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

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

Jan 1, 1951

By Howard C. Pyle, John E Sherborne

Core analysis is a recent development in the field of petroleum technology. The earliest work on this subject was done in connection with evaluating and planning secondary oil recovery by water-flooding. Present-day analysis of sands of flush fields requires new and independent interpretations of the data provided by cored material. Particular attention is being paid to the development of rapid, routine methods for measuring physical characteristics of sandstone, such as permeability, porosity and grain size, as well as the sand's fluid content. Permeability may be defined as the fluid-passing capacity of a rock. For a sandstone to be permeable it must be possible to pass a measurable quantity of fluid through the material in a finite period of time. The common unit of permeability is the darcy, which may be defined as the rate of viscous flow, in milliliters per second, of a fluid of one centipoise viscosity through a porous medium having a cross section of one square centimeter, under a pressure gradient of one atmosphere (76.0 cm. Hg) per centimeter.' For convenience the subunit millidarcy, or one-thousandth darcy, is often used. Porosity is defined as the fluid-containing capacity of a rock and is usually expressed as a percentage ratio of the total pore volume to the rock or bulk volume. Since measurement of only the effective or communicating pore volume is often made, porosities are distinguished as total or effective.2,3 Net effective porosity is defined as the net pore volume available for oil and gas. Oil and water content of sand is measured and expressed either as the percentage saturation of the total pores or of the bulk rock. The oil content may also be expressed as the percentage saturation of the net effective pores. In connection with water-flooding, methods of core analysis were developed to furnish data that could be used in determining the quantity of recoverable oil14-6 and the probable rates at which various sands or divisions of a sand open to the wells would take water or produce oil. In flush fields, the analytical data are used to predict the productivity of a cored interval. They indicate the presence of oil, gas and water and may

Jan 1, 1939

By Cyril Stanley Smith

Although not of the same importance as electrical conductivity, the capacity for conducting heat is nevertheless a very important property of metals and alloys. A knowledge of thermal conductivity is of value in selecting alloys for many purposes and in the calculation of the efficiency of apparatus which is being designed. Unfortunately, the determination of thermal conductivity is extremely slow and tedious, consequently few data have been obtained. A further reason for the lack of information is that there has long been an impression that the thermal conductivity of an alloy is directly proportional to the electrical cónductivity and that it can therefore be calculated from the latter. The Wiedmann-Franz-Lorenz law of constant ratio of the two conductivities holds with a considerable degree of precision for all the pure metals, but appreciable deviations occur in certain alloys—particularly those containing nickel—and it seems difficult to predict exactly what the ratio will be. Therefore direct determinations of thermal conductivity should be made whenever the results are needed with any accuracy. This research is intended eventually to cover all the alloys of copper that are of commercial importance, including the binary alloys of copper with zinc, tin, aluminum, nickel, silicon, manganese, cadmium and phosphorus, and the ternary alloys copper-nickel-zinc, copper-nickel-silicon, copper-manganese-silicon, copper-zinc-tin, etc. Most of these alloys are customarily used in the wrought condition and therefore were tested in the form of annealed rods. A limited number of sand castings were also obtained and examined. This paper contains a complete review of all the previous work that has been done on copper alloys, and includes a detailed description of the apparatus and method of procedure used in the present research, together with the new results obtained on the copper-zinc series, which is the only one completed at the present time. Subsequent papers describing the other alloys will contain the experimental results and discussion only. Previous Work Copper The conductivity of copper has been studied by many observers since the pioneer work of Wiedemann in 1859. The majority of these measure-

Jan 1, 1930

By Howard C. Pyle, John E. Sherborne

Core analysis is a recent development in the field of petroleum technology. The earliest work on this subject was done in connection with evaluating and planning secondary oil recovery by water-flooding. Present-day analysis of sands of flush fields requires new and independent interpretations of the data provided by cored material. Particular attention is being paid to the development of rapid, routine methods for measuring physical characteristics of sandstone, such as permeability, porosity and grain size, as well as the sand's fluid content. Permeability may be defined as the fluid-passing capacity of a rock. For a sandstone to be permeable it must be possible to pass a measurable quantity of fluid through the material in a finite period of time. The common unit of permeability is the darcy, which may be defined as the rate of viscous flow, in milliliters per second, of a fluid of one centipoise viscosity through a porous medium having a cross section of one square centimeter, under a pressure gradient of one atmosphere (76.0 cm. Hg) per centimeter.' For convenience the subunit millidarcy, or one-thousandth darcy, is often used. Porosity is defined as the fluid-containing capacity of a rock and is usually expressed as a percentage ratio of the total pore volume to the rock or bulk volume. Since measurement of only the effective or communicating pore volume is often made, porosities are distinguished as total or effective.2,3 Net effective porosity is defined as the net pore volume available for oil and gas. Oil and water content of sand is measured and expressed either as the percentage saturation of the total pores or of the bulk rock. The oil content may also be expressed as the percentage saturation of the net effective pores. In connection with water-flooding, methods of core analysis were developed to furnish data that could be used in determining the quantity of recoverable oil14-6 and the probable rates at which various sands or divisions of a sand open to the wells would take water or produce oil. In flush fields, the analytical data are used to predict the productivity of a cored interval. They indicate the presence of oil, gas and water and may

