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By R. E. Zimmerman

The separation of fine sizes of coal from its impurities by means of various flotation methods has become of increasing importance in the coal industry. This, no doubt, will be even more so in the future as the quantity of high grade coal is depleted, particularly that used for metallurgical purposes. The purpose of this paper is to describe and report the results of research work done under the auspices of the Pittsburgh Coal Co. to determine the amenability of their bituminous fine sizes of coal to flotation, to investigate the value of various reagents and factors affecting their use, and compare the results between froth flotation and bulk oil flotation. Compared with the preferential flotation of complex minerals, or ores, the flotation of coal is comparatively easy. However, this statement should not lull one into the feeling that there are no special problems involved. For instance, the separation of coal from pyrite in high sulphur coals is still far from being 100 pet successful. Size consist has considerable effect on reagent consumption and recovery. Other factors will be described and finally it must be remembered that in the flotation of coal a low priced material is being treated and thus economic considerations govern more closely its application than is generally the case in treating other minerals. As a result of the research work done by the Pittsburgh Coal Co. on the flotation of coal, it was concluded that it was practical to clean the —48-mesh coal commercially by froth flotation and after several different types of flotation units and circuits were investigated by means of pilot plants, large scale units were installed at their Champion Nos. 1, 4 and 5 Preparation Plants for the cleaning of —48-mesh slurries. These large scale operations have been recently described by D. H. Davis.' C. P. Proctor and C. B. Carlson2 in their chapter on Froth Flotation of Coal in the AIME Seeley W. Mudd series book on Coal Preparation describe some of the practical applications of our Pittsburgh Coal Co. laboratory work in actual plant practice as well as summarizing part of the investiga-tional work. The author presents this paper, however, as a supplement to their reports, and records the basic research accomplished in the laboratory investiga-tional work as well as the results of experiments using bulk oil flotation. In presenting this work the author wishes to state much more work must be done in applying the principles of flotation to cleaning coal, especially in view of recent studies and practices in other mineral beneficiation fields. Methods of Conducting Laboratory Tests The bulk of the research work was conducted in the laboratory of the Champion No. I Preparation Plant. This plant has elaborate facilities for sampling and analyzing coal and proved to be an admirable location for the investigational work. Four types of laboratory flotation ma-

Jan 1, 1949

By J. B. Morrow, D. H. Davis

THERE are two general approaches to the problem of increasing profits from an operation. One is to lower expense; the other is to raise income. Mechanical preparation of coal may be used for either purpose but a prudent consideration of many details must precede any decision lest the results be negative instead of positive. It is quite possible that any net gain will result from a combination of the two. Since mechanically prepared coal invariably is a better product qualitatively than a hand-picked coal from the same mine, it is a reason- able expectation that the customer will be willing to increase the producer's income by paying a higher price. Or there may be the possibility that a combination of mechanical mining plus mechanical cleaning will give a lower over-all production cost for the coal in the railroad car. More likely, there will be found a combination of these two factors. From the customer's point of view, the competitive delivered cost per B.t.u. considered in relation to such incidental factors as dust nuisance, handling properties, ash disposal, and ash fusibility determines what he will pay. In a bulk tonnage product such as coal, freight is a very considerable part of the delivered fuel cost, and obviously freight paid on incombustible ash has no economic attractions. INCENTIVE FOR CLEANING Coal is prepared in four major ways: 1 (I) by screening or sizing, (a) by mixing or blending, (3) by cleaning, including hand picking and mechanical cleaning, (4) by dustless treatment. By a combination of any or all of these methods, coal can be prepared to standard specifications. It is easily possible to have good cleaning and still get a poor final product because of faulty screening or mixing,

