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By M. C. Leverett

KNOWLEDGE of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum pro-duction, but is as yet incompletely devel-oped. The object of this paper is to show the application of well established thermody-namic and physical principles to these prob-lems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: I. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion of mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. CAPILLARY EQUILIBRIUM IN SANDS Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treat-ment of problems of mixture flow, the con-cepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis-turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predict-able from the theory of capillary equi-librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, of course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is as-sumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reser-voir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems in-volving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately in-vestigated experimentally. Experimental evaluation of the pertinent properties of natural reservoir rocks will permit the ex-tension of the numerical treatment to prob-lems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids; that is, the manner in which the reservoir fluids are distributed vertically when the forces due to capillarity are just balanced by those due to gravitation.

Jan 1, 1940

By Charles Will Wright

The application of the camera as an adjunct to topographic mapping began practically with its invention, and it has been employed with varying success since that time. With the exception of the camera to be described, the plate-camera has been universally used in this work, thus giving a projection of the area photographed on a flat surface. From such projections or photographs, by the rules of geometry and of perspective, points defining topographic features and seen from at least two camera-stations may be projected upon a ground-plane—the map.' In 1904 I employed the plate-camera for this purpose in Alaska, but found that the labor necessary to plot the maps, even in a general way, was long and tedious. In 1905 a small Eastman panoramic camera was fitted with spirit-levels, a sight-alidade and a transparent scale, introduced inside the camera to register the degree-points in the sky-line of the film-negative ; also, arrows to indicate the horizon-line. This was, on the whole, successful; but the details in the topography were not brought out in the views with sufficient clearness, aid the photographs were too small. These difficulties were overcome by obtaining a larger and more carefully constructed instrument, which was satisfactorily employed in the field during the year 1906. A panoramic view is made up of an integral number of perspective views upon flat surfaces, and logically is the most accurate and direct means to obtain an impression of a field of * Published by permission of the Director of the U. S. Geological Survey. Stanley, H. M. Photographic and Co-ordinate Surveying, Bans., xx., 740 to 766 (1891). Also, Flemer, J. ,4. Phototopographic Methods and Instruments, Report U. 8. Coast and Geodetic Survey, pt. 2, app. 10, pp. 619 to 735 (1897).

Jan 1, 1908

The Hadsel Mill. By R. G HALL (Trans, vol 112 4000 words) This mill is designed to effect the entire reduction of ores by combined crushing and grinding from mine run size to material sufficiently fine for the usual operation of flotation or cyaniding The work is begun and completed in the same machine. The machine is designed on the principal of the elevator wheel, and crushing and grinding are accomplished by dropping a mixture of ore and water upon specially placed "breaker plates" in such a manner that the resultant material passes back into the buckets of the wheel for further elevation One method of removal of the finished product is to permit an overflow of wet pulp on one side of the mill through coarse screens A recent improvement provides for the removal of a pulp by a launder part way up the path of the buckets In either case the pulp passes to a classifier, and the oversize back to the mill in the manner familiar in ball-mill practice Although hardly through the development stage, the machine has given a very good account of itself in simplification of plant, by elimination of coarse and fine crushers with consequent reduction of installation cost and power consumption As compared with the ball mill alone, there is a reduction of power consumption as well as a material reduction of grinding steel There is an increase in cost of maintenance other than grinding steel, but as the machine passes out of the development stage there is a show¬ing of reduction of costs on this item It seems probable that with further develop¬ment and strengthening of the weaker parts further improvement may be made Ball Milling. By A. M Gow, M GUGGENHEIM, A. B. CAMPBELL AND W. H COGHILL. (Tech Pub 517; also Trans, vol 112. 24,000 words) This paper outlines a new philosophy in ball milling by using power as an index of mill operation and ascertaining the effects of the set and induced variables By recognizing the amount of ore in the mill as an important induced variable and recognizing that the amount of ore in the mill depends principally on the size of the discharge trunnion, ball volume, rate of feed, and speed of mill, obstacles formerly met were surmounted When the amount of ore in the mill is dealt with intelligently and the applied work is proportional to the amount of feed, series testing, which would otherwise give a hotchpotch, gives concordant results The study of ball paths and trajectories was seen to be fruitless when it was shown that the old attrition theory for slow mill speed

