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By A. B. Dyes

In the operation of a water-driven reservoir, a free gas saturation can he established by maintaining production rates fast enough to cause the reservoir pressure to decline below the bubble point. The benefit of such a procedure on the displacement efficiency of the oil by water is illustrated for two types of sandstone samples from one reservoir. Those rock samples showing the poorest recovery to water drive in the absence of a free gas saturation give the most improvement in the presence of a free gas saturation. Employing one type of reservoir fluid (low .shrinkage) the benefit of evolved gas on oil displacement is calculated at several reservoir pressures below the bubble point. This demonstrates the presence of air optimum pressure for water displace,rnent which is .several hundred pounds per .square inch below the bubble point. Displacement of oil at the optimum pressures results in the removal of 7 to I? per cent more oil than would be obtained by displacement at the bubble point pressure. In some instance. this magnitude of increase may be worthy of consideration in establishing the maximum efficient rate of production from many water-driven fields. INTRODUCTION For many years the belief that the use of gas could be combined with that of water to result in a better recovery operation than the use of either of these phases alone has been prevalent in the oil industry. This is evidenced by the several field trials which have employed the injection of gas and water in combination.1.2.v In most cases the small amount of any additional recovery, in combination with the limited knowledge available on the older reservoirs, has left uncertain the influence of gas on recovery in these earlier attempts to combine the use of gas with water. Research studies in recent years have demonstrated through laboratory. floods the magnitude of the benefit of the presence of gas on the displacement of oil from sandstones by water.5,6,7,8,9,10,11 In addition, studies of the distributions of the phases which are present during the displacement process have developed concepts concerning the mechanism by which this benefit is obtained."." It now remains for the engineer to incorporate these findings into the general technology of reservoir operations. It is the purpose of this paper to illustrate that the production of a water-driven reservoir at pressures below the bubble point is one such operation whereby improved oil displacement efficiency can be obtained as a result of gas evolution. The establishment of a gas saturation by evolution of dissolved gas was one of the techniques used by several investigators in the laboratory studies. The possibility of obtaining the benefit of gas evolution in water-driven reservoirs by producing at pressures less than the bubble point has 3150 been pointed out previously." The desirability of this operation has undoubtedly

Jan 1, 1955

By M. A. Torcaso, P. Raimondi

The distribution of the oil phase in Berea sandstone resulting from increasing and decreasing the water saturation by imbibition was investigated Three types of distribution were recognized: trapped, normal and lagging. The amount of oil in each of these distributions was determined as a function of saturation by carrying out a miscible displacement in the oil phase under steady-state conditions of saturation. These conditions were maintained by flowing water and oil simultaneously in given ratios and by using a displacing solvent having essentially the same density and viscosity as the oil. A correlation shows the amount of trapped oil at any saturation to be directly proportional to the conventional residual oil saturation Sor The factor of proportionality is related to the fractional permeability to the water phase. Part of the oil which was not trapped was displaced in a piston-like manner (normal part) and part was eluted gradually (lagging part). The observed phenomena are more than of mere academic importance. Oil which is trapped may well provide the fuel essential for forward combustion and thus be beneficial. On the contrary, in tertiary recovery operations, it is this trapped oil which seems to make current techniques uneconomic. INTRODUCTION A typical oilfield may initially contain connate water and oil. After a period of primary production water often enters the field either from surrounding aquifers or from surface injection. During primary production evolution and establishment of a free gas saturation usually occurs. The effect and importance of this third phase is fully recognized. However, this investigation is limited to a two-phase system, one wetting phase (water) and one non-wetting phase (oil). The increase in water content of a water-wet system is termed imbibition. In a relative permeability-saturation diagram such as the one shown in Fig. 1, the initial conditions of the field would be represented by a point below a water saturation of about 35 per cent, i.e., where the imbibition and the drainage curves to the non-wetting phase nearly coincide. When water enters the field the relative permeability to oil decreases along the imbibition curve. At watered-out conditions the relative permeability to the oil becomes zero. At this point a considerable amount of oil. called residual oil, (about 35 per cent in Fig. 1) remains unrecovered. Any attempt to produce this oil will require that its saturation be increased. In Fig. 1 this would mean retracing the imbibition curve upwards. In addition, processes like alcohol and fire flooding, which can be employed at any stage of production, involve the complete displacement of connate water and an increase, or imbibition. of water saturation ahead of the displacing front. Thus, in several types of oil production it is the imbibition-relative permeability curve which rules the flow behavior. For this reason a knowledge of the distribution of the non-wetting phase, as obtained through imbibition, whether "coming down" or "going up" on the imbibition curve, is important.

Jan 1, 1965

By S. F. Ravitz

IN his excellent book on the Principles of Flotation, Wark' makes the following significant statement concerning the theory of flotation: Two questions of first-rate importance must be considered . . . First, it must be decided whether the sulfide minerals require a collector in order that they may float, or whether as has been claimed, they possess an inherent floatability and need no collector. Second, it must be decided whether the xanthate type of collector can react with or be adsorbed by the unchanged sulfide minerals themselves, or whether, as many claim, reaction with the collector is dependent upon initial oxidation of the mineral surface. In the theory of flotation there are no two questions of greater importance than these. Ravitz and Porter' presented evidence that galena can be floated without a collector, and even without any reagent, provided oxidation products are thoroughly removed from its surface. They found also that thoroughly cleaned galena floated faster when xanthate was used than when a frother alone or no reagent was used, and that, without a collector, the recovery decreased gradually upon exposure of the mineral to air. Their work, however, has met with considerable criticism. I(127).3-6 This paper is presented to answer the objections that have been raised, and to present additional data that confirm their results. EXPERIMENTAL PROCEDURE The apparatus used to provide oxygen-free conditions for flotation has been described in detail by Ravitz and Porter. An atmosphere of purified nitrogen was maintained within the apparatus; all water and solutions used were freed of dissolved air, and could be transferred where desired by the use of nitrogen pressure; nitrogen was used as the gaseous medium for flotation. The flotation cell was essentially a glass cylinder 15 cm. long and 4.6 cm. in diameter. Near the bottom was sealed a fritted glass filter, which broke up the gas into small bubbles, and 6 cm. above this filter was a side arm through which the froth overflowed. The pulp was agitated by a glass impeller, which entered the cell through a mercury seal. For each test 17 grams of galena and 75 ml. of water were placed in the cell, after which the speed of the impeller and the rate of gas flow were adjusted. Water was added gradually during the test to keep the froth level at the proper height. The mineral was prepared and cleaned in the following manner. Exceptionally pure galena was crushed by hand on a clean bucking board, screened to - 150+ 200 mesh, and deslimed on a zoo-mesh sieve with a fine spray of water. It was then boiled on a hot plate for a number of hours with several changes of the desired cleaning solution, after which both the solution and the mineral were placed in the "mineral flask" of the apparatus. The cleaning solution was drained off, and the mineral was boiled with oxygen-free water