Jan 1, 1943

By S. Gstalder, J. Raynal

Consideration was given to simple tests which could be performed on rocks to give a measure of rock drillability. Various methods of breaking rocks were considered and the hardness test developed by Schreiner was selected for this study. The test involves application of an increasing load on the rock face through a flat-faced cylindrical punch until rupture occurs. Test results show that hardness is a good measure of the breaking strength of rocks. Useful relationships are shown to exist between hardness and other physical quantities such as specific disintegration, Young's modulus and sonic velocity. Specific disintegration (volume of rock broken per unit of work input) provides a possible means of comparing the effectiveness of other methods of rock breakage. The relationship between hardness and sonic velocity may be very significant for it may be possible to deduce rock drillability from sonic log data. provided that a mineralogical factor is taken into account. TO test further the results of the work, laboratory drilling tests were performed which closely simulated down-hole pressure conditions. Correlations of drilling results with rock hardness measurements were quite good. It was concluded that rock hardness, as measured in the laboratory or as deduced from sonic logs, could be used in relations for predicting rock drilling performance. INTRODUCTION Drillability of rocks cannot be defined in an absolute manner by a single quantity or measured by a single test. Resistance of rock to drilling depends to a large extent upon the means used for rock destruction. This complicates drillability classification of rocks for there may be as many classifications as there are methods of rock breakage without known functional relations between them. The objective of this work was to develop. in terms of rock destruction behavior, means of selecting the best drilling method for a given rock or the conditions for optimum output from a given drilling method. ANALYSIS OF ROCK DESTRUCTION TESTS Gauthier and Baron' have reviewed the many test methods which have been developed for determining the resistance of rocks to breakage. These include drilling tests, punch tests, scratch tests, resistance to shock, wear tests, etc. A standard drilling test might be to determine the time required to drill a standard depth (1/16 in.) in a rock using a bi-cone microbit (1 1/4-in. diameter) when a standard load (417 Ib) is applied at a standard speed of bit rotation (110 rpm). From the standpoint of similarity, the results of microbit drilling tests would seem to be most representative of the several methods suggested above. However, evaluation of drilling performance by this method is only qualitative and cannot be applied directly to actual drilling conditions. Punch tests basically measure rock hardness. Punches of various shapes and sizes, including small cones for Vickers' and Knoop's tests, the wedge for Epstein's test and the right circular cylinder for Schreiner's test, have been used. Results of these tests lead to a quantitative hardness classification which would seem to be related to the resistance of rock to bit-tooth penetration. Scratch tests are related to the resistance of rocks to abrasion such as would be encountered in drilling with diamonds. Either the width of the scratch obtained at a fixed load or the load required to give a scratch of a fixed width may be used to evaluate surface hardness of the rock. This should be related to the resistance of the rock to wear. The above tests, and probably many others. give relative measurements of the breakage or destruction characteristics of rocks. There is no direct relation between results of these tests and the drillability of rocks. Also, the tests each measure different quantities which have different dimensions and they do not permit direct comparison of numerical values. As one step in rectifying the above difficulties. it is proposed that the results of all test methods be expressed in terms of volume of rock destroyed per unit of work required; this is referred to as "specific disintegration". Test results may then be reported in a form which shows both a classification of rocks in regard to each method and a comparison of methods with regard to each rock. The disadvantage in using specific disintegration is the difficulty of measuring this quantity with accuracy. The volume of rock damage is difficult to measure. as is the true value of work input. Rock heterogeneity adds to the

Jan 1, 1967

By Theodore B. Comstock

The existing topographical features of the United States present many points of interest to the student of dynamical geology, but there is, perhaps, no subject which offers a more promising field for investigation than the relations between the geological structure and the mineralogical characteristics of the principal mining districts. There are seven prominent culminating points in the relief of North America, each one of which can be used as a type of the physical features of all the others. Again, if we divide these seven elevated districts into two sets, we shall discover a still more striking parallelism between the individual members of each group. But the most remarkable revelation is the fact that each one of these points is more or less closely the centre of an area of economically important mineral resources. It is interesting to note in this connection that six of these mineral tracts lie mainly within the borders of the United States, three of them being almost wholly in our territory. For

Jan 1, 1883

By George Norman

A NUMBER of methods have been developed for the determination of the dust concentration in air, some of which have been reported as very efficient and for research may be more satisfactory than the method about to be described. In practical mine use, however, the accurate research equipment is unwieldy and requires a high degree of technical skill to manipulate it. Also, it gives less general practical information to the operator in the same length of time than the method described here. Moreover, it is doubtful whether at the present stage of affairs the results obtained from the precise methods have any more practical significance than those obtained with simpler and more portable appara-tus, which can rapidly give a sufficiently reliable indication of the rela-tive dust hazard.