Jan 1, 1935

By Leland Wemple

PREVIOUS to 1915, zinc refining had not become a general practice among the zinc smelters in the United States. Such refining as had been carried on was confined chiefly to remelting very high-leaded zinc, such as third-draw metal from the retort furnaces, and slab dross, and hard spelter from galvanizing pots. In this remelting operation, the lead and iron were settled out and the refined spelter obtained graded fifth class, i.e., Prime Western. Owing to the presence of lead in most zinc ores, the bulk of the spelter produced by direct smelting is of this Prime Western grade. Careful selection of ores of low lead content gave purer grades of spelter, i.e., Brass Special and Intermediate; and smelters which could secure ores carrying practically no lead produced high-grade spelter. Thus, in general, the grade of spelter produced by any smelter was pre-determined by the purity of the ore it could obtain. The needs of the warring nations of Europe for enormous quantities of cartridge and other high-grade brass resulted in such a demand for the purer grades of spelter that the available supply of lead-free and low-lead ores could not produce the quantity required. Prime Western grades went begging, so to speak, while high grades sold at times from 5 to 15 c. per pound over the Prime Western market. The great demand, coupled with the wide market margin, which permitted the inherent costs and losses, resulted in the conversion of the lower grades into higher grades by processes of refining. These conditions also accentuated the development and size of the electrolytic plants, which were being worked out at the time this increased demand for pure grade of metal occurred. The electrolytic process, where available, produces a higher grade of spelter from impure ores than does the fire process; a large portion of those impurities in the ore, which by the distillation process would be carried into the spelter, are removed in the leaching of the ores and the purification of the solutions. The refining process, adopted at a number of smelters for the purpose of converting low-grade spelter into "grades suitable for brash was that of redistillation.

Jan 11, 1917

By I. W. L. Finlay, H. R. Ogden, R. Jaffee, D. J. Maykuth

Aluminum has been found to be soluble in a titanium to about 26 pct, and to raise the temperature range of transformation from a to 8. Two intermediate phoses exist in the system, a new face-centered tetragonal phase, designated as 7, which occurs between 34 and 46 pct Al, and TiAI Metallographic and X-ray diffraction data were used to determine the diagram. ALUMINUM is one of the useful alloying additions for titanium-base alloys. It is an important constituent in two commercial alloys released in 1950, one containing 4 pct A1 and 4 pct Mn, and the other containing 3 pct A1 and 5 pct Cr as the metallic alloy content. It is probable that, in the future, other titanium alloys containing aluminum will be released. In the course of alloy development work, some of the features of the constitution of titanium-rich Ti-A1 alloys have been developed. These are described in the present paper. The only available information on the Ti-A1 system concerns the aluminum-rich end of the diagram. In summarizing the early work, Hansen' indicated that there is little solubility of titanium in aluminum, and that a two-phase region exists up to the intermediate compound, TiA1a (37.2 wt pct Ti), which has a congruent melting point at 1355°C. Fink' has reported that a peritectic reaction occurs at 665°C between the melt and TiA1³ to form the terminal solid solution of titanium in aluminum. The solubility of titanium in aluminum has been established at 0.24 pct at 510°C and is estimated to be between 1 and 1.5 pct at the peritectic temperature. No information has been published on the diagram above TiAl,, other than a statement- hat aluminum raises the a to ß transformation temperature of titanium. Materials and Preparation of Alloys Iodide-type titanium and high-purity aluminum were used in this investigation. Typical analyses of these materials are given in Table 1. Alloys were prepared by arc melting on a water-cooled copper hearth, using the techniques described previously for contamination-free melting.' Weight losses during melting were very low, ranging from 0 to 0.02 g in a 10 to 15 g charge, indicating that little or no loss of aluminum occurred during melting. This permitted the use of nominal compositions for these alloys. Alloy ingots containing from 0 to 7.5 pct A1 were rolled in air at 850°C to 0.040 in. sheet. Alloys containing from 7.5 to 16 pct A1 could only be rolled about 25 pct reduction at temperatures up to and including 1200°C. Alloys containing above 16 pct A1

Jan 1, 1952

By John J. Croston

The year 1935 witnessed one of the world's oldest industries—gold mining—attain the stature of a billion dollar business. Preliminary estimates indicate that somewhat over 30,000,000 oz. of gold was produced, the largest output ever recorded and exceeding the previous year by more than 11 per cent. Of this huge total the Witwatersrand field produced about 10,800,000 oz., compared with 10,480,000 oz. in 1934. Russia was apparently the stellar performer, and from incomplete data it appears that between five and five and a half million ounces were produced by the Soviets compared with 4,200,000 last year and 2,814,000 in 1933. The United States nosed Canada out of third place with a production of 3,546,000 oz. against 2,916,000 in 1934, while Canada increased her total from 2,965,000 to 3,291,000 oz. Similarly, gains of lesser magnitude were made in Australia, the Gold Coast and other countries. As a result of great activity in developing outlying areas on the Rand, and the great number of new companies building mills in Canada, Australia, the Gold Coast and the United States, the years 1936 and 1937 should see new high records, as these new producers will more than offset any decline in the older properties. The whole world has become "gold conscious" during the past three years. It has been the subject of innumerable articles by economists and others, but, unfortunately, because of their lack of actual mining knowledge, they have treated the production of gold as a static affair, ignoring geological and technical factors. It is hardly necessary to draw attention to the fact that the world's gold-mining industry was slowly but steadily shrinking in importance, owing to the gradual depletion of known deposits that were profitable to work at costs existing prior to 1929. The International Geological Congress at Pretoria and the League of Nations Committee drew attention to the estimates of the mining experts of the various governments predicting a steady falling off in world production. On the Rand there