Jan 1, 1940

By Walter R. Hibbard, Harold Margolin

DURING preliminary tests on the aging of a Cu-plus 5 pct Ag alloy,' a specimen which had been overaged 24 hr at 550°C was annealed in a nitrogen-hydrogen atmosphere first for 2 hr and then for an additional 28 hr at 600°C. After each anneal the specimen was cooled to room temperature in about ½ hr and X-ray photograms were made. The first film, Fig. la, revealed two sets of copper-base lines, one intense and corresponding to the parameter at 550°C, the other fainter and shifted away from the beam, corresponding to the larger parameter at 600°C (see arrows). The 30-hr film, Fig. lb, revealed the same two sets of copper-base lines with a reversal of intensity. In neither case do the copper lines form a broad band which would be indicative of a range of compositions. This phenomenon is thus a "discontinuous" type of solution. A similar phenomenon was observed in a Ag-rich Cu-Ag alloy.' Finlay and Hibbard9 have suggested that directional rather than random solution of precipitate occurs in some alloys. Conceivably, for Cu-Ag alloys, the matrix-transition-precipitate precipitation sequence is reversible for the re-solution of the precipitate caused by rapidly raising the annealing temperature of an overaged specimen. A copper-base transition structure supersaturated with solute might be formed around the precipitate as it dissolves, thus obviating the necessity for a gradually changing solute composition of the matrix. The solute atoms then might be transferred rapidly and locally from the transition to the matrix phase in the proper amount and at the proper location to obtain directly the new ex- panded solid solution. The theory implies a minimum of diEusion of solute in the matrix (i.e., no significant range of matrix composition) and possibly suggests that the composition of the transition structure will vary with the conditions of re-solution. A transition copper phase found in aged Cu-Ag alloys1 might fulfill this function. Evidence regarding this suggestion could be obtained in Cu-Ag alloys by overaging a specimen until no trace of the expanded copper lattice is present and then subjecting the specimen to a retrogression treatment. Re-appearance of the transition copper phase would confirm the theory. Additional details could be secured by varying both aging and retrogression temperatures. References 'H. Margolin and W. R. Hibbard, Jr.: Effect of Ternary Additions on the Age Hardening of a Copper-Silver Alloy. Trans. AIME (1951) 191, p. 174; Journal of Metals (Feb. 1951) TP 3002E. 2 W. Ageew, M. Hansen, and G. Sachs: Decomposition and Changes in Properties of Super-saturated Silver-Copper Alloys. Ztsch. Physik (1930) 66, p. 350. 3W. L. Finlay and W. R. Hibbard, Jr.: Some Effects of Applied Stresses on Precipitation Phenomena. Trans. AIME (1949) 180, p. 255; Metals Technology (Sept.

Jan 1, 1952

By A. U. Seybolt

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By S. D. Thompson

An AIME transaction by P.L. Allsman (1960), "Analysis of Explosive Action in Breaking Rock," contains many useful concepts applicable to blast design. Of special interest was the derivation of a heave blasting burden formula, which is important in establishing the maximum burden. Unfortunately, its derivation contains a fundamental error and then a compensating one. This formula was: [bImpulse _P d At max =nwuwu where: bmax = maximum burden in m (ft). P= average detonation pressure in N/m2 (lb per ft2). A= duration of the average detonation pressure in sec. n= 3.1416. w= specific weight of rock in N/m3 (lb per ft3). u= minimum velocity that must be imparted to the rock in m/sec (ft per sec). d= borehole diameter in m (ft).] The derivation used the impulse-momentum principle, with a 0.3 m thick (1 ft thick) radius of rock mass being acted on by an explosive impulse. However, the rock weight was not converted to mass by dividing by the gravitational constant. This mistake can be verified by checking the units in the formula, which resolve into m1/2-sec instead of meters. Adding the gravitational constant corrects this: [P d Atbmax =gu g = gravitational constant equal to 9.81 m/sect (32.2 ft per sec2).] If the minimum velocity is now taken as 0.3 m/sec (1 ft per sec), as was recommended, excessively large burdens result. Any appropriate rock velocity should be capable of throwing the rock mass a minimum distance so that the swell needed for breakage can occur. Unless the burden is extremely small and the bench height is very high, it is unlikely that a velocity of only 0.3 m/sec (1 ft per sec) will be sufficient. A review of the literature indicates that average rock velocities observed by camera studies typically range from 15 to 30 m/sec (50 to 100 ft per sec) (duPont deNemours and Co., 1977; Tansey, 1979). On this basis, a minimum rock velocity of about 15 m/sec (49 ft per sec) would be expected and not 0.3 m/sec (1 ft per see). When a velocity of 15 m/sec (49 ft per sec) is inserted into the corrected formula, the results approximate those of the original formula with a velocity of 0.3 m/sec (1 ft per sec). The errors were approximately self-compensating [(9 = 1.24)]. ? References Allsman, P.L., 1960, "Analysis of Explosive Action in Breaking Rock," Transactions, AIME, Vol. 217, pp. 475-476. E. I. duPont deNemours and Co., 1977, Blasters' Handbook, 175th Anniversary Edition, Dupont, Wilmington, DE, pp. 233. Tansey, D.O., 1979, "The DuPont Sequential Blasting System," CIM Bulletin, Vol. 72, July, p. 80. Thompson, S.D., 1981, "Critical Review and Revision of Surface Blasting Practice," MS thesis, West Virginia University, pp. 308-316.

