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By T. L. Berger, M. C. lnman, M. F. Rose

AFTER shock loading, mechanical twinning has been observed by several authors1-4 for a variety of fcc metals and alloys. It has been shown2,3 that low stacking fault energy materials deform primarily by the formation of mechanical twins and stacking faults during dynamic loading. Further, Inman, Murr, and Rose2 have shown that a correlation exists between the average hardness and the volume percent of mechanically twinned material in stainless steel. It has been observed in nickel' that mechanical twins are produced during shock deformation if the peak pressure associated with the shock wave is greater than 350kbar. It is the purpose of this work to discuss shock-hardening mechanisms in nickel and to determine to what extent the initial condition influences the final response. The "flying plate technique" was used to generate planar shock waves with peak pressures as high as 710 kbar. The details of the technique5" have been discussed elsewhere and will not be repeated here. The material used in this study was polycrystalline nickel of 99.98 pct purity and had an initial grain size of 0.18 mm. Prior to any deformation, all samples were given a stress-relief anneal of 6 hr at 600°C in a vacuum furnace. After annealing, the initial condition of the samples was changed by cold rolling individual samples from 0 pct to a maximum of 80 pct reduction in thickness. This provided samples with controlled initial histories for shock deformation. Immediately after shock loading, the specimens were slowed and quenched by suitable arrangement of buffer material and water bath. This technique minimized specimen damage and the effects of shock heating on the samples. Since deformation twins in high stacking fault energy fcc metals are only produced at high stress levels, the initial defect configuration prior to mechanical twinning should greatly influence the number of twins formed. In fact, Zukas and Fowler7 have found that prestraining in iron and steel greatly suppresses the formation of mechanical twins during the shock deformation process. Following the methods of Warren and warekois8 and Cohen and Wagner,9 X-ray diffraction profile analysis was performed to determine the incidence of stacking faults and mechanical twins in the deformed nickel. Analysis was made on samples in the annealed, cold-rolled, shock-loaded, and cold-rolled—shock-loaded states. The estimated accuracy of the peak position measurements is *0.01 deg in 2?. Therefore the accuracy in the measurement of the relative peak shifts between the (400) and (222) diffraction line profiles is on the order of *0.04 deg in 2?. None of our measurements indicated peak shifts greater than 0.04 in 28. This would correspond to a fault density of -1 pct and sets the limit on the sensitivity of our instrument. Similarly, analysis of the shift in the center of gravity of the diffraction line profiles yields the minimum measurable value of the twin fault probabilitya to be -0.002. Fig. 1 shows mechanical twinning in nickel shock-loaded to 400 kbar. In this photograph, fault intersections are clearly visible. The thickness of the individual fault lamellae was determined from the image widths of their lines of intersections by the

Jan 1, 1968

By C. S. Smith, E. W. Palmer

IN 1934, when Gregg and Daniloffl wrote their excellent monograph on the alloys of iron and copper, the most recent literature on the constitution of the alloys indicated a narrow single-liquid area for 20" above the liquidus with a closed liquid mis-cibility gap above this. Since that time, however, a number of investigators have confirmed the much earlier studies of Mushet2 and Stead3 who, among others in the nineteenth century, had described the true state of affairs. Liquid copper and iron are completely miscible in the absence of carbon, but small amounts of carbon cause liquid segregation. In 1934, one of the writers' mentioned evidence for the absence of liquid separation in carbon-free alloys at temperatures up to 1700°C. Two years later, Mad-docks and Claussen5 unequivocally established the absence of liquid segregation and published a revised diagram, reproduced in fig. 1. They also studied the limits of the two-liquid area in ternary alloys of iron, copper, and carbon as a function of carbon and iron content. In the same year Simpson and Bannister" and Schumacher and Souden7 described in some detail the properties of alloys containing 50 to 75 pct Cu. More recently Hodges et al.16 have developed the copper-rich alloys for use as high-strength conductors. In 1937, Iwase, Okamoto, and Ameniya8 published data on the miscibility gap in ternary alloys of iron, copper, and carbon that supported the conclusions of Maddocks and Claussen, and definitely located the two-liquid area at temperatures of 1450" and 1540°C. They also reported that additions of 1 pct Al, Ni, Pb, Sn, or Zn caused no segregation in 50 pct Cu alloys at 1540°C. The use of copper in amounts approximating 1 pct has found industrial employment to an increasing degree in both wrought and cast steels, for such steels are capable of being precipitation-hardened following normalizing, and have high yield strengths. This is summarized by Gregg and Daniloff,1 Sallitt,9 and Lorig and Adams,10 while Alexander" gives additional information on the heat treatment of copper-steel castings. Lippert12 has described Digby's two-phase steels containing copper and chromium. The work described in the present paper was done in the years 1932 to 1934, at which time much of the information was new. The excellent work subsequently done in other laboratories but more promptly published makes the present paper in part only a confirmation of what is now well known. There has not, however, been published any unified study of

Jan 1, 1951

By C. H. North, L. E. Lynd, W. W. Anderson, H. Sigurdson

CONSIDERABLE uncertainty is revealed in the literature regarding the nature of the titanium minerals which make up the bulk of the heavy, opaque fractions of numerous beach sand deposits of the world. An investigation was made, therefore, of beach sand concentrates of North Carolina, Florida, Brazil, and India. Magnetic concentration, X-ray, and microscope data were obtained which show that these concentrates consist essentially of ilmenite and its alteration products. The alteration, brought about by oxidation and leaching of iron values, has resulted in upgrading the ores to a range of 56 to 64 pct TiO2, as compared with 52.7 pct in ilmenite of theoretical composition. Conclusions drawn regarding the nature of the dominant titanium-bearing mineral in beach sand deposits have been based mainly on chemical composition, specific gravity, and petrography. This material has usually been referred to as ilmenite or weathered ilmenite. It has also been referred to as arizonite because in chemical composition it resembles an occurrence in Arizona which was described by Palmer1 in 1909.