Jan 1, 1937

By R. J. Watson

In an earlier paper, Ehrenburg and Watson1 published the develop ment for a potential function by which it is possible to obtain the electric potential at points on the surface of the ground when a current I passes between two electrodes and the subsoil is composed of parallel, homogeneous layers. In view of the continued interest in the resistivity method of electrical prospecting, the author has considered it desirable to publish the results of a number of theoretical studies making use of this potential function, and also the results of a considerable number of tests with models designed to show the soundness of the mathematical theory. It is hoped that these results will prove how erroneous the various empirical rules for depth determination may be. It has always seemed puzzling to the author that one can find, in papers published comparatively recently, statements upholding empirical rules for depth determination, and attributing most of the irregularities of resistivity curves to vertical discontinuities in resistivity in the subsoil. It would indeed be fortunate for the geophysical investigator if such a simple rule held. However, numerous investigators have proved both theoretically and by the success of their field work that such a rule does not hold, even by a "rough approximation" in many cases. On the other hand, as is shown in the development to follow, if the underground conditions are favorable it is possible for such empirical rules to give a satisfactory depth determination. Authors should be more careful about making such sweeping statements about the accuracy of these empirical rules because the relative simplicity of the field work places the method in the hands of any interested experimenter, and he is likely to become completely disgusted with the method after he has made several obviously wrong interpretations by empirical rules. There are simple and rapid methods for finding out whether the ground beneath the electrodes is sufficiently similar to the conditions

Jan 1, 1934

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Jan 1, 1938

By E. S. Machlin, S. Weing

GRAIN boundary stress relaxation has been the subject of several investigations in recent years, but as yet the phenomenon is not well understood. One of the major difficulties has been the lack of a sufficient amount of data with which to evaluate any proposed mechanism. Little information is available on the effect of small amounts of substitutional solutes on grain boundary stress relaxation. It is with this important phase of the problem that this investigation is concerned. The influence of substitutional solutes on grain boundary stress relaxation has been recently investigated in copper by Pearson: and in aluminum by Dorn et al.' Pearson studied the effect of zinc, gallium, germanium, and arsenic on the relaxation peak of OFHC copper.* The pure OFHC copper decreased the peak intensity and a second peak appeared at a higher temperature. This latter peak was termed the alloy grain boundary peak. At the lowest binary concentration studied, approximately 1 atomic pct, the primary peak was almost completely obliterated. Pearson found that the activation energy calculated from the alloy grain boundary peak for all solutes, irrespective of the concentration, was 44,000 cal per mol. Pearson concluded that the increase in activation energy from 33 to 44 kcal per mol is not continuous but abruptly changes from the lower to the higher value. As no attempt was made to investigate the intermediate range of concentration and hence calculate the possible variation of the activation energy for the initial grain boundary peak, this conclusion is hardly valid. In contrast to these results, Dorn et al. studied the effect of zinc, silver, copper, germanium, and magnesium on the grain boundary stress relaxation of aluminum. No change in the energy of activation was observed for binary alloys of the flrst four solutes, but a linear increase was found for increasing concentration of magnesium. Saturation was not found up to the maximum of 1.6 atomic pct. The energies of activation were obtained by plotting the horizontal displacement of the dynamic modulus curve vs temperature for two vibrational frequencies. As the modulus is proportional to the square of the frequency, this requires the measurement of the torsional frequency over a range of temperature. However, the technique does not lead to an unambiguous interpretation of the grain boundary

Jan 1, 1958

By J. B. Austin

IN considering so complex a process as the smelting of iron in the blast furnace, there is obviously no single method of calculating efficiency that gives a complete appraisal of the performance of the furnace in all its several functions; such a comprehensive view as is required to evaluate producing ability and manufacturing costs for a given furnace is obtained only by considering a group of efficiencies, each of which measures the performance of the furnace from a specific point of view. For instance, there is the rate of consumption of coke per ton of iron produced, which is probably the most frequently considered, and is certainly one of the most important of the group; there is the efficiency of recovery of iron charged; and there is the efficiency of utilization of energy, both chemical and thermal, in some respects related to the former two yet in other ways independent of either. In each of these cases, the calculation can be made on the basis of the actual input of material or energy, or it may be based . upon a comparison with the minimum amount of material or energy that would be required by a "perfect" furnace; that is, an imaginary ideal furnace analogous to the perfect steam engine used in thermodynamic calculations, when this furnace is operating under optimum conditions. Moreover, the furnace itself can be considered either as an apparatus for smelting iron or, taking a somewhat less common point of view, as a gas producer yielding iron and slag as by-products. Some of these effi-ciencies are more useful than others, yet all are instructive; for a knowl-edge of them not only leads to good engineering practice from the standpoint of control but also discloses limits to possible improvement in performance and indicates the lines along which improvement is most likely to be profitable. Estimates of some of these efficiencies have appeared from time to time in the literature, but many of them are open to objection because they are based on data of uncertain accuracy or because they have been calculated without due regard to the thermo-dynamic principles involved. Moreover, so far as the author is aware, no general survey of the blast furnace comparing its performance in all the aspects mentioned has been made.