Jan 1, 1937

By J. W. Lacey, F. H. Brinkman, J. E. Faris

This paper presents an analysis of the high-pressure, gas-driven LPG-slug process, based on fluid flow tests in areal models. Two types of tests were made. One series was made in low-pressure models which permitted observation of fluid movement. Three completely misci-ble analog fluids were used. A second series of tests was made in high-pressure models using methane, propane and a light refined oil saturated with methane at room temperature and 1,550 psig. Under the test conditions of room temperature and a pressure level of 1,550 psig, the phase diagram for the fluids used is similar to those for many of the field systems where the process is considered for use. A method for using these laboratory data to calculate field performance of the process is outlined. As a result of this work, it is concluded that small banks of LPG (5 per cent HV or less) are not effective in increasing oil recovery in horizontal reservoirs. Znstead, where small banks are used, the driving gas quickly penetrates the LPG bank because of fingering and channeling; and from this point on, the process behaves essentially as an immiscible gas-injection project. The validity of this conclusion was substantiated by: (1) laboratory studies of the effect of rate, model size and mobility ratio on miscible displacement in areal models; and (2) calculation of field recovery, which compared closely with actual field recovery. INTRODUCTION Field applications and pilot tests of the gas-driven, LPG-bank, oil-recovery process are on the increase. Most of these tests are employing small banks (2% to 5 per cent hydrocarbon volume) of LPG, which is miscible with both the driving gas and the oil in place, in an effort to attain an effective yet economical miscible displacement of oil by gas. The expectation of miscible displacement with small banks is based on the concepts that: (1) lengths of solvent-oil mixed zones, measured during miscible displacements in long slim cores, are representative of those that will occur in the field; and (2) areal sweep efficiencies5 measured in electrolytic model studies are applicable to miscible displacement in reservoirs. Our experimental evidence indicates that the mixed-zone lengths and sweep efficiencies mentioned are not applicable to miscible displacement in reservoirs. In this paper we present an evaluation of the gas-driven, LPG-bank oil-recovery process based on fluid flow experiments in areal models. These results are used to predict the performance of a field pilot test of this process, and the results are compared with the actual test results. THE EFFECTIVENESS OF LPG BANKS The effectiveness of LPG banks of various sizes in accomplishing miscible displacement of oil by gas was determined by displacement tests in a model representing one-quarter of a confined five-spot pattern. The model, 12 X 12 X 1/4 in. in size, was packed uniformly with glass beads. It was operated at a pressure of 1,550 psig and at room temperature; the fluids used were methane, propane and refined oil saturated with methane at 1,550 psig. The saturated oil had a viscosity of 1.2 cp at room temperature. The results of these tests are shown in Fig. 1, where recovery is plotted as a function of the volume of fluid injected for: (1) an immiscible-gas drive with an oil-to-gas viscosity ratio of 85; (2) three sizes of LPG banks; and (3) two completely miscible displacements with mobility ratios of 85:1 and 10:1. (The miscible displacement data plotted are the averages of several tests.) The results show that a 2½ per cent bank of LPG does not increase oil recovery over that obtained by immiscible-gas drive. The 7 and 17 per cent banks are, respectively, about 30 and 50 per cent effective (with reference to the M = 85 miscible-displacement curve) in increasing oil recovery at the point where 2½ hydrocarbon volumes (HV) of fluid have been injected. The percentage effectiveness of the banks at a given volume of fluid injected is defined as Recovery by Bank — Recovery by Gas Drive Recovery by Miscible Recovery by Flooding Gas Drive We conclude from these results that banks of LPG smaller than about 5 per cent HV in an individual stratum will cause from little to no increase in oil recovery. This finding was substantiated by work in low-pressure models, which permitted visual observation of fluid movements. In these tests, three completely miscible fluids having the same viscosity ratios as those used in

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By W. A. Bruce

Studies of reservoir behavior of 12 Smackover limestone oil and condensate pools are presented. Buckner, Midway, McKamie, Magnolia, Mt. Holly, Schuler (Reynolds) and Village are treated in considerable detail and subjected to analysis with an electrical device for analyzing reservoir behavior. Results and comparisons of these analyses are presented. In addition to these reservoir-behavior studies, an attempt is made to assemble trans-missibility and storage data on the Smackover limestone formation from cores and logs taken in dry holes and producers. This together with the behavior of individual reservoirs leads to a better understanding of the formation as a porous aquifer. The ultimate purpose of this type of study is to improve predictions concerning the future behavior of these pools in such a system. Predictions are presented for several pools. Introduction In 1937 the Phillips Petroleum Co. drilled its J. D. Reynolds No. I to the Smackover limestone formation at Snow Hill, Arkansas. This well found oil in the porous, permeable, upper part of the Smackover, thereafter referred to as the Reynolds lime. Since then, six oil pools and six condensate pools have been discovered in the Reynolds lime, and more than 75 dry holes have explored parts of this formation. By the first of 1943, 44 million barrels of oil and 83 billion cubic feet of gas had been withdrawn from the various reservoirs. The original reserves estimated by the Arkansas Oil and Gas Commission were 342 million barrels of oil and rzoo billion cubic feet of gas. So far all of the production has been from anticlinal structures, most of which are asymmetric and have their axes roughly perpendicular to the dip of the formation top. This is indicated in Fig. I, which shows the pools, dry holes drilled, and contours on top of the Smackover.' These pools are of particular interest for reservoir-behavior studies because the production and drilling has been controlled, and in most cases the records of reservoir data are complete. In addition to the excellent production and pressure information available, more than one half of the wells drilled were cored and all of them were electrically logged. All of the pools show evidence of water drive. While this paper is in a sense a collection of reservoir-behavior studies for several different pools, there has been an attempt to go one step further and to show the importance of the iormation as a porous continuum or a single aquifer in which the withdrawals of fluids from any pool has an important effect on the behavior of all of the pools. An effort will be made to show that the water drives of these pools are dependent upon a much larger area of the Smackover limestone than that occupied by the petroleum accumulations.