Jan 1, 1986

By V. R. Garfias, R. V. Whetzel, J. W. Ristori

Since the entry of the United States into global war, virtually all data and information necessary for compiling figures on world petroleum consumption have become unavailable. This situation undoubtedly will continue until the world petroleum industry can return to a peacetime basis. During the past 10 years, the authors, by publishing annual estimates of .world consumption, have attempted to emphasize the importance of a yearly world-wide survey of petroleum supply and demand. It is beconling more and more evident that statistics for the United States alone can no longer give a comprehensive idea of the state of the petroleum industry, even within the United States itself. Therefore, when conditions in the industry again become normal, it is the hope of the authors that those bureaus equipped to do so will carry forward the study of petroleum supply and demand on a world-wide basis. Enough data and information are available, however, to attempt a rough estimate of world output of crude petroleum and petroleum substitutes for 1942, which to some extent may reflect the trend of world consumption. This estimate by countries, as compared with the output in 1941, is shown in Table I. The world production of crude petroleum and petroleum substitutes for 1942 is estimated at 2,208,000,000 bbl., or a decrease of 171,000,000 bbl. under 1941. Crude production is believed to have decreased by about 200,000,000 bbl., (about 9 per cent); while petroleum substitutes increased by 28,500,000 bbl., (nearly 20 per cent). The decline of crude output in the United States is estimated at 19,000,000 bb1.—less than 2 per cent; while that in foreign countries is estimated at 180,000,000 bbl., or more than 20 per cent. The marked decline abroad is due largely to losses in Venezuela and Colombia, where the lack of ocean transportation became the controlling factor, and in the East Indies and Burma, where military invasion brought about the destruction of the fields. The production of petroleum substitutes in 1942 apparently reached a new high figure of 7.5 per cent of the total world petroleum output. The important features of petroleum production outside of the United States are the changes that have taken place during the year in the supply of the Axis countries. In Japan the output for 1941 was estimated at 8,800,000 bbl., 5,500,000 of which were petroleum substitutes. It is believed that the output of synthetic oils during 1942 substantially increased, raising the total interior production of Japan to nearly 10,-ooo,ooo bbl. Also, during 1942 Japanese armed forces gained possession of oil fields having a normal peacetime output of about 78,000,000 bbl. per year. The production of these areas for 1942 is estimated at some 23,000,000 bbl., which indicates that Japan is now getting at least 33,000,000 bbl. a year, which exceeds by 8,000,000 bbl. Its

Jan 1, 1943

By Ronald C. Koo

SMALL additions of potassium, aluminum, and silicon as oxides (referred to as dope) to tungsten have been known for several decades to have a very large effect in raising the recrystallization temperature and altering the recrystallized grain morphology of heavily drawn wire. Previous investigations of this doping effect1 6 have led to various speculations but all failed to deduce unequivocally the physical state or the mechanistic influence of the dopant. Recently, walter7 has observed, by transmission electron microscopy, strings of "fine particles" in heavily rolled and annealed doped tungsten sheet and concluded that they were particles of mullite (Al6Si2013). His conclusion was inferred from the electron diffraction patterns of large particles ex-trated by carbon replication of fractured surfaces of slabs rolled from sintered ingots. That the strings of "fine particles" in heavily rolled and annealed sheet were also mullite was an assumption for which no evidence was presented. A similar investigation has been carried out in this laboratory over the past 2 years on a variety of tungsten wire: doped tungsten, and undoped tungsten, as well as 218 doped tungsten purchased from the Lamp Metals and Components Department of the G.E. Lamp Division. Although the electron microscope observations are similar to those reported by Walter, the writer has reached a different conclusion concerning the physical state of the dopant in annealed tungsten. The purpose of this communication is to present evidence that the strings of "fine particles" observed in transmission specimens are not mullite, but are voids. In the present investigation, tungsten wire, 0.88 mm in diam, was rolled into ribbon 0.2 mm by 125 µ thick. The ribbons were annealed in vacuo at a pressure of -1 x 10-5 Torr and then thinned electrolytically in a 2 pct KOH solution. Fig. 1 shows a typical transmissicjn electron micrograph of a sample annealed at 1700°C for 30 min which reveals rows of closely spaced voids having a light contrast (referred to as "fine particles" by Walter) aligned parallel to the working direction. Stereo micrographs (by D. Moon, Westinghouse Research and Development Center) have shown that these voids do not exist on the surfaces of the specimens as a result of thinning but are within the thin-foil specimens. The following experiments have been performed to verify that these are indeed voids. I) Effect of Annealing. Voids are absent in unannealed specimens and appear only after annealing. This behavior cannot be explained if they were solid particles such as mullite. Precipitation (in an unquenched specimen) upon annealing requires solute elements having decreasing solubilities with increasing temperature. Although the solubility of aluminum in tungsten does decrease with increasing temperature, precipitation requires a concentration in excess of 1.4 wt pct,8 which is at least two orders of magnitude higher than the aluminum content in doped tungsten. It is also unreasonable to assume that particles aligned in rows initially present in unannealed specimens were too

