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By R. L. Dalton, L. A. Rapoport, C. W. Carpenter

Procedures have been developed to study the performance characteristics of unconfined pilot water floods using scaled laboratory models. The effects of operating conditions on pilot performance for variozrs well patterns have been investigated. The limitations of the laboratory model studies are outlined. Relationships between the oil recoveries of pilots and large-scale floods have been established. The applications of model studies to the prediction of large-scale waterflood performance and pilot flood design are discussed. INTRODUCTION Pilot water floods are undertaken to evaluate operational procedures and to gain advance information about the performance of an extensive water flood. In general, however, the performance of a pilot flood is not directly indicative of what can be expected from a large-scale pattern water flood. This difference stems from the fact that the over-all flow configurations are not the same for the two systems. A water flood normally consists of an array of identical well patterns. In such an array, the perimeters of the well patterns are axes of symmetry and act as impermeable boundaries. Thus, an extensive, pattern water flood can be visualized as a repetition of "confined" floods. In contrast, a pilot water flood involving only one or a few well patterns is "unconfined". Here the well patterns are not balanced by other flood units; hence, the perimeter of the pilot area does not act as an effective boundary. Accordingly, only a portion of the fluids injected (and also of those originally contained within the pilot area) is captured by the producers of the pilot. The rest escapes into the surrounding reservoir. This usually causes the amounts of oil and water produced in the pilot to be different from those recovered by a producer in an extensive water flood. Moreover, the recovery observed in the pilot can be expected to be greatly influenced by operating conditions, i.e., by the bottom-hole pressures at the injection and producing wells. The above considerations show that full utilization of pilot test results and reliable prediction of large- scale water floods require a knowledge of the relationship between the recovery performance of confined and unconfined well patterns. To date, only limited basic information is available on the behavior of pilot water floods. Craig, et al,' have investigated the effects of initial gas saturation, oil-to-water mobility ratio, and well damage on the oil recovered from a single, "normal" five-spot pilot pattern (Fig. 1). Rosenbaum and Matthews2 studied the effect of initial gas saturation and mobility ratio on the ratio of production rate to injection rate for various groupings of five-spot patterns. Paulse113 investigated the effect of mobility ratio and distance from the pilot to the edge of the reservoir on the areal sweep in a single "inverted" five-spot (Fig. 1). However, none of these studies considered the effect of operating conditions on pilot flood behavior. Moreover, hardly any of the work to date dealt explicitly with the oil-recovery performance of the pilot floods. The purpose of this paper is to introduce the concept of interrelation between pilot flood behavior and operating conditions, to illustrate this interrelation by means of experimental data and to compare the recovery performances of dif-

For the year ending February, 1919 PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS, NEW YORK, N. Y. PHILIP N. MOORE ST -Louis, Mo FIRST VICE-PRESIDENT C. W. GOODALE, BUTTE, MONT.. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y.

Jan 6, 1918

The Library of the above-named Societies is open frond 9 A.M. to 10 P.M., except on holidays. It contains about 70,000 volumes and 90,000 pamphlets, including sets of technical periodicals and the publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in localities isolated front sources of information. To these the Library, through Its Library Service Bureau, can render valuable service through correspondence; letters requesting information will receive especial attention. The Library is prepared to furnish references and photographic copies of articles on mining and metallurgical subjects; to determine the existence of mining neaps, and to furnish general information on the geology and mineral resources of all countries. All communications should he made as definite as possible so that the information received may be what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be, sent more promptly and in more usable shape.

Jan 1, 1917

By Claudia Gasparrini

Silver occurs in nature in major, minor and variable amounts in a very large variety of minerals and in several mineral species in the same ore. Because these minerals may respond differently to the same flotation or leaching agents, detailed studies to establish the correct silver mineralogy become essential for optimum recoveries in those situations where the silver is treated as a primary product. On the other hand, fine grain sizes, which often affect gold recoveries, are not generally as critical in silver metallurgy, due to the lower market price which allows for more of the element to remain In the tailings before incurring in economical losses.