Jan 8, 1954

By Charles Legrand

The problem of mine pumping is so much affected by local conditions, and those conditions are so liable to changes during the life of a mine, that the best system to use is difficult to determine. The experience of the writer has been that, in general, for copper mines, electric pumping is most satisfactory unless the quantity of water to be pumped is great or the mine does not use electric power for any other purpose. As a rule, however, figuring on the cost of necessary power plant, the total cost of installation is greater with electric pumps than steam pumps. As the water is liable to be gritty, outside-packed plunger pumps are to be recommended, and if the water is not acid, or only slightly so, chilled cast-iron plungers pay for their extra cost very quickly in diminished cost of packing. With chilled plungers it is possible to use metallic packing instead of soft packing, if the water is not too gritty or the lift too high. In vertical pumps this packing is satisfactory for lifts up to 400 ft., in the experience of the writer, and may be found satisfactory for higher lifts. For water slightly acid, cement-lined pump bodies have given good satisfaction. For acid water, both plungers and puhp bodies should be made of acid-resisting bronze. For high lifts, especially with gritty water, a satisfactory pump valve is difficult to find. To reduce the unbalanced pressure on the valve at time of opening it is advisable to have narrow seats; this, however, brings high pressures on the seats when the valve is closed. On large valves for lifts of 600 to 1,000 ft. we have used leather, hard rubber, vulcanized fiber, and soft brass; for clear water the latter has given best satisfaction. The difficulties due to grit make it advisable to have large sumps where water can settle, and if possible, to have two of them so that they can be cleaned alternately. At the mines of the Old Dominion Copper Mining & Smelting Co., Globe, it was found that a small air ejector discharging into a mine car provides a very convenient way to clean mud and sand from a sump.

Jan 1, 1916

By B. T. Wykoff

This paper describes an important function of mining in Southeast Missouri. The practice is a necessary procedure to prevent disintegration of the pillars. Although the technique is peculiar to this district, it might have application in other mines using room and pillar method. CONSIDERING the subject alone, this paper would cover only a mechanical treatise of pillar roping. Because the St. Joseph Lead Co. originated the practice, it is proper to give a short introduction to the company. It is also proper to describe pillars and discuss their purpose to justify expending large sums of money to preserve them after the surrounding area has been thoroughly mined. Because the St. Joseph Lead Co. originated the practice of back pinning with wedge bolts, patch plates and channel irons, and the pouring of substitute pillars of concrete, these too, are mentioned. The Southeast Missouri Division of the St. Joseph Lead Co. is the largest lead producer in the United States. About 95 pct of the present producing mines are in St. Francois County, which begins 60 miles south of St. Louis. The entire lead ore production of this county, at the present time, is mined and milled by this company, treatment plant capacity being about 22,000 tons per day. This area is also the oldest, lead having been mined at Mine La Motte, in Madison County, in 1723. Estimated production of all the various companies that have mined here is about 7,000,000 short tons of pig lead. Method of Mining The lead occurs in the ore as galena. Galena is found either in the form of disseminated or solid streaks, of varying thickness. Ore stratum is the Bonne Terre dolomite, which is about 350 ft thick, but almost all the ore is in the lower 100 ft. Ore is mined by room and pillar method in open stopes. These stopes vary in height from 7 ft to 200 ft, depending on the thickness of the pay ore in that spot. Back, or roof, is supported entirely by pillars. In a majority of stopes, after the loose scales are mined down, the back has remained solid for many years (fig. 1). Under ideal conditions pillars are spaced to form an equilateral triangle and are as small and as far apart as the height of the stope and the character of the back will permit. They vary in diameter from 10 ft to 50 ft and are from 18 ft to 50 ft apart, measured from the outer edges. In general, the pillars are approximately 12 ft in diameter, and 25 ft apart. The spacing is very uncertain because of the vagaries of the ore trend, the desire to better support breaks in the back, and the attempt to spot out the thinner ore by not placing one in the core of the ore body. Use of Structural Steel Channels In stopes where the back is bad because the overlying formations are thin with wet, weak and shaly