Jan 1, 1968

By J. W. Ristori, V. R. Garfias, R. V. Whetzel

Since the entry of the United States into global war, virtually all data and information necessary for compiling figures on world petroleum consumption have become unavailable. This situation undoubtedly will continue until the world petroleum industry can return to a peacetime basis. During the past 10 years, the authors, by publishing annual estimates of .world consumption, have attempted to emphasize the importance of a yearly world-wide survey of petroleum supply and demand. It is beconling more and more evident that statistics for the United States alone can no longer give a comprehensive idea of the state of the petroleum industry, even within the United States itself. Therefore, when conditions in the industry again become normal, it is the hope of the authors that those bureaus equipped to do so will carry forward the study of petroleum supply and demand on a world-wide basis. Enough data and information are available, however, to attempt a rough estimate of world output of crude petroleum and petroleum substitutes for 1942, which to some extent may reflect the trend of world consumption. This estimate by countries, as compared with the output in 1941, is shown in Table I. The world production of crude petroleum and petroleum substitutes for 1942 is estimated at 2,208,000,000 bbl., or a decrease of 171,000,000 bbl. under 1941. Crude production is believed to have decreased by about 200,000,000 bbl., (about 9 per cent); while petroleum substitutes increased by 28,500,000 bbl., (nearly 20 per cent). The decline of crude output in the United States is estimated at 19,000,000 bb1.—less than 2 per cent; while that in foreign countries is estimated at 180,000,000 bbl., or more than 20 per cent. The marked decline abroad is due largely to losses in Venezuela and Colombia, where the lack of ocean transportation became the controlling factor, and in the East Indies and Burma, where military invasion brought about the destruction of the fields. The production of petroleum substitutes in 1942 apparently reached a new high figure of 7.5 per cent of the total world petroleum output. The important features of petroleum production outside of the United States are the changes that have taken place during the year in the supply of the Axis countries. In Japan the output for 1941 was estimated at 8,800,000 bbl., 5,500,000 of which were petroleum substitutes. It is believed that the output of synthetic oils during 1942 substantially increased, raising the total interior production of Japan to nearly 10,-ooo,ooo bbl. Also, during 1942 Japanese armed forces gained possession of oil fields having a normal peacetime output of about 78,000,000 bbl. per year. The production of these areas for 1942 is estimated at some 23,000,000 bbl., which indicates that Japan is now getting at least 33,000,000 bbl. a year, which exceeds by 8,000,000 bbl. Its

Jan 1, 1943

By Walter Miller

Crude oil stocks were some 10,000,000 bbl higher on June I, 1947, than at any time during 1946 but the extremely heavy refinery runs the last half of 1947 cut crude inventories to approximately the 1946 closing level of 225,000,000 bbl. Many refiners were seriously short of crude oil during the year. This shortage was reflected in numerous advances in the posted price of crude, justified in part as an incentive for more production but more generally due to competitive bidding. Some purchasers of crude, endeavoring to keep their plants running, resorted to the payment, either directly or indirectly, of premiums above the posted price. Another common practice employed by some suppliers of crude oil was to demand refined products in exchange or trade for their raw material. The refined products picture has darkened in spite of record throughputs. Stocks of gasoline and light and heavy fuel oils were uncomfortably low at the beginning of the year and were in general still lower at the close. The rationing of some products, principally gasoline, to dealers and stations? initiated during the year, gained momentum as stocks continued to diminish. The emphasis placed by the manufacturers of oil-burning equipment on the convenience and economy of heating with oil, together with the tight situation in coal, has developed a tremendous demand for burning oils. Consumption of liquefied petroleum gas for domestic and household fuel had more than doubled in 1946 over 1943, and the demand seems to be limited only by the ability of the equipment builders to furnish necessary storage. transportation, and burning equipment. The supply situation is likely to become more acute in 1948. Demand for petroleum products is being pushed to new heights not only by the unprecedented domestic market but by a sudden and drastic upswing in estimates of military and governmental requirements. Additionally, oil exports are running far below the volume requested, amounting to less than forty percent in a recent quarter, and export licenses are reportedly being approved on the basis of urgent need *only. AX recent White House release sees little likelihood that estimated requirements of the sixteen nations participating in the proposed Marshall Plan can be met in full over its projected life—1948 to 1951. Present demand dictates maintenance of refinery operations at the highest possible level and the Bureau of Mines has forecast daily average crude runs in 1948 of 5,265,000 bbl. The Economics Advisory Committee of the Interstate Oil Compact Commission recently estimated the 1948 demand for petroleum products at nearly 6 pct above 1947. They further estimate daily average crude runs of 5,375,000 bbl in 1948, some 2 pct higher than forecast by the Bureau of Mines. Projected demand exceeds supply to the extent that Capitol Hill is reportedly investigating ways of enabling oil companies to act in concert without danger of antitrust prosecution, such as elimination of crosshauls, pooling of products, and lowering of octane.

Jan 1, 1948

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors' determined the constitution of copper-silicon-manganese alloys containing over 90 per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper .2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 20 c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. Table I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. A few other changes will be noted (No. 138 at 450°C., No. 149 at 550°C., Nos. 153 and 149 at 750°C.). The change from liquid to beta in equilibrium with kappa in No. 139 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. 1 to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the [K = a + ?] change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300° and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 ± 0.03 per cent or 2.42 ± 0.05 per cent were cast in ingots of 3-in, diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 900°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By F. W. Bloecher

