data obtained on the performance of several sizes of four typical bituminous coals will appear shortly. Because of the early appearance of that publication, the present paper includes few numerical data. The purpose of this paper is to follow the coal from the hopper through the furnace with a discussion of the various actions that occur, in the hope that it will lead to a clearer understanding of the relation of the type of coal, the size of coal, and other characteristics, to the performance. The authors do not pretend to have obtained the answers to all the complex questions involved; many unanswered questions will be proposed on which future research work is planned.

Jan 1, 1938

By G. C. Gould

The nature of freckle segregation is determined by chemical analyses, microradiograplzy, and electron microprobe. In addition, the influence of chemistry variation on freckle formation is studied in laboratory experiments. It is demonstrated that controlled laboratory solidification can produce freckle segregation. "FRECKLE" segregation is a discontinuous, rod-like segregation observed in vacuum consumable -electrode ingots. Figs. 1 and 2 show this segregation as pencil-like, dark etching areas of segregation found in longitudinally and transversely sectioned consumable-electrode ingots. In most cases the segregation is perpendicular with respect to gravity and parallel to the longitudinal axis of the ingot. The segregation is most often encountered at or around midradius in large vacuum consumable-electrode ingots. The austenitic alloys, A-286* and 718, † have shown particular susceptibility to this mode of segregation. The origin of these rodlike pockets of segregation is not well-understood. It has been suggested that the segregation is a result of a portion of the electrode dropping off and passing through the arc un-melted. On the other hand, smeltzer1 has demonstrated the freckle segregation in A-286 to be comprised of low-melting constituents relative to the matrix melting point. The discontinuous nature of the segregation is the most perplexing facet of the freckle-segregation problem. It was to gain some insight into this part of the problem that this work was undertaken. I) PROCEDURE At the outset of the work identification of the phases present and the elements concentrated in the freckle areas was undertaken. The electron micro-probe was used to determine general enrichment as well as -specific phase chemistry. Microradiography using cobalt and chromium radiation was also used on the freckle areas again to determine the elements involved in the segregation. X-ray diffraction patterns were made from portions of these same foil specimens. Optical microscopy and Knoop hardness measurements were also used

Jan 1, 1965

By T. F. McCormick

THIS year, 1950, is the golden anniversary of the construction and operation in this country of a tube mill for the sole purpose of fabricating aluminum alloy tubing. For a short period prior to the beginning of this mill, aluminum alloy tubing was obtained from foreign sources or produced in mills fabricating other metals. Indeed, it was a very short period because aluminum itself was a newcomer in the field of metals. The first sheet rolling mill had been in operation just eight years and a rod rolling mill for the production of wire and cable had been functioning one year. The first tube mill for aluminum was built by the Aluminum Co. of America in May 1900 and started production with four draw benches and five men, including the mill superintendent. The building itself was a lean-to attached to a sheet-rolling mill at New Kensington, Pa. The cost of equipment, including the draw benches, dies, mandrels, and other tools, was about $5000. This figure seems absurd in the present day but nevertheless it was questioned at that time whether or not such a large sum should be spent to embark on a new and uncertain venture. The initial production system for the new mill consisted of casting round hollow ingots in a tilting-type iron mold, reducing the ingots to bloom size outside the plant, and finally drawing to size on the draw benches. This method of producing aluminum alloy tubing survived just two years, as blooms of satisfactory quality were not obtained consistently. It was superseded by the cupping method in which a 24-in. diam circle cut from a rolled plate was formed into a tube bloom using first a small cupping press and then a push bench. It was stated that tubing so produced was limited to a maximum diameter of 2 3/4 in. and to wall thicknesses varying from 12 to 24 gage. However, for the first time all the operations were performed at one plant and the result was a quality product. Later larger cupping presses and push benches were obtained and the method continued to be the principal one for aluminum alloy tubing for almost a quarter of a century. During the interim the use of a Alan Mannesmann -type billet piercer was explored and it was used to some extent, but failed to produce consistently a smooth inside surface suitable for drawing with aluminum alloys. Experiments started during the latter stages of World War I in the production of tube blooms with a hydraulic extrusion press, led to the use of this type of equipment to make tube blooms for further drawing during a change-over period extending from 1925 until 1930. At this time the cupping method was discarded completely. From these humble beginnings, the aluminum alloy tubing business expanded until well over six million pounds were produced in a single month in the United States during World War II. The major portion of this production was in strong alloys which did not appear in the tubing picture until 1022, when 17S alloy tubing was introduced for aircraft construction.