Jan 1, 1984

By G. W. Leney

Iron ores occur in such a wide variety of forms that nearly every kind of prospecting, geological knowledge, and geophysical technique has some application in the search for them. The type of orebody that is considered desirable depends on political and economic considerations, on transportation and markets, on the characteristics of the orebody, on the metallurgy of the ore, and on its comparison with other available ores. In North America, materials that can be efficiently processed into high grade concentrates and pellets are now the object of most exploration work. These are usually shallow, relatively unoxidized, metamorphosed iron formations that are particularly suitable for geophysical methods of exploration. Magnetic surveys are used for the direct discovery of new orebodies, for mapping stratigraphy and structure, and at times to locate oxidized zones in magnetic iron formation. Gravity mapping provides supplementary information, indicates gross tonnages, is useful in regional studies, and can discover non-magnetic orebodies. Electrical methods have not been fully exploited but self-potential, resistivity, applied potential, electromagnetic and perhaps induced polarization surveys all have restricted but highly useful applications. The use of all geophysical techniques promises to increase as the number of exposed easily discoverable orebodies decreases. A high consumption of steel, and consequently of iron ore is the chief characteristic of an industrial society and this consumption has been increasing at an average rate of about 35% every ten years for the past century. To supply this demand, iron ores and iron bearing materials in a wide variety of forms have been exploited on every inhabited continent and in nearly every country. Nearly every kind of prospecting, geological knowledge and geophysical technique has some application in the search for them. The type of orebody that is con-

Jan 1, 1964

By B. K. Larkin, H. R. Bailey

A model Of heat flow in an underground combustion process is studied. This model includes convection effects and thus is more general than previous studies which considered conduction as the only mechanistn for heat transfer. Both linear (tube run) and radial (field application) geometries are considered. The effects of ignition heaters, vertical losses and finite source width are considered for the linear case. The results are in the form of equations and are presented in graphical form for a number of cases. Convection effects increase frontal temperatures about 25 per cent over those computed for conductive transfer for typical field operating conditions. This increase in temperature is a result of heat being transported toward the front by the injection gas. Even greater temperature increases are realized as the per cent oxygen in the injection gas decreases. It is well known that compression costs are of considerable importance in estimating the economic feasibility of underground combustion. By assuming an ignition temperature for the combustion fuel, predictions of limiting conditions on fuel density and injection rate necessary to sustain the combustion zone are made. For typical field conditions, at least 0.75 lb/cu ft of fuel are needed with air as the injection gas. If the injection gas is 10 per cent oxygen and 90 per cent nitrogen, this figure is 0.69 lb/cu ft. INTRODUCTION The possibility of increasing oil recovery by underground combustion has been considered for many years. Recent field tests indicate that the underground combustion process is technically feasible. The economic feasibility depends to a large extent on the amount of air which must be injected to sustain combustion. Prediction of the success of employing underground combustion in a particular reservoir must be based on existing field tests, laboratory tube runs"' and solutions of mathematical or analog models. Vogel and Krueger5 devised an electrical analog of the heat transfer problem in an underground combus-ion process. They considered the problem of heat conduction from a cylindrical source with increasing radius assuming no vertical losses. Bailey and Larkin and Ramey solved the corresponding problem including vertical losses by considering a mathematical model of the conduction process. Ref. 9, 10 and 11 also present information related to the subject study. The present paper generalizes these results to include both conduction and convection mechanisms for heat flow. A model of the conduction-convection process is described. The partial differential equations governing this model are written and solved for a number of cases of interest. The formulas are evaluated and the results are presented graphically. A CONDUCTION-CONVECTION MODEL Description of the Model A number of models are employed in this paper, each of which approximate a particular physical situation depending on the geometry, i.e., linear or radial flow, the type of vertical heat losses, the nature of the source, etc. The geometry for both the linear and radial case is shown in Fig. 1. A particular linear model is described in this section, and variations from this model are described in later sections of the paper. Consider a homogeneous, semi-infinite porous prism with lateral sides insulated as shown in Fig. 1. The left end, x = 0, is heated for a time t, with a plane heater supplying a constant heat flux and during this time; gas (nitrogen) is passed through the pores of the prism at a constant mass flux. At time t, the heater is turned off and air is injected in place of the nitrogen. This causes combustion to take place, and a uniform source of width 1 is formed which moves at a constant velocity v, to the right. The frontal velocity v, is related to the gas velocity v,, through stoichiometric considerations

The Library of the above-named Societies is open from 9 A. M. to 10 P. M. except on holidays. It contains about 70,000 volumes and 90,000 pamphlets, including sets of technical periodicals and publications of scientific and technical societies. Members of the Institute, with few exceptions are forced to spend a portion of their time in localities isolated from sources of information. To these the Library; through its Library Service Bureau, can render valuable service through correspondence; letters requesting information will receive especial attention: The Library is prepared, to furnish references and photographic copies of articles on mining and metallurgical subjects; to determine the existence of mining maps, and to furnish general Information on the geology and mineral resources of-all countries. All communications should be made as definite as possible so that the information received may be what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape. HARRISON W. CRAVER, Director.

