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By Leendert de Witte

A review is given of the principles on which recently proposed methods of electric log interpretation in shaly sands are based and of the evidence brought up in support of the theoretical derivations. It is. pointed out that the qualitative techniques suggested to date have a tendency to be too pessimistic in the prediction of the presence of commercial hydrocarbon accumulations. In the quantitative treatment, a new concept is introduced, namely that of strongly reduced activity of the double layer counter ions which are present near the negatively charged rock surfaces. This lemmu when applied to the calculation of the equilibrium concentratiotls of interstitial waters yields a set of very simple relations. The resulting expressions for electrochemical potentials across rock samples appear in satisfactory agreement with laboratory experiments. The formulae obtained for the electrical conductivity of shaly formatioris are of the same form as those arrived at empirirally by previous workers. Combination of the expres.riorls for potentia1s and conductivities gives a direct proof of the Tixier relation which states that for shaly water sands the product of apparent formation water resistivity and apparent formation factor equals the resistivity of the sand 100 per cent .saturated with formalion water and which was verified by the work of Wyllie and Perkins and their co-workers. The relations for the resistivities and spontaneous porer11inI.s have been extended to the case of hydrocarbon hearing shaly formations, thus laying a formal basis for the quantitative interpretation of electric logs in shaly oil sands. INTRODUCTION The presence of disseminated clays in porous rocks saturated with electrolytic solutions has a strong influence on the transference of ions taking place under electrical or chemical potential gradients. Both the electrochemical emf's in evidence on the SP curves of electric logs and the electrical conductivity measured on resistivity logs arc directly dependent on the ionic transference in the interstitial waters of the formations traversed by boreholes. A large number of researches have been carried out on the nature and magnitude of the effects of clays on ionic transference. The most recent of these have been described in papers by McCardell and Winsauer,1 2 Wyllie and Southwick,3 poupon, Loy, and Tixier,4 and by Perkins et al.5 Most of these authors consider the effects of the clays as due to the fixed negative charges on the clay lattice. These charges cause the formation of diffuse surface layers with a high concentration of positive ions. The internal solution of the shaly reservoir rock has therefore a different ionic composition and concentration than the electrolyte with which it is in equilibrium (connate water produced from the formation or mud filtrate by which the formation is invaded). To calculate the equilibrium concentration of the internal solution, use is made of the Donnan6 relation, which states that the mean ionic activities of the internal solution and of the external electrolyte must be equal. From this and the

Jan 1, 1956

By John Mullen

Impingers TWO types of midget impinger apparatus are used at Climax. The Mine Safety Appliances Company's midget impinger (MSA) and the Climax Molybdenum Company's midget impinger (CMC) (Fig. I). The Leiman Brother's No. 25, positive displacement pump is used in the CMC impinger instead of the four-cylinder radial pump that is used in the MSA impinger. With the MSA apparatus it is possible to obtain the proper vacuum by adjusting the needle valve on the vacuum chamber, while with the CMC impinger the proper vacuum is obtained by varying the rate at which the pump is cranked. The Leiman Brother's No. 25 pump is built to displace 0.1 cu. ft. of air per min. when operated at 145 r.p.m. In the CMC impinger this pump is so geared that the required crank speed is approximately 59 r.p.m. Both types of impinger apparatus are equipped with a water gauge mounted on top of the case and they are calibrated and operated in reference to the gauge. The MSA impinger flasks and nozzles are used with both types. Calibrating Impingers A calibrated precision Sargent wet-test meter (Fig. 2) is used in calibrating the impinger apparatus. The apparatus is set up as for taking a sample in the field, except that the hose from the outlet side of the meter is attached to the impinger nozzle. One revolution of the large hand of the meter indicates 0.1 cu. ft. of air displaced. The impinger pump is cranked for one minute, therefore, at a rate that will cause the large hand of the meter to make one revolution. The gauge reading is noted, then the impinger is cranked at this rate for 10 min. and is checked for error. If the meter indicates that more or less than I cu. ft. of air has been displaced, the impinger must be cranked—ither slower or faster according to the error—for another 10 min. and again checked for error. This operation is repeated until the proper gauge reading for a sampling rate of 0.1 cu. ft. per min. has been determined. This gauge reading is used in all sampling operations until the impinger is again calibrated. An impinger is calibrated at least twice each week. MlCROPROJECTOR A Bausch and Lomb model B micro-projector is used (Fig. 3). It consists of a substantial metal base supporting the light source and a microscope. Illumination is provided by a Bausch and Lomb 4.5-amp. arc lamp with mechanical feed. A glass water cell filled with a heat-absorbing and color-filter solution is placed between the arc lamp and the microscope. Two types of solution have been found satisfactory— a 2 per cent solution of copper sulphate or a 2 per cent solution of picric acid and distilled water. This percentage may be varied to give the desired color to the light reflected upon the screen. Any standard microscope may be used. A Bausch and Lomb microscope with

