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By J. S. Pascover, J. K. Abraham

The influence of the early stages of precipitation on the kinetics and structure of martensite formation in Fe-27Ni and Fe-29.5Ni alloys containing from 0 to 10 pct Ti was examined with X-ray and electron microscopy techniques. The formation of a coherent, ordered preprecipitate had a profound stabilizing effect on the austenite. The Ms was decreased by increased titanium content and aging time up to a critical time. When the critical aging time was exceeded, the Ms was observed to increase markedly. The formation of the clusters was insuppressible and the volume fraction of clusters formed during the quench was a function of the titanium content. Martensite resulting from transformation of the clustered austenite is tetragonal with the c/a ratio increasing with titanium content. A model for the tetragonality is suggested. The morphology and substructure of the m artensite is inter-preted in terms of the above information and the cur-rent models of twinned martensite. ThE ramifications of precipitation in austenite to the properties of austenite have been the subject of numerous investigations. The current research is concerned with the influence of precipitation in austenite on the kinetics and structure of subsequent marten-site formation. In a previous investigation, Abraham et al.1 followed the aging reaction in an Fe-29.5Ni-4.2Ti* (at. pct) alloy using an X-ray diffraction technique. This technique, employing a Guinier camera, provided kinetic measurements through observation of the side band position as a function of aging time. The salient results of this work were: 1) The initiation of precipitation was not suppressed by quenching, i.e., there was a finite cluster zone size at zero aging time; and 2) The hardness of the aged austenite correlated extremely well with the zone size. During the previous work it was noted that the mar-tensite formed after aging was tetragonal, substanti-ating an earlier observation.2 Systematic investiga-tion revealed that the martensite was tetragonal in both the solution-treated then quenched, and the solu-tion-treated, aged, and quenched condition, and, furthermore, that a marked stabilization of the austenite occurred as a function of aging time. The present work is concerned with documenting the tetragonality and the stabilization phenomena as well as the ob- served microstruction with a suggested rationale for the behavior noted. EXPERIMENTAL PROCEDURE The compositions of the alloys are listed in Table I. The analyses were performed after the solution treatment of the strip material. Nickel was determined using the standard dimethy1-glyoxime procedure whereas titanium was determined colorimetrically with hydrogen peroxide and volumetrically by titrating with ferric iron. The materials were melted in a 5-lb vacuum induction furnace, cast into 2-in.-diam ingots, and forged in a temperature range of 950. to 1200°C to 1/2-in. slabs. The three higher titanium containing materials cracked during forging; therefore, to get the alloys into strip form, slices 1/8 in. thick were cut from the slab, homogenized 4 hr at 1150°C, then cold-rolled to a 0.04-in. thickness. The remaining slabs were hot-rolled, homogenized 4 hr at 1065"C, then cold-rolled to a final thickness of 0.03 in. All of the heat treatments were performed under a protective atmosphere of argon. The Ms temperature for most of the alloys is below room temperature; therefore, it was possible to solution treat, quench to room temperature, polish, and then observe the transformation optically on a cold-stage microscope. To determine the effect of aus-tenitizing temperature on Ms, eight of the alloys were treated at two temperatures, 1025" and 1120°C. No measurable variations in Ms were noticed. The remaining alloys were treated at 1025°C. The specimens, : by 5/16 by 0.03 in., were austeni-tized in a vertical tube furnace under a dynamic argon atmosphere. The bottom of the tube was submerged in water for quenching purposes. The question of stabilization that may be operating at room temperature was investigated and found to be negligible. Many of the specimens were held at room

Jan 1, 1970

By C. B. Dudley

IN the spring of 1877, the Pennsylvania Railroad Company became so dissatisfied with the average life and wear of the steel rails it was then able to procure, that it determined to make an investigation into the chemical composition and physical properties of steel rails, with a view, first, to answering the question why one steel rail has to be removed from the track after, perhaps, eight months' service, while another lasts ten years ; and, secondly, if this investigation succeeded in throwing light on this important subject, to use this information in securing better rails in the future. The results

Jan 1, 1879

By Charles B. Dudley

In the spring of 1877, the Pennsylvania Railroad Company became so dissatisfied with the average life and wear of the steel rails it was then able to procure, that it determined to make an invest,igation into the chemical composition and physical properties of steel rails, with a view, first, to answering the question why one steel rail has to be removed from the track after, perhaps, eight months' service, while another lasts ten years; and, secondly, if this investigation succeeded in throwing light on this important subject, to use this information in securing better rails in the future. The results