Jan 4, 1919

UP TO and including 1931, the twelve mines that were treated in THE PORPHYRY COPPERS had produced 17.4 billion pounds of copper worth $2,820,000,000. With a little help from six others (three of them did not start output until 1954) that record had been increased at the end of 1955 to 60.5 billion pounds worth $10,440,000,000. Today, ten billion dollars is not as impressive as it once was; but it still represents a lot of value. It must be remembered that this is newly-created wealth, produced entirely from material considered worthless when the Porphyry era started about fifty years ago. At that time "rock" that contained less than forty pounds of copper per ton was regarded by competent mining engineers as value- less. It was not "ore" in the economic sense. Today, ore is being successfully exploited that contains less than twelve pounds of copper per ton. Also, in Peru, a typical Porphyry operation is being launched by a partnership of four United States mining companies that will involve an initial capital investment of $200,000,000 for mine development, plant construction, and the provision of related facilities. Of this project more will be said at the end of the chapter. The point I want to make now is twofold: (1) that phenomenal progress has been made in Porphyry engineering and technology; and (2) that exploitation of an important Porphyry copper deposit has become an industrial enterprise of truly great magnitude. Much had been accomplished by 1931; but that progress has been dwarfed by the achievements of the past 25 years- a fact that, in the nature of things, is as it should be.

Jan 1, 1957

By John H. Hollomon

THE interpretation of notched-bar impact results has been a matter of controversy since the introduction of more or less standard tests by Fremont,1 Charpy2 and others at the turn of the century. Many investigators3-l1 have contributed to the understanding of the significance of such tests. Several symposiums12,13 have been held with the express purpose of discussing the significance and interpretation of the impact tests. It is not the purpose of this paper to review all these contributions to the development of the knowledge on this subject, but rather to present an interpretation of notched-bar impact tests that appears to be in agreement with the available published data. Fundamentally, the interpretation discussed in this DaDer of the brittle failure of some steels in notched-bar impact test is similar to the qualitative analysis presented by Ludwik3 in the 1920's. Essentially, Ludwik stated that the function of the notch was to increase the tensile stress necessary for yielding, and that brittle failure occurred when the stress necessary for yielding exceeded the normal stress required for fracture (with no plastic de- formation). Ludwik, however, had no means of measuring this normal stress necessary for failure of a plastically* undeformed metal, therefore he could not extend his interpretation beyond the qualitative stage. Kuntze14 and recently MC- Adam15 attempted to determine the effect of deformation on the stress necessary for fracture by testing, in tension, specimens notched to various depths and angles. Because of the uncertainties in Kuntze's (and RlcAdam's) analysis of the stresses (which have been pointed out by SachsI6) and the inherent nonuniformity in the stress distribution in notched bars, the results of such investigations are difficult to interpret. A more direct method of measuring the effect of deformation on the fracture stress was suggested in previous papers17-l8 and has been utilized in the present investigation. The present paper concerns itself primarily with the behavior of notched impact specimens. The effects of strain rate, temperature, and stress distribution, which are discussed with reference to the impact specimen, apply just as well to the behavior of metal at the bases of notches in any engineering structure. All that is necessary is to determine the stress distribution in the structure at the base of the notches.