Jan 1, 1951

By B. T. Wykoff

This paper describes an important function of mining in Southeast Missouri. The practice is a necessary procedure to prevent disintegration of the pillars. Although the technique is peculiar to this district, it might have application in other mines using room and pillar method. CONSIDERING the subject alone, this paper would cover only a mechanical treatise of pillar roping. Because the St. Joseph Lead Co. originated the practice, it is proper to give a short introduction to the company. It is also proper to describe pillars and discuss their purpose to justify expending large sums of money to preserve them after the surrounding area has been thoroughly mined. Because the St. Joseph Lead Co. originated the practice of back pinning with wedge bolts, patch plates and channel irons, and the pouring of substitute pillars of concrete, these too, are mentioned. The Southeast Missouri Division of the St. Joseph Lead Co. is the largest lead producer in the United States. About 95 pct of the present producing mines are in St. Francois County, which begins 60 miles south of St. Louis. The entire lead ore production of this county, at the present time, is mined and milled by this company, treatment plant capacity being about 22,000 tons per day. This area is also the oldest, lead having been mined at Mine La Motte, in Madison County, in 1723. Estimated production of all the various companies that have mined here is about 7,000,000 short tons of pig lead. Method of Mining The lead occurs in the ore as galena. Galena is found either in the form of disseminated or solid streaks, of varying thickness. Ore stratum is the Bonne Terre dolomite, which is about 350 ft thick, but almost all the ore is in the lower 100 ft. Ore is mined by room and pillar method in open stopes. These stopes vary in height from 7 ft to 200 ft, depending on the thickness of the pay ore in that spot. Back, or roof, is supported entirely by pillars. In a majority of stopes, after the loose scales are mined down, the back has remained solid for many years (fig. 1). Under ideal conditions pillars are spaced to form an equilateral triangle and are as small and as far apart as the height of the stope and the character of the back will permit. They vary in diameter from 10 ft to 50 ft and are from 18 ft to 50 ft apart, measured from the outer edges. In general, the pillars are approximately 12 ft in diameter, and 25 ft apart. The spacing is very uncertain because of the vagaries of the ore trend, the desire to better support breaks in the back, and the attempt to spot out the thinner ore by not placing one in the core of the ore body. Use of Structural Steel Channels In stopes where the back is bad because the overlying formations are thin with wet, weak and shaly

Jan 1, 1951

By B. M. Larsen, K. Heindlhofer

THIS paper describes a relatively simple electrical apparatus that, through the close analogy between the flow of heat and of electricity, enables one to solve quickly and with satisfactory accuracy many complex problems in heat flow. This device, developed in 1935, has proved especially useful in the solution of certain practical problems relating to the design and efficiency of regenerators for an open-hearth furnace or coke oven, yielding within a few hours information that would take weeks or even months to acquire by mathematical1.2 or experimental3 methods of comparable accuracy. Its description now is prompted by growing interest in such analogues, as shown by several recent papers.4.5 The analogy between flow of heat and of electricity appears to have been recognized first by Maxwell who, in his famous Treatise on Electricity and Magnetism (1881) says: The analogy between the theory of the conduction of electricity and that of the conduction of heat is at first sight almost complete. If we can take two systems geometrically similar, and such that the conductivity. for heat at any part of the first is proportional to the conductivity for electricity at-the corresponding part of the second, and if we also make the temperature of any part of the first proportional to the electric potential at the corresponding point of the second, then the flow of heat across any area of the first will be proportional to the flow of electricity across the corresponding area of the second. .. Thus, in the illustration we have given, in which flow of electricity corresponds to flow of heat, the electric potential to temperature, electricity tends to flow from places of high to places of low potential, exactly as heat tends to flow from places of high to places of low. temperature He noted, however, that this analogy is restricted: ... there is, however, one remarkable difference between the phenomena of electricity and those of heat. Suspend a conducting body within a closed conducting vessel by a silk thread, and charge the vessel with electricity. The potential of the vessel and of all within it will be instantly raised, but however long and however powerfully the vessel be electrified, and whether the body within be allowed to come in contact with the vessel, or not, no signs of electrification will appear within the vessel, nor will the body within show any electrical effect when taken out. But if the vessel is raised to a high temperature, the body within will rise to the same temperature, but only after a considerable time, and if it is then taken out it will be found hot, and will remain so till it has continued to emit heat for some time. The difference between the phenomena consists in the fact that bodies are capable of absorbing and emitting heat, whereas they have no corresponding property with respect to electricity. According to this statement the application of the analogy would be limited to problems of steady flow that do not involve heat-capacity effects. In spite of this

Jan 1, 1945

By Guy W. Crane

The geology of the Tintie mining district, fully treated, would occupy an elaborate monograph. This less comprehensive paper is devoted primarily to the occurrence and origin of the orebodies of the district, while space is given to those phases of the general geology only which seem necessary to a proper setting of such a discussion. The first geological report on the Tintic district to be issued was that by Tower and Smith, published in 1899, in the form of a paper in Part III of the Nineteenth Annual Report of the U. S. Geological Survey, and also as Folio No. 65, Geologic Atlas of the United States. About four years ago a second investigation was begun by Waldemar Lindgren and G. F. Loughlin, of the U. S. Geological Survey. With the exception of a paper on the oxidized zinc ores of the Tintic district by Mr. Loughlin, the results of their work are still unpublished. The writer's acquaintance with the district began in the fall of 1913, and has extended over a period of about two years. 1. Location The Tintic district lies about 65 miles due south of Salt Lake City, and on the west central slope of the Tintic Mountains, a short range, which forms the connecting link between the Oquirrh Mountains on the north and the Canyon Range on the south—the group constituting the first of the Basin ranges to the west of the Wasatch Mountains. The productive portion of the district embraces an area about 6 miles long and 2 miles wide, which is divided between Juab and Utah Counties. Within this area are the towns of Eureka, Mammoth, Robinson, Silver City, and Knightsville. All these points are tapped by the Denver & Rio Grande and S. P., L. A. & S. L. Railways. 2. Topography As in most of the Basin ranges, topographic relief is strong, dropping rapidly from peaks of 8,100 ft. above sea level to elevations of 5,600 ft. in Tintic Valley on the west and 4,500 ft. in Goshen Valley on the east.