Jan 1, 1951

By A. Szirmae, Hsun Hu

The early stages of recrystallization in a 70 pct cold-rolled Si-Fe crystal of the (110) (0011) orientation were studied with a Siemens electron microscope. Orientation studies based on electron-diffractzotz. patterns confirm the results of previous texture analysis. The driving energy for recrystallizatior and the critical radius for growth were calculated from the dislocation energy and the energy of the subgrain bourzdaries, and it was found consistent with the observed size of the recrystallized grains. The recrystallization characteristics of crystals with different initial orientations are discussed. The recrystallization of cold-rolled (110)[001] crystals of Si-Fe has been widely studied by various investigators.1-4 Their results on both deformation and annealing textures are in good agreement. The rolling texture after 70 pct reduction consists mainly of two crystallographically equivalent (111) [112] type textures and a minor component of the (100) [011] type. The latter is derived from the deformation twins, or Neumann bands, which are formed during the early stages of deformation and later rotate to the (100) [011] orientation upon further rolling reduction. Between the two main (111) [112] type textures, there is some orientation spread, because of which very low intensity areas appear in the pole figure. If these very low intensity areas are considered to be a very weak component in the texture, then a (110) [ 001 ] orientation may be assigned to them. When this rolled crystal is annealed at a sufficiently high temperature for recrystallization, the texture returns to a simple (110) [001]. The purpose of the present investigation was primarily to seek a better understanding of the recrystallization process by using the electron transmission technique. The (110) [0011 type of crystal was selected because orientation data for it are well known from previous studies with conventional techniques. Direct observations on the recrystallization of such a crystal have also been made by using a hot-stage inside the electron microscope, and the results will be reported in another paper. MATERIAL AND METHOD A single-crystal strip of the (110) [001] orientation was prepared from a commercial grade 3 pct Si-Fe alloy by the strain-anneal technique.= The strip was approximately 0.014 in. thick, and was rolled 70 pct at room temperature to a thickness of 0.004 in. Specimens were cut from the rolled strip and were annealed in a purified hydrogen or argon atmosphere. They were then electrolytically polished in a chromic-acetic acid solution to very thin foils. Best results were found by polishing first between two narrowly spaced flat cathodes with the specimen edges coated with acid-resisting paint, followed by polishing between two pointed electrodes until a hole appeared in the center as described by Bollmann.6 It was found that a thin transparent film always formed along the thin edges of the polished specimen. This film was then removed by rinsing the specimen very briefly in a solution of alcohol with a few drops of HF or HCl. RESULTS AND DISCUSSION 1) The Deformed Crystal. From the electron-diffraction patterns taken at various areas of an as-rolled specimen, the texture components as deduced - from ordinary pole-figure analysis were confirmed. Over most of the areas where orientation was examined, a (111) pattern with a [112] direction parallel to the rolling direction was obtained. This corresponds to the main deformation texture of the (111) [112] type. In a few areas the diffraction pattern was (100) [Oil], corresponding to the minor-texture component derived from the Neumann bands. The (110) [001] orientation, which corresponds to the very weak intensity area in the pole figure, was found infrequently. A typical example of the deformed matrix having the (111) type main texture is shown in Fig. 1, where (a) is the microstructure and (b) is the diffraction pattern taken from that area. It was also frequently observed that in other areas more or less continuous rings of weaker intensity were superimposed on the simple (111) diffraction pattern, suggesting the presence of a wide range of additional orientations. Other evidence indicated that the recrystallization characteristics are different in these two different types of areas. The hot-stage observations which provide this evidence will be discussed in another paper. AS shown in Fig. l(a), numerous dislocation-free areas of very small size are embedded in the "clouds" of high-dislocation density. This indicates that the deformation of a single crystal, even after a rolling reduction of 70 pct, is far from uniform on a micro-