Jan 1, 1944

By T. E. Leontis, R. S. Busk

WORK was initiated several years ago at The Dow Chemical Company to determine the applicability of powder metallurgy processes to magnesium and its alloys. Although it was found possible to apply the normal techniques of compacting and sintering, it was discovered early that the technique of extrusion offered special promise. This technique and the alloys produced were therefore studied extensively, and the present paper is a partial report of those studies. It is expected that a second paper will discuss more extensively some of the alloy systems simply mentioned here. Although the literature on powder metallurgy is very extensive, there are only two articles dealing with magnesium13,14 and there is no reference to the direct extrusion of the powder of any metal without the preliminary step of compacting. Furthermore, no mention has been made of the possibility of designing alloys by the technique of powder extrusion, particularly alloys that cannot be made in any other way. Sauerwaldl3 discusses the extrusion of magnesium and aluminum powder to produce alloys containing nonequilibrium phases, but again he emphasizes the importance of pre-compacting before extrusion. There seems to be general agreement that some form of hot-pressing is essential to obtain in a compact the full theoretical density of the metal used.'-" The nearest approach to the technique of direct powder extrusion is that of extrusion of pre-sintered compacts,'-" for which the best review through 1944 is that by Kieffer and Hotop.11 Ensign* discussed a specialized technique of "extruding" already compacted and sintered gears for the purpose of sizing. Sauerwa1d13 discussed the compacting and extrusion of magnesium and magnesium-aluminum alloy band-saw chips. The properties of the extruded compacts were found to be comparable with those of extrusions prepared from solid billets. He also extruded a compacted mixture of magnesium and aluminum powder and found the properties to be somewhat different from those obtained on an extrusion made from a cast billet of the same composition. The second reference dealing specifically with the powder metallurgy of magnesium is Stern's patent," in which is described the extrusion of scrap chips and turnings following a hot-pressing and sintering step. Considerable emphasis in most of these articles is placed on the necessity of atmospheric protection to minimize the danger of oxidation. Experimental Procedure The first experiments were made with the small extrusion press shown in fig. 1. With this press, billets of about 1/2 in. diam are used to produce wire

Jan 1, 1951

By L. F. Tedsen, A. E. Flanigan, J. E. Dorn

SINCE aluminum-alloy sheet may be used occasionally at moderately elevated temperatures, the effects of temperature en the mechanical properties are of interest. Recently the short-time tensile properties of several high-strength materials have been studied at temperatures up to 375°F. This paper deals with stress-rupture and [ ] creep properties at the same temperatures. The work was done at the University of California as a portion of the project NRC-548. It was financed by the War Production Board and was supervised by the Office of Production Research and Development. This paper has been released for publication by the latter agency. The following materials were studied, all in the form of 0.040-in. sheet: Alclad 24S-T Alclad 24S-T8I Alclad 24S-T86 Alclad 75S-T R301-T (clad) [ ] Specimens were loaded in tension in the cross-grain direction. Testing temperatures included 94°F., 211°F., 300°F., and 375°F. Stress levels were selected to cause rupture in times ranging from several minutes to boo hr. In each test the following data were obtained: (I) fracture time, (2) elongation at fracture, (3) the complete strain-versus-time curve (creep curve), (4) creep rate (defined in a later section). MATERIALS Materials for specimens were obtained from the manufacturers' commercial

Jan 1, 1946

By M. D. Everell

A study has been made of the relationships between grinding selection functions and physical properties of rocks, particularly the failure loads of irregular particles and the compressive and tensile strengths of large regular specimens. The rocks used were limestones of various structures and impurity contents, a carbonatite, and a high-purity crystallized calcite. The selection functions were obtained from carefully performed grinding experiments on selected narrow size ranges in various grinding machines-a laboratory batch ball mill, a Hard grove grindability machine, and a mill of the type suggested by Yang, Mempel, and Fuerstenau. The specific rates of breakage during milling and the failure loads of irregular specimens correlated well for the rocks studied. The testing of irregular particles is suggested as a means of predicting the behavior of commercial mills.

Jan 1, 1973

By Ralph H. Sweetser

IN the recent world-wide deflation of commodity prices the coal industry, including both anthracite and bituminous coal, had reached a level where the actual delivered market prices received by the operators were usually less than the cost of production. Many steel companies and public utilities, operating their own "captive" mines, could have bought coal during the past three years for less money than the true cost of coal produced at their own properties. Competition within the coal industry itself was cruel to the point of profitless operation, and the competition of other forms of fuel was bearing heavily on the coal producers. They were thus forced into methods of production and utilization that they had hitherto ignored; there had been almost complete absence of any appreciation (by the bituminous operators especially) of the necessity of real research work in finding better methods of preparing coal for specific uses, and in finding new and profitable uses for different kinds and grades of coal.

