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By Michael B. Bever, Carl F. Floe

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By Carl F. Floe, Michael B. Bever

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By R. Kossowsky

In the course of a study concerned with structural stability of precipitation hardening nickel base super -alloys after exposures to elevated temperatures, some interesting effects of hydrostatic pressure treatment on Rene were observed. The evidence presented below suggests that hydrostatic pressure treatment of the solution heat-treated alloy can affect the dispersion of the y' (Ni3Al) phase upon subsequent precipitation heat treatment and long time aging. Rene 41 alloy has the following nominal weight percent composition: Al B C Co Cr Fe Mn Mo Ti Ni 1.4 0.006 0.7 11.3 19.2 1.0 0.05 9.4 3.3 balance The effect of successive pressure, precipitation heat treatment, and long time aging on the microstructure of this alloy was determined by subjecting a number of alloy buttons to five different thermopressure treatments. Pressure and precipitation heat-treatment parameters are listed in Table I. Fig. 1 shows y' morphology* of specimens in groups I and 11. The treatment results in a fine dispersion with particle size on the order of 950 and 1350A, respectively, see Table I. Fig. 2 shows the morphology of y' precipitate in

Jan 1, 1967

By John D. Morgan, Sylvain J. Pirson

An instantaneous and continuous analysis of a mineral suspension should be of great value in controlling various mineral preparation processes. Described herein is a method of analysis based on the use of high-frequency alternating current, which, under certain restrictive conditions, could be of use. Theoretical Considerations In a suspension of conductive minerals, the electrical effect primarily responsible for the variations in electric conductivity is the capacitance. In Fig Ia, let an alternating voltage E be applied across two electrodes F and F', between which are two rows (S and T) of mineral particles, all of approximately the same size, immersed in a fluid. Let the number of rows of particles between the electrodes be R and the number of particles in each row be N. If A is the area of a particle, D is the distance separating two particles, and k is a constant depending on the fluid, the capacity, CO, of the particle system will be given by: KRA C°= ND Referring now to Fig Ib, let R, the number of rows, be held constant, but let N, the number of particles in each row (S and T), be increased X-fold. The capacity, C1, of

Jan 1, 1949

C. Edward Stafford, Chester, Pa.:—Doring all my business life, I have been engaged in the manufacture of Bessemer and open-hearth steels, but, during my long connection with the Shoenberger Steel Co. of Pittsburg, I had some experience in the manufacture of high-grade puddled iron for horseshoes, and in making, by Dr. Otto Wuth's process, extremely pure, low-phosphorus puddled blooms (analyzing from 0.005 to 0.01 per cent. of phosphorus and sulphur), which were melted with low-phosphorus pig-iron in acid open-hearth furnaces, to make extra locomotive fire-box steel. I have also seen the Danks puddlers in operation at different times and places, notably where they were most successful, at the Otis Steel Works, Cleveland, Ohio; then under the management of our friend, Mr. S. T. Wellman. These Danks blooms were made solely for open-hearth melting-stock, to which they were well adapted. (The unavoidable presence of bits of ore-fix imbedded in the mass of the metal always prevents the profitable manufacture of merchant iron from Danks' blooms.) With the experience just described, I was to some degree in position to value fairly the means, methods and results of Mr. Roe's mechanical puddling from the metallurgical or technical and economic points of view, when given an opportunity by Mr. Roe to see his puddling-furnace or machine in operation in Pottstown, Pa. Briefly, the furnace, with water-cooled bottom, is rectangular in plan, about 20 by 8 ft. in the clear, suspended by trunnions at the middle of the long sides, at a height of 17 or 18 ft. above the general level. The oscillation (65" each way from the vertical) is accomplished by geared segments (attached to the downward-projecting side or trunnion-plates) with which engage pinions driven by a reversing engine. The whole section

