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By G. L. F. Powell, L. M. Hogan

Samples of silver and Ag-O alloy, 0.12 wl pet, have been undercooled to a maximum of 250°C by melting in a slag of commercial soda-lime glass. Grain refinement occurred in undercooled silver samples whet the degree of undercooling exceeded a critical value which varied from 153° to 175°C, depending on the melting conditions. In under cooled Ag-0 samples, the grain structure was fine and equiaxed at degrees of undercooling larger than 50oC. The grain refinement in both silver and Ag-0 alloy samples was the result of recrystallization during or immediately following freezing. When the oxygen content was increased, the degree of undercooling at which recrys-tallization occurred decreased. INVESTIGATIONS of the grain structure of strongly undercooled melts of nickel and cobalt1-4 have revealed a change in room-temperature grain size as a function of undercooling. At large degrees of undercooling the grain size was fine, but samples undercooled by smaller amounts exhibited a much coarser grain structure. The reported undercooling at which this grain size transition occurred in nickel varied between 140° and 175'C undercooling. Walker1 attributed this grain size change to an enhanced nuclea-tion rate. Cavitation at a melt-solid interface was con sidered to generate a high-pressure wave. This, in turn, produced nucleation in the liquid as a result of an elevated freezing point increasing the undercooling in the melt. A similar grain size transition was observed in undercooled silver between 133° and 153°C undercooling.5 The grain size transition in undercooled silver was found to be dependent on oxygen con tent. More recently, the authors5 showed that a simila transition occurred in an undercooled Cu-O alloy, =0.08 pet, but not in oxygen-free copper undercooled more than 200°C. The transition was attributed to recrystallization of the solidified grains after freezing; the greater the degree of undercooling, the more complete the recrystallization. In view of this effect of oxygen content on grain size transition, additional undercooling experiments were carried out with silver. This paper reports the results of these studies on silver and Ag-O alloys undercooled more than 50°C EXPERIMENTAL 1) Materials. The silver was supplied by Matthey Garrett Pty., Ltd., as fine granulate, silver mini' mum 99.9 pet, and contained the trace impurities shown in Table I. The silver originated from two different refineries resulting in the difference in impurity content shown in Table I. However, the variation in composition had no discernible effect on the undercooling behavior. Samples of the silver were melted in an open-ended, vertical, cylindrical resistance furnace, wound with Kantha] wire, the temperature of which was adjusted by means of a variable transformer, 2) Melting and Undercooling. Bulk samples of silver were undercooled by preoxidation and removal of oxidized impurities in a glass slag, as previously described,5 but special precautions were necessary to allow comparison between oxygen-free silver and a Ag-O alloy. Samples free of oxygen were prepared by first melting weights of granulate varying from 200 to 400 g in clean vitreous silica crucibles in air for approximately 15 min. A sample was frozen and a complete glass cover formed over the top surface by adding granulated glass rod. The sample was then melted and frozen several times until no oxygen bubbles appeared in the glass slag. Subsequent thermal analysis indicated that the oxygen content was negligible. The glass acted as an efficient barrier to absorption of oxygen from the air. Ag-O alloys were prepared by melting silver in silica crucibles with only a partial cover of glass, so that the top surface of the melt was in contact with air. The silver was held molten in air for several hours at 1000° to 1050°C, in the expectation that the oxygen in solution would reach equilibrium with atmospheric oxygen. At T - 1000°C the equilibrium oxygen content was calculated as 0.12 wt pet O, using Sieverts law and Eq, [l], derived by Mizikar et a!.7 from the data of Sieverts and Hagenacker8 for 1 atm of oxygen:

Jan 1, 1970

By M. R. Geer

THE increase in the number of coal-cleaning plants employing dense-medium processes occurring since 1946 is especially interesting when viewed historically. Both sand and magnetite were introduced as material for heavy mediums at about the same time, sand in the Chance process in 1921 and magnetite in the Conklin process in 1922, but from that point on their records diverge. The Chance process enjoyed a steady growth from its inception, whereas no additional magnetite plants were built in the United States for over 20 years. Then, following the close of the World War 11, magnetite was again introduced, this time with marked success. During the following years some 47 plants employing magnetite medium were built.