Jan 1, 1933

By D. A. Keyes

International Minerals & Chemical Corp. (Canada) Ltd. is presently exploiting by underground mining a potash-rich zone in the middle Devonian Prairie Evaporite formation near Esterhazy, Saskatchewan. Of the three main potash-bearing horizons denoted by Goudie as zones 1, 2 and 3 only the 1ower. two are present at Esterhazy and mining is confined to the lower or zone 1 horizon. The area in which the evaporites were deposited, although flanked on the west by a zone of geosynclinal deposition and tectonic activity, has been subjected to only very gentle epeirogenic activity. The sylvinite ore is coarsely crystalline and occurs in well-defined beds. The halite, sylvite and insoluble content of the ore bears a direct relationship to the lithological units, but the carnallite cuts across the beds. Local concentrations of salt produce blank spots in the ore horizon. Some of these appear to be salt-filled, post-ore channels and cracks while others have been formed by brines emanating upward from below the ore. INTRODUCTION International Minerals & Chemical Corporation (Canada) Ltd. is operating an underground potash mine near the town of Esterhazy in eastern Saskatchewan. The deposit was discovered by IMC in 1955. Subsequent drilling outlined extensive high-grade reserves, and in 1957 shaft sinking and plant construction began. Production from Yarbo No. 1 Shaft commenced in September, 1962 and quickly reached the initial capacity of one million tons of muriate product per year. Production is currently being expanded to 1.6 million tpy. The single mining level is 3140 ft below the surface at No. 1 Shaft. GENERAL GEOLOGY The Esterhazy district lies within the Interior Plains region of Canada and on the northeast rim of the Williston Basin (Fig. 1). Average dip of the rock formations in this area is about 40 ft per mile to the southwest. The potash ore occurs in the Prairie Evaporite formation of the Middle-Devonian Elk Point Group. The Prairie Evaporites are overlain by 3000 ft of Paleozoic shales and limestones and by Jurassic and Cretaceous sandstones and shales (Fig. 2).

Jan 1, 1967

By Paul Rhedey

Various commercial pelroleum cokes were heat-1,reated at temperatures between 500° and 1500°C, in a nitrogen atmosphere, in laboratovy induction furnaces. The rate of tenlperature rise was varied betzveen 10" and 300°C per min, or the green cokes were flash-calcined, orv a combination of heating rates was used. Changes in the rate of heating had only negligible effects on the degree of' calcination as characterized by mean crystallite thickness and the chemical properties of the calcined coke. The physical structure of the cake was however significantly affected when rate of heating during calcination exceeded 50°C per min over the temperature range of 600° to 900°C. Surface-accessible porosily increased with the .rate of temperature rise, and this was accompanied by a change in pore size distribution. Source and properties of the green coke also had an influence on the structure of the calcined coke. The evidence presented suggests a similar mechanism of porosity development in petroleuiiz coke during calcination in industvial equiplnenl, such as rotary kilns. An increase in surface accessible povosity incveased the pitch binder requirement when the coke was used as aggregate in Soderberg paste. A correlation was established between calcined coke porosity and paste binder requiremenl. ManY results have been published on the changes of properties of petroleum coke during calcination, such as chemical composition, real density, electrical resistivity, crystallite and pore structure. The correlation of these properties with temperature of calcination and time at maximum temperature has been rather well established in both laboratory and pilot plant experiments. Surprisingly little attention has been given however to the effect of calcination conditions, such as rate of temperature rise or furnace atmosphere, on the chemical and structural properties of the calcined coke. It has been observed that petroleum coke, when calcined in industrial equipment, acquires higher porosity and lower real density than those attainable in laboratory furnaces at apparently identical calcina- tion temperature and soaking time. This paper describes a study of the effect of rate of heating during calcination on calcined coke properties using green petroleum cokes of different volatile matter, hydrogen, and sulfur content. An attempt was made to correlate the changes in coke structure with the flowability of anode paste of the type normally used in aluminum reduction cells. EXPERIMENTAL Petroleum Cokes Used. In the study of release of volatile matter and sulfur during calcination and the effect of rate of heating on calcined coke properties two delayed cokes of different sulfur contents were used. The results of analysis of the green cokes are given in Table I. In the study of the effect of flash calcination thirty-six commercial petroleum cokes from twelve different refineries were used with a range of properties shown in Table 11. Calcination Conditions. Calcination experiments were carried out in a laboratory induction furnace. In each run a 200-g sample of dry green coke sized to 10 by 65 Tyler mesh was calcined in a graphite crucible. The crucible containing the sample was placed in the middle of a stack of eight others filled with metallurgical coke to reduce temperature gradients within the sample. Temperature was measured by two Pt, Pt-10 pct Rh thermocouples and controlled by a Celectray instrument. The two couples generally agreed within 5°C. In the study of volatile matter and sulfur release the samples were heated to temperatures in the range of 500" to 1500°C at a rate of 10°C per min in a nitrogen atmosphere and held at the final temperatures for 30 min. In the study of the effect of heating rate on calcined coke properties the desired rates between 10' and 300°C per min were obtained by manually adjusting the power input. Flash calcination was carried out by dropping 100 g of the green coke into the graphite dish preheated to the calcination temperature. Because of the small heat capacity of the furnace the coke was introduced in 20-g portions at a time. For this purpose a 2-in.-long nipple between two 1-in. gate valves installed on the top flange of the furnace served to provide a gas seal while feeding coke to the furnace. It was estimated that the temperature of the coke reached that of the furnace at a rate of approximately 1000°C per min. Holding time at final temperature was also 30 min. Calcined Coke Proper- Determined. Porosity was determined on 20 by 35 Tyler mesh samples using an Aminco-Winslow mercury pressure porosimeter with an operating range of 1.8 to 3000 psi absolute pressure (100 to 0.05 p pore diameter range).' Apparent density was obtained by the mercury poro-simeter. It represents a particle density of the 20 by