Jan 1, 1946

By J. H. Carpenter

LMENITE, rutile, zircon, and other heavy minerals are found in small amounts in the sand that covers most of Florida. Small enriched deposits occur on the beaches and coastal dunes. One beach deposit east of Jacksonville was worked during World War I and another near Vero Beach during World War 11. Both ceased operation when the resumption of imports reduced prices. Early in World War II reduction of rutile imports made a domestic source of the mineral necessary to maintain the expansion of armaments. Explorations made near Jacksonville discovered a relatively large body of low-grade ore about 10 miles inland from the beaches. A plant installed by Rutile Mining Co. of Florida using both flotation and tables encountered difficulties because of low plant capacity and organic slimes in the ore. In 1944 Humphreys Gold Corp. solved the problem of concentrating the low-grade ore by using the newly developed Humphreys spiral concentrator and by mining with a hydraulic dredge. This combination of low cost mining and concentration permitted the plant to continue operation in competition with foreign ores when imports were resumed following the war. The success of the Jacksonville operation renewed interest in Florida as a source of titanium. An extensive survey of the state was made by E. I. du Pont de Nemours and Co., Inc., under the direction of J. L. Gillson in 1945 to 1946. Sampling was carried on by drive pipe drilling to depths of 20 to 25 ft. Encouraging values were discovered near the location of the present Trail Ridge mine, 50 miles southwest of Jacksonville, near the town of Starke. The United States Bureau of Mines was interested in exploring for heavy minerals in Florida, and on the recommendation of both the state geologist of Florida and of Du Pont geologists, drilled deeper where marginal indications were found on Trail Ridge. In 1947 it was discovered that sufficiently higher values occurred at depth to make the deposit commercial. The orebody at Trail Ridge is a long sand deposit averaging about 1 mile in width and 35 ft in depth. It is approximately 1 1/2 miles wide at the north end of the portion now being worked, tapering to a blunt point 3 miles to the south. The ore reaches a maximum depth of 65 ft near the center and feathers out into barren sand at the edges. The ground surface is relatively flat and is covered with vegetation including pine, scrub oak, palmetto, and occasionally in swampy areas, cypress. The remain of a dense woody growth underlies and marks the bottom of the Ore 'One. It is difficult to drill through this layer, but in some cases where it is less than 5 ft thick it has been possible to drive through the wood. Sand lying below is coarser than that in the ore zone and contains no values. The wood layer consists of unconsolidated carbonized fragments of branches and other forest trash associated with a considerable amount of ar-

Jan 1, 1954

By R. Taggart, D. H. Polonis, J. C. McMillan

Thin foil electron microscopy techniques have been used to study the micros tructure of a Ti- 7.5 wt pct vanadium alloy in the quenched and aged cond_itions. Selected area diffraction has identified a (1011) twinning mode accompanying the martens ite t9.an.sfo?rn~ation. Precipitation of the 0 phase during the aging of quenched alloys has been obsevced to occuv in the form of plates and needles with preferential growth along the (1120) direction in the a' matrix. In the present work, the micro structures of quenched and aged alloys of the 0 isomorphous Ti-V system have been investigated by means of thin-foil electron-microscopy techniques. Most of the previous studies of martensitic phases in titanium-base alloys have utilized optical microscopy and X-ray diffraction techniques. The application of transmission electron microscopy is more recent, and only a few such studies have been reported.1-5 This paper is concerned particularly with the crystallographic nature of substructures formed in the martensitic a' plates. The early stages of aging or tempering have also been examined to determine the modes of precipitation from the martensitic solid solutions. Such information is essential in studying strengthening mechanisms and in determining the feasibility of high-strength rnartensitic alloys based on titanium. Liu and Margolin6 reported several types of substructures within the martensitic plates of quenched Ti-Mn alloys. It was later suggested by Liu7 that the structure of martensitic plates might be very complex and not single crystals as normally assumed. The sub-markings could not be identified with the two possible habit-plane orientations {334}ß and {344}ß, and it was not positively determined whether they are associated with mechanical twinning. The recent studies by Armitage5 on titanium martensites in a variety of commercial alloys have indicated that twinning does not generally accompany the transformation. This observation is in accordance with the Mackenzie and Bowles model for the transformation in pure titanium8 which suggests that twinning is not to be expected. However, a number of other recent investigators have reported twinlike substructures in the martensitic plates of several titanium systems including commercia1 titanium,2,3 Ti-Cu,5,9 Ti-Ta,1 and the commercial alloy Ti-8A1-1Mo-1V. Blackburn* has reported that the structure of quenched Ti-8A1-1Mo-1V depends on the prior solution temperature. He identified two types of martensitic structures, one of which is described as a heavily faulted hcp or twinned fcc structure and the other an hcp structure with a high internal dislocation density. The latter type exhibited some twinning with a (1011) twin plane. EXPERIMENTAL PROCEDURES AND RESULTS The alloy used in the present work was a 7.5 wt pct V alloy that was prepared by conventional arc-melting techniques. This alloy composition was selected