Jan 1, 1906

By Ronald Gibala

THE Au-Ni alloy system is one of many binary systems in which the supersaturated solid solutions may exhibit a multistaged precipitation behavior during aging. In addition to the equilibrium phase separation, which was studied extensively years ago in the range 400" to 600",' there exists at least one earlier stage of precipitation, i.e., preprecipitation, which occurs below 300°C in quenched alls.-This note reports on some effects of composition on the preprecipitation in Au-Ni alloys as determined from resistivity measurements. The kinetics of the preprecipitation were studied in alloys of 15 to 85 at. pct Ni which were water- were found in alloys which after various quenching-and-aging treatments were slowly heated and cooled (1Z"C per hr) between room temperature and about 300°C. Two such heating-cooling curves for a 40 pct Ni alloy are shown in Fig. 2. Similar effects were observed in other 15 to 50 pct Ni alloys. These curves are characterized upon heating by two changes in slope indicated by A and B in the figure and upon cooling by a resistivity hysteresis of approximately the size of the original decrease in resistivity after the aging treatment. The inflection at B generally falls at about the same temperature for all heating curves for a given alloy and appears to be a critical temperature (T,) for the preprecipitation for that alloy. The values of T, for most of the 15 to 50 pct Ni alloys fall in the range 200" to 220°C. The position of the inflection at A depends upon the heat treatment prior to the heating-cooling run and perhaps the heating rate, which was held constant in these runs. The preprecipitates grown in by the appropriate aging treatments seem to decrease in size as the alloys are heated from A to T,, dissolve at T,, and do not reappear after cooling below T,. When similar heating-cooling treatments were performed on 60 to 85 pct Ni alloys, an entirely different behavior was observed. Typical results are shown in Fig. 3 for an 85 pct Ni alloy. In these

Jan 1, 1964

By K. G. Davis

Dilute alloys of silver and of thallium in tin have been solidijzed unidirectionally under controlled conditions, to study the segregation associated with a cellular interface under conditions where both thermal and solute convection are present. Autoradiography and radioactive tracer counting techniques were combined with electron-probe microanalysis to study both macro- and microsegregation. It was found that, for concentrations giving only small amounts of constitutional supercooling, cell formation had little effect on the macroscopic distribution of solute along the specimen. At higher concentrations the effective distribution coefficient was higher than that expected for a smooth interface. Node spacing was independent of initial solute content at lower concentrations, becoming greater as keff increased. Silver content at the segregation nodes of silver in tin alloys was independent of initial concentration and considerably in excess of the eutectic composition. SINCE the investigation of cell formation at advancing solid-liquid interfaces by Rutter and Chalmers,' a large volume of work has been dedicated to the determination of solidification conditions under which a planar interface will break down into cellular form. Early experiments were explained satisfactorily by the concept of constitutional supercooling,2 but, due to poor measurement of temperature gradients in the liquid, lack of accurate data on liquid diffusion and equilibrium distribution coefficients, and uncertainty about the effects of thermal and solute convection, these experiments cannot be used as proof for the theory. More recent work, however, has shown that under conditions where convection is eliminated or can be ignored good correlation is observed.3,4 Investigations into segregation at cell caps5 and at cell nodes6-'' have been made, but no measurements appear to have been done on the overall, macroscopic segregation down a unidirectionally solidified rod of material which has solidified with a cellular substructure. This has practical importance in casting, where regions of material with cellular substructure are often encountered, and also in zone refining where the thermal conditions necessary for a planar interface are unattainable. Further, as will be shown, the macroscopic segregation can give information on the following question. Granted that a cellular solid-liquid interface develops from a planar one when the conditions for constitutional supercooling are exceeded, how much supercooling is present after the cells have formed? EXPERIMENTAL PROCEDURE AND RESULTS Specimen Preparation. Specimens 25 cm long with a square cross section 0.6 by 0.6 cm were grown in graphite boats by solidification from one end. Alloy compositions are given in Table I. Two specimens of each composition were grown. The tin was 5-9 grade and the silver and thallium both 4-9 grade. Ag110 and Tl204 were used as tracers. Each composition had the same quantity of tracer so that auto radiographs of specimens containing different concentrations of the same element could be easily compared. Thermocouples inserted through the lid of the boat into a dummy specimen showed that, over the first 10 cm of growth, thermal conditions were quite steady, with a rate of interface advance of 5.8 cm per hr and a temperature gradient in the melt ahead of the interface of 3.0°C per cm. The specimens were seeded from tin crystals of a common orientation to eliminate orientation effects. Dilution of the specimen by seed material was minimized by the provision of a narrow neck between specimen and seed crystal. Macrosegregation. After growth, the specimens were sectioned with a spark cutter. The rods of silver alloy were cut into 1-cm lengths and analyzed for Ag110 using a y -ray counter with fixed geometry. The specimens containing thallium were cut into 2-cm lengths and analyzed for T1 204 by taking 13 counts from each end of the cut lengths through an aperture in lead sheet approximately 0.4 cm square. The results are summarized in Figs. 1 and 2. To find the effective distribution coefficient for the silver in tin alloys under smooth interface conditions, the region of substructure at the bottom surface of one of the 10 ppm specimens, see Fig. 3, was removed by spark machining before counting. Autoradiography. For both alloy systems the samples were polished on sections taken alternately parallel and perpendicular to the growth direction, and autoradiographed by placing the polished surfaces in contact with Kodak "Process Ortho" film. Figs. 3 and 4 show the structures revealed. The alloy containing 10 ppm Ag showed substructure only after a few centimeters of growth, and then substructure was limited to a narrow layer at the base. The "speckled" substructure reported previously in this system4 is here clearly seen to be an intermediate stage between planar and cellular interface conditions. The other samples show a remarkable similarity considering