Jan 1, 1944

By W. A. Bruce

Studies of reservoir behavior of 12 Smackover limestone oil and condensate pools are presented. Buckner, Midway, McKamie, Magnolia, Mt. Holly, Schuler (Reynolds) and Village are treated in considerable detail and subjected to analysis with an electrical device for analyzing reservoir behavior. Results and comparisons of these analyses are presented. In addition to these reservoir-behavior studies, an attempt is made to assemble trans-missibility and storage data on the Smackover limestone formation from cores and logs taken in dry holes and producers. This together with the behavior of individual reservoirs leads to a better understanding of the formation as a porous aquifer. The ultimate purpose of this type of study is to improve predictions concerning the future behavior of these pools in such a system. Predictions are presented for several pools. Introduction In 1937 the Phillips Petroleum Co. drilled its J. D. Reynolds No. I to the Smackover limestone formation at Snow Hill, Arkansas. This well found oil in the porous, permeable, upper part of the Smackover, thereafter referred to as the Reynolds lime. Since then, six oil pools and six condensate pools have been discovered in the Reynolds lime, and more than 75 dry holes have explored parts of this formation. By the first of 1943, 44 million barrels of oil and 83 billion cubic feet of gas had been withdrawn from the various reservoirs. The original reserves estimated by the Arkansas Oil and Gas Commission were 342 million barrels of oil and rzoo billion cubic feet of gas. So far all of the production has been from anticlinal structures, most of which are asymmetric and have their axes roughly perpendicular to the dip of the formation top. This is indicated in Fig. I, which shows the pools, dry holes drilled, and contours on top of the Smackover.' These pools are of particular interest for reservoir-behavior studies because the production and drilling has been controlled, and in most cases the records of reservoir data are complete. In addition to the excellent production and pressure information available, more than one half of the wells drilled were cored and all of them were electrically logged. All of the pools show evidence of water drive. While this paper is in a sense a collection of reservoir-behavior studies for several different pools, there has been an attempt to go one step further and to show the importance of the iormation as a porous continuum or a single aquifer in which the withdrawals of fluids from any pool has an important effect on the behavior of all of the pools. An effort will be made to show that the water drives of these pools are dependent upon a much larger area of the Smackover limestone than that occupied by the petroleum accumulations.