Jan 1, 1938

By K. K. Kershner, W. A. Calhoun, C. W. Funk

Future resources of aluminum may require the utilization of low grade ores to provide a more permanent protection for the nation. Aluminum minerals such as cloy, shale, and high iron laterites may become important sources. An evaluation of reserves is given. New laboratory results are reported on the Vereinigte desilication process. THIS report on future resources of aluminum metal emphasizes the necessity for investigating utilization of low grade potential ores to provide more permanent protection for the nation. Partial or complete interruption of the importation of high grade aluminum ores must be given consideration. Ultimately, aluminum minerals such as clay, shale, and high iron laterites may become the principal sources of aluminum. The development of extractive processes for treating these low grade materials is a step in long-range national preparedness that should receive more attention. In formulating such processes, the application of beneficiation methods for the purpose of classifying the several types of minerals before subjecting each type to the more expensive extractive procedures should be considered, and a careful survey of the basic factors of power sources, transportation facilities, and sources of raw material should be made. Domestic Bauxite Resources Of the domestic supply of current, treatable-grade bauxite, 95 pct comes from Arkansas. The present reserve of Arkansas bauxite suitable for metal production, including abrasive-grade, Bayer-grade, and modified Bayer-grade ores, is 34,000,000 tons. The total reserve of bauxite of all grades is approximately 75,000,000 tons. Reserves are estimated on a mined and dried basis. Data available to the Bureau of Mines in 1948 to 1949 were used in preparing Table I, which shows a breakdown by grades of bauxite for about a half of the reserves of the state. The modified Bayer ore, 10,555,500 long dry tons, is based on a cutoff of 8 to 15 pct silica. The sub- marginal 10,074,700 long dry tons is assumed to contain more than 40 pct gibbsite, more than 15 pct silica, and less than 32 pct available alumina. A considerable amount of this low grade material was consumed in 1949 and 1950. Additional tonnages of bauxitic and kaolinitic clays are indicated by the Bureau of Mines drilling project.' Applying a 50 pct factor to arrive at long tons mined and dried, the results of this project are approximately 31,500,000 tons kaolinitic clay at +35 pct Al²O3 and 11,800,000 tons kaolinitic clay at 20 to 35 pct A1,0,. Total reserves of kaolinitic clays are probably quite extensive—several times the reserves shown in the Bureau's work. Total reserves of bauxitic and high iron clays from the drilling program and previously established figures are 63,980,000 tons. The mineral dressing methods,' the lime-sinter process, he lime-sinter modification of the Pederson process," the lime-soda sinter process,"-' and the Alcoa combination processa. have been described in the literature and will not be elaborated upon here. The less familiar Vereinigte Aluminium-Werke process used by the Germans during World War 11 may require some amplification. It was used to bene-ficiate boehmite ores containing 12 to 18 pct silica for a feed to the European Bayer process. Ore was

Jan 1, 1952

By A. H. Daane, B. J. Beaudry

The Sc-Ti system was studied by thermal, metal-lographic, and X-ray methods. Scandium was found to transform at 1334 °C from a (hexagonal) to ß which was concluded to be bee since a continuous series of solid solutions is formed between ß scandium and ß titanium at elevated temperatures. There is a minimum in the solidus at 51 wt pet Ti and 1300°C, a monotectoid at 1050°C and 49 wt pet Ti, and a eutectoid at 875°C and 91.5 wt pet Ti. The maximum solubility of titanium in a scandium is 13.5 wt pet at the monotectoid temperature, while the maximum solubility of scandium in a titanium is 6.5 wt pet at 875°C. SCANDIUM, a member of Group 111 A of the periodic table, and now called a rare-earth metal,' has become of interest recently due to its low density (2.99 g per cc) and relatively high melting point (1539°C).Spedding,' et al. have described a method of preparation of pure scandium metal and have made a study of its basic properties. Since scandium is approximately 10 to 12 pet smaller in at. diam than the other rare earths while its electronegativity and valence are the same, a knowledge of its alloying behavior in contrast to these elements should be very helpful to fundamental alloy theory. Since scandium is quite scarce and difficult to prepare in pure form, its use as a structural material by itself seems quite unlikely. However, its use in special cases as an alloying addi- tive to other low-density materials is a possible application; the Sc-Ti system was chosen for this reason and for others of fundamental interest. Scandium was suspected of having a high temperature bee form as do some of the other rare-earth metals.3'4 Since titanium has a high-temperature bee form, a continuous series of solid solutions at elevated temperatures between ß scandium and ß titanium would prove the existence and structure of the high-temperature form of scandium. The existence of a continuous series of hexagonal solid solutions at room temperature was predicted by Burkhanov and Savitskiy,5 but Hias shown to be incorrect in early X-ray studies. EXPERIMENTAL METHODS Materials. The metals employed in this investigation were crystal bar titanium and distilled scandium prepared by the method described by Spedding,2 et al. The major impurities are listed in Table I in PPm. Alloy Preparation. All the alloys examined were initially formed in a nonconsumable electrode are-melting furnace under an atmosphere of purified helium or argon. A curve based on the observed weight loss of 0.6 pet* when titanium was melted