Jan 1, 1969

By Robert Bedford

THE objects of this paper are: 1. To give cost data on drilling obtained at the North Star mine in California; 2. To describe the methods of testing drills employed there, giving the results of shop tests, and the correlated data obtained underground; 3. To demonstrate that these tests form a satisfactory basis upon which to judge rock drills. The rock at this mine is either close-grained diabase in the upper levels, or tough grano-diorite in the lower levels. The vein, which has an average dip of 23°, consists of about 5 ft. of "formation" lying between walls of unaltered country rock. Of the 5 ft., solid quartz and stringers make up 18 in. of pay ore. The formation, which consists of but slightly altered country rock, is almost as hard as the unaltered walls. From 4 to 42 ft. is sent to the mill. One-third of the holes are drilled in the quartz; two-thirds in the formation. The holes are about 42 ft. deep and break on the average of 1.15 tons per hole. The average number of holes per stope drill shift is at present 5.65. The number of drill shifts throughout the mine in 1913, was 18,679, and the cost of labor for drilling, power, supplies, upkeep of machines and air lines, tool sharpening, and distribution, amounted to 33 per cent. of total mining expense. To do this work there are in commission 43 No. 12A, three No. 17V and eight No. 16V Waugh stopers, three Jackhamers, two Waugh pluggers, and 17 No. 8 ,and two No. 7 water Leyners. For the past three years a record has been kept of the repairs on each machine and number of shifts operated by it. The figures given in Tables I and II for the cost of repairs per drill shift have been taken from this record. The underground air pressure is about 90 lb. The air consumption per drill shift was measured by, aerometers. The leakage of pipe lines between compressor and meter is not included. From the number of pieces of steel sharpened for each type of drill during the year the average used per drill shift has been ascertained. For other supplies the figures given represent a year's average.

Jan 8, 1914

By William Hague, Robert H. Bedford

The objects of this paper are: 1. To give cost data on drilling obtained at the North Star mine in California; 2. To describe the methods of testing drills employed there, giving the results of shop tests, and the correlated data obtained underground; 3. To demonstrate that these tests form a satisfactory basis upon which to judge rock drills. The rock at this mine is either close-grained diabase in the upper levels, or tough grano-diorite in the lower levels. The vein, which has an average dip of 23", consists of about 5 ft. of " formation" lying between walls of unaltered country rock. Of the 5 ft., solid quartz and stringers make up 18 in. of pay ore. The formation, which consists of but slightly altered country rock, is almost as hard as the unaltered walls. From 4 to 44 ft. is sent to the mill. One-third of the holes are drilled in the quartz; two-thirds in the formation. The holes are about 4 1/2 ft. deep and break on the average of 1.15 tons per hole. The average number of holes per stope drill shift is at present 5.65. The number of drill shifts throughout the mine in 1913 was 18,679, and the cost of labor for drilling, power, supplies, upkeep of machines and air lines, tool sharpening, and distribution, amounted to 33 per cent. of total mining expense. To do this work there are in commission 43 No. 12A, three No. 17V and eight No. 16V Waugh stopers, three Jackhamers, two Waugh pluggers, and 17 No. 8 and two NO. 7 water Leyners. For the past three years a record has been kept of the repairs on each machine and number of shifts operated by it. The figures given in Tables I and II for the cost of repairs per drill shift have been taken from this record. The underground air pressure is about 90 lb. The air consumption per drill shift was measured by aerometers. The leakage of pipe lines between compressor and meter is not included. From the number of pieces of steel sharpened for each type of drill during the year the average used per drill shift has been ascertained. For other supplies the figures given represent a year's average.