Jan 1, 1944

By J. E. Dorn, S. K. Mitra

The low -temperature tensile and creep behaviors of single crystals of copper were evaluated and analyzed in such a manner as to provide an estimate of the separate contributions of short-and long-range stress fields to strain-hardening. Furthermore, the average force-displacement diagram for thermally activated intep-section of two dislocations was estublished. This diagram plus a knowledge of the variation of dislocation spacing and the long-range back stresses with strain permits on accurate prediction of creep rates. The calculated activation energy for intersection under conditions of a constant strain rate increases linearly with the absolute tempevatus-e as required by theory. AN understanding of the detailed mechanisms for strain hardening constitutes one of the principal unsolved problems in dislocation theory. Two major models for strain hardening have been advanced in the past. The one that has received greatest attention assumes that strain hardening arises exclusively from long range interaction stresses between moving dislocations and piled-up arrays of blocked dislocations on the slip planes. This type of interaction was first announced by Taylor' who revealed that the back stress fields due to a simple uniform array of positive and negative dislocations entrapped in the deformed crystal would result in parabolic hardening. Shortly thereafter Andrade and Henderson" demonstrated that the strain hardening of fcc single crystals was not parabolic, as previously thought, and finally it was recognized that a typical stress-strain curve consisted of three successive stages of deformation, niz., the easy glide, Stage I, linear hardening, Stage 11, and the parabolic hardening, Stage 111, ranges. The objections to Taylor's somewhat na'ive model, which were presented so forcefully by cottrell; were largely removed by the more realistic details incorporated in Mott's analysis.5 But because Mott's theory for hardening via long range stress fields gave somewhat analogous results to that of Taylor's (inasmuch as it also predicted a parabolic rate of strain hardening whereas the observed rate of strain hardening in Stages I and I1 were linear), it was not widely accepted. Major consideration was therefore given to models, such as those which were advanced by Friedel and seegere that were formulated for the ad hoc purpose of yielding linear rates of strain hardening. The second major thought regarding strain hardening is based on the concept that it arises principally from short-range stress fields due to the interactions between intersecting dislocations. Cottrell and stokes7 showed, several years ago, that the constancy of the flow stress ratio at two temperatures regardless of the strain was inconsistent with the concept that strain hardening arose exclusively from long-range back stresses. The argument that strain hardening was primarily due to local interactions of intersecting dislocations was presented in considerable detail by asinski.' Extending Basinski's method of analysis of the intersection process, Mitra, Os-borne, and dorn recently demonstrated that indeed the strain hardening in aluminum single crystals arises principally from local effects coincident with intersection; however, these conclusions, too, must be modified, as will be shown later in this report. The present investigation, devoted principally to the low-temperature deformation of copper single crystals, was initiated in an attempt to ascertain whether or not the same conclusions arrived at for aluminum also apply to metals, such as copper, which have much wider stacking faults. It was soon observed that the strain hardening in copper could not be attributed exclusively to local effects between intersecting dislocations. Previously no analytical method for arriving at the possible simultaneous contributions of long-range stress fields and localized forces on intersecting dislocations was available; consequently, the separation of these two factors could not be readily accomplished. In the present report a method of estimating the separate contributions of each of these two factors to strain-hardening will be presented. The authors will show that both long-range stress fields of the type contemplated by Seeger and Friedel as well as short-range forces of the type considered by Basinski are responsible for strain hardening in fcc metals at low temperatures. This method of analysis also accounts for, in a satisfactory way, the effect of stress, temperature, and strain on the creep rate under constant stress. Furthermore, in the course of presenting their methods of analysis the authors will also reveal the rather complete agreement of their experimental data with the concepts of the theory for thermally activated intersection of dislocations. INTERSECTION MODEL As shown by seegerl0 the strain rate arising from thermally activated intersection of dislocations is given by

Jan 1, 1962

By Lincoln F. Elkins, John T. Cooke

Injection of gas to increase oil recovery has been considered for almost all important discoveries during the past ten or fifteen years. However, the number of gas injection projects having sufficient history and data is too limited to permit valid generalities of effectiveness of gas injection. Management and engineers are faced with a difficult problem of selecting those reservoirs which are susceptible to profitable application of gas injection. Injection of gas to maintain high pressure favors some factors affecting reservoir performance such as viscosity, surface tension, and formation volume factor of oil by keeping gas in solution and favors some operating features such as extending flowing life of wells and storing part of the produced gas for future use or sales. Injection of gas at low pressure involves lower compression ratio, or at least a single gas-gathering system, larger displacement volume in the reservoir per unit of gas handled, and permits effective utilization of the naturally existing energy and agent for oil displacement that is gas dissolved in oil. Each program is thus a compromise to meet optimum economic conditions while striving to attain maximum recovery of this important nautral resource. The statement has often been made that pressure maintenance would greatly increase oil recovery by permitting abandonment of formation oil inflated with gas in solution rather than abandonment of the same liquid volume of tank oil, if the same terminal oil saturation could be attained. Simple calculations indicate increases in oil recov- ery as high as one hundred per cent on this basis for high formation volume factor oil encountered in current deep drilling. Important in this statement is "if the same terminal oil saturation could be attained." Implicit in this statement are the requirement of physical