Jan 1, 1879

By H. H. Stoek

Among the mining and metallurgical achievements of the latter part of the nineteenth century, not the least is the incep tion and successful prosecution by mining men of a technical educational movement which in magnitude surpasses any similar movement ever before set on foot. The following account of this undertaking has been prepared at the request of the Secretary of the Institute :*

Jan 1, 1899

By J. Edgar Pew

As MOST of the oil production comes from leased-lands and not fee property, I shall refer to "leases" as covering the producing tracts. To produce oil, leases on land must first be obtained. Well-selected leases are all important. Not many years ago, the location for drilling for oil in wildcat territory was too frequently determined by the nearness, of adequate water and fuel supply, or with a view to cheapness of transportation. To some extent, the "creekology" theory is the result of the number of wildcat tests made near streams, to obtain water for operations. Now, an up-to-date operator will depend on his geologists for his location and, in many cases, will spend thousands of dollars to get water to it. The wisdom of following the geologist rather than the creek has been abundantly demonstrated in the past few years. In vast territories, where dry holes are spotted at intervals of a few miles or less. apart, and by reason of which these territories have been condemned for oil, the geologist is now finding many more spots that are producing large quantities of oil. No better tribute to the work of the geologist can be found than the surface and subsurface work being done in practically all parts of Oklahoma and the development had as a result of this, work. A land department is usually organized by placing in charge a man who is not only acquainted with the oil development, but who is a shrewd buyer, a first requisite for which should be unquestioned integrity. It takes a shrewd buyer to resist the persuasive lease broker, frequently backed by a geological picture from which the oil fairly drips. The geologist can help a lot by being absolutely honest when he makes these pictures; he will also thus strengthen his own cause. A geologist should interpret his own work and put his name behind his interpretation. If he does not he is liable to be misquoted and often discredited, as a result, by some overzealous lease broker giving an interpretation never intended by the geologist.

Jan 8, 1925

By E. W. Lithgow, E. G. Williams, R. R. Holbrook, B. R. Wilson

The mineralogy and geochemistry of Pennsylvanian shales and underclays were studied to determine their suitability for lightweight aggregate and refractory ladle brick. Eighty percent of the variation in bloating of shales and clays was explained by the variation of Si02, A1203, and fluxes (Fe203, MgO, CaO, Na20, and K20); 60% by variation in quartz, kaolinite, illite, and chlorite. The best bloating was exhibited by marine shales, whereas freshwater shales and underclays experienced little or no expansion. Regional paleogeographic maps o f Pottsville and Allegheny shales permit bloating to be geographically predicted. It was found that clays meeting the specifications for refractory ladle bricks were obtained from underclays having over 34.5% mica, over 40% kaolinite and less than 15% quartz. Underclays of this composition are confined to the lower Allegheney outcropping along the near-margins of the coal basin. The best clay is that underlying the Lower Kittanning coal. Porosity of the first fired brick was found to be inversely correlated with reheat expansion.

Jan 1, 1975

By Colin C. Harris, Nathaniel Arbiter

The flotation operation can be analyzed in terms of three groups of variables. The first, largely independent of control by the operator, embraces the fixed physical and chemical properties of the ore minerals. The second includes all chemical and physical effects imposed on an ore after mining that influence its floatability. These can be either purposefully or accidentally applied. The third embodies the flotation-machine characteristics which realize the potential floatability of selected ore minerals in terms of grade and recovery levels. The machine effectiveness thus depends not only on its own contribution, but on the prior influence of all other variables on floatability. HISTORICAL DEVELOPMENT From the earliest days, flotation mills used many types of machines. Hoover 20 in 1914 mentioned as then important the Potter-Delprat tank for gas generation by acid, the DeBavay cones for skin flotation, the Elmore mixer and separation chamber for vacuum flotation, and his own modification of the Mineral Separation cell for the agitation froth process. Less important at the time were the MacQuisten tube and the Hyde cell. By 19274~ scores of machines had been developed and dozens had found their way into mills. From then on, however, under the scrutiny of competitive tests, many fell into disuse. Taggart in 19454~ classified processes broadly as skin flotation and froth flotation, dividing machines for the latter into the three categories: bubble column, pulp body, and combination.* Under 'bubble column' he listed all pneumatic, cascade, and subaeration cells; and under 'pulp body' those cells in which gas was generated by boiling, chemical action, and pressure reduction, as well as the agitation-froth type. At that writing skin flotation, the cascade machines, and all pulp body and combination machines were said to be extinct, leaving pneumatic and subaeration types dominant (u. S. practice). The process of elimination has continued to the present, with almost all pneumatic cells succumbing to the pressure of competition from subaeration machines. The only new machines to appear in recent years have been double-impeller types f and these have met with only limited acceptance.