S. Mortsell and J. Svenssofi (Royal Institute of Technology, Stockholm, Sweden)—Bloecher states that the apparatus described by him should be a suitable instrument in the mineral dressing laboratories for determining the specific surface of such granular products that are generally investigated. We want to express a somewhat different opinion, as we doubt that the gas adsorption method of surface measurement really is the most suitable method in mineral dressing laboratories. It is well known that the surface area, as measured by this method, does not coincide with the surface area calculated from the size, shape, and number of particles, i.e. the superficial surface of the particles. It can be seen easily from Mr. Bloecher's own determination on ilmenite-leucoxene concentrate that the surface area measured according to this method may be several hundred times larger than the superficial surface. It is supposed that the surface of cracks, fissures, and pores within the particles also is included in the measured surface. However, this is an assumption which scarcely can be proved and certainly has not been proved. We believe that the mineral engineer could better use a method giving the superficial surface of the particles, as in most cases this surface only is of importance to him. Such is certainly the case when calculating the resistance of the fluid flow through granu- lar materials and the capillary forces of such materials, problems which are of great importance in connection with dewatering, filtration, and pelletizing'" etc. The same may also be the case when studying flotation problems, partly since the quantities of the introduced reagents usually are so small that they can only cover the most accessible surface of the particles, and partly since the molecules of at least the collecting reagents are so large that they cannot enter the smallest cracks and pores. As to the surface, which is of consequence in the application of Rittinger's law of crushing, one is inclined to believe, from theoretical reasons and from the work by Gross and Zimmerley, that the total surface here is the most important one. However, it seems as if in that case the superficial surface was as important as the total surface. Other reasons making the gas adsorption method less suitable for use in the mineral dressing laboratories are that the granular materials there very often are too coarse to be measured by this method, that the experimental technique is rather difficult, and that it takes a long time to measure the specific surface of a sample. Besides, the validity of the method must still be considered questionable. It is thus well known that with different gases one usually gets different values of the specific surface of the same sample, which values, even with such an ideal material as metal foils, can differ as much as about 50 pct.'" Still more serious

Jan 1, 1952

By E. R. Williams

Continuous casting of nonferrous metals has become a commercial reality. After years of slow and arduous experimentation by a number of independently working inventors, starting with Lord Henry Bessemer in 1865, success has finally been achieved. Nonferrous metals—aluminum, copper and brass—extremely vital to our production of war equipment, are being continuously cast every day in large quantities. In fact, some nonferrous metals —for instance, high-strength aluminum alloys—could not have been produced in the huge quantities required for planes and other war equipment if it were not for continuous casting. These casting processes for nonferrous metals have not been entirely perfected but continuous casting is here to stay. Continuous casting of carbon and alloy steel has not yet gone into commercial production but it is well on its way. A great deal of hard work has been expended and -small fortunes in money have been and are being spent in marching down the long road to success. Considerable tonnage of plain carbon, stainless and other alloy steels of high quality have been produced by pilot-plant continuous-casting units and at speeds that give indisputable evidence of commercial success. What has made the difference between failure and success? What is there left to do to revolutionize completely the method of casting metals, which has existed for centuries? These questions are being rapidly answered. Fundamental Methods Present continuous casting processes have many common problems but differ considerably in their methods of solution. The two fundamental methods are: I. Forming the solidifying metal against mold walls that move with the metal, so that there is no relative movement between the walls and the metal. This is a development of Lord Bessemer's idea of pouring metal between two rotating rolls. 2. Moving the solidifying metal along a stationary mold wall so that there is relative movement between the wall and the metal. This was proposed by Trotz in Germany as far back as 1889. Neither Bessemer nor Trotz achieved commercial success. The chief reason seems quite apparent today, inasmuch as they did not solve the fundamental problem of rapid heat removal from the molten metal. The Williams Continuous Casting Process is based upon this fundamental idea of fast heat removal and dissipation. The bessemer method of forming the ingot against a moving mold wall—either rotating rolls or endless moving plates—was carefully considered by the author and promptly abandoned as being commercially impractical. Primarily, only a very small tonnage output was possible except at terrific lineal speeds, because the very nature of this method required casting thin sheets rather than ingots. Secondly, the casting of a sheet between lolls that are pressed together meant the rolling of two layers of solidified skin separated by a molten core. Internal bursts and segregation of the metal usually resulted. Moving Solidifying Ingot Along Mold Wall It was decided therefore to devote our research activities chiefly to- the idea of moving the solidifying ingot along. a stationary mold wall. It was soon dis-

Jan 1, 1945

By H. R. Hendricks

THE ore of the Iron King Mine, being very hard and having a very fine crystalline structure, presents many problems in milling that are not present in ordinary lead-zinc ores. This very fine crystallization causes much interlocking of minerals and is most prevalent between the gold and pyrite and the sphalerite and pyrite. The recovery of gold is extremely important in the economic value of the ore and therefore constitutes a large part of the metallurgical problem to be solved. All of the gold is free but it has not been observed in any of the mill products except under very high magnification. Some of the gold is tarnished, and this condition also makes recovery difficult. The gold values have been determined to be highest in association with chalchopyrite and arsenopyrite. The silver occurs mostly in association with galena and tennantite. A small amount of native silver has also been observed occasionally. The galena, being softer than the other minerals, frees much better in grinding. Some oxidation of galena is present in the ore, as the nonsulphide lead content amounts to approximately 10 pct of the total lead. Some oxidation of sphalerite is also present in the ore. Microscopic examination of the zinc concentrate shows many grains in the minus 325-mesh to be half pyrite, together with the fact that some of the zinc is marmatite, makes production of a high-grade zinc concentrate very difficult unless recovery is sacrificed. In the grinding, it has been determined that the flotation feed must be maintained at 85 pct minus 200-mesh to free the minerals sufficiently to make the best economic recoveries. Table I illustrates the effect of fine grinding. It shows that the bulk of the recovered minerals is in the minus 325-mesh size and is the part of the minerals that is more readily freed. The pyrite concentrate is not given in the table because it contains practically no minus 325-mesh. DEVELOPMENT OF PRESENT FLOWSHEET AND MILLING PRACTICE The first milling operation started in 1938, with a mill capacity of 140 tons daily, producing a bulk gold-silver-lead concentrate. After several stages of expansion and changes of the mill flowsheet, the mill is currently treating 380 tons of ore daily and three separate concentrates are produced. In order of their importance and value, these are: (1) lead concentrate, (2) zinc concentrate and (3) pyrite concentrate. The present average grade of mill heads is: gold 0.11 oz, silver 4.00 oz, lead 2.50 pct, zinc 7.60 pct, copper 0.22 pct, iron 22 pet and 30 pct insolubles. Specific gravity of the ore is 3.8. During the period when bulk flotation was practiced, the flowsheet was very simple. The ore was ground fine enough to liberate as much gold, silver and lead as possible. Necessary collectors and frothers were added in sufficient quantity