Jan 1, 1949

By John T. Cooke, Lincoln F. Elkins

Injection of gas to increase oil recovery has been considered for almost all important discoveries during the past ten or fifteen years. However, the number of gas injection projects having sufficient history and data is too limited to permit valid generalities of effectiveness of gas injection. Management and engineers are faced with a difficult problem of selecting those reservoirs which are susceptible to profitable application of gas injection. Injection of gas to maintain high pressure favors some factors affecting reservoir performance such as viscosity, surface tension, and formation volume factor of oil by keeping gas in solution and favors some operating features such as extending flowing life of wells and storing part of the produced gas for future use or sales. Injection of gas at low pressure involves lower compression ratio, or at least a single gas-gathering system, larger displacement volume in the reservoir per unit of gas handled, and permits effective utilization of the naturally existing energy and agent for oil displacement that is gas dissolved in oil. Each program is thus a compromise to meet optimum economic conditions while striving to attain maximum recovery of this important nautral resource. The statement has often been made that pressure maintenance would greatly increase oil recovery by permitting abandonment of formation oil inflated with gas in solution rather than abandonment of the same liquid volume of tank oil, if the same terminal oil saturation could be attained. Simple calculations indicate increases in oil recov- ery as high as one hundred per cent on this basis for high formation volume factor oil encountered in current deep drilling. Important in this statement is "if the same terminal oil saturation could be attained." Implicit in this statement are the requirement of physical

Jan 1, 1949

PHILIP D. BLOCK, JR., vice president of Inland Steel Co., visualizes a fine future for the Menominee Range of the Upper Peninsula of Michigan. He sees a future unclouded by threat from foreign ore imports or the development of low grade ore processing in Minnesota. The statement was made during the opening of Inland's new Cayia mine near Crystal Falls. Inland, according to the vice president, is planning to use an increased amount of the high phosphorous ores found on the Menominee Range. He said that other steel companies will probably do the same, because the steel industry has learned how to use ores of high phosphorous content. He said: "I do not mean to imply that we can use an unlimited amount of high phosphorous ores or that we can burden our blast, furnaces with 100 pct high phosphorous ores, but we have reached the point where we can absorb a much larger percentage of these ores without any detrimental effects. Foreign ores and lowgrade Minnesota ores cost too much to offer real competition, Block said. Transportation costs from the Menominee range to steel producing centers in Chicago and on Lake Erie are less than for any other range in this country. In the meantime, the American operators of the Bomi Hills iron ore mine in Liberia, have reportedly signed a new agreement with the Government. Several months ago, President Tubman of Liberia expressed a definite dissatisfaction with the original contract. Informants state that the agreement only needs the approval of the Export-Import Bank, which loaned Liberian Mining Co. $4 million to develop the iron ore properties. Majority stockholder of the Liberian Mining is Republic steel, with 61.57 pct of the stock. Under the new contract, the Liberian Government will start to share in the profits when the indebtedness is liquidated and the return of invested capital accomplished, or April 1, 1957, whichever is earlier. Under the old agreement the Liberian Government received a 5 cent per ton royalty and an additional sum based on the price of pig iron. The royalty rate reached more than 17 cents per ton this year. After debt liquidation the Liberian Government will receive 25 pct of net profits for the first five years; 35 pct for the next ten years; and 50 pct thereafter. Until the Government starts to share in profits it will receive a royalty of $1.50 per ton in U. S. currency, in addition to royalties provided for in the old agreement.

Jan 1, 1952

By Lyle L. Marsh, David L. Douglas

CORRELATION was made between the heat treatment and hardness of three U-Ti alloys ranging in composition from 8.5 to 50 atomic pct Ti. The following important observations were made: 1) A direct quench of y U-Ti solid solution resulted in the formation of a hard martensitic phase in low-titanium alloys. 2) Subsequent tempering initially increased the hardness by the precipitation of a fine dispersion of U2Ti; further precipitation of U2Ti with tempering time eventually resulted in softening. 3) High-hardness levels were obtained also by isothermal transformation of an 8.5 atomic pct Ti alloy at 400º and 500°C. 4) The crystal structure of the phases present at the solution-treating temperature (one region in the phase diagram excepted) and the temperature within a given phase region affected the hardness of both quenched and isothermally transformed alloys. Introduction It has been known since 1887 that the mechanical properties of metals were dependent upon their microstructure. Sorby pointed out in that year that annealed gray iron castings were softer than chilled iron castings by virtue of the graphite which had replaced hard cementite in the microstructure. Over the years, interest has increased in the effect of microstructure on the mechanical properties of metals, and now high-strength levels may be achieved by bringing about the dispersion of a second phase or by other microstructural adjustments. The nature of a second phase in an alloy strongly influences the properties. For example, the size, shape, amount, and distribution of a second phase plays a very important role in the ultimate properties of an alloy. Microstructural control is achieved by heat treatments. Hence, any alloy system of potential use should be understood in terms of its response to heat treatment and the resultant effects upon the properties.