Jan 1, 1962

By J. C. Mertz, C. H. Mathewson

Accurate knowledge of the solid solubilities of the elements that dissolve in the important base metals is needed for guidance in the preparation and heat-treatment of the alloys derived from these components. While there is still difference of opinion concerning the merits of the X-ray and microscopic methods of determining such solubilities, it is certainly true that the recent extensive use of X-ray diffraction to review the existing constitutional data has revealed many glaring inaccuracies and has brought about a much improved knowledge of phase-boundary locations, which will inevitably come to include all of the important alloy systems. When the work is done with all necessary precautions it appears that in the majority of cases where the solubilities extend beyond a few tenths of a per cent the X-ray back-reflection technique is capable of furnishing the best of information in this field. For the most prolonged and thorough studies it is obviously advisable to combine the results of several methods, in particular, to obtain an agreement between X-ray and microscopic data. This paper reviews the work previously done on the solubilities of phosphorus, arsenic, antimony and bismuth in copper and, in consideration of the uncertainties thus made apparent, presents new X-ray data obtained with the first three members of this group. Copper-phosphorus System Heyn and Baurl found that in slowly cooled alloys phosphorus forms a solid solution with copper up to about 0.175 per cent. Huntington

Jan 1, 1937

By Henry M. Howe

THIS paper gives the composition of the iron and slag at different stages in the "air-furnace" process of preparing "hard metal," or white cast-iron, for conversion into malleable cast-iron by annealing. The details of the process are given in an appendix. One of us had been trying for years to work some chemist of some of our malleable-iron works up to a degree of enthusiasm which would lead him to make such au investigation. It would have had the advantage of the greater familiarity with the conditions which one habitually on the spot must have. Failing in this, he made use of an opportunity which presented itself of taking samples here represented, with such fairness as the conditions permitted, holding firmly that a rough approximation to the truth is better than the complete lack of data, or that a bird in the hand is worth two in the bush. We hope that this attempt may stimulate others effectively to duplicate this work, and thus correct or confirm it. Our results are shown in Table I. and graphically in Figs. 1 and 2. Discussion.-At the time when the first two samples were taken, the metal and slag were still too sluggish to permit fair sampling, and not until sample 6 were the conditions really favorable, because at the time of the fourth sample the metal was not fully melted, and even at the time of sample 5 it was still sluggish. Indeed, the slag was probably very heterogeneous throughout, because it took up silica and alumina rapidly from the bottom, and because it was so siliceous as to be sluggish at this relatively low temperature. This hetero-geneousness is exaggerated in the two samples of slag 8, apparently by the great viscosity due to its extraordinary acidity. Note that the manganous oxide of one sample is about two and

Mar 1, 1909

By Charles R. Fettke

BefoRe the Drake well on Watson Flats below Titusville, Pa, inaugurated the modern petroleum industry on Aug. 28, 1859, a considerable industry, based on the manufacture of mineral oils through the destructive distillation at relatively low temperatures (750' to 800' F.) of cannel coals and shales in closed, air-tight retorts, had already sprung up in Europe and America because of the increasing cost of animal and vegetable oils and fats and the growing demand for illuminating and lubricating oils. In 1860, eight out of 55 such coal-oil companies in the United States had plants located in Pennsylvania.' Of these, the Lucesco Works, costing $120,000, situated near Kiskiminetas Junction, was the largest operating in the country. It was equipped with 10 revolving 2.5-ton retorts and 16 stills for rectifying the oil, each holding 2000 gal. The total output of crude oil was almost 6000 gal. per day.2 The discovery of an abundant supply of natural petroleum by the Drake and other wells stopped the distillation of coal oil in America. Most of the smaller plants were closed and others were converted into petroleum refineries. At present, in spite of the temporary over-production of petroleum, the coal and oil-shale carbonization industries are again attracting the attention of far-sighted oil companies who realize that the gradual exhaustion of the American petrol-