Jan 1, 1916

By T. B. Counselman

AfteR several years study, the Universal Atlas Cement Co. decided to rebuild its plant at Leeds, Alabama. The entire old plant, which was to operate during the new construction, was then to be scrapped with the exception of two kilns. The quarry was to be mechanized, new and larger kilns installed, with the most modern type of equipment all through the plant. Raw grinding operations at all of the Universal Atlas plants were dry. However, the dust hazard of this operation and the growing emphasis on occupational diseases made wet grinding attractive. Coal at Leeds is cheap, so that a slightly higher coal practice was unimportant. Power was cheap, so that waste-heat boilers were not desirable. Since new kilns were to be installed, these could be made long enough to make filters unnecessary. Wet raw grinding could be either the old practice of open-circuit compartment mills or closed-circuit grinding in accordance with metal-lurgical practice. The latter saved power and steel wear and saved initial investment. This had been demonstrated in cement plants. Also, the elimination of tramp oversize was a most important advantage. Ease of chemical control was another factor. Blending in the thickener, with elimination of slurry mixers had been found practicable. Therefore, if wet raw grinding were used at all, the advantages were clearly in favor of closed-circuit grinding. Detailed layouts of the most modern possible closed-circuit dry-grinding plant and of a closed-circuit wet-grinding plant were prepared, and careful estimates were made of initial investment and operating costs. Full consideration of all the factors involved resulted in a decision to install wet closed-circuit grinding. The capacity of the new kilns was established at 4000 bbl. per day. Two new kilns were installed, each with a capacity of 80 bbl. per hour. Since 625 lb. of raw material is required to make a barrel of finished cement, the capacity of the grinding plant for the new kilns had to average only 1250 tons per day. Sufficient additional grinding capacity had to be provided for the two remaining old kilns, or their possible replacement by a third new kiln. The grinding rate, therefore, was set at 90 tons per

Jan 1, 1939

By T. B. Counselman

AfteR several years study, the Universal Atlas Cement Co. decided to rebuild its plant at Leeds, Alabama. The entire old plant, which was to operate during the new construction, was then to be scrapped with the exception of two kilns. The quarry was to be mechanized, new and larger kilns installed, with the most modern type of equipment all through the plant. Raw grinding operations at all of the Universal Atlas plants were dry. However, the dust hazard of this operation and the growing emphasis on occupational diseases made wet grinding attractive. Coal at Leeds is cheap, so that a slightly higher coal practice was unimportant. Power was cheap, so that waste-heat boilers were not desirable. Since new kilns were to be installed, these could be made long enough to make filters unnecessary. Wet raw grinding could be either the old practice of open-circuit compartment mills or closed-circuit grinding in accordance with metal-lurgical practice. The latter saved power and steel wear and saved initial investment. This had been demonstrated in cement plants. Also, the elimination of tramp oversize was a most important advantage. Ease of chemical control was another factor. Blending in the thickener, with elimination of slurry mixers had been found practicable. Therefore, if wet raw grinding were used at all, the advantages were clearly in favor of closed-circuit grinding. Detailed layouts of the most modern possible closed-circuit dry-grinding plant and of a closed-circuit wet-grinding plant were prepared, and careful estimates were made of initial investment and operating costs. Full consideration of all the factors involved resulted in a decision to install wet closed-circuit grinding. The capacity of the new kilns was established at 4000 bbl. per day. Two new kilns were installed, each with a capacity of 80 bbl. per hour. Since 625 lb. of raw material is required to make a barrel of finished cement, the capacity of the grinding plant for the new kilns had to average only 1250 tons per day. Sufficient additional grinding capacity had to be provided for the two remaining old kilns, or their possible replacement by a third new kiln. The grinding rate, therefore, was set at 90 tons per

Jan 1, 1939

By Donald W. Scott

Generally speaking, there is nothing very difficult about taking good microgrztphs of photogenic thin sections or grains with a petrographic microscope-camera setup. However, sometimes it is desired to show some detail that cannot be illustrated satisfactorily by the usual micrographs taken with parallel polarized light, with crossed nicols, or even with two micrographs. A simple procedure giving good results has been used at Battelle Memorial Institute for subjects falling into this classification, and it is believed to be of interest, especially to research people who must sell a point to executives through the medium of well-illustrated reports. The following problem illustrates a typical application: It is desired to photograph a thin section of an iron ore to illustrate the character and association of the iron oxides and the individual quartz crystals. A magnification of 75 dia. is acceptable. A micrograph of the field in question (Fig. Ia) was taken with parallel polarized light. Due precaution was taken to provide critical illumination, correct exposure, a sharp focus, a good darkroom technique, and other essential conditions. It illustrates correctly the iron oxides, but it fails to show the individual quartz crystals. A micrograph of the identical field (Fig. Ib) was taken under the same precise conditions, but with crossed nicols. It gives a better idea of the character of the individual quartz crystals but is likely to be misinterpreted unless accompanied by a lengthy descriptive note. This micrograph suggests that the centrally located, large black area is composed entirely of iron oxides. That this' is an incorrect interpretation is evident by reexamining the micrograph of Fig. Ia. The correct interpretation is that the dark area contains quartz crystals oriented with their optical directions parallel to, or nearly parallel to, the vibration directions of the polarizer and analyzer of the microscope. Thus, the executive, or anyone who had not done the work personally, would get no more than a fair interpretation, even if two micrographs were included; and in the interests of both brevity and clarity, one micrograph usually is more desirable. Exactly how many quartz crystals occur in this region cannot be told from the two micrographs, and a printing of the two negatives in register would likewise not show the detail desired. Thus, it is evident that some subjects cannot be satisfactorily illustrated by the usual procedures. In photographing Fig. Ic the light was subdued and, during the entire exposure of 75 sec., the analyzer nicol was rotated uniformly in its mounting from a crossed position to 45° uncrossed position to introduce the desired amount of contrast in the various individual quartz crystals. The true reproduction of the character and association of the iron oxides, and the additional structure and detail in the quartz areas, is apparent. It might be