Jan 1, 1968

By N. A. D. Parlee, N. M. El Tayeb

Fe-V alloys with small percentages of vanadium show no deviations from Sieverts' Law up to P~, = 1 atm in the 1600º to 1750ºC region. At somewhat under 8 pct V and up to at least 20pct V, at 1604" and 1661 °C, nitrogen absorption follows Sieverts' Law at low Pn2 values, but deviates from this law beyond critical values of pn2, due to formation of a nitrzde phase of approximately VN composition. The behavior below these solubility limits can be described at all temperatures by the equations: RAO and parlee1 suggested that the nitrogen absorption curve for liquid iron alloys takes the general form shown in Fig. 1 when an alloy nitride precipitate is formed. They showed that the precipitation of 6 titanium nitride from liquid Fe-Ti alloys follows this general scheme and dealt with the general theory involved. Recently, Evans and Pehlke2 reported their research on the precipitation of aluminum nitride from liquid Fe-A1 alloys. Fountain and Chipman's recent paper3 on the precipitation of boron nitride from solid solution contains a fine example of the analogous behavior which they have been studying in the solid state. Researches on the absorption of nitrogen by liquid Fe-V alloys have been described by various authors.1,4-7 Most of this work has been confined to fairly low vanadium concentrations and rather high temperatures because of difficulties variously described as, formation of surface scums, bridging, and so forth. This behavior and the rough thermo- dynamic calculations made by chipman,8 over eleven years ago, indicated that excessively high vanadium concentrations should not be required for vanadium nitride precipitation. It seemed desirable to look for and study this precipitation in order to fill out the thermodynamically interesting nitrogen absorption data on these alloys. EXPERIMENTAL METHOD The general method used was essentially the same as employed by Rao and parlee,1 in which a Sieverts type of apparatus was used and the precipitation of the nitride detected by the "break-point" in the Sieverts' Law line, and by the visual observation of the formation of the new phase on the surface of the melt. There were, however, a few differences in apparatus and technique as described below. The oil manometer used by Rao and parlee' to measure low partial pressures of nitrogen was not employed. The present authors sought to avoid as much as possible the exposure of the liquid alloy to low total pressures of gas during the 6 to 10 hr long runs because of the heavy iron evaporation-loss errors involved. This was achieved, partly by keeping evacuation times to a minimum with fast pumping but largely by the use of two burettes, one for argon and one for nitrogen, and using them to equilibrate the alloy with mixtures of argon and nitrogen rather than nitrogen alone. Each run involved a careful sequence of operations. After melting, de-

Jan 1, 1963

By J. E. Gould, H. J. Hand

Many independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types. In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final de-oxidation. In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding overdeoxidation to minimize the amount of inclusions present and to make as sound a steel as possible. For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved. While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or low FeO values. The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests. With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishiug the state of oxidation at a given time. Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors. Data obtained are from actual iurnace operations, the metal test being of the I spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States I Steel Corporation. This method of taking open-hearth metal temperature was invented by Collins and Oseland,l and was developed into its present form by L. 0. Sordahl,2 of the Research Laboratory. The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications.3,4,5 lag components were obtained by chemical analysis. Data were taken from four 165-net-ton furnaces during the working period of the heat. Recognizing that additions of ore affect the metal FeO. no tests were included within 30 min. after ore additions. In all, 65 tests (48 heats) were used in this study.

Jan 1, 1942

By J. E. Gould, H. J. Hand

Many independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types. In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final de-oxidation. In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding overdeoxidation to minimize the amount of inclusions present and to make as sound a steel as possible. For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved. While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or low FeO values. The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests. With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishiug the state of oxidation at a given time. Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors. Data obtained are from actual iurnace operations, the metal test being of the I spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States I Steel Corporation. This method of taking open-hearth metal temperature was invented by Collins and Oseland,l and was developed into its present form by L. 0. Sordahl,2 of the Research Laboratory. The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications.3,4,5 lag components were obtained by chemical analysis. Data were taken from four 165-net-ton furnaces during the working period of the heat. Recognizing that additions of ore affect the metal FeO. no tests were included within 30 min. after ore additions. In all, 65 tests (48 heats) were used in this study.

Jan 1, 1942

By E. M. Tory, P. T. Shannon

An analysis of batch and continuous thickening in terms of the movement of planes of constant concentration (i.e. continuity waves) is presented. Use of solids flux as a primary variable greatly facilitates the analysis and clarifies the relationship between batch and continuous thickening. An "ideal" slurry is defined as one whose settling rate is a function only of the local solids concentration. An analysis of continuous thickening of this ideal slurry in an ideal thickener explains many aspects of the steady — and unsteady — state behavior of real slurries, such as the main features of a thickener's "solids profile" (including the break attributed to rake action), the sudden appearance at abnormally high feed rates of a zone of constant concentration and the velocity with which it rises, and the effect of detention time at constant weight of sludge per unit area. Where deviations exist, they are explained in terms of the batch settling behavior of real slurries. The purpose of this paper is to interpret continuous thickening phenomena in terms of batch settling behavior. Both types of thickening may be considered as the process of propagating concentration changes, due to the downward movement of the solids, from the bottom of the settling vessel upward through the slurry.' These concentration changes may be either finite or infinitesimal as in the case of the propagation of a continuous concentration gradient. The slurry itself may be moving downward as in the case of continuous thickening. The downward velocity of the slurry may be such that the concentration changes being propagated up from below remain stationary relative to the thickener walls. This is the case for steady-state thickening. It seems appropriate to analyze continuous thickening in terms of the movement of planes of constant concentration. This has already been done for batch settling."3 Although our main interest is in real slurries, there are certain aspects of both types of settling which can be deduced from a theoretical analysis of highly idealized systems. To this end, an "ideal slurry" is defined as one for which the dimensionless settling rate at any point is a function only of the local solids concentration.1,2 An "ideal thickener" is one in which there is no radial variation in either the solids concentration or in the downward component of slurry velocity. The underflow outlet is a point sink. It is to be expected that the behavior of non-ideal systems will deviate in some measure from theoretical results. However, the same characteristics which cause deviations in continuous thickening should be evident in batch settling, permitting a rational explanation of the former in terms of the latter. PREDICTED RESULTS FOR AN IDEAL SLURRY IN AN IDEAL CONTINUOUS THICKENER General Theory: In continuous thickening, the downward solids flux (mass/area-time) relative to the thickener, G, results from two different