Jan 1, 1915

By G. R. Leverant, M. Gell

The high- and low-cycle fatigue poperties of MAR-M200 directionally -solidified into columnar-grained and single crystal forms were determined at 1400" and 1700°F. These results were compared with the corresponding properties of conventionally -cast MAR-M200. The low-cycle fatigue lives of the columnar-grained and single crystal materials were similar at both temperatures and were one to two orders of magnitude greater than those of conventionally-cast material. The variations in the fatigue lives among the three forms of MAR-M200 were related to the more rapid rate of intergranular muck propagation compared to that of transgranular propagation. In conventionally-cast MAR-M200, cracks were initiated in grain boundaries and crack popagation occurred rapidly along an almost continuous grain boundary path. In the columnar-grained material, crack initiation occurred on short transverse segments of grain boundaries, but crack propagation was transgranular. The fatigue lives of columnar-grained and single crystal materials were approximately the same because most of the life in both materials was spent in trans-granular propagation. For the directionally -solidified materials, the number of cycles to failure, Nf, can be related to the total strain range, , by: heT = K where n and K are 0.16 and 0.044 at 1400'F and 0.29and 0.098 at 1700, respectively. In addition to intergranular crack initiation in the columnar-grained material, initiation also occurred at we-cracked MC carbides and micropores in both directionally-solidified materials. At 1400°F, fatigue life was reduced with increasing MC carbide size, but at 1700 there was no effect of carbide size. THE creep and stress-rupture properties of conventionally-cast nickel-base superalloys can be greatly improved by directional solidification into either single crystal or columnar-grained forms. The improvement in properties results from a reduction in intergranular cavitation and crack growth in the columnar-grained materials and the complete absence of this fracture mode in the single crystals. This paper describes the effect of grain boundaries on the elevated temperature fatigue properties of the nickel-base superalloy MAR-M200. The effect of cycling frequency on cracking arid fatigue life and the role of MC carbides and micropores on crack initiation are also emphasized. The fatigue properties of columnar-grained and single crystal MAR-M200 at room tem- perature,4,5 and the change in the mode of fatigue crack propagation with temperature6 have recently been described. I) EXPERIMENTAL PROCEDURE The material used in this study was the nickel-base superalloy MAR-M200, directionally-solidified into columnar-grained and single crystal forms. The columnar grains were approximately 0.5 mm in diam. The nominal composition of these materials in wt pct was 0.15C, 9Cr, 12.5W, loco, 5A1. 2Ti, lCb, 0.05Zr. 0.015B, bal Ni. They were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr. which resulted in 0.2 pct offset yield stresses of 150,000? 144,000, and 95,000 psi at room temperature? 1400°, and 1700°F, respectively. The corresponding elastic moduli parallel to the testing direction were 19.2. 15.0, and 12.5 x 106 psi, respectively. Specimen design, testing procedures and alloy mi-crostructure have been described previously and will only be summarized here. Following the 1600°F aging treatment. MAR-M200 contains an ordered, cuboidal, y' precipitate 0.3 1 on edge, which is coherent with the 1 matrix. The y' precipitate is quite stable; even after testing at 1700°F. the precipitate is only slightly enlarged and its corners somewhat rounded. The alloy also contains a small volume fraction of micropores, and MC carbides. some of which contain preexisting cracks5 formed during casting. These cracks are always parallel to the long dimension of the carbide. Measurement of MC carbide size has been described previously.5 Axial fatigue tests were conducted in air over a wide range of strain amplitudes in both the high - and low-cycle fatigue regions, with specimen lives varying from about 10' to 10' cycles. Low-cycle fatigue (LCF) tests were strain-controlled with strain varied between zero and a maximum tensile value at a frequency of about 2 cpm. High-cycle fatigue (HCF) tests were stress-controlled with the stress varied between 5000 psi and a maximum tensile value less than the yield stress at a frequency of either 10 cps or 0.033 cps (2 cpm). The temperature in the gage section was controlled to 52°F. Specimen axes were within 5 deg of the [001] growth axis of the single crystals and the common [001 ] growth axis of the columnar-grained material. Specimen gage sections were electro polished prior to testing. After the standard heat treatment, three specimens were coated with a typical aluminide coating applied as a slurry. An additional specimen was given the coating heat treatment without actually being coated. In all cases: specimens were reaged at 1600°F for 32 hr after receiving the coating heat treatment at 1975'F for 4 hr.