Jan 7, 1953

By Dorsey A. Lyon, Robert M. Keeney

The utilization of hydro-electriic power in electro-metallurgical industries, aside from purely mechanical operations, may be of two kinds. The electric energy may be used to supply the heat necessary for the performance of the chemical reactions of a metallurgical process, or the electrolytic action of a direct current may be employed for extraction of metals, either in a reduction process or a refining process. In discussing this subject, it is well to distinguish between established industries, which are producing metals and alloys at a, profit by use of the electric current, and the many processes which are either still in the experimental stage or have not even passed the paper stage of development of a patent. That is, we consider electro-metallurgical industries as commercial operations which are now consuming large blocks of electric energy, while processes which are not in commercial operation are only prospective consumers. Also, owing to the difliculty and risk of any attempt to foresee the effect of the European war upon electro-metallurgical industries, we have felt obliged to disregard the war entirely, and state our opinions regardless of its existence. Application of Electric Energy to Metallurgy Disregarding electrolytic refining processes, the applications of electric energy to metallurgy, when considered from a commercial viewpoint, may be classified as follows: Industries Experimental Processes Manufacture of aluminum Electric-furnace smelting of: Electric-furnace manufacture of: Ferro-alloys Copper ore Pig iron Zinc ore Steel In this paper only the above industries and experimental processes will be considered as possible consumers of hydro-electric power in large quan-

Jan 1, 1916

By W. W. Stephens, W. J. Kroll, H. P. Holmes

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,' was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made

Jan 1, 1951

By G. Pizzi, G. M. Ciucci, G. L. Chierici

The use of the material balance equation to estimate the volume of hydrocarbons originally present in a reservoir, whose producing mechanism is partly due to water drive, has been discussed in the literature by several authors. There is no general agreement upon the possibility of obtaining reliable results by this method. Gas reservoirs in contact with an active aquifer are considered in this paper. Theoretical considerations based on the cybernetic principle of uncertainty (which states that the internal structure of a system cannot be uniquely determined from its observed external behavior) lead to the conclusion that the volume of gas originally present in a reservoir of this type cannot be uniquely determined from its past history. The range of values which encompasses the actual value of the reserves varies from case to case and must be determined by either numerical or analogical methods. Results obtained for six gas fields are reported. All these fields were produced with small fluctuations in their production rates, as is common practice for gas reservoirs; no gas storage fields were considered. Results obtained show that reserves values in a range of 1 to 2, associated with appropriate aquifers, allow the matching of the reservoir past history with mean-square deviations less than the experimental errors involved in pressure and produclion measurements. Similar results have been found in several other partial water drive gas reservoirs. From these results it is concluded that gas reserves cannot be uniquely determined from the past performance of partial water drive reservoirs, at least in cases where the reservoir has been submitted to small fluctuations in the production rates, and pressure data of normal accuracy are available. INTRODUCTION A number of authors have analyzed the problem of estimating the reserves originally present in a partial water drive reservoir from its past pressure-production performance. Literature which deals with this subject can be grouped, according to their conclusions, as follows. 1. A reliable value for the reserves can be obtained even if reservoir data (pressure and cumulative production) are affected by errors within the normal range.'-' 2. A reliable value for the reserves can be obtained only if reservoir data are very accurate'- or if past production performance has been subjected to abrupt variations in the production rate."' 3. No unique value for the reserves can be obtained from reservoir past production performance. This conclusion has been based upon theoretical considerations" and verified in several field cases. The purpose of this paper, which deals only with partial water drive gas reservoirs, is to test the above conclusions against actual field cases. Some theoretical considerations on this problem are also presented. THEORETICAL CONSIDERATIONS As the behavior of a gas reservoir communicating with an aquifer depends on both the aquifer and the reservoir characteristics, the physical system to be studied is the combined gas reservoir plus aquifer. The information which is available for studying the performance of such a system is the well production rates and bottom-hole pressures, all given as functions of time. The external behavior of the reservoir-aquifer system is therefore described by 2n input variables (Gp, Wp,) and n output variables (p,), n being the number of wells in the reservoir. In reservoir engineering it is common practice to consider the reservoir as a whole, disregarding the internal distribution of pressures and of producing wells. This practice is equivalent to substituting the above multi-variable system with a single-variable system, where the average reservoir pressure is the only output variable and the cumulative production G,(t) and W,(t) are the input variables. The internal structure of such a system, defined by initial gas reserves G, aquifer shape and dimensions, boundary conditions and petrophysical parameters distribution throughout the aquifer, is unknown. Therefore, from a cybernetic point of view the system is a "black-box It has been demonstrated" that for a blackbox the indetermination principle holds. Accordingly, the number of different internal structures (or set of parameters) which can account for the observed external behavior is infinite. As a consequence, the initial reserves cannot be uniquely determined from the reservoir past performance. When W,(t) is known, the determination of G from