Jan 1, 1967

By Stuart E. Buckley, C. R. Hocott

The viscosity of the oil in the reservoir is one of the properties that influence its movement through the sand to producing wells. Measurements of viscosity, therefore, are pertinent to problems associated with well behavior and with the estimation of recoveries, and afford an indirect means for partial evaluation of various methods of controlling reservoir behavior. The effect of dissolved gases on the viscosity of crude oil has been determined,ls2 but no data have been published on the viscosity of representative samples of reservoir oils. This paper describes a simple instrument that has been used to determine the viscosities of a number of subsurface oil samples at the temperatures and pressures existing in the reservoirs, and presents the results of the determinations for typical fields. Construction oF the Apparatus The principal requirements of any instrument used for the examination of subsurface samples are that it be strong and simple both in design and in method of operation. Accuracy beyond that of the degree of reproducibility of subsurface Sam-~les from various wells in a reservoir or exceeding that of the common measure-merits of reservoir temperatures and Pressures is not required. Because of the expense of procuring subsurface samples, it is necessary also that the instrument operate on a relatively small fraction of a sample, leaving the remainder for other tests, and that there be few or no failures of the equipment to cause undue delay or loss of a sample. After preliminary experiments with a falling bullet, the results of which were not satisfactory, a simple viscosimeter was built of the rolling ball type first proposed by Flowers3 and later used by several investiga-tor. 5.8 The apparatus consists essentially of a removable, accurately bored cylindrical barrel of 1/4-in. nominal internal diameter, 8 in. long, in which a closely fitting steel ball rolls through the oil with the barrel inclined at a definite angle. The ball makes contact at one end of the barrel with ail insulated electrode, closing an electrical circuit, which actuates a buzzer. The meas-urements consist essentially in determining the time required for the ball to travel the length of the barrel. The details of the construction are shown in Fig. I. The barrel in which the ball rolls was made from a section of 25-caliber blank rifle barrel, specially bored to an exact uniform diameter and polished. The barrel slides snugly into a hole bored in a solid stainless-steel cylinder, an upper external shoulder of the barrel compressing a small spring, and is held in place by a hollow nut. The spring prevents the barrel from seating against the bottom of the bored hole in the cylinder, while narrow external longitudinal slots in the barrel permit fluid to flow around it and through the bottom. The upper part of the recess in the steel cylinder is enlarged to form a tapered chamber, which acts as a reservoir for the oil and affords space for agitation to ensure

Jan 1, 1941

By L. J. Dijkstra, R. J. Sladek

IN earlier work the effect of manganese on the general behavior of nitrogen in iron was the subject of a careful examination by Fast.' Part of the investigation was made, in collaboration with one of the present authors (L.J.D.), by using the internal friction method. This technique, which has been described elsewhere,' showed some significant changes in the properties of Fe-N alloys by the addition of a small amount of manganese namely: 1—Under standard conditions the maximum of the nitrogen peak in pure iron appears around 20 °C and the half width is about 27 °C. By addition of 0.5 atomic pct Mn a general broadening of the internal friction peak occurs. The half width is increased by about 9°C. Moreover, a shift of the maximum of about 5°C toward a higher temperature takes place, Fig. 2. 2—The precipitation of nitrogen from the supersaturated solution, measured, e.g., at 200 °C, was inhibited by the addition of the amount of manganese given in effect 1. The broadening of the nitrogen peak was confirmed in more recent work3 on samples which were prepared from Westinghouse Puron iron. The effect of manganese on the rate of precipitation, however, was much less striking than in the earlier work' based on Philips high purity iron. Theory To explain the first change in properties just referred to, effect 1, the following two assumptions were made:' First, every manganese atom in sub-stitutional solid solution creates around it six interstices located between an iron and a manganese atom, as is evident from Fig. 1. These interstices, conveniently called Fe-Mn interstices, have for nitrogen a free energy level which is AG* lower than the normal Fe-Fe interstices between two iron atoms. For such low concentrations of manganese as 0.5 atomic pct, the possibility that two manganese atoms will be nearest neighbors can be disregarded. Second, it is assumed that in addition to the normal relaxation time TFe at least one new relaxation time, Mn, Fe, enters in the phenomena which is associated with the elementary diffusion jumps between a Fe-Mn interstice and an adjacent Fe-Fe interstice. Fig. 1 gives schematically the free energy for a nitrogen atom as a function of its position along the line ABC. A tentative analysis of the nitrogen peak in a 0.5 pct Fe-Mn alloy based on these assumptions has been made in Fig. 2. The dotted curve with a maximum at 22°C is caused by jumps between Fe-Fe interstices, the dotted curve with maximum at 32°C by jumps between an Fe-Mn and an Fe-Fe interstice. The two effects added together give the dash-dot internal friction curve for the alloy. In the following these two components will be referred to as the normal peak at 22°C and the abnormal one. (The small secondary peak at