Jan 1, 1962

By W. C. Browning

The influence of the hydroxyl factor is more damaging to formations penetrated and causes greater consumption of drilling mud additives than previously realized. This hydroxyl effect on clays is essentially independent of the cations present in the drilling fluid and thus differs from the base exchange reactions that have preoccupied mud chemistry with sodium and calcium bentonite concepts for nearly two decades. The new organic polyelectrolyte-con-ditioned muds haw made it possible to use materials other than sodium hydroxide to maintain the alkalinity of such muds. The properties of silicates, as indicated by their dissociation characteristics and buffering action, are such that they can control he pH and alkalinity of drilling muds at the desired level and, at the same time, minimize undesirable hydroxyl effects associated with sodium hydroxide. This use of silicate compounds is different and distinct from prior applications of silicates as deflocculants or shale preservers. Laboratory and field data presented in this report show that silicate compositions can be utilized to adjust the alkalinity of drilling muds and, at the same time, minimize hydmxyl-promoted clay cleavage. INTRODUCTION Studies for improving the efficiency of rotary drilling techniques must consider the chemistry of drilling fluids and of the formations being penetrated. The chemical aspects of drilling must be studied in conjunction with and in relation to the mechanical factors if, for example, penetration rates are to be optimized. Drilling fluid technology has been largely influenced by chemical reactions of the montmorillonite (bentonite) clay minerals. Most of the literature of mud chemistry concerns the properties of bentonite. Clays of the kaolin or illite type, which are nonswelling, are not generally regarded as sources of drilling mud problems. If these nonswelling shale clays are considered, they are commonly regarded as inert solids. Particularly noteworthy is the fact that the relation of surface and colloid chemistry to massive shale bodies has received only scant attention from drilling technologists. Clay studies reported in the drilling mud literature have dealt, for the most part, with the properties of clays in a finely divided state, and often in very dilute suspensions. Yet frequently during drilling, shale problems not related to the rheology of clay suspensions develop in massive non-bentonitic shale sections of zero or near zero permeability. This paper is concerned with surface chemical reactions that can influence the behavior of these non-bentonite clay masses in such a manner as to adversely affect drilling operations. Browning and Perricone1,2 have pointed out that some of the most troublesome shales to drill, such as the Atoka, contain no montmorillonites. They also pointed out that mud problems can frequently be mitigated by reduction of clay cleavage achieved by using drilling fluids with a minimum of available hydroxyl ions. If pronounced clay cleavage occurs during drilling, the borehole may soften, increasing the possibility of sloughing. In addition, the resulting increased incorporation of high-surface-area clay solids into the mud system can reduce penetration rates and necessitate greater chemical treatment. This increase of shale, of colloidal or near-colloidal dimensions, into the drilling mud is due to clay aggregate cleavage and not to base exchange or swelling reactions, such as occur with bentonites. Searle and Grimshaw3 point out the difference between cleavage or slaking reactions of nonswelling clays (such as illite and kaolinite) and the swelling of bentonite. They further state that the speed of slaking is increased in alkaline water. Eitel1 cites Salmang and Becker, who recognized that clay surface reactions impart plasticity and workability to clay masses. Their results clearly show that all liquids which contain hydroxyl groups in their molecules favor the workability of clays. The ancient technique of aging clays in the moist condition to increase their "workability" is evidence that these clay cleavage phenomena are of considerable importance. The same hydration cleavage that occurs during the aging of nonswelling clays for ceramic use also acts to break up cuttings and soften the borehole during drilling operations. The mechanism of cleavage of the crystalline aggregates of illitic, kaolinitic and other nonswelling clays; and the chemical means of controlling this cleavage are therefore of considerable significance to the drilling mud chemistry. Inasmuch as there is little reference in the drilling mud literature to the cleavage reactions of nonswelling clays, the structure of these clays and certain properties that relate to the mechanism of clay cleavage will be reviewed briefly. STRUCTURE OF NONSWELLING CLAYS Clays such as kaolinite, illite and montmorillonite are compmed of alternate layers of (1) silicon-oxygen tetra-

Jan 1, 1965

Jan 1, 1927

By W. M. Peirce, E. A. Anderson

A FEW metals have been known since the dawn of history. Many have been prepared in quantity only within the present century. Zinc falls into an intermediate category, although there is some evidence of its existence in elemental form in Greece as early as the third or fourth century B.C. Nevertheless, the first important use of zinc antedates the earliest records of civilization. This first use was in the alloy, brass, which is roughly one third zinc. This continues to the present time as one of the major uses of the metal. The first production of brass, in light of present knowledge, was perhaps one of the 'most romantic and fortuitous of technical discoveries. Copper, the major constituent of brass, had been given to man by Nature in the native state; that is, as lumps of fairly pure copper. The art of melting and working it had been learned. But zinc does not occur as the metal in Nature and even if some early metallurgist happened to heat zinc ore with a reducing agent, the reduced metallic zinc passed off as vapor and was lost. Doubtless some early coppersmith, melting copper in accidental contact with zinc ore, reduced the zinc, and the vapor was absorbed by the molten copper. Its color, hardness, and other properties were thus wonder- fully changed. And so the earliest metallic form of zinc, as nearly as we can deduce, existed in the alloy brass. Probably knowledge of the kind of rock with which to heat copper to change it to brass, the best