Jan 1, 1947

By Walter Miller

Crude oil stocks were some 10,000,000 bbl higher on June I, 1947, than at any time during 1946 but the extremely heavy refinery runs the last half of 1947 cut crude inventories to approximately the 1946 closing level of 225,000,000 bbl. Many refiners were seriously short of crude oil during the year. This shortage was reflected in numerous advances in the posted price of crude, justified in part as an incentive for more production but more generally due to competitive bidding. Some purchasers of crude, endeavoring to keep their plants running, resorted to the payment, either directly or indirectly, of premiums above the posted price. Another common practice employed by some suppliers of crude oil was to demand refined products in exchange or trade for their raw material. The refined products picture has darkened in spite of record throughputs. Stocks of gasoline and light and heavy fuel oils were uncomfortably low at the beginning of the year and were in general still lower at the close. The rationing of some products, principally gasoline, to dealers and stations? initiated during the year, gained momentum as stocks continued to diminish. The emphasis placed by the manufacturers of oil-burning equipment on the convenience and economy of heating with oil, together with the tight situation in coal, has developed a tremendous demand for burning oils. Consumption of liquefied petroleum gas for domestic and household fuel had more than doubled in 1946 over 1943, and the demand seems to be limited only by the ability of the equipment builders to furnish necessary storage. transportation, and burning equipment. The supply situation is likely to become more acute in 1948. Demand for petroleum products is being pushed to new heights not only by the unprecedented domestic market but by a sudden and drastic upswing in estimates of military and governmental requirements. Additionally, oil exports are running far below the volume requested, amounting to less than forty percent in a recent quarter, and export licenses are reportedly being approved on the basis of urgent need *only. AX recent White House release sees little likelihood that estimated requirements of the sixteen nations participating in the proposed Marshall Plan can be met in full over its projected life—1948 to 1951. Present demand dictates maintenance of refinery operations at the highest possible level and the Bureau of Mines has forecast daily average crude runs in 1948 of 5,265,000 bbl. The Economics Advisory Committee of the Interstate Oil Compact Commission recently estimated the 1948 demand for petroleum products at nearly 6 pct above 1947. They further estimate daily average crude runs of 5,375,000 bbl in 1948, some 2 pct higher than forecast by the Bureau of Mines. Projected demand exceeds supply to the extent that Capitol Hill is reportedly investigating ways of enabling oil companies to act in concert without danger of antitrust prosecution, such as elimination of crosshauls, pooling of products, and lowering of octane.

Jan 1, 1948

By P. M. Kelly

TWO analytical methods for calculating the positions of matrix and twin reflections on electron-diffraction patterns of a twinned cubic crystal have recently been published.1,2 Meieran and Richman1 considered the case of twinning on (1 12) in a bcc structure, while a more general treatment, capable of analyzing twinning on any plane in a cubic crystal, was developed by Johari and Thomas.2 The latter authors applied their general rotation matrix to both (111) twinning in face-centered crystals and {112} twinning in body-centered crystals and they derived separate expressions for these two cases. This separate treatment masks the fact that in a holosymmetric cubic crystal a (111) twin is crys-tallographically equivalent to a {112} twin.3 This is analogous to the crystallographic equivalence of rotation and reflection twins in centrosymmetric crys tals. A particularly simple example of this equivalence occurs when the two twin planes are perpendicular to each other—for example (111) and (112). Then, if twinning on (111) moves a point P to a new position P1, and twinning on (112) moves P to P2, P1 and P2 will be related to each other by a 180-deg rotation about [110]— the direction normal to both (111) and (112). Since there are diad axis axis along (110) direction in a holosymmetric cubic crys tal the two positions P1 and P2 must be crystallo-graphically equivalent. In other words if a particular pole (hk l) is in a position P1 after twinning on (Ill), then after twinning on (112) a pole of the type {hkl}—but not the particular pole (hk1)—will also be in the position P1. As a result, when only the general (as opposed to the particular) indices of poles after twinning are required, twinning on (111) gives the same results as twinning on (112). To convert the results for a (111) twin to those applicable to a (112) twin, when the particular (as opposed to the general) indices of poles after twinning are required, all that is necessary is to multiply the indices of the twin poles by the matrix for 180-deg rotation about [lie], i.e., The analytical methods suffer the disadvantage that a new set of calculations must be performed for each different diffraction pattern or, as is done in the Meieran and Richman treatment,1 a lengthy list of the location of the twin spots in reciprocal space must be prepared. All the tedious computation involved in these analytical approaches can be avoided by simply plotting, on tracing paper, a stereographic projection of a crystal twinned on say (112). By superimposing this twin stereogram on a standard (001) projection (preferably with the points and indices in a different color from those on the twin stereogram) the relative positions of both matrix and twin reflections can be determined by inspection. Alternatively, a composite projection can be