Jan 1, 1954

By C. R. Hocott, Stuart E. Buckley

The viscosity of the oil in the reservoir is one of the properties that influence its movement through the sand to producing wells. Measurements of viscosity, therefore, are pertinent to problems associated with well behavior and with the estimation of recoveries, and afford an indirect means for partial evaluation of various methods of controlling reservoir behavior. The effect of dissolved gases on the viscosity of crude oil has been determined,ls2 but no data have been published on the viscosity of representative samples of reservoir oils. This paper describes a simple instrument that has been used to determine the viscosities of a number of subsurface oil samples at the temperatures and pressures existing in the reservoirs, and presents the results of the determinations for typical fields. Construction oF the Apparatus The principal requirements of any instrument used for the examination of subsurface samples are that it be strong and simple both in design and in method of operation. Accuracy beyond that of the degree of reproducibility of subsurface Sam-~les from various wells in a reservoir or exceeding that of the common measure-merits of reservoir temperatures and Pressures is not required. Because of the expense of procuring subsurface samples, it is necessary also that the instrument operate on a relatively small fraction of a sample, leaving the remainder for other tests, and that there be few or no failures of the equipment to cause undue delay or loss of a sample. After preliminary experiments with a falling bullet, the results of which were not satisfactory, a simple viscosimeter was built of the rolling ball type first proposed by Flowers3 and later used by several investiga-tor. 5.8 The apparatus consists essentially of a removable, accurately bored cylindrical barrel of 1/4-in. nominal internal diameter, 8 in. long, in which a closely fitting steel ball rolls through the oil with the barrel inclined at a definite angle. The ball makes contact at one end of the barrel with ail insulated electrode, closing an electrical circuit, which actuates a buzzer. The meas-urements consist essentially in determining the time required for the ball to travel the length of the barrel. The details of the construction are shown in Fig. I. The barrel in which the ball rolls was made from a section of 25-caliber blank rifle barrel, specially bored to an exact uniform diameter and polished. The barrel slides snugly into a hole bored in a solid stainless-steel cylinder, an upper external shoulder of the barrel compressing a small spring, and is held in place by a hollow nut. The spring prevents the barrel from seating against the bottom of the bored hole in the cylinder, while narrow external longitudinal slots in the barrel permit fluid to flow around it and through the bottom. The upper part of the recess in the steel cylinder is enlarged to form a tapered chamber, which acts as a reservoir for the oil and affords space for agitation to ensure

Jan 1, 1941

By J. K. Edgar

FOR a number of years the production and use of super-purity aluminum (better than 99.99 pct) has been steadily increasing. High-grade lots of such aluminum show certain outstanding characteristics not found in lower grades containing principally silicon, iron and copper as impurities. One such characteristic is the so-called "self annealing," that is, the recrystallization of the heavily cold worked metal at room temperature.' Interest therefore is aroused as to the effects of the impurities. It is well known that the amounts of silicon and copper which occur in aluminum of better than 99.95 pct are completely soluble, at least at elevated temperatures (above 200°C). Iron, on the other hand, is known to be fairly insoluble in solid aluminum. Thus, a knowledge of the limits of this solubility would be of considerable use in studying the characteristics of the high purity metal. All investigators have agreed that iron has very low solubility in solid aluminum. Rosenhain, Archbutt and Hanson2 reported traces of an aluminum-iron phase in the "purest samples of aluminum obtainable." Gwyer and Phillips3 reported that an iron constituent was visible under the microscope in metal containing ".0088 per cent iron." Roth1 found that in the solid state the solubility of iron in high purity aluminum was 0.01, 0.01, 0.017 and 0.022 pct at 225, 320, 500 and 600°C respectively. Dix5 working with alloys containing less than 0.03 pct impurities, concluded from microscopic and chemical analyses of eutectic areas that the eutectic composition was close to 1.7 pct iron. Dix placed the eutectic temperature at 655°C'. Archer and Fink,6 using high purity aluminum-iron alloys, found that the hypoeutectic liquidus intersects the eutectic horizontal at 1.7 pct. This is in fair agreement with the investigation of the aluminum-iron system by Gwyer and Phillips who placed the eutectic at 1.89 pct iron with a freezing point of 653° PREPARATION AND CHEMICAL ANALYSIS OF ALLOYS Electrolytically refined aluminum (99.991 pct aluminum) and a high purity aluminum-iron alloy (11.45 pct iron) were used in the preparation of the alloys for this investigation. To aid in controlling the iron content of the experimental alloys, an alloy of lower iron content was prepared first from these materials. The high purity aluminum was melted and heated to about 700°C in a plumbago crucible coated with alundum cement and the aluminum-iron alloy was then added. The alloy was thoroughly stirred, fluxed and skimmed and then chill-cast into notch bars. The analyses of the three materials are given in Table I. The alloys for the determination of the solid solubility of iron in aluminum were prepared by melting 600 g total of the aluminum plus the required quantity of the aluminum-iron alloy (No. 92531). These