Jan 1, 1970

By Kenneth F. Whinery, John M. Campbell

Basically, the Buckley-Leverett theory involves two systems which are similar in nature but are differentiated by time. These systems may be described by the fractional flow and frontal advance equations which essentially characterize the mechanics of oil movement while being expelled from the reservoir. The fractional flow equation originally developed by Leverettl may be expressed in the more usable form The development of this equation is based on Darcy's law describing fluid flow through porous media and applies to the flow at only one point (it is a point function). For simplification, the fractional flow equation is written in the above form because the capillary forces always increase the fractional flow of the displacing phase regardless of the direction of flow or the displacing phase. If, for simplicity, the effects due to gravity and capillary pressure differences are neglected, the fraction of the displacing fluid, f, at any point in the flowing stream is related to the properties of the system by 1 Thus, it is seen that in the absence of capillary and gravitational effects, fd for a given sand and fluids varies only with saturation and pressure. The magnitude of the viscosity ratio, —a has an effective range (range of about 30) in the system where gas is displacing oil and a much smaller range for water displacing oil. In order to make the fractional flow equation more versatile, it is necessary to connect the fractional flow at a given point and saturation with time. This problem was approached by Buckley and Leverett" who developed the frontal advance equation, Eq. 3 states that the rate of advance of a plane that has a fixed saturation, Sd, is proportional to the change in composition of the flow stream caused by a small change in the saturation of the displacing fluid. It is, essentially, a transformation of a material balance equation representing the net rate of accumulation of the displacing phase within a homogeneous sand block. This accumulation is proportional to the difference between the rate at which the displacing fluid enters the sand and that at which it leaves. Eq. 3 describes the velocity with which a plane of constant displacing phase saturation advances through a porous system. Buckley and Leverett," Babson,' Kern," Welge, and others have adequately discussed the basic mechanism and application of the fractional flow and frontal advance equations. APPLICATIONS OF THE FRONTAL ADVANCE THEORY TO PETROLEUM RECOVERY Two general applications of the Buckley-Leverett frontal advance theory involve the system in which the oil is being displaced by an expanding gas cap overlying the oil zone and that in which the oil is being displaced by water. Displacement by Gas in the Presence of an Immobile Water Saturation A system in which gas is the displacing phase may be thought of as having two forces effecting the displacement process. These forces are the gravitational force and that force exerted by the displacing gas. The gravitational effects control the displacing efficiency of the gas. The gravitational effect will be less at higher rates of flow, thereby reducing the effectiveness of the displacement of the oil by the gas. The more efficient displacements occur at flow rates which are less than the gravity free fall rate. Capillary forces can be neglected without materially changing the magnitude of the gas saturation. The Mile Six pool is used herein to illustrate the calculating procedures in evaluating gas drive-gravity drainage field perfomlance. These calculations represent the determination of the gas-oil contact when the distribution of the hydrocarbon pore volume is considered. Two methods