Jan 1, 1949

By Donald W. Scott

Generally speaking, there is nothing very difficult about taking good microgrztphs of photogenic thin sections or grains with a petrographic microscope-camera setup. However, sometimes it is desired to show some detail that cannot be illustrated satisfactorily by the usual micrographs taken with parallel polarized light, with crossed nicols, or even with two micrographs. A simple procedure giving good results has been used at Battelle Memorial Institute for subjects falling into this classification, and it is believed to be of interest, especially to research people who must sell a point to executives through the medium of well-illustrated reports. The following problem illustrates a typical application: It is desired to photograph a thin section of an iron ore to illustrate the character and association of the iron oxides and the individual quartz crystals. A magnification of 75 dia. is acceptable. A micrograph of the field in question (Fig. Ia) was taken with parallel polarized light. Due precaution was taken to provide critical illumination, correct exposure, a sharp focus, a good darkroom technique, and other essential conditions. It illustrates correctly the iron oxides, but it fails to show the individual quartz crystals. A micrograph of the identical field (Fig. Ib) was taken under the same precise conditions, but with crossed nicols. It gives a better idea of the character of the individual quartz crystals but is likely to be misinterpreted unless accompanied by a lengthy descriptive note. This micrograph suggests that the centrally located, large black area is composed entirely of iron oxides. That this' is an incorrect interpretation is evident by reexamining the micrograph of Fig. Ia. The correct interpretation is that the dark area contains quartz crystals oriented with their optical directions parallel to, or nearly parallel to, the vibration directions of the polarizer and analyzer of the microscope. Thus, the executive, or anyone who had not done the work personally, would get no more than a fair interpretation, even if two micrographs were included; and in the interests of both brevity and clarity, one micrograph usually is more desirable. Exactly how many quartz crystals occur in this region cannot be told from the two micrographs, and a printing of the two negatives in register would likewise not show the detail desired. Thus, it is evident that some subjects cannot be satisfactorily illustrated by the usual procedures. In photographing Fig. Ic the light was subdued and, during the entire exposure of 75 sec., the analyzer nicol was rotated uniformly in its mounting from a crossed position to 45° uncrossed position to introduce the desired amount of contrast in the various individual quartz crystals. The true reproduction of the character and association of the iron oxides, and the additional structure and detail in the quartz areas, is apparent. It might be

Jan 1, 1949

By D. Havlena, A. S. Odeh

The use of the straight-line method of solving the material balance equation is illustrated by means of six field cases. Also, the application of statistical criteria to arrive at the most probable answer is shown. The theory underlying the straight-line method of solution and the applicability of the statistical criteria was presented in a previous paper.' The field cases include saturated and undersaturated oil reservoirs with and without water drive. The aquifers discussed are: limited radial, infinite radial, very small aquifer and infinite linear. The field cases also include a gas reservoir producing under water drive. INTRODUCTION In a previous paper,' the authors presented the theory underlying the solution of the material balance as an equation of a straight line. The appropriate equations for various material balance cases as well as the methods of analysis and interpretation with comments and discussion were also included. To illustrate the various theoretical cases treated previously, five field cases are analyzed in this paper by employing the straight-line method of solving the material balance equation (MBE) and one example previously published is referred to. The use of statistical criteria to arrive at the most probable answer is also shown. All the field examples presented, except Case 2, are excerpts from complete reservoir studies. To illustrate the method, only sections specifically dealing with the material balance principles are included. Additional geologic information and basic data are reported to better acquire an understanding of the cases and thus to better follow the reasoning that suggested the successful application of the straight-line method of solving the MBE. The six cases are: (1) saturated reservoir, small gas cap, limited aquifer; (2) saturated reservoir, very small gas cap, infinite aquifer; (3) undersaturated-saturated reservoir, very small aquifer; (4) highly undersaturated reservoir, no water drive; (5) high undersaturated one-well reservoir, limited aquifer; and (6) gas reservoir, infinite linear aquifer. THE D4 SAND, GUICO FIELD, VENEZUELA The D, sand, which was discovered in 1943, is presently in a depleted state. Since its discovery it has produced under water drive, gas-cap-gas expansion, and solution gas drive. In Nov., 1947, water injection was initiated to arrest further pressure decline. When discovered, the D, sand was a saturated reservoir with a gas cap /oil zone volume ratio m estimated volu-metrically at 0.0731, an average permeability of 500 md, a porosity value of 25 per cent, and an oil viscosity at reservoir conditions of 0.3 cp. The volumetrically determined stock-tank oil initially in place was 23.1 million bbl. The volumetrically weighted physical data and production data available until Nov., 1953 are reported in Table 1. In Ref. 1, the effects on the straight-line plot of various values of ro/r for a constant ?to, or of various dimen-sionless times for a constant r8/r10 were theorized and were illustrated in Fig. 3A of that reference. In this field case, the previously theoretically predicted effects are established. Thus, the MBE calculations using Eq. 3c of Ref. 1 were performed for various r6/r10 and dimension-less time values. Eq. 3c of Ref. 1 is:

Jan 1, 1965

By Ihor A. Kunasz

Lithium minerals occur predominantly in pegmatites which contain mineral assemblages derived from the crystallization of postmagmatic fluids or from the metasomatic action by residual pegmatitic fluids. They have been the traditional sources of raw materials for ceramic and chemical industries. However, with the discovery of Searles Lake, brines became new sources of lithium. Indeed, the 1960s may well be referred to as the "brine decade" because several brine bodies of significant economic importance were discovered. In the United States, the brines of Clayton Valley, Nevada, presently exploited by Foote Mineral Co., and the Great Salt Lake of Utah, to be exploited by the Great Salt Lake Chemicals Corp., have been defined as major sources of lithium. Also a lithium-bearing brine has been discovered in Chile. Following the termination of the AEC purchase program in 1959, several companies such as Maywood Chemical Co., American Lithium Chemicals, and Quebec Lithium Corp. were forced to close down their operations. Nevertheless, with the development of new applications in glass ceramics, air conditioning systems, synthetic rubber, and metallurgy (aluminum potlines), the lithium industry grew steadily, and with the potential application of lithium metal in batteries and nuclear reactors, a healthy growth can be foreseen. New products and new applications are likely to stimulate exploration for expanded reserves as well as the search for new sources from which lithium could be extracted economically. Geochemistry of Lithium Lithium is the third element in the periodic table. It is the lightest of all the metals, having an atomic weight of 6.938. Its ionic radius is 0.60A and its charge is + 1. The geochemistry of lithium has been extensively studied and has been summarized by Rankama and Sahama (1950), Goldschmidt (1937), and Hortsman (1957). The distribution of lithium in igneous rocks is controlled by its size and its charge, and by the (MgO+FeO)/Li2O ratio. In the early stages of crystallization of a magma, that ratio is very large. Consequently, both magnesium and iron are removed by ferromagnesian minerals in preference to lithium which is then concentrated in the residual magma. This results in an enrichment of lithium in silicic rocks and pegmatites (Strock, 1936). Pegmatites are coarse-grained igneous rocks formed by the crystallization of postmagmatic fluids. Minerals within pegmatites may also form by metasomatism (Jahns. 1955). Genetically, the pegmatites are associated kith neigh- boring intrusives. Mineralogically, granitic pegmatites contain feldspar, quartz, and mica as the main constituents and a variety of exotic elements such as lithium, beryllium, tantalum, tin, and cesium, which may or may not occur in economically significant concentrations. Detailed studies by numerous investigators (Cameron et al., 1949, 1954; Hanley et al., 1950; Jahns, 1953, 1955; Page et al., 1953) indicate that pegmatites often exhibit an internal zonal arrangement, with each zone containing a specific suite of minerals. The lithium minerals are usually found in the intermediate zones, and although as many as 13 zones have been recognized by Cameron, a complete zonal arrangement is rarely found. Zoning of pegmatite bodies has also been observed on a regional basis. The regionally zoned pegmatite sequences exhibit mineral assemblages and complexity according to their respective distance from the granitic bodies to which they are genetically related (Mulligan, 1965). Lithium is also found in small proportions in a variety of rocks. The average lithium

Jan 1, 1975

By Gerhard Derge

A series of studies of the corrosion of tin is under way in the Metals Research Laboratory at the Carnegie Institute of Technology. The complete program includes examination of the corrosion properties of high-purity tin and the changes produced in these properties by the addition of varying amounts of alloying elements. Other studies of this subject have been made recently under the sponsorship of the International Tin Research and Development Council, but these researches have been confined largely to the weakly acid environments commonly encountered in the canning industry.' There is little information available regarding the corrosion of tin under alkaline conditions, but such data would be of value, for a large amount of the metal is used under such conditions. The potential measurements to be described were made because they seemed to offer the most rapid method for obtaining a general view of the conditions to be encountered in such service. These experiments will also serve to establish a technique that will be of value in further studies. It must be emphasized that the results reported are those of controlled laboratory experiments and that the conclusions drawn cannot yet be applied to service conditions; rather, they point to the directions in which more exhaustive experimental work may be done to best advantage. Experimental Procedure The first work was devoted entirely to the problem of obtaining reproducible results from a series of potential measurements. Only the methods finally adopted as standard will be described here, except when the variations from these have furnished results of interest. The cell used is shown schematically in Fig. 1. The electrolyte is contained in the vessel A (an inverted bell jar), whose ground top is fitted to the transite-board lid B. The controlled atmosphere can be admitted