Jan 1, 1948

By R. F. Mehl, M. L. Swanson, J. P. Hirth, G. M. Pound

The sorption of zinc in a-brass was investigated. By analyzing the elliPtically polarized light reflected from the surfaces of a-brass solid-vapor couples, their optical constants and surface compositions were determined. It was shown that the surface compositions approached an equilibrium value exponentially with time. The bulk diffusion coefficient, surface diffusion coefficient and condensation coefficient for a-brass solid-vapor couples were calculated near 350°C from the experimental results. It has been assumed during various diffusion experiments with bimetallic solid-vapor couples (Dunn,1 Seith and Kraus,2 Jenkins,3 Balluffi and Seigle,4 and others) that the surface composition of such couples reaches its equilibrium value immediately. Although this assumption is probably valid at elevated temperatures, it is certainly not expected to be confirmed at lower temperatures.* consequently, it was decided that a fundamental experiment, designed to solve this problem as well as to examine all aspects of bimetallic sorption, would be the investigation of the rate of approach to equilibrium of the surface composition of solid-vapor couples. The sorption (i.e., adsorption, absorption, and desorption) of metals is obviously dependent on the state of the metallic surface and substrate. Much recent theoretical8"9 and experimental10-12 work on condensation and evaporation of pure metals has shown that the surface contour in atomic dimensions is a critical factor in sorption, so that any deformation or contamination13,14 of the surface exerts a profound influence. It is also known that absorption or diffusion occurs much more rapidly along grain were and in other deformed regions. Thus an effective sorption experiment must utilize a strain-free and clean surface, or at least a clearly defined and reproducible surface state. A mechanically polished surface is in a highly deformed17-l9 state. Because the degree of this deformation is uncertain, it is clear that for most experimental purposes a strain-free (i.e., etched, chemically polished, or electropolished) surface is desirable. Although adsorbed gas molecules on metallic surfaces are unavoidable even in the highest vacuum,20 oxide films can in some cases be removed by suitable vacuum annealing. Electrolytically polished and annealed surfaces, being relatively without strain, smooth and free of bulk oxides, were considered adequate for the present sorption experiments. Measurement of the surface composition of a solid-vapor couple presents a unique problem. Since experiments to determine the approach to equilibrium of the surface composition must be performed at temperatures where diffusion is very slow, solute penetration is so small that conventional analytical methods are unsuitable. An optical reflectivity method utilizing a polarization spectroscope was employed because of the relatively small penetration (~200A) of visible light in metals. By this method, elliptically polarized light reflected from the metal surface was analyzed and compared with that reflected from samples of known composition. The a phase of the copper-zinc system was

Jan 1, 1962

By J. W. Spretnak, G. W. Cunningham

A study has been made of the growth and disappearance of voids in the interface of pressure bonded copper. The formation of visible voids is primarily due to spheroidization and coalesence of microvoids produced during the application of pressure. The microvoids could be prevented from forming by the application of high pressures or by increasing the ductility of the copper. Migrating grain boundaries were found to be more effective in void removal, than stationary grain boundaries. DURING the course of an investigation on the mechanism of pressure bonding, it was found that voids formed in the bonding interface which inhibited migration of the interfacial boundary and grain boundaries in the bond region. Therefore, an effort was made to determine the nature of the voids and how they form, grow, and disappear. This paper reports the results of such an investigation. The existence of interfacial voids is not solely a characteristic of massive components of metal which have been bonded by the application of heat and pressure, but is a phenomenon which has been observed in sintering as well. Simonsen attempted to study the sintering process by hot-stage microscopy and thereupon observed the formation of interparticle porosity as sintering proceeded. It was assumed that the porosity was due to grooves created at the location where grain boundaries joined the surface of the particle. Pranatis, Castelman, and seigle2 have also observed voids along the areas of contact in wound-wire specimens used for sintering studies. They did not discuss the point in detail since this behavior was not general, but they did suggest that the voids might develop as a result of stresses along the interparticle contact area. In previous investigations on pressure bonding, workers3 have suggested that voids may exist in the region where mating surfaces are placed in intimate contact, but the existence of the voids was not verified and no attempt was made to study the growth and disappearance of these voids. Durst noted the existence of pores in roll-clad structures prepared by cold reducing two sheets to force them in contact and then annealing to improve the bond. Since his unbonded regions contained a gas which he assumed to be insoluble, he proposed a mechanism which consisted of spheroidization of the unbonded regions and a growth of the contact area, but no speculations were made regarding disappearance of the gas filled pores. One interesting comment made by Durst was the suggestion that flattened voids with sharp corners which are produced during roll bonding will have a greater driving force for spheroidization than the more rounded pores created by pressing metal powders and thus spheroidization and neck growth will occur at lower temperatures. In this study it was necessary to demonstrate conclusively that voids can actually exist in the interfacial bond area. Experimental work was then directed toward a study of the mechanism whereby the voids grow and subsequently disappear.

Jan 1, 1963

By R. H. Jacoby, V. J. Berry, R. C. Koeller

The experimental phase behavior of several field gas-condensate systems, one field volatile oil system, and a series of synthetic systems having gas-oil ratios from 2,000 to 20,000 scf/bbl stock tank oil was measured. The data were used to calculate the depletion performance of the field systems at their respective reservoir temperatures and of the synthetic systems at various temperatures. The results of the performance calculations were used to prepare correlations of total stock tank oil and separator gas in-place, and the amount of each recovered by primary depletion. Data needed to use the correlations are initial gas-oil ratio, initial tank oil gravity, reservoir temperature and reservoir pressure. The correlations presented should be useful for estiinating recovery from reservoirs producing volatile oils or rich gas condensates having gas-oil ratios from about 2,000 to 30,000 scf/bbl of stock tank oil. INTRODUCTION Prediction of depletion performance for gas-condensate reservoirs usually requires extensive laboratory work or lengthy phase-behavior calculations. For many small gas-condensate bearing zones the expense of such work is often not justified. Furthermore, where large holdings are involved, it is useful to have estimates of future oil and gas production in advance of the results of a laboratory analysis, even if such work is ultimately planned. For these reasons, it would be of value to have a method for rapidly estimating the depletion performance of gas-condensate reservoirs from the type of field data usually available. Few data on the reservoir depletion performance are available for the purpose of developing correlations. The increasing number of gas-condensate discoveries and the advent of high-speed computers have stimulated the development of methods for predicting performance. Such calculated performance data have been shown to be reliable and are becoming accepted as a basis for reserve estimates and for engineering studies. It therefore seems satisfactory to use results of performance predictions themselves for the purpose of developing the desired correlations. Such an approach is described in this paper. Several rich natural gas-condensate systems (gas-oil ratios of from about 3,600 to 60,000 scf/bbl) and one natural volatile oil system were studied (2,363 scf/bbl). In addition, to provide a more systematic basis for correlating purposes, a series of related, synthetic reservoir fluid mixtures was also studied (GOR's from about 2,000 to 25,000 scf/bbl). The purpose of this paper is to show how the recovery of oil and gas by primary depletion may be estimated from surface gas-oil ratio, reservoir temperature and pressure, and tank oil gravity. procedure Experiments Companion samples of gas and oil were collected from the high pressure separators in nine different fields at the time of their discovery. These samples were each recombined in accordance with the respective producing GOR to reproduce the reservoir fluids. Eight of these fluids, designated F-2 through F-9, were rich gas-condensate systems at the respective reser-