Jan 1, 1923

By Charles R. Fettke

BefoRe the Drake well on Watson Flats below Titusville, Pa, inaugurated the modern petroleum industry on Aug. 28, 1859, a considerable industry, based on the manufacture of mineral oils through the destructive distillation at relatively low temperatures (750' to 800' F.) of cannel coals and shales in closed, air-tight retorts, had already sprung up in Europe and America because of the increasing cost of animal and vegetable oils and fats and the growing demand for illuminating and lubricating oils. In 1860, eight out of 55 such coal-oil companies in the United States had plants located in Pennsylvania.' Of these, the Lucesco Works, costing $120,000, situated near Kiskiminetas Junction, was the largest operating in the country. It was equipped with 10 revolving 2.5-ton retorts and 16 stills for rectifying the oil, each holding 2000 gal. The total output of crude oil was almost 6000 gal. per day.2 The discovery of an abundant supply of natural petroleum by the Drake and other wells stopped the distillation of coal oil in America. Most of the smaller plants were closed and others were converted into petroleum refineries. At present, in spite of the temporary over-production of petroleum, the coal and oil-shale carbonization industries are again attracting the attention of far-sighted oil companies who realize that the gradual exhaustion of the American petrol-

Jan 1, 1923

By C. S. Samis, J. C. Mitchell

Sodion activity data have been obtained for the Na-A1 system for sodium concentrations in aluminum between NN, = 25 . 10-and 300 x 10'. This concentration intert-a2 encompasses those sodium concentrations nor1)zally encountered in aluminum reduction cell operation. The sodium activity data were measured by a two-phase equilibration of sodium between a lead and an aluminam rich phase. The Na-Pb system was emplojed as a reference for the determination of the actiz7itj 0.f sodium. The activity of sodiin in aluminuwz exhibits large positi2.e deviations frorn ideality and a strong dependence, on concentration below NN, = 100 x 1K6. The inteated data indicate that the activity of aluminium is equal to its mole fraction over the range of miscibility of the Na-A1 sgstem. The data on the Na-A1 binary have been combined with experimental data on the cryolite-A1 system at 1025°C to obtain the activities of Na F and AlF, in liquid cryolite oz2er the cornposition 1-ange encountered in aluminum cell operation. The results are in agreement with activities calculated from the NaF-AlF, phase diagram. ALUMINUM is produced commercially by the electrolytic reduction of aluminum oxide dissolved in molten cryolite. There is considerable controversy over the actual mechanism of the discharge processes, but sodium potentials in the systems appear to play an important role in the reduction mechanism. The metal-salt reaction involving NaF and aluminum to produce A1F3 and sodium is responsible for the presence of sodium in the aluminum metal phase. Additional sodium may be produced from the simultaneous deposition of sodium and aluminum at the cathode as a result of a cathodic overvoltage. runert' has suggested that sodium gas at atmospheric pressure would be the result of reaction between cryolite and aluminum at 1000°C. Subsequent investigations have shown that production of sodium at atmospheric pressure does not occur. These later investigations can be conveniently separated into two categories. The first involves sodium, aluminum, and cryolite, in which the sodium activity was measured. The second includes a lead phase for sodium activity measurement. Jander and errmann,' studied the reaction: at 1090°C in alumina crucibles under an atmosphere of dry, oxygen-free nitrogen. The equilibrium constant for the reaction was expressed in terms of concentration. Their results in Fig. 1 show an increase in sodium content of the aluminum with increasing NaF/A1F3 weight ratio. Pearson and waddington3 performed similar experiments at 1000°C. Their results are included in Fig. 1. Dewing and ollinshead have measured the sodium content of aluminum as a function of the NF/AF, ratio at 1025"C, Fig. 1, and ewin' measured the sodium content of the aluminum in a system involving the solid reactants NaF, cryolite, and liquid aluminum. This reaction is different from those discussed above. Two solid phases, NaF and Na3A1F6, and a liquid aluminum phase were present. The sodium concentration in the aluminum was determined by the temperature. Dewing's measurements covered the temperature range 679" to 896°C. Omo, Matsushima, and 1t02" investigated the equilibrium 6NaF ential thermal analysis. Stokes and Frank6 determined sodium activities by