Jan 1, 1938

By Gerhard Derge

A series of studies of the corrosion of tin is under way in the Metals Research Laboratory at the Carnegie Institute of Technology. The complete program includes examination of the corrosion properties of high-purity tin and the changes produced in these properties by the addition of varying amounts of alloying elements. Other studies of this subject have been made recently under the sponsorship of the International Tin Research and Development Council, but these researches have been confined largely to the weakly acid environments commonly encountered in the canning industry.' There is little information available regarding the corrosion of tin under alkaline conditions, but such data would be of value, for a large amount of the metal is used under such conditions. The potential measurements to be described were made because they seemed to offer the most rapid method for obtaining a general view of the conditions to be encountered in such service. These experiments will also serve to establish a technique that will be of value in further studies. It must be emphasized that the results reported are those of controlled laboratory experiments and that the conclusions drawn cannot yet be applied to service conditions; rather, they point to the directions in which more exhaustive experimental work may be done to best advantage. Experimental Procedure The first work was devoted entirely to the problem of obtaining reproducible results from a series of potential measurements. Only the methods finally adopted as standard will be described here, except when the variations from these have furnished results of interest. The cell used is shown schematically in Fig. 1. The electrolyte is contained in the vessel A (an inverted bell jar), whose ground top is fitted to the transite-board lid B. The controlled atmosphere can be admitted

Jan 1, 1938

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the 'ultimate recovery somewhat increased' The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3' per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the 'ultimate recovery somewhat increased' The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3' per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

By E. S. Messer

A knowledge of the magnitude of the irreducible inter.;titial water in a porous medium is so important to petroleum engineering that its determination has become routine in core analyses. The method of determination, being a production problem, should encompass the basic requirements of simplicity in technique and calculations, with reproducible results obtainable in a short interval of time. The results of the evaluation tests outlined in this report indicate that the evaporation method for determining the irreducible water is a technique which meets the requirements. The procedure consists, as the name implies. of permitting the saturant in the pore spaces to evaporate until only an irreducible volume remains. The determination of this volume can be made either graphically or by a mathematical comparison of fluid flows; the time required for each determination being dependent on the fluid used. When fluids other than those having reservoir characteristics were used, a volume factor had to be calculated which was based on the relative volume of various liquids adsorbed on grain surfaces and retained in pores. This factor made possible the calculation of an irreducible water volume when more volatile fluids such as toluene and benzene were used as the saturants. Also presented is the theoretical discussion necessary for the calculation of the capillary pressure as determined from the evaporation curve. A comparison is made between the calculated values and those obtained by experimental means. INTRODUCTION In all geological formations there exists, in the pore spaces of the rock structure, water that is held in a state of equilibrium between capillary and hydrostatic forces. "Interstitial water" is the term given to this water and is defined as that water coexisting in the pore space with the oil prior to exploitation. The term ''connate water" has often been used synonymously with this term; however, this can be true only by a specific definition since, geologically, it means the water in place at the time the rock structure was formed. The quantity of the interstitial water is a variable factor in any formation, since it depends on the hydrostatic forces present in any multiple-phase system. These forces may become unbalanced by the introduction of an extraneous force such as the raising or lowering of the "water table" or the migration of oil into a water-filled formation. Any unbalanced force results in a change in the interstitial water. There exists, however, an irreducible interstitial water. for a particular sand, that is the fraction of the pore space occupied by water when the capillary pressure at the particular point in question is at an equilibrium with the hydrostatic head of the oil sand in the reservoir. For this discussion the term "irreducible water saturation" will be used in place of "irreducible interstitial water saturation" for the sake of brevity; however, they are understood to be identical. A great amount of work has been devoted to the theory and methods for studying the irreducible water saturation and its related capillary pressure. As a result of the publications of Leverett;' Hassler, Brunner and Deahl;2 Calhoun and Lewis;3 and others, the role of capillary pressure studies is being accepted by the industry as a tool for studying suhsurface phenomena. Many techniques have been developed and published for determining the capillary pressure and irreducible water. In general, these techniques may be grouped into three classifications. One of the first was the capillary pressure method described by Leverett1 and expanded by Bruce and Welge.4 The experimental results were compared with water saturation of cores obtained using oil-base mud. Thornton and Marshall compared the irreducible water saturation of core samples determined by the capillary pressure method and by salinity and reported good agreement between the two methods. The second classification for determining the irreducible water and capillary pressure may be referred to as the "centrifugal force method." The general technique is similar to the capillary pressure method except that the force driving the reservoir fluid from the sample is of a centrifugal nature. A complete description of this method was presented by J. J. . McCullough and F. W. Albaugh.6 A process, the reverse of the capillary pressure method, was presented by W. R. Purcell.7 Mercury under pressure is driven into the pores of the rock and the saturation of the core determined at each applied pressure. The resulting capillary pressure curve is used to evaluate the irreducible water saturation. The techniques mentioned are singular in their approach to the irreducible water saturation. In all cases. an external force was applied to the core. The forces employed in the evaporation method are the vapor pressure of the liquid causing evaporation, the kinetic diffusion forces. adsorptive forces and. to a lesser degree, the viscous forces resisting flow to the surface. The basic definition of irreducible water is that water held in a state of equilibrium between capillary and hydrostatic forces This water has been described by previous investigators as being held in the microcapillaries too small to support fluid flow. Actually, this fluid volume is made up of the water in the microcapillaries and as a film adhering to the surface of the crystals. All capillaries. therefore, possess some liquid as a film, the thickness of the film being dependent on the properties of the fluid and solid. A discussion of experiments with references pertaining to the measurement of this immobile layer next to the solid surface can be found in the text by J. J. Bikerman.8 Eversole and Lahr calculated the thickness of this layer to be in the order of 10 ' to 10' cm for aqueous solutions and glass. Between two quartz surfaces they found the thickness to be 2 x 10 cm. The work of Volkova, on the capillary movement of water and toluene in quartz grains, indicated the thickness of the Immobile layers to be near 10' cm. Since any measurement is an average value, it is easy to understand that an absolute value would depend on the roughness of the surfaces involved and the complexity of the system. A calculated effective pore radius of 2 x 10 cm is obtained at the, irreducible saturation of a porous media in a water-air system when a capillary pressure of 100 psi is applied. Since the separation of the sand grains is of the same approximate magnitude as the immobile layer.