By Ramesh Malhotra, Hubert E. (Deceased) Risser

THE WORLD Coal, as a source of energy and as a source of coke for the smelting of iron ore, has contributed significantly to the development of every major industrial nation of the world A number of other materials-oil, natural gas, wood, waste materials, water, and, in some applications, nuclear materials -can be used satisfactorily for the generation of heat and energy, but no generally acceptable and economic substitute has been found to supplant coke in iron ore smelting in conventional blast furnaces. In the development of many nations, coal provided the initial source of energy for industrialization Although coal provided more than 60% of the world's energy each year between 1902 and 1929, oil and natural gas have surpassed it as a source of energy in more recent years (Ref. 38, pp. 439, 441). Despite the rapid rise in importance of other fuels, a considerable amount of the total energy consumed is still supplied by coal. In 1972, coal supplied 32.1 % of the total world energy (Ref. 49, pp. 2-3). To produce this energy, 2.4 billion metric tons of coal were consumed-a 16.0% increase over the amount consumed in 1962. A further worldwide increase in the amount of coal used to supply energy is projected. According to Dr. Karlheinz Bund (Ref. 37, p 145), by the year 2000 world coal consumption could amount to 5 billion mt. Coal Resources and Production The world's coal resources are estimated to be about 10,872 billion mt. Of this amount, 1,297 billion mt are classified as measured reserves (Ref. 50, p. 57). In Table 13.A.1 the estimates of measured reserves and total resources, recent production, and the ratio of measured reserves to production of major coal-producing countries are shown. About 90% of the world's total coal resources are estimated to be in the USSR, the United States, and China. The United States ranks second in the world in coal resources, but in measured reserves, it ranks first. Because of the difference in rate at which available coal resources are being exploited, the ratio of measured reserves to actual production varies widely among areas and countries. France and East Germany have the lowest reserve to production ratios, 49.5 and 60.1, respectively. In Mexico, where currently less than 5 million mtpy of coal are produced, the ratio is 1257 For all countries producing more than 200 million mtpy of coal (except East Germany), the ratio ranges from 350 to 670. For the United States, the ratio is 669.7. In Table 13.A.2, distribution of the world's coal resources by area is shown. More than 97% of the total resources lie in the northern hemisphere, with Asia, including European USSR, having 63.4%. Only 1.9% of the total coal resources are estimat-

Jan 1, 1976

By Robert B. Fulton, Gill Montgomery

Fluorspar is the commercial name for fluorite, a mineral that is calcium fluoride, CaF2. The name, derived from the Latin word fluere (to flow), refers to its low melting point and its early use in metallurgy as a flux. It is the principal industrial source of the element fluorine. Cryolite, sodium aluminum fluoride, Na3AlF6, is a rare mineral which has been found in commercial quantities only in Greenland. The natural material has been supplanted by synthetic cryolite for its principal industrial use in the manufacture of aluminum. History Fluorspar was used by the early Greeks and Romans for ornamental purposes as vases, drinking cups, and table tops. Various peoples, including the Chinese and the American Indians, carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola in sixteenth century Europe. Fluorspar mining began in England about 1775 and at various places in the United States between 1820 and 1840. Production grew substantially following the development of basic open-hearth steelmaking, wherein it is used as a flux. Use was stimulated by growth of the steel, aluminum, chemical, and ceramic industries, particularly during World Wars I and II. Fluorocarbons entered the picture in 1931. The use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel began in 1942. Differential flotation for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940s were outstanding technological advances that facilitated increased production. Recently, pelletizing and briquetting of flotation concentrates for use in steel furnaces and the development of flotation schemes for beneficiating ores containing abundant dolomite and barite have been major improvements in the industry. Uses of Fluorspar Fluorspar is used to make hydrogen fluoride, also called hydrofluoric acid, an intermediate for fluorocarbons, aluminum fluoride, and synthetic cryolite. It is used as a flux in the steel and ceramic industries, in iron foundry and ferroalloy practice, and has many minor specialized uses. Hydrogen fluoride (HF) is produced by reacting acid grade (97% CaF2) fluorspar with sulfuric acid in a heated kiln or retort to produce HF gas and calcium sulfate. After purification by scrubbing, condensing, and distillation, the HF is marketed as anhydrous HF, a colorless fuming liquid, or it may be absorbed in water to form the aqueous acid, usually 70% HF. Synthetic cryolite, organic and inorganic fluoride chemicals, and elemental fluorine are made from hydrofluoric acid. The acid itself is important in catalysis in the manufacture of alkylate, which is an ingredient in high-octane fuel for aircraft and automobiles, in steel pickling, enamel stripping, glass etching and polishing, and in various electroplating operations. The manufacture of one ton of virgin aluminum requires about 50 to 60 lb of fluorine content in synthetic cryolite and alumnium fluoride. This quantity, through improved technology and recovery practices, is being lowered significantly.