Jan 1, 1970

By G. L. F. Powell

Bulk samples of silver have beat undercooled lo a large degree in contact with crystalline siliceous and ceramic oxide materials, indicating lhat stable oxides and oxide compounds are not the heterogeneous nucleants which normally catalyze cryslallization within a feu degrees of the equilibrium freezing point. Since 400-g samples were undercooled 250°C in contact with cristobalite, it is concluded that the undercooling required for homogeneous nucleation of sil11er is greater than 250°C. Undercooling was Jacilitated by precleaning the crucibles with a high-fires -sure blast of gas. IN numerous experiments on the undercooling of metal melts it has been assumed that a solid glassy surface, being non crystal line, will have no effect in catalyzing crystal nucleation from the melt. Conversely, it is usually accepted that any crystalline surface, in contact with a metal melt, will catalyze nucleation of metal crystals from the melt at degrees of undercooling less than that at which homogeneous nucleation will occur. Both these assumptions were implicit in the claim that homogeneous nucleation was observed in experiments1'2 on the undercooling of small metal droplets (10 to 100 mp diam). The droplets were thought to be freed of suspended crystalline particles which would otherwise catalyze heterogeneous nucleation. They were supported on flakes of silica glass which were assumed to be amorphous, and therefore incapable of acting as substrates for heterogeneous nucleation. In later experiments, large samples of molten metal were undercooled to temperatures similar to those achieved by the droplet technique by melting in a fused-silica crucible3 or a boro-silicate glass slag.4 Since these samples were usually fully enclosed in glass at the moment of freezing, it seemed possible that nucleation was homogeneous when maximum degrees of undercooling were achieved, despite the large size of the samples (up to 500 g). In experiments on the undercooling of silver5 the metal was contained in vitreous silica crucibles, the

Jan 1, 1968

By W. G. Bearden, P. P. Scott, G. C. Howard

This paper concerns the rupture or breakdown of rock formations as related to drilling, completing, and stimulating production of wells, and comprises data compiled from a study of literature and records of treatment of oil and gas wells. and from tests conducted in bores drilled into rock cores and outcrops of rock. Results of the investigation indicate that the internal pressure to rupture cylinders of rock and to breakdown rock formations surrounding a bore in the earth is dependent upon the extent of intrusion of fluids. the position of bedding planes. the ratio of internal to external diameter, the tensile strength of rock, and magnitude of confining pressure, and is independent of the size of bore, degree of fluid saturation. and temperature of rock within practical limits. It is concluded that the mathematical relationship of pressure in bores and stresses in the surrounding rock must not be limited by the simplifying assumptions of homogeneity. isotropy, and impermeability; that the incidence of lost circulation of drilling fluids to induced fractures may be reduced by preventing intrusion of fluids into the small intrinsic fractures along weak bedding planes; and that the magnitude of the breakdown pressure of wells to be treated may be lowered by removal of mud cake. INTRODUCTION The purpose of this paper is to present and discuss the results of tests which may serve to broaden the understanding of the phenomena of rupture or breakdown of rock and thus contribute to the improvement of the techniques for drilling and completing wells. including such operations as preventing lost circulation, stimulating production, and placing cement. Since the early recognition of the possibility of rupturing rock adjacent to a well by fluid pressure, the distribution and magnitude of stresses around a well and the internal pressure to cause failure have been expressed mathematically by application of the principles defining the elastic and inelastic behavior of thick-walled cylinders of a homogeneous. isotropic, impermeable material. In either the elastic or plastic state, if the conditions of homogeneity. isotropy, and impermeability were the normal characteristics of rock. there would be no reason to question the validity of the above principles when applied to rock. However. since most rock formations are characteristically permeable to some degree, contain bedding planes and small intrinsic fractures. and are heterogeneous, rendering invalid the assumptions of homogeneity, isotropy, and impermeability, the application of the thick-walled cylinder theories to the behavior of rock formations penetrated by a bore appears illogical. Also the failure to consider the effect of the properties of the drilling fluids, which certainly intrude in various degrees into most rock formations. is further cause for questioning the application of these principles. Even in the case of cylinders of hardened chrome-nickel steel, which would he considered relatively homogeneous isotropic. and impermeable, as compared to rock, it has been observed that the internal pressure capable of being withstood by the cylinders varied with the sizes of molecules comprising the rupturing fluid used. Because of these apparent weaknesses in the theories of the behavior of thick-walled cylinders when applied to bores in rock, and the importance of knowing the true behavior of rock under the influence of fluid pressure when planning drilling and completing procedures for wells, tests were undertaken to determine by observation the actual rupturing pressure of cylinders of rock and the effects of such variables as environmental conditions and characteristics of rock formations, fluid properties, and bore dimensions. It was intended that by these tests the validity of the thick-walled cylinder theories when applied to rock would be determined and, if found invalid, mathematical expressions would be derived for predicting stress and rupturing pressure of rock formations under various conditions. Since the derivation of mathematical expressions has been only partially completed, all of the results of the latter phase are not included in this paper. PROCEDURE The investigation was initialed with a study of the theories pertaining to the rupturing of thick-walled cylinders of homogeneous. isotropic, impermeable material and a study of the