Jan 1, 1951

By E. S. Messer

A knowledge of the magnitude of the irreducible inter.;titial water in a porous medium is so important to petroleum engineering that its determination has become routine in core analyses. The method of determination, being a production problem, should encompass the basic requirements of simplicity in technique and calculations, with reproducible results obtainable in a short interval of time. The results of the evaluation tests outlined in this report indicate that the evaporation method for determining the irreducible water is a technique which meets the requirements. The procedure consists, as the name implies. of permitting the saturant in the pore spaces to evaporate until only an irreducible volume remains. The determination of this volume can be made either graphically or by a mathematical comparison of fluid flows; the time required for each determination being dependent on the fluid used. When fluids other than those having reservoir characteristics were used, a volume factor had to be calculated which was based on the relative volume of various liquids adsorbed on grain surfaces and retained in pores. This factor made possible the calculation of an irreducible water volume when more volatile fluids such as toluene and benzene were used as the saturants. Also presented is the theoretical discussion necessary for the calculation of the capillary pressure as determined from the evaporation curve. A comparison is made between the calculated values and those obtained by experimental means. INTRODUCTION In all geological formations there exists, in the pore spaces of the rock structure, water that is held in a state of equilibrium between capillary and hydrostatic forces. "Interstitial water" is the term given to this water and is defined as that water coexisting in the pore space with the oil prior to exploitation. The term ''connate water" has often been used synonymously with this term; however, this can be true only by a specific definition since, geologically, it means the water in place at the time the rock structure was formed. The quantity of the interstitial water is a variable factor in any formation, since it depends on the hydrostatic forces present in any multiple-phase system. These forces may become unbalanced by the introduction of an extraneous force such as the raising or lowering of the "water table" or the migration of oil into a water-filled formation. Any unbalanced force results in a change in the interstitial water. There exists, however, an irreducible interstitial water. for a particular sand, that is the fraction of the pore space occupied by water when the capillary pressure at the particular point in question is at an equilibrium with the hydrostatic head of the oil sand in the reservoir. For this discussion the term "irreducible water saturation" will be used in place of "irreducible interstitial water saturation" for the sake of brevity; however, they are understood to be identical. A great amount of work has been devoted to the theory and methods for studying the irreducible water saturation and its related capillary pressure. As a result of the publications of Leverett;' Hassler, Brunner and Deahl;2 Calhoun and Lewis;3 and others, the role of capillary pressure studies is being accepted by the industry as a tool for studying suhsurface phenomena. Many techniques have been developed and published for determining the capillary pressure and irreducible water. In general, these techniques may be grouped into three classifications. One of the first was the capillary pressure method described by Leverett1 and expanded by Bruce and Welge.4 The experimental results were compared with water saturation of cores obtained using oil-base mud. Thornton and Marshall compared the irreducible water saturation of core samples determined by the capillary pressure method and by salinity and reported good agreement between the two methods. The second classification for determining the irreducible water and capillary pressure may be referred to as the "centrifugal force method." The general technique is similar to the capillary pressure method except that the force driving the reservoir fluid from the sample is of a centrifugal nature. A complete description of this method was presented by J. J. . McCullough and F. W. Albaugh.6 A process, the reverse of the capillary pressure method, was presented by W. R. Purcell.7 Mercury under pressure is driven into the pores of the rock and the saturation of the core determined at each applied pressure. The resulting capillary pressure curve is used to evaluate the irreducible water saturation. The techniques mentioned are singular in their approach to the irreducible water saturation. In all cases. an external force was applied to the core. The forces employed in the evaporation method are the vapor pressure of the liquid causing evaporation, the kinetic diffusion forces. adsorptive forces and. to a lesser degree, the viscous forces resisting flow to the surface. The basic definition of irreducible water is that water held in a state of equilibrium between capillary and hydrostatic forces This water has been described by previous investigators as being held in the microcapillaries too small to support fluid flow. Actually, this fluid volume is made up of the water in the microcapillaries and as a film adhering to the surface of the crystals. All capillaries. therefore, possess some liquid as a film, the thickness of the film being dependent on the properties of the fluid and solid. A discussion of experiments with references pertaining to the measurement of this immobile layer next to the solid surface can be found in the text by J. J. Bikerman.8 Eversole and Lahr calculated the thickness of this layer to be in the order of 10 ' to 10' cm for aqueous solutions and glass. Between two quartz surfaces they found the thickness to be 2 x 10 cm. The work of Volkova, on the capillary movement of water and toluene in quartz grains, indicated the thickness of the Immobile layers to be near 10' cm. Since any measurement is an average value, it is easy to understand that an absolute value would depend on the roughness of the surfaces involved and the complexity of the system. A calculated effective pore radius of 2 x 10 cm is obtained at the, irreducible saturation of a porous media in a water-air system when a capillary pressure of 100 psi is applied. Since the separation of the sand grains is of the same approximate magnitude as the immobile layer.

Jan 1, 1951