Jan 1, 1962

By R. C. Edwards, Will Mitchell, T. G. Kirkland

THREE years ago, when the Process Research Laboratory at Allis-Chalmers Manufacturing Co. sought a remedy for the increasing cost of disposing of great quantities of spent sands from foundries, R. C. Edwards developed a continuous inclined paddle scrubber which removed a substantial amount of the charred coatings from the grains with a surprisingly small amount of degradation of the sand itself.1 The satisfactory results obtained on foundry sand, using this piece of equipment in conjunction with classification, suggested that a similar procedure could probably be applied to the cleaning of other sands, such as those required by the glass and chemical industries. This paper describes the flowsheet and the results of tests performed on impure natural sands. The four materials tested were silica sands obtained from widely separated geographical areas. Three of the sands tested contained various amounts of iron oxide and the fourth an excessive amount of calcareous bonding material. The iron oxide was present predominantly in the form of grain coatings, which were scuffed by the paddle scrubber, and in all cases a product was manufactured which would meet one of the sets of specifications imposed by the glass industry' The Edwards paddle scrubber used in these tests consists of a rubber-lined steel cylinder 18 in. in diam and 48 in. long, mounted on a frame so that its slope can be varied 5 ° to 35º from horizontal. This variable slope permits controlled flow of material through the machine. Rubber paddles rotate inside the cylinder and are secured to a center shaft 2 in. square, which extends through the entire length and is turned at both ends so that it can be supported by sleeve bearings centrally fixed in the end plates of the shell. At the upper or feed end it extends through the bearing on the end plate into a sheave, to which the motor drive is connected by means of Texrope transmission. The four sets of paddles mounted on the shaft, two in each set, are made of rubber belting, 1/4 in. thick, 9 in. wide, and 16 in. long. The two paddles in each set are secured on opposite sides of the square shaft, but in the same longitudinal position along the shaft axis. In other words, the two paddles in the set operate 180° apart. Each successive set is mounted 90º from the preceding one. One end of each paddle is bolted to the square shaft and the other weighted by a steel bar, 1x1 ½ x9 in. long, which is attached about 1/ 2 in. from the outer tip of the paddle. By centrifugal force at proper shaft speed, these weights force the paddle surface to rub smoothly against the rubber lining of the cylinder. During operation, the sand forces its way between the paddle face and the surface of the cylinder, providing the necessary abrading action as the pulp flows by gravity down the length of the cylinder. The capacity of the machine is limited by the amount and the hardness of the coating material and by the quality of product desired. The degree of scrubbing is governed by the retention time in the scrubber, which in turn may be changed by varying the feed rate, water content of the feed, and

Jan 1, 1952

By C. D. Stahl, E. E. Templeton, R. F. Nielsen

It has been customary, in predicting saturation changes, to use the Leverett fractional flow formula", obtained by eliminating the unknown pressure gradient from the generalized Darcy equations for the separate phases. The formula presents difficulties in the case of counterflow, since the "fractional" flow may be negative, greater than unity, or, in the case of a closed system, infinite. Recently, it has been shown by several authors that the corresponding equations (with capillary pressure and gravity terms) for actual flow of the phase may be used just as well. These equations are in agreement with Pirson's1 statement that, if the two mobilities differ considerably from each other in a closed system, the flow is largely governed by the lower value. The present study was undertaken because of an apparent lack of experimental data on gravity counter-/low with which to test the theory. A 4-ft sand-packed tube in a vertical position was employed. Electrodes for determining saturations by resistivity were spaced along the tube, one phase being always an aqueous salt solution. Air, heptane, naphtha, or Bradford crude oil was used for the other phase. A reasonably uniform initial saturation was set up by pumping the phases through the system, alter which the tube was shut in and saturation profiles obtained at definite intervals. Cumulative flows over certain horizontal levels were obtained by integration of the distributions; hence, differentiation of the cumulative flows with respect to time gave instantaneous flow rates. To compare experimental and theoretical flow values, capillary pressures were assumed given by the final saturation-distribution curve. The upper part corresponds to the "drainage" region and the lower part to the "imbibition" region, where trapping of the nonwetting phase occurred. While calculations indicated that the capillary pressure saturation function and, probably, the relative permeability saturation functions changed during the segregation, the relation of the measured rates to saturation distributions are in general accord with the frontal-advance equation. It appears that the Darcy equations, as modified for the separate phases, are generally valid for counterflow due to density differences. The usual method of predicting saturation changes, which involves a continuity equation and the elimination of the unknown pressure gradient from the flow equations, should therefore be applicable. However, the need for advance knowledge of drainage and and imbibition "capillary pressures" and relative permeabilities during various stages presents difficulties. INTRODUCTION The present study was undertaken because of a seeming lack of experimental data relating to vertical counterflow of fluids of different densities in porous media. In particular, it was desired to determine whether data obtained from these laboratory tests were in accordance with certain mathematical treatments of counterflow which have been proposed. The gravity "correction" has been incorporated into the flow equations (and, hence, into displacement theory) nearly as long as both have been used. field4 and laboratory5 data have generally borne out the validity of the theory as applied, for instance, to downward displacement by gas, with all fluids moving downward. However, the modifications for counterflow have only recently been pointed out. 2-3 It has been customary to use fractional flow rates instead of actual flow rates in displacement calcuIations. In the case of counterflow, this results in negative values, values greater than unity and, when rates are equal and opposite, in infinite values. As pointed out by Sheldon, et a1,3 and by Fayers and sheldon,2 actual flow rates may be used just as well. The fact that these may be of opposite signs for the two fluids does not present any difficulty.