Jan 1, 1953

By Theodore P. Holt

The Mines Operating Co.'s plant at Park City, Utah, was designed to treat the low-grade fillings in the old stopes of the Ontario mine. These fillings carry 6 to 14 oz. of silver, 1 to 2 lb. of copper, 0.01 to 0.015 oz. of gold, and a small percentage of lead and zinc. The treatment consists in mixing the crushed ore with coal dust and salt and then roasting in a new type of furnace by combustion of the contained fuel. The roasted ore is leached with an acid salt solution to dissolve the silver, gold, copper, and lead. At present these metals are precipitated together on scrap iron and the product sold to a refinery. The only new feature of importance in this scheme of treatment is the roasting process, which makes possible the chloridizing of ores without any loss of the valuable metals, and at a very low cost. History of the Development of the Process The roasting process- had its beginning in connection with research work at the Utah State School of Mines. N. C. Christensen, Jr., who held one of the School of Mines' fellowships, was engaged in some experimental work on blast roasting. At the same time I was doing some work on the insoluble gold in Mercur base ores. Mr. Christensen roasted some of this base gold ore in his pot furnace, and found that when he mixed a sufficiently low percentage of fuel with the ore, it did not sinter but roasted to a leachable product. We considered this a new application of blast roasting, and proceeded to test out a large number of ores in several different types of small roasters which we constructed.. This experimental work continued well into the summer of 1911. In August, 1911, the Consolidated Mercur Gold Mines Co. installed a small roaster of our design, which we proposed to operate on the counter-current principle, feeding mixed ore continuously on top, and at the same time drawing off the roasted ore from the bottom. By proper adjustment we hoped to maintain a permanent roasting zone near the center of the column, the ore moving downward as roasted. However, we

Jan 1, 1915

By B. M. Larsen, L. S. Darken

SOME years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2 by a high concentration of active (or "free") lime and of manganese oxide dis) solved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. DISTRIBUTION OF MANGANESE BETWEEN SLAG AND METAL AT EQUILIBRIUM On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction [FeO + Mn = MnO + Fe [A]slag metal slag metal] the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as [K" aMoO aFeI1 dFec) aMn] where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term [afe] may be combined with K" to give a new constant K'. Making these changes,

Jan 1, 1942

By Rex W. Woods, Morris Muskat

A leastmsquare analysis procedure has been developed and applied for the study of the deviations in estimations of oil in place as given by the material-balance equations. The data used were those obtained from field observations on the Jones sand in the Schuler pool, Arkansas, and the Monroe dolomite in the Reed City pool, Michigan. Possible effects of water intrusion were taken into account by expressing the cumulative water influx in terms of various functions previously proposed in the literature. Formulas were developed and values calculated for the minimum deviations and minimal percentage deviations in the calculated volumes of oil in place from the average values, as could be obtained by suitable choice of the water encroachment and initial gas-cap volume parameters. The results show that the fluctuations in these calculated volumes are very insensitive to the values chosen for the rate of water intrusion and initial gas-cap volume, and hence cannot be safely used in discriminating between spurious values for these parameters and such as actually pertain to the producing reservoirs. Moreover, the exact form of the water-intrusion function seems to have but little effect on the fluctuations in the computed oil in place. Accordingly, it is concluded that the material-balance method does not of itself provide a satisfactory criterion for determining the basic physical unknowns of producing reservoirs or in making conclusive decisions regarding the production mechanism, unless independently established geological control data are available for eliminating unreasonable values for the reservoir parameters, even though they may still satisfy the material-balance formulas. If, however, from core or logging data the initial oil in place and the gas-cap volume can be established in advance, the material-balance formulas can be inverted to find the water intrusion. Moreover, by determining by such calculations the water-intrusion coefficient, the iuture production performance can then be predicted by the aid of the materiaI-balance formulas for specified operating conditions. This type of application may be of particular value in predicting the results of Pressure-maintenance operations. Introduction The evaluation of the forces acting upon an oil reservoir is a problem of considerable interest to the operator as an aid in determining the proper method of operation for the reservoir to obtain an optimum recovery of oil. In many pools, the nature and magnitude of the forces acting upon the reservoir remain unknown until an appreciable amount of ultimate recovery is obtained. To be of value to the operator, a reliable interpretation of reservoir performance should be available in the early life of the pool to permit an optimum plan of operation. Progress has been made in an understanding of reservoir behavior and the importance of the different factors involved. The material-balance method of estimating oil in place has been proposed as a tool in analyzing reservoir-performance problems.l The solution of such problems by this method ordinarily involves two or more unknown values relating to the nature of the reservoir, and the results