Jan 1, 1953

By A. Blake Caldwell

Northwest frontier is here defined as Alaska, the Yukon, the Northwest Territories and northern British Columbia. The mineral potential of this area is great and will unfold in the decade ahead but now the largest single producer is the Pine Point lead-zinc mine in the NWT about 1200 km north of Edmonton, Alta., close to the south shore of Great Slave Lake. The mill, initially designed for 4540 mtpd, was expanded to 7250 mtpd in 1969. This operation is described in detail in Mining and Concentrating of Lead and Zinc, Vol.1, Chapt. 17, SME/AIME in the article by W. H. R. Gibney.

Jan 1, 1971

By B. H. Bergstrom, Will Mitchell, T. G. Kirkland, C. L. Sollenberger

SEVERAL constructive and fundamental studies have been made in the analysis of data obtained from experiments carried on with batch ball and rod mills. The operating characteristics of ball milling in small continuous circuits have also been appraised. It is from these analyses that some of the theories of comminution have been developed. Relatively few studies of continuous rod milling have added significantly to the fundamental concepts, because seldom have they yielded sufficiently consistent results. Perhaps they have been too limited in their scope. Careful control of the variables in batch grinding is simple compared with that encountered in a continuous operation. This factor alone has discouraged many investigators. Occasionally results of systematic changes made in industrial rod mill circuits have been published, but usually the data are sketchy and are restricted because -of the unwieldiness of the equipment used. The work, in general, has not been comprehensive; nevertheless it has provided empirical relationships that have bridged the gap between postulate and practice so that by proper manipulation of formulae, a mill designer can anticipate mill size and power requirements.1-3 Although operating variables of a small continuous mill are not so easy to control as with the batch mill, with present day devices, and with careful experimental work, consistent results can be obtained.

Jan 10, 1954

By John F. Elliott, John R. Rawling

The rate of reduction of silica to silicon by carbon at 1550° to 1700°C in iron blast-furnace type slag-metal systems has been investigated. In the tower portion of the temperature range oxygen transport in the metal boundary layer at the slag-tal interface is probably rate limiting. A second step, which apparently involves a chemical process in the slag at the slag-metal interface, appears to be rate limiting when the oxygen-transport limitation is avoided. Above 1650°C rate control of the reduction by carbon probably is mixed between the two steps. INVESTIGATIONS1.2 into the equilibrium distribution of silicon between graphite-saturated slags and metals typical of iron blast-furnace practice show that, under the experimental conditions specified, the reduction of silica to silicon is relatively slow compared with the rates of other slag-metal reactions under similar conditions. For this reason, the reduction of silica in blast-furnace slag-metal systems was considered to be an interesting subject for further study. Investigations of the kinetics of the reaction3-5 suggest that several possible steps may be rate controlling, and that the rate-controlling step depends not only on the physical state of the systems but also on the configuration of the apparatus. The main objects of the investigation reported here were to sug- gest plausible reaction paths for the reduction of silica under the experimental conditions chosen and to determine the step or steps which control the rate of reduction of silica. EXPERIMENTAL Two types of experiments involving the reduction of silica from the slag were carried out. In the first, the only reducing agent present was carbon (graphite), for which the over-all reaction is (SiO2) +2C(gr) —Si + 2Co(g) [l] The second type was a graphite-saturated ferro-silicon-iron concentration cell. In it silica in the slag could be reduced either by carbon according to Eq. [I], or by a reaction of electrochemical nature in which silicon was oxidized at the ferrosilicon-slag interface and silica was reduced at the slag-iron interface without the formation of CO. The two types of experiment are described below. Reduction of Silica with Carbon as the Only Available Reducing Agent. The reduction of silica was accomplished by allowing a liquid lime-alumina-silica slag and graphite-saturated iron to react in an induction-heated graphite crucible. The crucible was 2.25 in. diameter and 5 in. deep; it was fitted with a graphite stirrer which penetrated through the slag and into the metal, Fig. 1. The slag and metal charges weighed 350 g each. Pure carbon monoxide at a pressure of 1 atm was maintained above the melt by passing the purified gas through the crucible at a rate of 0.5 liter per min. The gas did not stir either the slag or metal. Temperature measurements were made by sighting an optical pyrometer down the hollow stirrer rod into a 1/4-in. hole drilled in the stirrer blade. The crucible temperature was maintained within *15"C of the required value by manual control of the power supply to the