By M. R. J. Wyllie, Michael A. Torcaso

With the continued deep drilling of today, increasing numbers of high pressure and high temperature gas-condensate reservoirs are being discovered. Correspondingly, the ranges of properties of gas-condensate reservoir fluids are also being increased. The literature1*'." contains several excellent reviews of the property ranges in presently known condensate reservoirs. When one examines these property ranges, it becomes apparent that the need for reliable data is great if the engineer is to evaluate properly or appraise a gas-condensate reservoir. It is the purpose of this paper to present phase-behavior data that will point out some of the important variables that influence recovery from gas-condensate reservoirs produced by pressure depletion. All these variables may be resolved into two major categories: the hydroc:arbon composition of the reservoir fluid and the physical properties of the reservoir. But the variables which we will consider are those which are usually determined from well tests shortly after discovery and are, consequently, readily available to the engineer. They are as follows: (1) the producing separator gas-stock-tank liquid ratio, (2) stock-tank liquid gravity, and (3) reservoir temperature. Laboratory depletion studies have been performed on several reservoir fluids to illustrate the effect of changes in the cronsidered variables upon ultimate recoveries. The deviation factors, Z, of a series of reservoir fluids were determined experimentally to illustrate their order of magnitude and their effect upon the calculation of in-place reserves existing at high pressurcs and temperatures. The procedures followed in conjunction with the performance of these studies and their associated calculations are illustrated in Fig. 1. For the purpose of this paper, the depletion recoveries are expressed only in terms of pcr cent of initial stock-tank liquid, with the abandonment pressure assumed to be 500 psig. VARIATION OF RECOVERY WITH INITIAL PRODUCING SEPARATOR GAS-STOCK-TANK LIQUID RATIO The producing separator gas-stock-tank liquid ratio has long been one of the principal criteria in assumptions and generalized correlations' used for the estimation of ultimate recovery from gas-condensate reservoirs. Fig. 2 presents a plot of the cumulative recovery of stock-tank liquid at abandonment as a function of the initial producing separator gas-stock-tank liquid ratio. The graphical illustration represents the results of 44 laboratory depletion studies performed on actual gas-condensate fluids. These data are presented not only to illustrate the general trend of ultimate recovery increase with initial producing ratio increase but to emphasize the considerable variation in possible recovery at any given producing ratio. Table 1 presents the properties of two actual reservoir fluids chosen to illustrate the approximate extremities of producing ratios for gas-condensate systems. The fluids designated as A and B exhibited initial producing ratios of 3,400 and 114,000 scf/bbl, respectively. Fig. 3 presents a graphical comparison of the cumulative stock-tank liquid recoveries, calculated from the well-stream compositions and produced volumes for each fluid during depletion. It is to be noted that Fluid A exhibited a recovery of only 16.5 per cent when produced to an assumed abandonment pressure of 500 psig while the corresponding recovery for Fluid B was calculated to be 62.2 per cent. This difference in recovery, which exemplifies the general trend of recovery increase with initial producing ratio increase, is readily explained by consid-

By Ove Alm

Wet and dry specimens of three rocks of approximately granitic composition were deformed at different experimental conditions. These experiments were carried out in order to study the extent to which water, either added or released from mineral reactions, may affect the mechanical properties and the microstructure of these rocks. The experiments were conducted in a Griggs&apos; hot creep apparatus at temperatures and pressures up to 900ºC and 1000 MPa respectively; and most of them were performed in the constant strain rate mode [(1.10-6 < t < 1 • 10-4 s-1 )]. All three rocks were low porosity rocks, and the wet specimens never contained more than 0.9 wt % of added water. The experimental results are, however, quite unequivocal: They show that wet rocks are weaker than dry ones. A significant difference is even found for rocks tested in uniaxial compression at room temperature. A few experiments carried out on specimens obtained from larger prestressed rock cores indicated that the central parts of these cores were more likely to contain more microcracks than the ends. Optical microscope examinations revealed that extensive microcracking takes place even at the highest temperatures, where other mechanisms such as slip and dislocation creep also become important. Very little partial melting could be observed except for the specimens deformed at 900ºC.

Jan 1, 1982

By Franz R. Dykstra

DEFINITIONS The ores of iron are classified in three general categories: direct shipping, concentrates, and agglomerated-i.e., pelletized or sintered. Direct Shipping As the name implies, direct-shipping ores are shipped as mined or, perhaps, after screening. Generally, direct-shipping ores are hematitic (R203), magnetitic (R304), or limonitic (2Fe2O3.3H20) in nature. Grades of direct-shipping ores vary widely. Prices are frequently related to the historical Mesabi standard of 51.5% iron, although certain premium lump ores may contain up to 68% iron. The use of direct-shipping ores is diminishing as the advantages of beneficiated ores become evident and reserves are depleted. Concentrates Where the nature of the deposit and economics allows, certain ores are upgraded. This may include no more than washing and screening, or may be as elaborate as fine grinding followed by magnetic, gravity, or even flotation procedures for separation. Coarser concentrates may be smelted "as is.&apos;; Fine concentrates usually are sold as sinter feed. (Sinter, as used here and in the following, refers to a process by which a fine ore-carbon mixture is agglomerated at elevated temperatures on a direct-fired moving grate to eliminate fines and improve chemical and physical homogeneity.) Agglomerates-Pellets or Sinter The development of economic techniques of mining and concentrating taconite (fine-grained, ferruginous jasperoids) led to the introduction of the iron-ore pellet, which is now becoming the major form in which iron is introduced into the furnace. The tremendous reserves of magnetic taconites of the northern United States and Canadian Precambrian shield had been recognized for many years. A century of mining has seen the reserves of the direct-shipping or "red ores" of the Minnesota, Michigan, and Wisconsin ranges approach depletion. Research started in the 1930s has seen the evolution of motives and techniques to concentrate these stubborn refractory ores. The efficacy of concentrate pellets in iron-making has been such as to induce mines throughout the world to grind, concentrate, and pelletize otherwise shipping-grade ores. Table 14.1A.1 shows typical analyses of iron ore. Marketing-Prices of iron may be quoted on a value per long-ton (2240 lbs) or metric-ton (1000 kg or 2204 lb) basis, or on a value per long-ton-unit or metric-ton-unit basis. One iron unit represents 1 % of contained iron per ton. (Thus, a price of $0.45 per iron unit for ore containing