Jan 1, 1945

By American Institute of Mining Engineers

David J. Mack (University of Wisconsin, Madison, Wise.)—Have the authors considered that the effects reported in their paper are readily explainable on the basis of equilibrium grain boundary segregation rather than ordering? It seems to the writer that all of their experiments and observations correlate well with known behavior associated with equilibrium grain boundary segregation. Although at first glance one would tend to dismiss such a possibility because of the similarity of the gold and copper atoms, their sizes differ by 12.8 pct which is in the range where segregation at grain boundaries would be expected. Then, too, the electrochemical differences between the copper, the Cu3Au, and the gold strongly suggest that a segregation mechanism is involved in the corrosion of the Cu-Au alloys. R. Bakish and W. D. Robertson (authors' reply)—The authors would like to thank Dr. Mack for his consideration of the problem of grain boundary segregation as an explanation of the observed phenomena. We had considered the problem in the following terms: Assuming a pure binary Cu-Au alloy and an ideal solid solution, the surface excess, T2= N25 — N2, of the second component (gold) may be expressed in the following way20 1 —exp (—da/kT) where 8 is the difference in surface tension of copper and gold, and a is the surface area per atom. In the present case, 6 is positive which implies that the component in excess at the boundary is gold. Since the only chemically active component in ferric chloride is copper, it does not appear that the segregation of gold is likely to increase the boundary activity. A small concentration of a third component could profoundly affect the situation. Analysis indicated only spectrographic traces of impurities, all of which are soluble in both copper and gold. Quenching experiments, reported in the paper, also tended to eliminate significant effects attributable to a third component.