Jan 1, 1958

By Wido Tilmann

13.6-1. Importance. In Germany there are large tertiary brown coal reserves, most of which are located close to the surface. Therefore, brown coal has been recovered for many years by means of opencast methods. By utilizing a high degree of technology, a rational operation has been achieved, and as a result, the mining techniques have become renowned all over the world. After the war, all the dredgers and overburden spreaders, as well as the means of conveyance, had to be redeveloped for adapting this equipment to the changing conditions of the deposits. Numerous auxiliary machines were adopted from the American earth moving industry and altered according to the different requirements. As a result of such technical developments, the output per man and per shift was increased remarkably in spite of the deterioration of the geological conditions. In the whole of Germany, the total reserves of brown coal amount to 100 billion metric tons, of which 60 billion tons are situated in the Federal Republic of Germany. In the latter area, 8.5 billion tons will be recover- able by opencast means, of which 3.5 billion tons are already developed. The annual output reached 102 million tons in 1965. This total figure comes from four different mining districts: Rhineland, Helmstedt (town at the border of the Soviet occupied zone), Hesse, and Bavaria. The production figures (1965) are as follows: [ ]

Jan 1, 1968

By E. R. Dean

A wire-feed mechanism has been employed to fabricute metal alloy film resistors to various sheet resistivities on oxidized silicon substrates. The effect of several thousand hours storage in air at elevated temperatures on the resistance and temperature coefficient of resistance is presented. Unprotected films of- sheet resistivity between 100 and 500 ohms per sq fabricated at 300°C substrate tenzperatures were unstable when stored at 150°Cfor extended periods. The higher sheet resistivity films exhibited the greatest instability; however, even the 100 ohms per sq films drijted excessively for device application. When stored at still higher temperatures, the normalized resistance increases to maximum, then decreases until a minimum value is obtained, then finally increases in resistance until open. The use of a protective overcoating of SiO has had considerable benejicial effects on the film stability, so that 250 ohms per sq films deposited on 300°C substrates are now stable after 1000 hr storage at 250°C and possess a temperature coefficient of resistance less than 200 ppm per C. The use of a low substrate temperature during depositon (100°C) enables the preparation oj resistors with very low tenperature coefficients of resistance (10 to 20 ppnl per 'C). However, these films are less stable than their higher substrate temperatuve counterparts. During extended storage, the resistance of the protected films always decreases with lower substrate films exhibiting larger normalized resistance decreases. This resistance decrease is accompanied by a linearly related increase in the temperature coefficient of resistance. The electrical behavior of these films may be explained by postulating That the structure of the films is in the transition region between thick continuous films and ultrathin island structure films so that the conductivity is the restlt of both electron scattering and tunneling-activated charge carrier creation between neighboring grains. The annealing behavior when thermally aged is the result of defect anneal, grain growth, and selective oxidation. TheRE is a considerable interest in thin metallic films for use as resistor elements in microelectronic circuits.1,2 These resistor films must be stable when exposed to elevated-temperature storage or operating ambient, possess low temperature coefficients of resistance (hereafter referred to as T.C.R.), and be of a high enough sheet resistivity to be useful. The resistivity and T.C.R. of a thin metallic film are determined by the structure and thickness of the film. Hence the stability of the film when exposed to stress would depend on the stability of the structure. The resistivity of a thin film is the result of the electrons' interaction with the lattice vibrations (electron-phonon scattering), scattering of electrons due to impurities, defects, and grain boundaries and specula reflection from the film surfaces.3' All of these effects serve to reduce the electron mean free path and result in a resistivity higher than the ideal bulk. In ultrathin films possessing essentially an island structure consisting of a planar array of aggregates separated by a few to a few tens of angstroms, conduction is dominated by a combination of tunneling and activated charge carrier reation. Thin films would be characterized by relatively low resistivity, positive T.C.R., and reasonable structure stability whereas ultrathin films possess unstable structures, negative T.C.R., and exhibit high resistivity. Feldman6 has investigated films intermediate between the two regions and postulates that the resistivity of a film in the transition region is composed of two linearly additive parts: that due to the resistance of the grains and that due to the gaps. The grain resistivity would represent the scattering of the conduction electrons by defects, surfaces, and phonon interaction while the gap term represents the tunneling contribution. For gold and platinum films, he found as the film structure becomes progressively less continuous, corresponding to thinner films, the absolute value of the T.C.R. becomes progressively smaller until negative values are observed with respective zero T.C.R.'s at about 35 and 150 ohm per sq, respectively. Recently the author7 investigated the behavior of a multicomponent alloy of nickel, chromium, and iron and found the T.C.R.'s of these films decrease with decreasing substrate temperature during deposition. The lower T.C.A. associated with lower substrate temperatures was attributed to an increased contribution to the total resistivity from the negatively temperature-dependent gap tunneling since it is well-known that thin films deposited on low-temperature substrates consist of a higher density of smaller grains than the same sheet resistivity films deposited on higher-temperature substrates. Under conditions of thermal anneal, the author found that, when various sheet resistivity films fabricated at 300°C substrate temperature are exposed to extended storage in air at 300°C, the thinner films increase in resistance until open, while the thicker films