Jan 1, 1965

By E. J. Pasierb, H. W. Paxton

Mavkers ill a diffusion couple in the iron-chromium system move towards the high chromium side indicating Dcr > DFe at the marker composition. By a combituztion of measurements of D& and D a: a function of composition, this is also shown independently. DFe is calculated as a function of composition. and shown to be in reasonable agreement with measured values by other workers. MEASUREMENTS of marker movements in diffusion couples have been used from time to time to demonstrate that a vacancy or interstitial mechanism may be operative. Since there is a possibility that ring diffusion1 may be operative in chromium, the present experiments are of interest in showing some non-ring mechanism in iron-chromium alloys around the equiatomic composition. EXPERIMENTAL PROCEDURE The movement of markers originally at the interface between 1-in. sq sections of pure Cr (6 mm thick) and outer slabs of 30 Cr-70 Fe alloy was followed as a function of time at temperatures from 1150" to 1425"C, in a Kanthal-wound furnace. Temperature control was +5°C over extended periods. The analyses of these alloys are given in Table I. Selection of suitable markers presented a considerable experimental problem; the eventual solution was to draw quartz rod down to 0.01 cm and seat this in V-grooves 0.01 cm deep on each side of the chromium prior to welding. A preliminary experiment in which the groove was machined in the alloy gave identical results. Welding was accomplished by passing a heavy current through specimens under moderate pressure in a helium atmosphere. This method produced good welds with a planar interface as shown by subsequent metallo-graphic investigation. Any markers which did not adequately fill their groove and showed subsequent contamination from the atmosphere during heat treatment were not considered reliable. The composite sample was ground and metal-lographically polished on the four sides perpendicular to the interface. Fiducial marks (deep milled slots) were made outside the diffusion zone to check on total volume change. All necessary measurements were made on a metallograph reading to +0.0005 cm. The samples were wrapped in tantalum foil and given diffusion anneals for times to 200 hr in carefully purified dry hydrogen in a sealed McDanel porcelain tube. Chromium-zirconium chips were introduced near the specimen as an additional getter. The specimens were cooled relatively slowly after the diffusion anneal to preserve the McDanel tube but no significant error in effective time at temperature was thereby introduced. At least 1 mm was ground off the surface before measurements were taken. It was observed that the grain size following short diffusion anneals was several mm and was appreciably larger in the 30 Cr alloy than in the pure Cr. No significant grain boundary penetration was present as indicated by the etch limit. The results are presented in the next section. Measurements of D were made by standard sectioning techniques with chemical analysis. Machining difficulties limited the

Jan 1, 1961

By William S. McAleer

Two major trends in the coal industry today focus attention on the need for heat-drying equipment of a simpler, more flexible and less expensive type than has been considered standard equipment for drying coal. These trends are: I. The tremendous growth in the use of mechanical equipment to load coal both in underground mining and strip mining, which necessitates efficient mechanical cleaning of the fine as well as the coarse coal and thus means a growing tonnage of washed fine coal? with its attendant moisture problems. 2. The growing consumer demand for the smaller sizes for use as domestic stoker coal, with increasingly rigid specifications covering size, ash, and moisture analyses. ACCEPTED PRACTICE In the past, when, for example, 4 in. too coal has been washed, there was little trouble in producing a washed product 4 to o with a satisfactory resultant moisture. The 4 to 3/8-in. could be taken from dewatering screens at a surface moisture ranging from 2.5 to 3.5 per cent, depending upon the size consist. The 3/8-in. to o coal was generally dewatered satisfactorily with centrifugal driers, to final surface moistures from 5.5 to 8 per cent, again depending upon size consist. The centrifugal type of drier has definitely proved itself to be the most economical type of machine to handle coal approximately 3/8 in. to o as recovered by dewatering screens or drainage elevators with 15 to 25 per cent surface moisture and turn out a product with moistures as stated above. Sometimes such moistures (5.5 to 8.0 per cent) in the product are satisfactory. If not, an ultimate moisture, lower than 3 per cent, is seldom required and the centrifugal drier removes 70 to 85 per cent of the total moisture to be removed. In certain districts there has been a growing tendency to circumvent the use of centrifugals or other types of driers, by dewatering over screens of the wedge wire type and wasting all the finer sizes. Sometimes all the minus 28-mesh has been wasted and often the size wasted has been as large as 1/8-in. By wasting these finer sizes, a lower moisture can be obtained in the finished product, but taking into account the cost of the tonnage so lost, plus the added cost of ultimately disposing of this wasted tonnage, often the cost will be greater than the cost of heat-drying in a modern plant, which makes possible the recovery of all the tonnage. Moreover, with the moisture standards for domestic stoker equipment even these wasteful approaches to its solution do not solve the problem and there remains only the alternative of heat-drying. HEAT-DRYING Until about four years ago, heat-drying of coal at the preparation plants was confined chiefly to drying the fine sizes (approximately 3/8 in. to 0). Occasional

Jan 1, 1941

By Herbert D. Drechsler

The objective of this paper is to identify the components of income above that necessary to keep a mine in production and relate those components to the profits of a mining firm. This is a discussion of "Economic Rent". Economic rent is the payment to the factors of production -- capital, labour, entreprenuer and the owner of the mineral deposit -- above the minimum necessary to keep all of these factors cooperating in the production of minerals from a particular deposit. THE SOURCE OF ECONOMIC RENT IN THE MINING INDUSTRY In the mining business each mine has a unique cost of production unrelated to any other mine. The cost of production is developed from many factors such as the technical characteristics of the deposit: depth of deposit, depth of overburden, areal extent, and type of deposit. Furthermore, there are locational factors which also alter cost of production. For example, identical mineral deposits located in Zambia or in the southwest U.S.A. would have different capital and operating costs. These differences occur because of different qualities of labour, ease of acquisition of operating supplies or investment capital and other similar factors. To explain the source of rent, we shall use ideas developed by Alfred Marshall and Kenneth Boulding. Suppose a meteorite with special qualities exploded over earth and sent showers of small meteorites to the ground in various places. At some point in time, people learned of the special qualities of these meteorites and a demand arose and one mine was started. Suppose further that the cost of production to produce these meteorites was different for each deposit. Probably the lowest unit cost mine would commence production because if a higher unit cost mine started-up, eventually someone would discover a deposit that had a lower unit cost of production. The lower unit cost mine would take over the market and the high unit cost mine would cease production. The cost curve for the first mine would look like the following Figure 1. [ ] The output for the first mine is on the horizontal axis with the cost per ton on the vertical axis. The curve labelled AC I is the average total cost of production over the range of possible production that could occur at the property. The total costs are composed of variable costs, which are dependent on output and fixed costs, which are dependent on time. For example, the cost of operating supplies would be a variable cost and normal profit would be a fixed cost.1 The opportunity cost of the investment would also be part of the fixed costs. In our example, all factors of production, are receiving the minimum necessary payment that will keep the mine operating. The average total cost curve is U-shaped because at zero output, the meteorite mine has no variable costs, only fixed costs which, on a unit basis, obviously are very high. To produce a small output of meteorites, the mining firm adds