Jan 1, 1958

By H. W. Mossman

Three aspects of magnetite smelting are discussed. The first is the working out of equilibrium conditions for eliminating sulfur. The second is the influence of magnetite solubility on the difficulty of tapping the reverb matte. The third is an approximation of the equilibrium conditions in the reverb gases which govern whether magnetite is mode or reduced in the reverb slag by these gases and by any iron sulfide in the slag. MAGNETITE has had a varied history in the Hurley Smelter since its start in 1939. Magnetite determinations on the smelter products are made regularly only on the monthly composite samples. Variations on the monthly averages are shown in Table I. Magnetite which drops from the slag and matte in the reverb has some slight bottom buildup which comes and goes, but no substantial accumulation from this source has been found at the end of a normal nine months' furnace campaign. However, there has been some low grade magnetite bearing material mixed with considerable A1,0,, which has slid down from the bottom of the sloping flue between the reverberatory furnace and the waste heat boilers. This accretion has required drilling and blasting near the skimming end of the furnace. The magnetite has interfered with tapping at times. When the smelter was first started, tapping trouble from magnetite was extremely severe. Increasing the reverberatory furnace temperature by putting in an air preheater and a Dutch oven has helped greatly, although there still is occasional tapping trouble. When the present series of physical chemistry articles on copper smelting started coming out in 1950, they were read with interest, but no immediate application was seen for them. Results of some laboratory work in 1952 aroused a much stronger interest in this physical chemistry. A series of melts was made on some converter slags, which had magnetite in very large grain sizes, with the object of reducing the grain sizes in the slag, as it was known that it was easier to handle in the reverb in that condition. Anything done in the tests greatly reduced the grain sizes—even in the controls, where nothing was done except melt the slag and cast it. There was more magnetite in the slags after the tests than before, and with wide variations. There were no obvious reasons lor much of what happened in these tests. Much of the base material published in English in this field was made available for study. Recalculations were made on many of the type problems, and part of the data was reduced to local temperatures and compositions. Explanations were found for what happened in the 1952 series of tests on converter slags, and the same principles turned out to be a description of much of what magnetite does in the reverb. This article is to present the results of that study, from the viewpoint of applying the technical material in definite numerical form to the operating conditions in both the converters and the reverberatory furnaces at the Hurley smelter. Table I. Magnetite Variations on Monthly Averages, 1939 to 1955 Pet Magnetite Lowest Highest Average Converter slag 13.6 43.3 25.4 Roverb slaa 2.7 20.9 8.7 Matte 28 15.9 98 In general it was found that magnetite is made or reduced in both the converters and the rever-beratory furnace, depending on variations of temperature, matte composition, and reverb gas composition occurring in ordinary plant operation. Within reasonable limits, the field conditions for formation or reduction can be predicted, and probably can be set up and maintained. Converter conditions affecting magnetite formation can be put into numerical values better than for the reverb from purely technical calculations. The converter can be operated so as to keep the magnetite in the slag down to between 12 and 14 pct and still give satisfactory life for the converter brick. This depends upon having converter flux available which will make a slag with a good separation without raising the temperature too high. In the Hurley reverb and others with similar conditions, it is likely that a compromise of conditions will give a reasonably good control of combustion and still keep the magnetite from building up on the bottom. This discussion consists of three main parts. The first is the working out of the equilibrium conditions in the converter for determining in which direction the reaction 3 Fe,,O, (s) + FeS (1) F? 10 FeO (1) + SO, will go under actual converter operating conditions. The second deals with the influence of the solubility of magnetite in the slag and matte in the reverb on the difficulty of tapping matte. The third is an approximation of the equilibrium conditions in the

Jan 1, 1957

By R. S. Moehlman

IN recent years, exploration and development by diamond drilling has become a popular attack on the problem of finding new ore shoots and developing extensions of known shoots. Diamond drilling has been used in recent years in extensive sampling of disseminated copper deposits, in preference to churn drilling. At the Harvard gold mine, near Jamestown, California, Philip R. Bradley, Jr., general superintendent, reports that: "The Harvard work was a singular example of the reliance that can be placed on diamond drilling in evaluating an ore body." Drilling at the Harvard mine will be discussed in a subsequent section of the paper. So popular has diamond drilling become, indeed, that many who have had slight experience with drilling are inclined to regard it as a cheap cure-all. This paper proposes to show some of the limitations on the application of drilling and some of the steps that should be followed in drilling programs to obtain reliable results. COST OF DRILLING Drilling has the advantage, over shaft sinking and drifting, of lower cost and greater speed. As compared with churn drilling, the advantage of bringing up a coherent sample instead of fine cuttings for a sample is obvious. Diamond drilling is generally more expensive, however, and more engineering effort is required in combining the average of core and sludge samples. Exploration of drift walls by hammer drills to a depth of less than 50 ft. is generally cheaper than diamond drilling, but beyond this depth the diamond drill is cheaper and more efficient. The principal factor in determining cost of drilling is the character of the ground drilled. Broken ground with many fissures is most expensive to drill. Hard ground is less of a problem with diamond drills than with ordinary machine drills. Hardness or softness affects only the speed of drilling. Caving, easily washed, sandy or clayey ground requires continual cementing and casing, which is the greatest cost problem. Thus, soft, incompetent ground is more costly to drill than hard, massive ground. Cost of drilling per foot in good to fair ground varies from less than $1 per foot, achieved in some districts in Ontario, the Mother Lode, and Missouri, to $5 per foot in many western states. In bad drilling ground, costs may range from $5 to $15 or more per foot, thus approaching the cost of drifting. Other factors that increase the cost per foot are: I. Short total length of hole drilled, so that the cost of moving in crews and equipment must be spread over a relatively few feet. 2. Cost of drilling per foot increases with depth beyond about 500 ft., as more time is consumed in pulling rods. 3. Cost of preparing drilling stations, getting air underground to stations, etc. 4. Inaccessibility and lack of water on the job make for higher costs.

Jan 1, 1946