By Meguru Nagamori

DURING the smelting of the sulfide ores of copper, nickel, and certain other metals, a matte phase is formed. For a better understanding of the physico-chemical properties of mattes, binary systems such as Cu-S, Ni-S, Fe-S, and so forth, should be studied, especially in the vicinity of liquid compounds such as Cu2S, Ni3S2, FeS, and so forth. These compounds are relatively stable in the solid state although they can exhibit appreciable deviations from stoichiometry. With small deviations from stoichiometry there are large changes in the activity of both sulfur and metal this is a characteristic of both solid and liquid sul-fides near the stoichiometric compositions. In the vicinityof molten Cu2S,1 for instance, the activity of sulfur increases about 100 times for a 0.012 increase in the mole fraction of sulfur and, correspondingly, the activity of copper decreases greatly. In this sens the minor deviations from stoichiometry should be carefully taken into account in studies of such metal-sulfur melts. Metal-sulfur melts may be considered to have properties intermediate between metallic solutions and molten salts, i.e., neither entirely metallic nor entirely ionic. The radius of the ion sZ- is 1.84 as compared with 1.04? for a single bond covalent s.2 It is therefore inferred that when the sulfur is more ionic its partial molar volume is larger, although metal-metal, metal-sulfur, and sulfur-sulfur interactions may bring about further complexities. Thus, it is to be expected that the molar volumes, which are derived from density-composition relations, will help in resolving the structure of the melts. In this study the maximum bubble pressure method with bubbling gases of H2, H2S, and Ar, .was employed to measure the density. EXPERIMENTAL Materials. Silver of 99.95 pct purity was melted in an alumina crucible and hydrogen gas was then bubbled through the liquid for the deoxidation. In preparation of Cu2S, electrolytic copper powder (>99.9 pct Cu) was mixed with precipitated sulfur and heated to 1200°C in an alumina crucible under a hydrogen atmosphere. Mixtures having the approximate compositions FeS and Ni3S2 were prepared by heating reagent grade electrolytic iron or reduced nickel powder with precipitated sulfur under a hydrogen atmosphere. The H2S gas was of 98.5 pct purity, the impurities being mostly CO2 and CS2 which hardly contaminate the melts. Apparatus. The crucible system is shown schematically in Fig. 1. To minimize the variation of melt composition during a density measurement, the apparatus was designed in such a way that either Ar, H2, H2S, or mixtures of these gases could be used as the bubbling gas. When the melt had a high partial pressure of sulfur, H2S gas was used. When the partial pressure of sulfur was so low that oxygen might dissolve in the melt, the use of H2 was preferred. In intermediate cases, argon or mixtures of H2-H2S were used. Density of Dibutylphtalate. Dibutylphtalate was used as the manometer fluid. Relative to distilled water, the density of the dibutylphtalate, pdib g per cc, was measured and found to be: pdib (25°C) = 1.046 i 0.002. With the use of the temperature coefficient reported by Kemppinen and Gokcen,3 the following value was

Jan 1, 1970

By F. W. Bloecher

DETERMINATION of the surface area of finely divided minerals is of interest to mineral engineers engaged in flotation, comminution, and de-watering studies. In the industrial minerals field, many materials are classified as to fineness according to their specific surface (surface area per unit weight). A method of surface area determination has been tested and used in the Richards Mineral Engineering Laboratories at M.I.T. It involves low temperature krypton adsorption measurements using the technique described by Beebe.' During the past fifteen years a number of new surface measurement techniques have been developed. Those that are broadly applicable to materials dealt with by mineral engineers include the permeability method in which a gas or liquid is passed through the sample, and the low temperature gas adsorption methods first described by Brunauer, Emmett, and Teller."" Efforts to make surface determinations from size distribution curves have long been attempted"."." but because of the uncertainty of sub-sieve size distribution and inaccuracies in screen analyses, the method is at best only a rough approximation. The most widely used gas adsorption method utilizes nitrogen gas." Nitrogen adsorption, however, is not particularly suited as a tool for most mineral engineers because the method is not applicable for surface determinations on coarse materials, that is, materials coarser than approximately 150 to 200-mesh. Other gases have been used in mineral engineering studies, particularly ethane."' lo The use of ethane gas, however, involves .a technique that is too sensitive for most mineral engineering work. The permeability method of surface area determination has the disadvantage of not being sensitive enough to detect the surface represented by minute cracks, the so-called internal surface of a particle. The low temperature krypton adsorption method described by Beebe1 utilizes apparatus and techniques that are essentially the same as those used in the ethane adsorption method."1° The surface area is calculated by the B.E.T. method."-' The krypton adsorption technique is particularly suited to the needs of the mineral engineer because: (1) The method can be used for making surface area measurements of rather coarse materials (35 to 48-mesh), as well as extremely fine materials, such as clays or colloidal slimes with specific surface that might be as high as 20 to 30 mb er g. (2) The use of krypton gas offers the advantage of low saturation pressures (2-3 mm) at the conveniently obtained liquid nitrogen temperature. Therefore the krypton vacuum system need not be designed to measure or withstand internal gas, pressures above one atmosphere as is the case with the nitrogen gas method. (3) The krypton technique offers the safety feature of employing liquid nitrogen, as contrasted to the ethane technique in which liquid oxygen is required. Furthermore, ethane vapor pressure at liquid oxygen temperatures is low (about 10 microns), and a high sensitivity McLeod gage is required for pressure readings. (4) The measurement technique with krypton gas is much simpler and faster, and the apparatus is less elaborate than that required with either nitrogen or ethane gases. Apparatus A krypton surface measurement apparatus like that used at M.I.T. is shown in Fig. 1. It is constructed of pyrex glass. A vacuum is maintained by two mercury diffusion pumps in series backed by a mechanical vacuum pump."' The vacuum thermocouple gage is used for checking the vacuum within the system. This type of gage is quite sensitive down to a pressure of 1 micron of mercury," but may be used to indicate pressures much lower than that