Jan 1, 1967

By Alan Probert

IN his inaugural address in 1949, President Truman made a policy declaration which launched the foreign technical assistance program known to the world as Point Four. Congress passed Public Law 535 defining the scope of the program and holding activities to certain limitations. It also provided $34.5 million for the first fiscal year. The Technical Cooperation Administration was established within the Department of State to coordinate and direct a program to include "economic, engineering, medical, educational, agricultural, fishery, mineral and fiscal surveys, demonstration, training and similar projects." The mineral programs of Point Four have been staffed and managed by two agencies of the Department of Interior, the Geological Survey and the Bureau of Mines. The Geological Survey is concerned primarily with water-supply problems, the discovery of mineral deposits, and the determination of habit, shape, and grade of mineral deposits. The Bureau of Mines is concerned with determining the commercial potentialities of mineral deposits, mineral technology, and the production and distribution of mineral commodities. Mineral projects comprised only 1 pet of the first year's budget. In spite of the relatively insignificant expenditure compared to those for food, agriculture, and health, a commendable record has been achieved.

Jan 1, 1952

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By Henry E. Wood

In my opinion, the concentration of minerals by flotation is the most interesting problem in ore-dressing, and will command eventually far more consideration than it has at present. For many ores it furnishes a complete method of concentration absolutely independent of specific gravity, and thus simplifies the milling of many difficult combinations. Not having to recognize the influence of specific gravity, we are also able to dispense with some of the complications resulting from classifying-conditions. Where flotation cannot be used for a complete separation of the minerals from the gangue, it will be found, in nearly all cases, to save those portions which are generally lost by reason of their fine state of division. For this reason, it should be looked upon mainly as an aid to general concentration, although there are many ores so well adapted to flotation that more than 90 per cent. of the valuable metals can be recovered from them in one operation by this process. In presenting the results of my investigations in flotation, I have endeavored to theorize as little as possible. That side of the subject has been extensively discussed by others. My earliest work with flotation was done in 1895, when I used various oils, grease, soap, etc., with results that were remarkable. I did not realize then that with water alone equally good separations could be made. Up to 1906, my endeavors were confined to attempts to keep the concentrates on the tables well wetted and away from exposure to the air. In common with others, I observed that when there mas any obstruction in the wash-water on the table of sufficient size to divert the water to either side, the concentrates collected, and, on exposure to the air, would promptly float away. This convinced me that the sulphides were all good "swimmers," and that if,

Jan 1, 1913

By F. M. Lewis, J. F. Myers

The selection of the proper type of flotation machine involves the consideration of a wide variety of factors. Under any condition, all types of machines will promote some kind of separation. Obviously, the correct way of deciding which type of machine is best suited for a particular problem would be to set up all types of machines and test them out in a competitive manner, but the vast number of small concentrating plants are unable to make such complete and exhaustive tests. The experience of the authors of this paper indicates that if all the factors involved in any particular problem can be determined, and if all the flotation-machine characteristics are understood, some basis for selection could be arrived at other than actual comparison. This paper is presented to show how the process factors and machine characteristics have been combined at the mills of the Tennessee Copper Co. from studies of several types of flotation machines. At the two mills of the Tennessee Copper Co. in the Ducktown Basin of Tennessee, four distinct flotation separations are made on the complex sulphide ore. Three different concentrates are produced from the ore—in the order of their importance: iron concentrate, copper concentrate, and zinc concentrate. Four different types of flotation machines are used. The selection of these four machines, for the plant operation, was based upon the study and operating experience of the machine units shown in the following list: Fagergren machine; square cell, size 56 inches Fagergren machine; level type, size 56 inches Denver machine; conical disk impeller, size 24 inches Denver machine; receded disk impeller, size 24 inches Minerals Separation Sub-A, size 24 inches Munro-Pearse deep cell, pneumatic Southwestern air machine, Hunt principle To date the study of flotation machines has been confined almost entirely to the rougher circuits. The various cleaning operations, being relatively a much simpler matter, have not been investigated so thoroughly. Table I shows a typical analysis of the two ores as well as of the mineral content.

Jan 1, 1947