By James Gayley

The atmosphere, which plays such an important part in the manufacture of iron and steel, is the most variable element involved in its several processes; and particularly is this true of the blast-furnace process, which consumes air in large quantitiee. At no time since the blast-furnace became an important and widely used apparatus—even when it was operated in the most crude manner—have the variations in composition of the raw materials used been as frequent and as great as the variations in humidity of the atmosphere. Important improvements have been made in the blast-furnace and its accessories, such as the hot-blast stoves, the increase in size and change in the shape of the furnace, more efficient blowing-engines, the increased protection given to the bosh-walls, and the careful preparation of the raw material, all of which have exerted a pronounced influence on the furnace-operations from a metallurgical standpoint. But during the past eight years little advance has been made in this direction; the fuel-consumption has not diminished, nor has there been any material increase in production. Within that period, however, there has been witnessed the greatest development in appliances for the economical handling of material. So complete has been the work in this direction, that, except in isolated cases, in this country at least, a further extension does not hold out much promise of a satisfactory return on the investment required. It seemed that, with the exception of the gas-engine, we had about reached the limit, for like a strong wall, the atmosphere, with its humidity as variable to-day as when first blown into a primitive blast-furnace, appeared to stand as a barrier to

Jan 1, 1905

By P. Somasundaran

An experimental and theoretical treatment of the depressing effect of inorganic electrolytes on the amine flotation of quartz is presented. Experimental data obtained for the amine flotation of quartz as a function of pH with potassium nitrate as depressant was used to test the models for the effectiveness of inorganic ions as depressants. The validity of commonly used assumptions are examined. The surface tension data obtained for dodecylammonium acetate solutions as a function of KNO3, concentration indicated that the collector adsorption on bubble cannot be neglected in the treatments, since this adsorption changes significantly with the addition of the inorganic electrolyte. It also indicated the possibility of significant changes in the specific adsorption potential of the collector occurring with the addition of inorganic electrolytes.

Jan 1, 1975

By Cyril Stanley Smith

The method of thermal analysis, so important in the development of metallographie science, has of recent years been falling into disuse owing to the development of other physical methods which give result's easier of interpretation and which can be used for the study of either equilibrium or transitional conditions because they do not require a continuously changing temperature. Nevertheless thermal analysis remains useful in the study of reactions that take place rapidly, and the simplicity of the experimental technique and the general availability of the apparatus involved are point's in its favor. Theoretically, thermal analysis is capable of giving specific and latent hat measurements and therefore should permit the study of reactions on a more fundamental basis than any other method. It is, however,difficult or impossible to obtain quantitative heat measurements from cooling curves obtained in the usual way. Even if the furnace containing the sample is cooled or heated at a linear rate, or if a gradient furnaec is employed to maintain a constant rate over a large range of temperature, the heat flow from or to the specimen depends on its previous history, for the difference of temperature between the specimen and its surroundings varies. The emissivity of the specimen surface, moreover, is unlikely to be constant. The able mathematical analysis by Russrll,1 although it prevent,s misinterpretat,ion of data, has an effect rather the reverse of that intended, and leaves the reader doubtful of the possibility of ever obtaining quantitative results from thermal curves. Nothing can be done to apply thermal analysis t'o the study of equilibrium conditions of reactions that arc not completed at rates of temperature change above about 1° C;. per minute, and this unfortunatetly excludes most solid transformations in alloys.† For the determination of liquidus

Jan 1, 1940

By Cyril Stanley Smith

The method of thermal analysis, so important in the development of metallographie science, has of recent years been falling into disuse owing to the development of other physical methods which give result's easier of interpretation and which can be used for the study of either equilibrium or transitional conditions because they do not require a continuously changing temperature. Nevertheless thermal analysis remains useful in the study of reactions that take place rapidly, and the simplicity of the experimental technique and the general availability of the apparatus involved are point's in its favor. Theoretically, thermal analysis is capable of giving specific and latent hat measurements and therefore should permit the study of reactions on a more fundamental basis than any other method. It is, however,difficult or impossible to obtain quantitative heat measurements from cooling curves obtained in the usual way. Even if the furnace containing the sample is cooled or heated at a linear rate, or if a gradient furnaec is employed to maintain a constant rate over a large range of temperature, the heat flow from or to the specimen depends on its previous history, for the difference of temperature between the specimen and its surroundings varies. The emissivity of the specimen surface, moreover, is unlikely to be constant. The able mathematical analysis by Russrll,1 although it prevent,s misinterpretat,ion of data, has an effect rather the reverse of that intended, and leaves the reader doubtful of the possibility of ever obtaining quantitative results from thermal curves. Nothing can be done to apply thermal analysis t'o the study of equilibrium conditions of reactions that arc not completed at rates of temperature change above about 1° C;. per minute, and this unfortunatetly excludes most solid transformations in alloys.† For the determination of liquidus