Jan 1, 1968

By P. E. Rider, K. A. Gschneidner, O. D. McMasters

The solid solubilities for thirteen rare-earth metals in gold were determined by using the X-ray parametric method. Solubilities ranged from 0.1 at. pct for lanthanum in gold up to 8.8 at. pct for scandium in gold. The solubilities from lanthanum to gadolinium were very small and essentially constant, but a sharp increase occurred from gadolinium to scandium. The large solubilities for the heavy rare-earth metals were not expected because of the large size and electrochemical differences between rare-earth atoms and the gold atom. Contributions from first- and second-order elasticity theory plus an electronic contribution were found to reasonably account for a more favorable size factor. Electron transfer from the rare-earth metal to the gold Is thought to occur such that the resultant rare-earth and gold electronegativities are favorable for solid-solution formation. It was also found that this mutual adjustment of size and electronegutivity does not occur if the pure-metal size factors are greater than a critical value of 25 pet. The eutectic temperatures for ten systems were determined and these remained fairly constant at approximately 809 "C for the lighter lanthanide metal-gold systems until the Er-Au system was reached, at which Point the eutectic temperature successively increased reaching a maximum of 1040°C in the Sc-Au system. This rise was correlated to the size factor becoming more favorable for solid-solution formation at erbium. The valence state of ytterbium was found to change from two in the pure metal to three when ytterbium is dissolved in the gold matrix. RECENT results1 reported concerning the solubility of holmium in copper, silver, and gold, showed that the solubility of holmium in gold was quite large, 4.0 at. pct, compared with 1.6 in silver and 0.02 in copper. The small solubilities of holmium in silver and copper are quite reasonable in view of the large size difference (22.2 and 38.2 pct, respectively), large electronegativity difference (0.59 for both systems), and possible unfavorable valency factor (assuming one for silver and copper and three for holmium). The large solubility in gold, however, is unexpected because these same factors are also unfavorable for holmium and gold (22.5 pct size difference and 0.69 electronegativity difference), and because the light rare-earth metals, lanthanum, cerium, and praseodymium, have negligible solid solubilities in gold.2 In view of this unexpected behavior, it was felt that a study of the solid solubilities of most of the rare-earth metals in gold would be desirable to better understand the factors involved in the formation of solid solutions. Of the rare-earth metals added to gold in this study, only ytterbium is divalent in the pure metallic state (the other rare-earth metals are all trivalent) and many of its physical properties (such as the metallic radius, electronegativity, and so forth) are much different from those of the normal trivalent rare-earth metals.' The properties of ytterbium are such that one would expect solid-solution formation to be less favorable for ytterbium in gold than for any of the normal trivalent rare-earth metals. But chemically ytterbium is known to possess a stable trivalent state, and it is quite possible that ytterbium may alloy as a trivalent metal under certain conditions rather than as a divalent metal. Because of the dual valency nature and because so little is known about the alloying behavior of ytterbium, the gold-rich ytterbium-gold alloys are of special interest. EXPERIMENTAL PROCEDURE Materials. The gold used in this investigation had a purity of 99.99 pct with respect to nongaseous impurities. In general the rare-earth metals were prepared by reduction of the corresponding fluoride by calcium metal.3 The impurity contents of the metals used in this study are given in Table I. Preparation of Alloys. Two- or 3-g alloy samples were prepared by arc melting. The samples, with the exception of some of the Er-Au alloys, had weight losses of 0.5 pct or less. All alloy concentrations noted in this paper are nominal compositions. After arc melting, the alloys were wrapped in tantalum foil, sealed off in quartz tubing under a partial atmosphere of argon, homogenized for approximately 200 hr at 780°C, and then quenched in cold water. X-Ray Methods. The X-ray parametric method was used in determining the solubility of the rare-earth metals in gold. filings were sealed in small tantalum tubes by welding under a helium atmosphere. The tantalum tubes were then sealed in quartz tubing under a partial argon atmosphere, and annealed for times ranging from 1/2 to 3 hr (the length of time was inversely proportional to the an-