Jan 1, 1976

Jan 1, 1963

By Homer S. Frankhouser

Materials may be dredged, processed, stored and loaded for shipment at a single site in water depths ranging from 250 to 1200 ft. Solution mining may also be accomplished in deep sea situations. And, open air subsea mines with direct surface access may be developed and worked under the ocean floor. These concepts for deep sea mining are the results of extensive testing of individual components of the proposed systems by Dravo Ocean Structures, Inc., a subsidiary of Dravo Corp. A basic structure in these systems is the articulated platform. The platform consists of a gravity- type base and a buoyant cylindrical column which is constructed at an onshore location, towed to the offshore site and installed in a matter of days without use of heavy equipment. The base is also buoyant for towing purposes. This allows for gradual flooding to the point of negative buoyancy for positioning and anchoring to the ocean floor.

Jan 1, 1971

By R. H. Edsal, G. Horvay

The transient one-dimensional heat-conduction equation is solved for two semi-infinite media, at different initial temperatures, brought into (poor) thermal contact. It is shown that the two interface temperatures gradually approach the well-known, instantaneously assumed, common interface temperature of the case of zero contact resistance. The present analysis, with slight modifications, may be used in fair approximation also for the class of problems involving a change of phase. One particular application of the boundary value problem solved in this paper concerns the determination of the temerature distribution in metal castings and molds.P This problem has been treated extensively by analytical methods (see e.g., the literature listed in Refs. 1 to 4) by electrical analogs (see e.g., Refs. 11 to 14) and also by experimental methods (see the literature listed in Refs. 4, 5), but prior to the work of Pellini and Ruddle the experimental results were rather unreliable. Immediate motivation for the work described in this paper was to better understand the results of Pellini,&apos; which are typified by the curves of Fig. 1. Pellini cast 20-in. high, 7-in. sq steel ingots into cast-iron molds of various thicknesses. He measured the temperatures at mid-height, at a number of stations in the casting and the mold, and obtained the cooling curves shown in Fig. 1. The most conspicuous thing about Fig. 1 is the large temperature discontinuity at the interface between casting and mold, due presumably to the shrinking away of the casting from the wall and the attendant creation of an airgap, as the casting cools. Such a contact resistance slows down the anticipated freezing rate; an analytical prediction of this is of much interest in foundry practice. The determination of the effect of contact resistance in the presence of a change of phase will be dealt with, by an approximate method, in a separate paper.&apos; In the present paper the much simpler problem is considered in which there is contact resistance but no change of phase. This problem frequently arises in the analysis of aircraft structures.+ It can initial temperature, and may be regarded as semi-infinite. We suppose the thermal properties in the two media to be time, temperature, and space independent; there are no sources or sinks within the media. In Fig. 2(a) we illustrate, schematically, the case of no contact resistance. The semi-infinite media "0" and "2:&apos; initially at temperatures 8 (- m) and 8(+ -), respectively, are brought into contact at time t =0. A common interface temperature 8,i = is instantaneously established, and thereafter remains constant. Temperature curves are drawn for three instants of time. When there is contact resistance between the two media, the temperature equalization occurs as sketched in Fig. 2(b). Fig. 2(c) illustrates a temperature curve, using the dimension-less notation Barber-Weiner-Boley6 have stated the equations [23a, b] given below, which govern the heat transfer in the two media, and solved them for a rather complicated special case. In their example both media "O" and "2" are finite, are insulated at their far ends, and there is steady heat input into medium 2. In Eq. [27] we give the general solution of the most important special case, where the two media are semi-infinite and there are no sources or sinks. In this case the results may be stated in simple closed form. In Fig. 3, to be discussed in the next section, we illustrate the variation of the interface temperature when steel at 2760" is brought into contact with iron at 100". This example, if we disregard the effect of the heat of fusion, is comparable to Pellini&apos;s experimental results, Fig. 1. (Unfortunately, however, experimental determination of the interface temperatures was difficult to carry out, and hence Fig. 1 is not very accurate near the interface.) In Figs. 4 and 5 of the following section, we similarly compare Pellini&apos;s sandcasting tests with analytical results for the case where steel at 2760" is brought into contact with sand at 100". It will be pointed out that, insofar as the interface temperatures are concerned, heat of fusion has a minor effect, and so the present approximation, with small modifications, may be