Jan 1, 1940

Note Any member who desires to be designated as being "Available for Consulting Work" can arrange it simply by sending a written request to the office of the Secretary of the Institute The following list of members is primarily arranged geographically, with secondary consideration to political subdivisions arranged alphabetically First, the states of the United States , then other North America, in order Alaska, Canada, Mexico, the West Indies, and Central America Then cones South America, Europe, Africa, and Asia, each including the near by islands associated with those continents Australia, the islands to the north, and the Pacific islands except Japan are grouped together under Oceania The various countries are indexed on the preceding page NORTH AMERICA UNITED STATES ALABAMA America -Dyar, G C Anniston -DePriest, S H Klugh, B G Lefforge, J W Auburn Poor, R S Bankhead -Armstrong, W D Bessemer -Beck, A IV, Jr Carnes, D Chabot, L S , Jr Creveling, J C

Jan 1, 1952

By Kenelm C. Appleyard

In introducing to an American audience a description of the work done in dry coal separation in England and in Europe generally, it is perhaps desirable to give a short history of the development outside the United States of the particular processes with which the author is connected, and perhaps to stress a little the differences in the nature of the conditions to be faced. England actually presents one set of problems and the Continent of Europe another, since the character of the coals to be treated is entirely dissimilar, and the attitude of the coal industries towards coal preparation is also dissimilar. England for generations has been working by hand good seams of clean coal of the highest possible quality and has not felt any pressing need to clean its coal. Most Continental countries, however, especially in Central and Western Europe, have been working friable and often very dirty coals for so long that a washery is accepted as a part of the normal equipment of a colliery, with the result that the art of wet washing has reached a high state of perfection, particularly in Belgium and Germany. The advent of machine mining has intensified the problems to be faced in all countries, and in England has been coupled with the working out of the best seams in the older coal fields, thus bringing about the necessity of working thinner and dirtier seams with resultant difficulties as regards marketing the products, while Poland, with clean and well prepared coal, has in recent years been attacking established British markets in Scandinavia. In recent years, therefore, interest in coal preparation has been steadily gaining ground in England, although it has not yet reached Continental dimensions. Broadly speaking, the differences in preparation problems between England and the Continent boil themselves down to one of size. In England, for example, with the exception of the Kent coal field, the proportion of coal of a size less than ? in. to the coal less than 2 in. is very much less than on the Continent, and since the principal difficulties in dry cleaning lie in the fines it is easier to produce good figures on

Jan 1, 1931

By Hugh M. Roberts

In the spring of 1915, then a 30-year old geologist in the employ of the E. J. Longyear Co., of Minneapolis, Minn., I accompanied prospectors to ex- amine outcrops of supposed nickel ore situated a mile or two in from the shore of a lake in the Kenora district of northwestern Ontario. The deposit proved to be bog iron ore containing traces of nickel. We were stormbound there for three days, a circumstance which gave rise to a tale that was told at our fire one night. It seems that Sandy and Jock, two prospectors, were crossing the bay of a large lake in a canoe. They were bucking headwinds; the waves grew higher. Jock called out from the stern, "Sandy, can ye na pray a little." Sandy pressed his knees a little closer into the bow and, between strokes of his paddle, sought for words, which came haltingly, "Save us this time . . . Oh Lord . . . and we promise . . ." when Jock, peering through the spray sang out, "I would na commit yourself, Sandy, I think I see lond ahead."