Jan 1, 1965

By P. D. Zemany, G. W. Sear, B. W. Roberts

Vanadium metal is embrittled by hydrogen at a temperature as low as 250°C when held in the presence of manganese metal and water vapor in a rough vacuum. It is established that the property changes are caused by the catalytic decomposition of water vapor at the vanadium surface and the diffusion into and solution in the vanadium of the resultant hydrogen. It is found that manganese is a necessary component of the catalyst. The manganese is transported in the vapor phase by an unknown molecule. A deuterium tracer experiment demonstates the role of water vapor in the embrittle-ment process. VANADIUM metal foils were observed to become embrittled' at a temperature of about 300 °C when held in the presence of manganese metal and a small amount of moist air, This paper describes the investigation to find the embrittling agent and an understanding of the relatively low temperature reactions that are involved. Experimental The vanadium metal foil used was prepared by cold-rolling and pack-rolling 32 mil sheet" in a series of steps down to 1 mil foil. The original observation was confirmed by sealing vanadium foils of 3 x 10 sq cm into individual Pyrex tubes with manganese powder† and a con- trol tube containing only the vanadium foil. These tubes were evacuated to 10 -5 mm Hg without baking and sealed. After heat treatment for 200 hr at 300°C, the control foil showed no change in duetility, whereas the foil contained in the manganese— containing tube was embrittled. The visual appearance of each was unchanged. A series of Pyrex sample tubes, about 2.5 cm diam and 25 cm long, were prepared, each containing a 3 x 10 sq cm piece of foil and 5 g manganese powder at the lower end of the tube. By reducing the time of anneal and the temperature of these samples, it was found that embrittlement could be created at 250°C in a time as short as 1 hr. Since the vanadium metal used here has been drastically cold-worked by rolling, it is assumed that it contains a maximum number of dislocations. To check the possible necessity of dislocations in this low temperature reaction, a vanadium foil sample was annealed in Vycor for 2 hr at 800°C to re crystallize and reduce the dislocation concentration. Metallographic examination showed grains which were not visible before annealing. The embrittlement procedure was carried out at 300°C and 3 hr. Upon checking the foil no embrittlement was observed. Further experiments demonstrated that about 6 hr at 300°C are required to create embrittlement in the foil. This delay in the onset of embrittlement in the vanadium foil suggests but does not prove that dislocation channels play a role in the embrittlement phenomena. If manganese metal is necessary for this low temperature embrittlement, do other elements in the transition metals group yield the same result? To check this qualitatively, a group of elements of similar atomic radii were obtained and sealed as before into Pyrex tubes with a sheet of vanadium foil. These tubes were annealed at 250°C for 6 hr and included (with radii)-2 A1 (1.4A), As (1.25A), Be (1.2A), Co (1.25A), Cr (1.45A), Cu (1.25A), Fe (1.25A), Ga (1.2A), Ge (1.25L%), Mn (1.3A), Ni (1.25A), Si (1.2A), Ti (1.45A), Zn (1.3A), air, H,O, 10 cm Hg of dry hydrogen, and MnO, powder. Upon testing the above sample foils for brittleness, only the manganese-containing tube yielded a brittle foil. Manganese Transport—To eliminate contact of manganese metal powder and vanadium foil, sample tubes were prepared with fritted glass barriers. The embrittlement reaction was still found to occur. Thus, the mode of transfer of manganese is certainly vapor transport. A vanadium foil was embrittled by this mechanism in an evacuated Pyrex tube for 8 hr at 300°C. By means of X-ray fluorescence analysis,' the amount of manganese added to the surface was established at 5 ±2 x 10 -6 g per sq cm. Since the average rate of manganese deposition is known, an effective average pressure of an assumed carrier compound can be computed. ___ P = M/T v2p mkT