Jan 1, 1985

By C. Norman Cochran

The pllnse diagvam for the NaF-AlF3 system was used to calcutate an ionic model for the NaF-AlF3 system. Assuming an ideal solution,a series of simultaneous equations expressing equilibria be-tween solid and liquid phases at the euleclic, perilec-tic, and melting points were solved for the activities of the ionic species, the dissociation constants, and the entropies and heats of fusion. The calculations suggest the existence of A13F1415 ions in addition to the F-1+AlF6-3 , and AlF4-4 ions previously proposed by others. The calculaled valnes give better agreement with vapor pressures than the previous model without Al3Fl14-5. Additional possible vefinements of the model are proposed. CRYOSCOPIC1 investigations and density data2 for the NaF-A1F3 system have previously been used to study the dissociation mechanism of Na3A1F6 and to derive equilibrium constants for its dissociation to NaF and NaAlF,. Depending primarily on the heat of fusion assumed for cryolite, the dissociation constants ranged between 0.02 and 0.18 from cryoscopic studies, and from 0.09 at 1273°K to 0.16 at 1363°K from density data. In most cases the values were unable to reproduce satisfactorily the experimental liquidus lines very far on the A1F3 side of the Na3A1Fe composition. This suggested the existence of at least one other ionized compound in the melt besides NaA1F4 in the Na3A1F6-A1F3 side of the system. This is assumed to be liquid Na&13F14 (chiolite), which is already established as a stable solid in phase studies of this system. MODEL FOR THE MELT The melt is assumed to be an ideal solution with ion activities equal to anion fractions. The only cation in the model is sodium so that Temkin and simple anionic activities are identical. Although the compounds are completely ionized to Na' and the respective anion in the melt, molecular rather than ionic notation is used throughout this work. The Na3A1Fe is assumed to dissociate to NaA1F4 and NaF as in the former model, and Na&13F14 to dissociate to Na3A1Fe and NaA1F4. Other valid dissociation equilibria can be written involving these four compounds, but all of these can be obtained by combinations of the two described dissociation reactions and, thus, are automatically considered in these calculations. The model allows for no free AlF3 so that compositions for NAIF3 > 0.5 (mole fraction A1F3 on the NaF-A1F3 basis) cannot be treated. The question of the existence of free AlF3 in the melt will be discussed again later. The constants in the model were evaluated from points along the entire known liquidus line of the NaF-A1F3 system. Previous work employed only the liquidus line or densi- ties near the Na3A1F, composition. The liquidus line compositions used in the solution of the model are from unpublished work by Mr. P. A. Foster, Jr., for compositions between the Na3A1F6 melting point and the Na&13F14-A1F3 eutectic, and from the published works of Grjotheim,1 Phillips,3 and Foster4 for the remainder of the system. The relationships used in solving for the desired dissociation constants and heats and entropies of fusion are listed in Table I, and the points along the liquidus line at which each apply are indicated to the right of the relationships. The mole fractions of each of the separate species in the melt are symbolized by N. Relationships [I] and [2] are the respective dissocia-ation constants, Kl and K2, of Na3AIF6 and Na5A13F14 for this model. For simplicity, these constants will be assumed to be independent of temperature. Relationship [3] follows from the assumption of the ideal solution. The expression relating the values of N to the experimental values of NAIf3, is given in Relationship (41. Relationships [5], [6], and [7] each state the equilibrium between a compound in the melt and its pure solid phase for the portion of the liquidus lines where it precipitates. The heats of melting, AH,, and entropies of melting, AS,, used in [5], [6], and [7] are assumed to be independent of temperature. The compositions and temperatures of all five invariant points (two melting points, two eutectics, and one peritectic) along the liquidus lines from NAIF3 = 0 to NAIF3 = 0.5 were employed in the solution. The eutectic and peritectic compositions were particularly useful because each of these is involved in one more equation than other points along the liquidus lines and thus reduces the number of points required to solve for the constants. Also, their use assures that the inflection points in the derived liquidus line will correspond exactly with those on the experimental liquidus line. The total number of equations is 5k1 — 1, where n is the number of experimental composition points used. The number of unknowns is 4n + 5 (4n- 3 values of N, 3 values each of AH, and AS,, and 2 values of K). Thus, six points must be used in the solution to obtain an equal number of equations and unknowns. The one additional required experimental composition was taken on the liquidus line between the Na3A1Fe melting point and the Na3A1F6-Na5A13F14 peritectic. Previous work indicated this was a difficult portion of the curve to fit. The temperature used for the point was 1161°K, the same as for the NaF-Na3A1Fe eutectic. This choice of temperature gave two points with identical NNa3AIF6 values which simplifies the algebraic solution. The second point at this temperature is denoted 1161°'K. PROCEDURE FOR SOLUTION OF EQUATIONS Values were assumed for NNa,AIF and NNaF at the NaF-Na3A1F6 eutectic at 1161°k. By an iterative procedure, the corresponding values for NNa5A13F14 and NNaAlF4 at 1161°K were determined from 131 and 141. A value was assumed for NNaAlF4 at 1161°'K and

Jan 1, 1968