Jan 1, 1965

By H. H. Klepfer, M. E. Snyder

UNTIL very recently, the commercial availability of the rare earths as metals has been very limited. Fabrication of mill products from these metals has not been studied in most cases. This note reports the results of the development of fabrication techniques for thulium. Thulium has a melting point of about 1550°C and a hexagonal close-packed crystal structure. It oxidizes in air to give a black oxide (TmzO,). The procedures for producing thin thulium foil were developed on one ingot weighing about 220 g and were subsequently applied in processing about a pound of metal to foil. Several alternates for the various fabrication steps were investigated and will be discussed. The metal fabricated was in the form of commercial chill-cast ingots 1 in. in diam and 2 in. long weighing approximately 220 g. Impurities in the ingots were reported by the vendor to be 4000 ppni tantalum, 2000 ppm calcium, 200 ppm nickel, 100 to 200 ppm iron, 100 ppm europium, and less than 100 ppm copper, lutetium, and ytterbium. In addition to these impurities, several salt-like inclusions as large as l/8 in. in diam were revealed along the center line of the one ingot sectioned. Preliminary tests indicated that small wafers cut from the as-cast ingot would not fabricate readily by rolling. Forging of copper-jacketed wafers was therefore attempted. At 1550"F forging was satisfactory but an apparent reaction of copper with thulium demanded investigation of lower temperatures. Therefore, the remainder of the test ingot was forged at 1450°F—with only minor cracking. All ingots forged were inserted into copper tubes of 1 in. 1D and 0.125-in. wall thickness. The jackets were sealed by flattening the ends of the tubes and welding under helium. Heating time at 1450°F was 30 min. Press forgings of 1/8 in. per pass were used, followed by 10 min reheats. When the ingots had been squared and reduced to 0.250 in. in thickness, the original copper jacket was stripped off and replaced by a new jacket in preparation for hot rolling. Hot rolling at 1450" F without edge cracking was readily accomplished after forging. Excellent results were obtained with 10 pct reductions of thickness followed by 5 to 10 min reheats. After reduction of thickness from 0.250 to 0.100 in. the copper jacket was removed. It was found, in fact, that hot rolling in air was possible. A tenacious black oxide similar to that seen on zirconium was formed during 3 min reheats at 1450°F. Reduction in air to 0.010 in. foil was possible taking 10 pct reductions per pass. The oxide coat formed during hot rolling in air could best be removed by sand blasting and pickling. Common pickling solutions containing polar solvents were found to attack the metal too rapidly and a concentrated nitric-hydrofluoric acid mixture attacked neither the oxide nor the metal. The most satisfactory pickling solution was 52 vol pct concentrated nitric acid-48 vol pct glacial acetic acid. After forging to 0.250 in., vacuum annealing and cold rolling was found to be another satisfactory alternate to hot rolling in copper jackets. After forging. a hardness of Rockwell B76 was found. Annealing in vacuum (2 X l0-5 mm of Hg) for 1 hr at 1200"F did not alter this value. Annealing at 1470"F for 1 hr brought the hardness down to R;]63. With cold rolling (5 pct per pass) the hardness returned to about R,1:76 after 20 pct reduction and edge cracking became noticeable. However, cold rolling to a total of 40 pct reduction in thickness (RI,,83) was possible before edge crack propagation became serious. Good surface finish was obtained, and the metal loss due to oxidation was minimized by cold rolling and vacuum annealing. Using this procedure the yield of 1.25 in. wide by 0.010 in. thick foil from a 1-in. diam ingot was about 40 pct.

Jan 1, 1961

By Nathaniel Arbiter

THE separation of minerals by flotation can be regarded as a rate process, with the extraction of any one mineral determined by its flotation rate, and the grade of concentrate by the relative rates for all the minerals. So regarded, the significant variables for the process are those that control the rates. These variables are of two types, the first describing the ore and its physical and chemical treatment prior to flotation and the second characterizing the separation process in the cells. This paper will examine the variation in rates for a group of separations, will show that a simple rate law appears to govern, and will consider the relation of the control variables to the rates. The use of rate constants for evaluation of performance and efficiency will be discussed.

Jan 9, 1951

By Daniel R. Hull

In 1926 Gendersl reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan3 and by Phillips and Brick,2 so that no résumé is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. Vapor Segregation There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table 1, which represents a cylindrical billet 7 in. in diameter by 55 in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. the lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps UP a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By Daniel R. Hull

In 1926 Gendersl reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan3 and by Phillips and Brick,2 so that no résumé is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. Vapor Segregation There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table 1, which represents a cylindrical billet 7 in. in diameter by 55 in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. the lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps UP a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By Wilbur T. Stuart