Jan 1, 1959

Jan 1, 1919

By George F. Weaton, Eugene P. Pfleider

13.4-1. History. During the past ten years the mining and production of iron ores has been through a revolution. From 1939 through 1948, which included World War II, 561,000,000 tons of iron ore was mined and shipped from Minnesota's Mesabi Range to the blast furnaces of the United States for the production of iron and steel products (20, 28, 29). The iron mining industry, anticipating the exhaustion of this highly productive source of raw material, instigated a worldwide search for new sources of iron ores. This search was highly successful, both as to quantity and quality. Venezuela (38), Canada (17, 28, 42), Peru (19, 23, 50, 52, 54, 56) Chile, (1, 66, 75), Brazil, and Liberia were among the countries where enormous deposits of high quality iron ores were discovered. The exploitation of these deposits took away the monopoly held by the Lake Superior region for so many years and created a highly competitive market for high quality natural iron ores. 13.4-2. Exploration and Development Practices. SPECIFIC TO IRON MIN- ING. American industries are motivated to continue exploration because new ore discoveries often lead to an improved competitive position with respect to raw material supply. Exploration techniques have advanced rapidly in recent years, to a degree that potentially important iron ore reserves, stratigically located, may now be detectable by application of a combination of refined and diversified geophysical exploration methods. Since the days of the dip needle, iron ore people have placed greatest reliance on the magnetometer. Its successive stages of development progressed from the balance and the torsion type to the fluxgate, and then to the "sophisticated" magnetometers-conceived and developed in th field of atomic physics. By far the greatest advancement in magnetometer prospecting was made when the self-orienting fluxgate magnetometer took to the air. This was not a new development, but it was a breakthrough in reconnaissance investi-

Jan 1, 1968

By H. Shaw

Gravitational measurements made by means of the Eotvos torsion balance over any area enable a representation to be obtained of the total gravitational effects over the surface of that area arising from the combination of all sources of gravitational disturbance. The investigation of gravitational anomalies occurring in the upper layers of the earth's crust, in this way, has been attended with considerable success, and, especially in areas in which no undesirable disturbing factors were present, it has been possible to locate geological structures and mineral deposits with remarkable accuracy and also to delineate their confines and to indicate their depth below the surface with a certain amount of precision. Before this can be done successfully, however, it is necessary to determine the gravitational effect arising from all other extraneous anomalies in order that these may be satisfactorily eliminated. Disturbing features giving rise to these gravitational anomalies may be divided into two classes, according to whether they are situated at or below the surface. The former are determined readily by a detailed leveling of the ground surface, and may be satisfactorily eliminated provided the specific gravity of the terrain material is known, but the latter are generally unknown, and can only be ascertained with difficulty. When, therefore, the observations obtained by means of the Eotvos torsion balance have been corrected for all surface irregularities, known as terrain and topographical effects, there remain residual gravitational values which are due entirely to subterranean conditions. The. task of interpreting these results consists in disentangling the various subsurface anomalies, and subsequently in computing and recombining the effects of these various masses in order to verify the interpretation. When the gravitational anomalies are due to large and comparatively simple structures it is a matter of little difficulty to arrive at a satisfactory interpretation of the subterranean conditions, but in more complex areas, where the geological conditions are more complicated and several irregular features exist, the process of disentangling the various constituents of the complex mass arrangement is more difficult and requires the expenditure of considerable time and labor. When the subterranean effects have been obtained, they are subjected to a critical examination, and an effort is made to recognize and

Jan 1, 1932