Jan 1, 1952

By L. Frank, Nason

THE complete statistics of zinc-ore production in the United States for 1916 are not yet available. The following figures are, therefore, only approximate. The total production of concentrates for this year, including New Jersey and Tennessee, amounts to 1,280,000 tons. Of this tonnage, five mines produced approximately 536,000 tons, or about 42 per cent. The remaining concentrates came mainly from the "Valley States," Missouri, Wisconsin, Kansas, Oklahoma, and Arkansas. The 1,280,000 tons of concentrates represent about 25,000,000 tons of crude or run-of-mine ore. Of the five mines producing the 42 per cent., the dimensions of three are approximately 25 by 1,500 by 2,000 ft. (7.6 by 457 by 610, m.) or more. Tour of the five mines are undoubtedly veins in the common acceptance of the term. They are located in great vein systems. The mines of "Valley States" have not, so far, been classed as veins; simply as "secondary deposits." The origin of these secondary deposits has been a warmly debated subject. Many geologists contend that they are the results of leaching from overlying and from adjacent rocks carrying but traces of zinc, these traces leached out and deposited in favorable loci. If this theory is correct, deposition is strictly limited to shallow depths. No volume of ore comparable to that of "true fissure veins" is to be expected. Just what this means to the future of zinc mining in these States is here indicated. The total zinc areas of these States amounts to about 9,124- sq. miles (23,631 sq. km.).- Assuming that 10 per cent. of this total will be more or less productive, there are 912 sq. miles (2,362 sq, km.) of "mineral? ground. The average depth of the operated mines is something like 100 ft. or less. In Bulletin 606, U. S. Geological Survey (1915), p. 202, Siebenthal makes the following statement: "The writer is informed by William Waugh, one of the drillers of the Stone City well, that cuttings from other wells which he drilled in the vicinity of Pittsburgh, Kan., have shown galena and sphalerite taken from a depth of 591 ft. (180.14 m.) and that the showing of ore at some places would be considered good enough to justify the sinking of a shaft had it been found in the Joplin district and at shallower depths." Leaving out of the question the prohibitive cost of such a shaft, there is

Jan 5, 1917

By Douglas A. Karvonen

INTRODUCTION Although the economy in the Province of Saskatchewan has historically been agriculturally oriented, a major source of wealth has been realized through natural resources such as petroleum and natural gas, coal and uranium and since the 1960's - potash. Potash or potassium chloride, in the form in which it is presently produced in Saskatchewan, is used primarily as fertilizer, a source of potassium, one of three essential elements required for healthy plant growth, with about 5% of production sold to the chemical industry for use in such products as soap and liquid detergent, glass and ceramics, textiles and some pharmaceuticals. Saskatchewan is estimated to have approximately 40% of known world potash reserves and its ten active mines account for some 25% of annual world production. POTASH CORPORATION OF SASKATCHEWAN In an effort to guarantee a fair and lasting economic benefit to the Province of Saskatchewan, the Potash Corporation of Saskatchewan (PCS) was created on February 4, 1975 through an Order-in-Council under the Crown Corporation's Act and later on April 1, 1976, the Potash Corporation Act provided for its continuation. PCS was given the mandate to acquire ownership of a significant portion of the potash mining capacity in Saskatchewan and to establish an organization capable of operating the facilities, marketing the product, and conducting all of the other activities necessary for a successful corporation competing in the world potash industry. The corporation is the largest potash producing and selling organization in the Western World - or third largest in the world. (See also Figure 1). PCS through its wholly-owned subsidiary, PCS Mining, has acquired a whole or partial interest in five geographically distinct producing properties or divisions, representing today more than 40% of Saskatchewan's potash producing capacity. The acquisition of each division was followed by a program designed to exploit and maximize the particular opportunities at each minesite for increased production. To that end, PCS Mining has taken an active lead in expanding to meet future demand and has implemented expansion programs at all properties except for its Esterhazy Division where it has a long-term processing agreement with International Minerals & Chemical Corporation (Canada) Limited. Through its wholly-owned subsidiaries, PCS Mining, PCS Sales and PCS Transport, this provincial crown corporation has the ability to operate as a producer and marketer of Saskatchewan's potash. In certain instances PCS, the parent company, assists in the financing of various projects undertaken by the subsidiaries and in other cases the subsidiary involved arranges its own financing. POTASH RESERVES As a background to the specific issue of financing, it is helpful to describe briefly the nature of the deposit which supports the industry - our collateral, if you like. The potash beds underlying Saskatchewan are sedimentary rock deposits formed by the gradual evaporation of an inland sea during the Middle Devonian period roughly 400 million years ago. Now known as the Prairie Evaporite, this formation stretches from North Dakota and Northeast Montana through Southern Saskatchewan into North-Central Alberta. These beds lie at mining depths ranging from 950 - 1000m (3,000 ft) below the surface, where conventional mining methods can be used, and to 1,650m (5,000 ft), where solution mining must be