Jan 1, 1965

By C. W. Drury, E. J. Hall

The iron-nail method of assaying has been used for a number of years, but has not met with the approval of all assayers. The method possesses advantages which may be given as follows: (1) no preliminary treatment is required; (2) a lead button of proper size can be obtained; (3) it is economical. On the other hand, it has its disadvantages, which may be summed up as follows: (1) it is not applicable to ores containing large amounts of impurities other than sulphur, as practically all the base metals will contaminate the lead button ; (2) the slag is unsatisfactory in the larger number of fusions; (3) the method was known to give low silver results under certain conditions and the gold results were questionable. It was with the idea of determining the extent of this latter disadvantage that the following investigation was undertaken. It is well known that the fusion obtained in the lead assay is far more satisfactory than that in the " nails method" for gold and silver. The principal difference in the charges as a class is the presence of considerable reducing agent in the lead charge, and a limited oxidizing action in the nails charge, dud to PbO. The possibility of improving the nails fusion by simulating the lead charge was the reason for using argol in some tests, even though there were reasons for expecting this would have an objectionable effect on the results. Preparation of the Gold-Bearing Material. The materials containing gold and silver used in the following experiments were prepared rather than selected, in order to have a definite working product excluding undesirable elements. A high-

Jan 1, 1914

By E. C. Barfield, D. G. McCarty

Two-dimensional analyses offer considerable promise in providing the basic information required to effect more precise control of petroleum reservoir performance. This paper describes a method for conducting some engineering analyses of this type using a high-qreed digital computer. The general approach is to (I) develop a representative numerical model of the reservoir and (2) employ a suitable numerical technique to solve the basic equation of flow and to develop the required engineering information for the particular case represented by the model. This technique has been used to calculate pattern performance in connection with several field projects involving water injection into oil reservoirs. This type of analysis involves sequentially (I) calculating the pres-' sure distribution in the reservoir and (2) tracking the progress of the interface between the displaced and displacing fluids in a step-wise manner to provide a depletion history of the operation. The particular analysis presented in this discussion is subject to the restriction that the mobility of the displaced and displacing fluids be equal and assumes that the fluids are incompressible and that gravity and capillary pressure do not affect the shape of the flood pattern. Complete two-dimensional .flexibility is maintained with regard to definition of reservoir rock and fluid characteristics, placement of physical restrains and boundary conditions, investigation of flow characteristics in the reservoir, and movement of the displaced and displacing fluid interface. The results of these studies indicate that the highspeed digital computer is well suited for conducting reservoir performance studies in two-space dimensions and that dependable numerical techniques are available for making such analyses. INTRODUCTION One of the problems facing petroleum engineers is that of providing more precise engineering control over reservoir operations at all stages during the depletion cycle. The most direct approach to this problem is to simulate the reservoir with some type of physical or mathematical model and use the information developed from the behavior of the prototype to predict the performance of the actual reservoir. This principle is, of course, not new, and a variety of simulation techniques have been developed to provide information on the behavior of oil and gas reservoirs. One straightforward refinement of present reservoir analysis techniques is the progress from one-dimensional reservoir models to those where the reservoir can be represented in two- and three-space dimensions. Multidimensional reservoir analyses are desired in order to show not only what is happening in the reservoir but in addition to show where in the reservoir the various phenomena of interest are occurring. Thus far, two-dimensional analyses have been confined predominantly to potentiometric and electrolytic model studies. However, when large numbers of wells are involved and where large-scale models are required, such problems become very tedious and instrumentation problems become acute." It is possible through use of numerical methods and general purpose digital computers to avoid many of the instrumentation difficulties and to relax some of the restrictions of previous techniques. The purpose of this paper is to discuss some recent experiences with the use of high-speed digital computers for predicting pattern performance in fluid injection operations and to describe the numerical procedures which have been used for making such analyses. THE NUMERICAL MODEL The problem of representing the reservoir with an appropriate numerical model is composed of at least two important considerations. The first requires that an adequate description of the reservoir mechanism be formulated in the form of the basic differential equation describing the process. The second consideration is definition of the physical characteristics of the reservoir. The latter requires that representative basic data be obtained, examined, and interpreted to provide sufficient detailed definition of the pertinent physical properties throughout the system. The Differential Equation One of the basic assumptions made for the purpose of performing the two-dimensional studies being dis-