Jan 1, 1983

By Ferit Gurses

Extensive coal and lignite deposits exist in Turkey. Bituminous coal is the nation's principal mineral resource; important not only as fuel for the industrial development of the country, but also as a means of obtaining foreign exchange. Of the electrical power generated during 1939, 82.8 per cent was derived from coal.' It is anticipated that the lignite deposits will be one of the major sources of power for the electrification of the country. Bituminous Coal The locations of the four principal bituminous-coal2 basins are indicated on Fig. 1. The Eregli-Zonguldak basin lies on the Black Sea northwest of Ankara; the Canakkale basin lies near the junction of the Dardannelles; the Trakya basin is in European Turkey northwest of the Bosphorus and the Erzurum basin lies far to the east. The Eregli-Zonguldak basin is the most important of the four. This coal basin was discovered in 1829 but did not arouse interest until 1848; up to 1865, its annual production had not exceeded 50,000 metric tons. In 1865, during the Sultanate, working of coal mines was started by the Navy department, and the annual production was 61,145 metric tons. In 1908, the Minister of Commerce and Agriculture was authorized to develop the whole coal basin. Production reached 264,397 metric tons in 1910, and during 1915-1922, preceding the revolution, the total produc- tion of the basin was' 2,676,043, or an average of 334,000 metric tons annually. The period of national revolution that followed was marked by a steady increase in coal production in Turkey, although world production decreased, because of the crisis of 1929-1932, about 52 per cent. ARea and Geology of the Coal Basin The geology of the Eregli-Zonguldak area is not yet completely known. The basin begins -at Gungazi, to the west of Eregli, and extends to Sogutozu, a distance of about 106 miles. The coal beds, however, appear only in places and the overlying Cretaceous strata hide them elsewhere. This area includes the most important centers, such as Kandilli, Alacaagzi, Teflenli, Kozlu, Gelik (see Fig. 2). The geological sequence of the district is correlated with the Cretaceous of the Balkans; which is, in turn, a prolongation of the Alpine zone. Geological surveys made by G. Ralli, R. Zeiller and P. Arni3 show that the Eregli-Zonguldak formations fall into three natural divisions. Series a, The Alacaagzi in the district of that name (Fig. 2), is of the Culm stage. The strata strike generally east-west and dip about 30" south. This series appears also around Kandilli and Camli, with a steeper angle of dip, but the deposits there lack regularity. The Alacaagzi stage appears also farther east, to the south of Kozlu and Gelik. The Alacaagzi series contains 15 seams of an average thickness of 2 ft. of good coal. Series b, the Kozlu, best represented in Zonguldak, Kilimli, Catalagzi, and between

Jan 1, 1944

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By Ferit Gurses

Extensive coal and lignite deposits exist in Turkey. Bituminous coal is the nation's principal mineral resource; important not only as fuel for the industrial development of the country, but also as a means of obtaining foreign exchange. Of the electrical power generated during 1939, 82.8 per cent was derived from coal.' It is anticipated that the lignite deposits will be one of the major sources of power for the electrification of the country. Bituminous Coal The locations of the four principal bituminous-coal2 basins are indicated on Fig. 1. The Eregli-Zonguldak basin lies on the Black Sea northwest of Ankara; the Canakkale basin lies near the junction of the Dardannelles; the Trakya basin is in European Turkey northwest of the Bosphorus and the Erzurum basin lies far to the east. The Eregli-Zonguldak basin is the most important of the four. This coal basin was discovered in 1829 but did not arouse interest until 1848; up to 1865, its annual production had not exceeded 50,000 metric tons. In 1865, during the Sultanate, working of coal mines was started by the Navy department, and the annual production was 61,145 metric tons. In 1908, the Minister of Commerce and Agriculture was authorized to develop the whole coal basin. Production reached 264,397 metric tons in 1910, and during 1915-1922, preceding the revolution, the total produc- tion of the basin was' 2,676,043, or an average of 334,000 metric tons annually. The period of national revolution that followed was marked by a steady increase in coal production in Turkey, although world production decreased, because of the crisis of 1929-1932, about 52 per cent. ARea and Geology of the Coal Basin The geology of the Eregli-Zonguldak area is not yet completely known. The basin begins -at Gungazi, to the west of Eregli, and extends to Sogutozu, a distance of about 106 miles. The coal beds, however, appear only in places and the overlying Cretaceous strata hide them elsewhere. This area includes the most important centers, such as Kandilli, Alacaagzi, Teflenli, Kozlu, Gelik (see Fig. 2). The geological sequence of the district is correlated with the Cretaceous of the Balkans; which is, in turn, a prolongation of the Alpine zone. Geological surveys made by G. Ralli, R. Zeiller and P. Arni3 show that the Eregli-Zonguldak formations fall into three natural divisions. Series a, The Alacaagzi in the district of that name (Fig. 2), is of the Culm stage. The strata strike generally east-west and dip about 30" south. This series appears also around Kandilli and Camli, with a steeper angle of dip, but the deposits there lack regularity. The Alacaagzi stage appears also farther east, to the south of Kozlu and Gelik. The Alacaagzi series contains 15 seams of an average thickness of 2 ft. of good coal. Series b, the Kozlu, best represented in Zonguldak, Kilimli, Catalagzi, and between

Jan 1, 1944