Jan 1, 1985

By John Wulff, Richard P. Seelig

THE importance of the pressing operation in the forming of articles by powder metallurgy depends to a great extent on the type of product to be made. While in some few cases the pressing is merely a means of compacting loose powder particles into a solid mass preliminary to a sintering treatment in most applications it constitutes a molding operation with the purpose of shaping the raw material in powder form into a certain predetermined, accurately defined part not altered in shape by sub- sequent sintering. In still other cases, no pressing at all but sintering in molds gives useful articles. A limited number of products are made by the simultaneous application of pressure and heat. The factors that control the product of the pressing operation are raw material, lubricant, type, size and shape of die and compact, magnitude and time of application of pressure, as well as temperature of pressing. All such factors need to be con- trolled; yet, depending on the function of the pressing operation, greater emphasis may be placed on processing factors other than the pressing operation. In any complete discussion of pressing, subsequent sintering cannot be disregarded. For the sake of brevity, the present paper has been limited to the mechanics of pressing and only occasionally refers to sintering. For the same reason, hot-pressing has been omitted as beyond the scope of this paper. In any survey of the literature on the pressing of metal powders, the 1938 paper of Balshin1 on the theory of the process of pressing deserves mention. The first attempts at an interpretation of pressing phenomena were made by Balshin1 and Rakovski.2 The experimental results of both are of great interest. Since the experimental results are not described, the work was repeated, using our own interpretation of the possible techniques, and is reported in the following pages. The basic theory of Balshin,1 based on a hydro- dynamic analogy, however, leads to but another way of plotting density and pres- sure against height of a pressed compact. Since it does not give any new insight into the phenomena, nor account for the influence of side-wall friction, a discussion of the theory has been omitted from this paper. DENSITY GRADIENTS IN COMPACTS The process of pressing metal powders in a die (disregarding for this consideration the powder filling and ejection operations) may be divided into three phases: (I) packing, (2) elastic and plastic deformation, (3) cold-working with or without fragmentation. It must be emphasized that these three steps do not follow each other in sequence; on the contrary, in practice

Jan 1, 1946

By C. E. Berner

Since 1933, the Coal Mine Rating Schedule in Pennsylvania has provided credits in the Workmen's Compensation insurance premium rates for the use of safety hats, goggles and shoes. In that year, the worth of such protective clothing had just been well established and satisfactory articles were being made by a number of manufacturers. Standards for these three items of safety clothing' were written in the Rating Schedule and have been little changed through the years. The credit in the premium rate for a bituminous mine is $0.14 for hats, $o.08 for goggles, $o.08 for shoes. In order to earn such credit, it is necessary that all the employees in the particular mine be equipped with safety hats, goggles or shoes, as the case may be. In fact, it is not unusual for mines to qualify in all three categories, thus earning a rate reduction of $o.30 per $100 of payroll. These credits have been a decided stimulus to the use of safety clothing, and at present insured bituminous mines are credited as follows: Hats........ 63 per cent, or 22,600 employees Goggles..... 28 per cent, or 10,000 employees Shoes....... 44 per cent, or 15,800 employees Of course, many other employees wear these protective articles but they are in mines that are not fully equipped and so are not given the rate credit. The growth in use of this equipment has not been spectacular but it has been steady, as shown in Table I. An interesting thing about this is that it covers virtually all of the small and medium-sized bitumi- nous mine operations in Pennsylvania. A number of large operations are included, but many large mines are self-insured. It is difficult to keep alive interest in safety work in the smaller mines: first, because employment of safety engineers is out of the question and the one or several mine officials employed are often concerned only with production; second, because the life of many small mines is brief, so that safe conditions although established do not last long. Conditions as to safety in mines of this class rest chiefly with inspectors of state mine departments and of casualty insurance companies. Many millions of tons of production come from these mines, so that

Jan 1, 1944