Jan 1, 1961

By Leo Horvitz

PETROLEUM and natural gas are composed principally of the saturated hydrocarbons ranging from methane, the lightest, to nonvolatile liquids and solids containing approximately thirty-five carbon atoms. A technique for locating buried accumulations of these hydrocarbons before drilling obviously requires that some of the hydrocarbons leave the deposit and migrate toward the surface of the earth where they may be detected in their original form. Earliest attempts to link near surface hydrocarbons to petroleum at depth were apparently made by Laubmeyer1 in Germany and by Sokolov2 in Russia. These investigators collected samples of soil air from boreholes one to two meters deep and analyzed them for traces of hydrocarbons. They found that soil air over producing areas is richer in these constituents than is soil air over barren areas.

Jan 12, 1954

By C. B. Smith, A. G. Guy

The power and convenience of tensor analysis are employed in deriving the equations that describe three-dimensional diffusion in an n-component system plus vacancies. A "Kirkendall coordinate system, &apos;&apos; defined in principle by Kirkendall markers, is used in defining the intrinsic diffusion coefficients that are of primary interest. The defining equations are then transformed to local cartesian coordinates and to fixed cartesian coordinates, the latter being convenient for experimental measurements. Finally, it is shown how the intrinsic diffusion coefficients can be calculated from the experimentally determined quantities. It is generally recognized that any treatment of the essential diffusion phenomena in metallic systems—the jumping of atoms from one lattice position to another—must be based on movement of the atoms past Kirkendall interfaces.&apos; A logical extension of this idea is the proposal that, fundamentally, diffusion must be described mathematically in terms of "Kirkendall coordinates." The basic equations thus obtained may then be transformed into other coordinate systems, when such transformation leads to simplification of either the experimental or mathematical treatment of diffusion data. Tensor analysis is clearly the appropriate mathematical tool for this purpose, since it provides methods both for determining general equations that are valid for all coordinate systems and for conveniently transforming the equations from one coordinate system to another system related to the first in some known fashion. For the present purpose three coordinate systems are used, and it is convenient to begin with a description of the relations among these three systems. FICK LAW FOR KIRKENDALL COORDINATES The reference coordinate system, and the one that is useful for most experimental measurements, is a cartesian coordinate system, xi (i = 1, 2, 3), fixed with respect to some point in the specimen, such as an end of the alloy bar undergoing diffusion. A second set of coordinates, the Kirkendall coordinate system, is one that in principle can be described by the location of inert markers (Kirkendall interfaces). A convenient mathematical relation between Kirkendall coordinates, x&apos;i, and the reference cartesian coordinates, ii, is obtained by specifying that the Kirkendall coordinate system coincide with the cartesian system at time, t = 0. After diffusion has occurred for some time, t = t, the Kirkendall coordinate system will differ from the reference system in the manner shown schematically for the one-dimensional case in Fig. 1. The third coordinate system is Darken&apos;s1 local cartesian-coordinate system, xi, which is identical with ii in orientation and units, but which moves with the point under consideration in the Kirkendall coordinate system. Even though most diffusion problems are essentially one-dimensional, there is an advantage in first carrying out the analysis of the three-dimensional problem to gain a clearer insight into the assumptions that are made in the usual one-dimen-

Jan 1, 1962

The income of the Institute is derived from dues, subscriptions to MINING AND METALLURGY and sale of publications. These sources are fortunately supplemented by the interest from invested funds now amounting to over $500,000, a considerable portion constituting endowments for especial purposes. Aside from the medal funds the principal endowments are the James Douglas Fund for support of the Library, the Rocky Mountain Fund and the Seeley W. Mudd Memorial Fund. The income from the two last named is available for the support of research and a variety of other purposes. It is allocated by the Board of Directors upon recommendation of standing committees in each case. An active effort is being made to increase the endowments of the Institute, it being felt that unusual opportunities exist for research and public and professional service through the organization and at a minimum of expense. J. V. W. Reynders is chairman of the Endowment Committee.

Jan 1, 1923