TO assist the mining industry in attacking problems of water control, the U. S. Geological Survey has begun a program of research in mining hydrology. In certain fundamental respects water control is similar to development of water supplies from wells or to the drainage of agricultural lands, as many of the tools developed in recent years for quantitative ground-water problems are applicable, with modification, to mine-water problems. In 1952 a 30-day pumping test conducted jointly by the Eureka Corp. Ltd. and the Defense Minerals Exploration Agency provided an opportunity to gain knowledge concerning water movements around a flooded mine shaft. The methods of analyzing the data may be used as a guide for the evaluation of similar problems elsewhere. The Fad shaft of the Eureka Corp. is on Ruby Hill, 1 1/2 miles west of Eureka, Nev. The shaft was completed at a depth of 2465 ft in November 1947 at a site adjacent to the downfaulted block in which the ore was found. As the drift on the 2250 level progressed toward the ore zone, a large flow of water was encountered after the Martin fault was intersected. This flow exceeded the installed pump capacity, and an unsuccessful attempt to recover the shaft and the 2250 level was made in 1948.1, 2 Geology and Hydrology: The complex structure of Ruby Hill is that of an anticline broken first by thrust faulting and later by normal faults. The present orebody comprises several mineralized zones within a block of the Eldorado limestone of middle Cambrian age which was downfaulted 1400 to 1600 ft, and it may be related to a similar body mined at a higher level south of the Ruby Hill fault. At the depth of the largest zone of ore the block is roughly rectangular in shape, about 1000 ft wide and 1500 ft long, and dips about 30" NE, see Fig. 1. It is apparently bounded on the south by the Ruby Hill fault, on the east by the Jackson fault, on the north by the Martin fault, and the west by the Bowman fault. Within the block, but between the Ruby Hill and the Martin faults, are the Office and Adams Hills faults; west of the block and the Bowman fault are the Albion and Spring Valley faults. There are many conflicting reports concerning the water-yielding characteristics of the Eldorado limestone and the condition of the fault zones, that is, whether they are open or tight. However, the diamond-drill records indicate that open spaces as much as 2 or 3 ft across were encountered, and considerable cementing and lining of holes was necessary to maintain circulation of drilling fluid. There is also evidence that the Eldorado limestone was cavernous where it was mined in the early days south of the Ruby Hill fault. At the site of the Fad shaft the formations encountered from the surface down included the Pogonip limestone, Dunderberg shale, Hamburg limestone, and Secret Canyon shale. These formations did not yield large quantities of water to the shaft. The Pogonip limestone, which appears to be permeable and might yield water elsewhere, is above the water table in the vicinity of the shaft. The Secret Canyon shale, immediately overlying the Eldorado in some places but in most places separated from it by the Geddes limestone,3 is apparently tight and does not transmit water. During the 30-day test period the shale briefly confined the water in the underlying formations so that artesian conditions were observed in drillholes E and F, which are cased into the Eldorado limestone, whereas unconfined conditions were observed in drillholes B, C, and D, which were open to the shale. The Geddes limestone, which normally lies between the Secret Canyon shale and the Eldorado limestone, was not encountered in the Fad shaft. The Geddes, a flaggy, fractured limestone, is reported capable of yielding large volumes of water. Water stored in the interstices of this thin-bedded limestone within the Ruby Hill fault zone on the 1200 level of the Locan shaft drowned the pumps in 1923 when the Richmond-Eureka Mining Co. attempted to explore the area along the fault. Eldorado limestone was not encountered in the Fad shaft. In the ore-block area the Eldorado limestone was not entirely offset from other water-yielding formations by movement along the Bowman fault; therefore it may be hydraulically connected with the other formations. Adjacent to the Ruby Hill, Jackson, and Martin faults, the Eldorado lies in contact with other possible water-yielding formations. One of these, the Prospect Mountain quartzite, is separated from the Eldorado by thin, sheared, and broken beds of the Geddes within the Ruby Hill fault zone. A limited examination by the author of the Prospect Mountain quartzite in the Richmond mine at a higher level and south of the Ruby Hill fault indicates that the quartzite is poorly permeable. The monzonite mass south of the quartzite would be a further barrier to the flow of water. The poor permeability of this area is substantiated by records of levels at which water was encountered south of the Ruby Hill fault. In view of the normally low rate of ground-water recharge, if this desert area had been permeable, water levels could not have been maintained at altitudes of many hundred feet above the present water table west and north of Ruby Hill. Thus the ore-bearing block of Eldorado limestone is in contact with possible water-yielding rocks on at least two sides, and if the fault zones are possible conduits for water circulation the geologic and hydrologic conditions are suitable for the infinite-aquifer type of analysis as used and modified here. History of Pumping: During sinking of the Fad shaft a maximum pumping rate of 1500 gpm kept the shaft dewatered sufficiently, but in March 1948, after the 2250 level drift passed through the Martin fault into the Eldorado limestone, the pumps and shaft were flooded. Subsequently additional pump-