By N. A. D. Parlee

The diffusion rate of hydrogen in liquid iron has been measured by a gas-liquid metal diffusion cell technique. The diffusion cell was formed by immersing an alumina tube containing hydrogen gas at 1 atm in a bath of stagnant liquid iron. The change in the composition of the melt in the cell was determined by measuring the rate of absorption of the gas in the cell. The appropriate solution to Fick's second law was used to examine the data and calculate diffusivi-ties. The absorption of hydrogen in stagnant pure liquid iron has been found to be diffusion-controlled. The results show that the chemical diffusion coefficient, D, of hydrogen in pure iron in the range of 1547" to 1726°C can be represented by the following Arrhenius relation: D(sq cnz per sec) = 3.2 x X exp(- 3300 i 1800/RT) where the uncertainty in the activation energy corresponds to the YO pct confidence level. Oxygen in the melt (above 0.015 pct 2) increased the apparent rate of absorption of hydrogen. The importance of diffusion data on liquid metals for predicting the rates of certain metallurgical processes has been recognized for a long time. Moreover, these data are much needed to test and develop theory for diffusion in liquid metals. Despite this practical and theoretical interest, however, relatively little reliable information about diffusion in liquid metals is available in the literature. This is particularly true for gas components such as hydrogen, oxygen, and nitrogen in liquid metals, where almost no data on chemical diffusion coefficients are to be found. This is probably due to a multitude of experimental difficulties particularly associated with high-temperature melts. In an effort to fill this gap in information, a research program was undertaken to study the diffusivities and rates of solution of gases in liquid metals. This paper presents the results of a study of the diffusion of hydrogen in liquid iron. EXPERIMENTAL METHOD Two methods for the study of the kinetics of dissolution of gases in liquid metals are being employed in this laboratory. Both involve the measurement of the volume of gas absorbed by the melt as a function of time and as such both avoid the uncertainties involved in chemical analyses of quenched samples for relatively small amounts of gas. In the first method, the gas dissolves in an inductively stirred melt and, in the absence of a slow surface reaction, the results are often interpreted in terms of mass transport across a liquid "boundary layer" between the homogeneous gas phase and well-stirred part of the melt. Other interpretations of the results of such experiments have also been described in the literature.1'5 In the second method a gas-liquid metal diffusion cell is used.' The gas dissolves in a cylindrical column of stagnant liquid metal and, in the absence of a slow surface reaction, the results are interpreted in terms of a non-steady-state diffusion solution to Fick's second law. The weakness of the first method is that while it gives information on the mechanism of absorption by stirred melts it yields an overall rate constant which even in the simplest cases depends on the nature and the thickness of the "mass transport layer" or "boundary layer". It yields no values of diffusion coefficients. The second method was used in this research because in many cases it is possible to determine the diffusion coefficient of the gas component in the liquid metal. In this research it has been utilized to measure diffusion coefficients of hydrogen in liquid iron. The apparatus used was essentially the same as that described by Mizikar, Grace, and par lee but certain modifications have been introduced to meet the elevated temperatures and special conditions of this research. Fig. 1 is a schematic drawing of the apparatus and Table I gives the identification of various parts in this figure. The diffusion cell, shown in detail in Fig. 2, was formed by immersing an impervious alumina tube (hereafter called absorption tube) in a bath of pure liquid iron contained in an alumina crucible. Two types of tubes were used, Morganite triangle RR and McDanel AP35. The crucible was contained in a vertical impervious alumina combustion tube (32 mm ID by 914 mm long) which was closed at both ends by water-cooled brass heads employing O-ring compression seals, Fig. 1. A protection tube enclosing a Pt, 5 pct Rh-Pt, 20 pct Rh thermocouple was introduced through the lower end of the combustion tube

Jan 1, 1968

US 4,152,143-Continuous precipitation of cement copper from an aqueous ore leach solution mixed with pieces of iron as the precipitant Copper depositing on the pieces of iron is loosened and removed therefrom by means of constant but regulated oscillating movement of the pieces of iron in a horizontal elongated chamber, and the loosened copper is separated and collected from the mixture E Kausel and R Nissen, assigned to Klockner-Humboldt-Deutz A G May 1, 1979 8 pp (75-100) Filed 1-12-78 (868,981) (Drawings below) [ ] US 4,156,711-Removal of metal impurities from an acidic zinc or cadmium solution prior to electrolysis. Impurities such as manganese, cobalt, nickel, and thallium are selectively precipitated by contacting the solution with persulfuric acid or an ammonium or alkali metal salt thereof while maintaining a pH value of from 1 5 to 4 5 This patent is a continuation-in-

Jan 1, 1980