Jan 1, 1956

By H. I. Aaronson, H. A. Domian, G. M. Pound

Zener's two-parameter theory of the y a reaction in Fe-X alloys is extended to encornpass austenite-stabilizing as well as fewite-stabilizing elements, and is then cottzbitzed with statistical thermodynamic theories of Fe-C alloys to permit development of a ther-modynamic description of the proeutectoid fewite reaction in Fe-C-X alloys. Equilibrium tielines are calculated for tile a + y rep'on from experimental data and frort extrapolations of the y/y +a equilibrium surface. Sectzovs of the y/y + 0 surface are calculaled for the tzetastable sstuation LYL u-kich alloyrtg eleitzents do not partition betzseen azrstenite andfer-rite. The finding that the metastable y/a + y curves Lie close to their equilibriuwz counterparts when X = Si, .Vo, Co, Al, and Cu but well below them when X = A/ln or Ari pr-elides a thermodunamic explanation for the expcri1?7e?ztally obserted absence of partition during the proeutec toid ferrite reartlon in the fortner alloys and for the occurrence of partition at hzgher ternperatures in the latter alloys. Cotarison ofno- patitzoa free-energy changes and y/y i a curr,es in Fe-C-X alloys with the equilibrium 11al1es of these quantities in Fe-C alloys furnishes additional qualitative insight into the irqluence of allojling elements upon the kinetics of the proeutectoicl ferrite reaction. THE introduction of a substitutional alloying element, X, appreciably complicates calculation of the thermodynamics of the formation of proeutectoid ferrite from austenite. As noted in the preceding paper,' the positional entropy of the interstitial species is the principal component of the free energy of an interstitial solid solution with which theory has so far been able to deal. One would expect, however, that other components of the free energy of this type of solid solution may be significantly altered by the addition of a substitutional alloying element. Even if the assumptions are made, by analogy to the case of Fe-C alloys,' that changes in the positional entropy of carbon represent a significant part of the thermodynamic effects of an alloying element, and that the remaining effects can be taken into account by fitting the equations developed on this basis to experimental data on Fe-C-X phase diagrams or on the activities of carbon in alloyed austenite and ferrite, the experimental information available on either of these quantities is not yet sufficiently accurate or extensive, respectively, to make such an approach useful. An attempt made by Zener on the former basis to explain the effects of alloying elements on the thermodynamics of Fe-C alloys in terms of a temperature-independent "free-energy change" (actually enthalpy hane') required to transfer 1 mole of an alloying element from austenite to ferrite, in which the "free-energy change" was determined by fitting the theoretical relationships developed to Fe-C-X phase diagrams, thus proved inadequate in part because of deficiencies in the available ternary-phase-diagram data.= Other difficulties of a more fundamental nature, however, also indicated the desirability of a different approach to the problem.3y4y6 zener6 subsequently proposed that the free-energy change associated with y — a transformation in pure iron can be decomposed into magnetic and nonmagnetic components. Alloying elements were assumed to affect those components separately. One parameter was used to describe the quantitative effect exerted on each component. These parameters were evaluated from Ms (martensite-start) temperature data and from other experimental information usually either readily available or measurable with acceptable accuracy. Zener applied this treatment only to the calculation of Fe-X phase diagrams in which X is a ferrite-stabilizing element. In the present study, this treatment is extended to include austenite-stabilizing elements, and then combined with treatments previously considered for Fe-C alloys1 to permit calculation of the thermodynamic quantities of interest in the austenite - proeutectoid ferrite transformation in Fe-C-X alloys, where a number of representative, and commonly used alloying elements are chosen for X, including Si, Mn, Co, Mo, Al, Cr, and Cu. The results are used to explain important features of the partition of alloying elements between austenite and proeutectoid ferrite, as reported in a companion paper7 on the basis of electron-probe analysis, and to provide some additional understanding of the influence of alloying elements upon the kinetics of nucleation and growth of proeutectoid ferrite. Portions of this treatment6 have been clarified in the course of a review by Kaufman and Cohen.3 The consolidated summary of these developments with which this section is begun provides a basis for further clarification of the treatment, from which extension to include austenite- as well as ferrite-stabilizing elements is a natural consequence. The division of the free-energy change associated with the 7 - a transformation in pure iron, into two independent components is formally stated as:

Jan 1, 1967

By H. A. Guess

For a number of years I have used for the commercial wet assay of lead generally the ammonium molydate, and occa-sionally the ferrocyanide method. These well-known methods need no detailed description here. In the ore-selling and ore-buying establiahments of the West, 90 per cent. of all wet lead-assays are made by one or the other, and at least nine-tenths of this proportion by the molybdate method. A procedure so well-established must have merit; and, in

Jan 1, 1905

By B. H. Caudle, W. J. Bernard

Factors which influence the success or failure of a waterflood can seldom be determined in the laboratory. For this reason pilot waterfloods are initiated in a repreventative portion of the oil reservoir in question. For a pilot flood to predict quantitatively the recovery to be expected in a field-wide waterflood operation, the pilot area must behave as though it were confined (surrounded by similar areas). In this study, laboratory fluid-flow models were used to determine the simplest pilot pattern, for particular conditions of mobility ratio and initial gas saturation, that would behave as though it were confined. Pilot patterns studied ranged in complexity from a single inverted five-spot to a grouping of nine regular five-spots. Only the innermost producing well in each pattern was studied. Model results showed that the optimum number of wells in the pattern depends upon the oil-water mobility ratio and the expected oil-bank size. Unfavorable mobility ratios will, in general, require more wells in the pilot pattern than will favorable mobility ratios. Pilot patterns in reservoirs which contain a dispersed, flowable, free gas saturation will require fewer wells than for the under-saturated case. The single inverted five-spot pattern was found to be unsatisfactory for predicting behavior of fully developed waterfloods. In particular, it is possible that, in reservoirs which contain a flowable, dispersed gas phase, the oil bank will never be observed at the producers due to the large amounts of free gas which continue to be produced with the oil. INTRODUCTION One method which has been used to predict the performance of a waterflood is the pilot flood. The pilot waterflood is a flood which involves only a small cluster of the reservoir wells and is located in a small, representative portion of the reservoir. The object is that oil produced from the pilot can, in some way, be related to the oil recovery to be expected from a field-wide expansion of the waterflood. However, these field pilot waterfloods have often been unreliable in the prediction of oil recovery in a fully developed waterflood. This unreliability has also been demonstrated in several laboratory studies of pilot floods. Some of the investigators have shown that there are situations in which the pilot flood oil production is far too optimistic with respect to the oil recovery in the fully de- veloped flood. Others4-G have shown that the pilot results can also be pessimistic, especially if the pilot waterflood is initiated in an oil reservoir which has been depleted by primary recovery and is at very low pressure. The major reason for this unreliability of pilot water-floods is the migration of fluids into or out of the pilot area. By the well-known method of images, if straight lines can be drawn to represent vertical planes of symmetry in a porous medium which contains pressure sources and sinks (injectors and producers), then these lines are invariant streamlines, or lines across which there is no potential gradient, and therefore no flow. In an actual reservoir, these lines of symmetry can never be established exactly because of reservoir inhomogeneities and irregular reservoir boundaries. However, if the reservoir is relatively large and contains wells in repetitive patterns, these lines of symmetry are commonly assumed to exist for the pattern units sufficiently far removed from the reservoir boundary. Lines of symmetry for the five-spot injection pattern are shown in Fig. 1. Each five-spot unit in this figure can be considered confined with respect to flow across its boundary. In pilot floods this is not the case. The lines of symmetry for the pilot patterns investigated in this study are shown in Fig. 2. It is obvious that the fluid within these pilots is not confined and is therefore able to migrate into or out of the pilot area. Intuitively, one can see that, if more wells are added to the pilot, the innermost unit tends to behave more and more like the confined pattern. However, there is a practical limit to the number of wells which should be placed in the pilot. This limit is usually determined by economic factors. It was the purpose of this study to use laboratory fluid-flow models to determine which of the previously mentioned pilot patterns will force the innermost producing well to behave as it would in a fully developed waterflood. Since fluid migration is influenced by initial saturation conditions and the mobility ratio, these factors were included in the study. The ultimate objective of this study was to develop data which would allow the operator to choose a pilot pattern and operating conditions that will yield a production history which can be applied directly as an estimate of the performance of each production well of the fully developed waterflood. BASIS FOR THE STUDY The basic problem of field pilot floods is the migration of the reservoir fluids into or out of the pilot area. This problem has been the subject of previously reported model studies on pilot floods. These studies have been concerned mainly with the development of arbitrary "correction factors" to be applied to the simple, unconfined pilot systems such as the single five-spot. The correction factors were intended to adjust the production history of the un-