Jan 1, 1939

By O. R. Wagner, R. O. Leach

Immiscible displacement tests were performed in a consolidated sandstone core over the interfacial tension range from less thdn 0.01 to 5 dynes/cm to better define how interfacial tension (IFTJ reduction can lead to increased oil recovery. Data obtained were displacement efficiency at breakthbrough vs IFT for both drainage and imbibition conditions. These tests simulate water flooding under oil-wet and water-wet conditions, respectively. Results of the study have shown that displacement efficiency under both oil-wet and water-wet conditions can be markedly improved by a sufficient reduction in IFT. In the particular porous media used and for the low pressure gradients employed, the IFT must be reduced to a value less than about 0.07 dynes/cm to achieve increased recovery at the time of breakthrough of the injected phase. Below 0.07 dynes /cm, further small reductions in IFT result in large increases in displacement efficiency. Observed increases in recovery were obtained at pressure gradients which are well below those which can exist in the interwell area of a reservoir under water flood. The effect of pressure gradient on recovery is discussed. INTRODUCTION A residual oil saturation remains in rock which has been water flooded because, under usual reservoir conditions, the driving force which can be generated is inadequate to expel oil trapped by capillary forces. Since these capillary forces can be reduced by reducing the IFT a frequently studied method of increasing oil recovery has been the use of surfactants to reduce the water-oil interfacial tension. Mungan l observed improved recovery in both water-wet and oil-wet systems at 1.1 dyne /cm IFT, finding that the amount of improvement was greater in oil-wet systems. Moore and Blum,2 working with visual flow cell micro-models, con- cluded that recovery cannot be improved in water-wet systems by injecting surfactant solutions. They calculated that, for a pressure gadient of 1 psi/ft in their model, the IFT must be reduced to 0.03 dynes/cm to release oil trapped under water-wet conditions. Berkeley et al.3 indicated that, at representative field flooding rates, the IFT must be reduced to 0.001 dyne/cm to improve recovery, Thus, there is a wide variation of opinion about the IFT levels needed to improve recovery under field conditions. These previous investigators all have used as their experimental method the addition of surfactants to the injected water. The use of surfactant solutions to reduce IFT creates two experimental problems: (1) the loss of surfactant through adsorption on reservoir rock can obscure the true IFT value which exists at the displacement front, and (2) at very low values of IFT emulsifica-tion of oil and water commonly occurs. It is difficult, therefore, to determine whether the increased recovery is caused by IFT reduction as such, or is instead caused by emulsification. Also the properties of the available surfactants limit the IFT range which can be studied. In the present study the purpose is to better define how interfacial tension reduction can lead to increased oil recovery. A matter of great interest is the amount of recovery improvement potentially achievable in this way. The study was made using very low pressure gradients which was well within the range achievable by water flooding in the interwell region of petroleum reservoirs. A unique experimental approach was chosen to avoid adsorption and emulsification problems, and to allow convenient control of IFT. The fluid phases used were the equilibrium vapor and liquid phases of the methane-n-pentane system. The interfacial tension level was varied by changing the equilibrium pressure of the methane-pentane system over the range from 1,200 psia to near the critical pressure (2,420 psia). All tests were performed at a controlled temperature of 100F. The IFT-vs-pressure relationship for the methane-pentane system was based on the data of Stegemeier and Hough,6 and on new data obtained in this study. With this experimental approach it has been possible to study displacement at lower values of IFT than have been previously investigated.

Jan 1, 1967

By Margaret Dienes, Karl L. Fetters

It is recognized that ingot structure is important in determining the quality of finished steel. Such elements of ingot structure as the size, shape and distribution of primary crystals; the size, shape and distribution of shrinkage cavities; the degree and kind of segregation (both macro and micro); the distribution of nonmetallic impurities and gas cavities are each the result of solidification phenomena. 'These structural features vary with variations in ingot practice. Their control requires a knowledge of their correlation with the variables of ingot practice. The structures of full-sized commercial steel ingots have been studied extensively by the Steel Ingots Committee of the Iron and Steel Institute.l This work has contributed much to our knowledge of ingot structure and the factors that control it. These investigations of necessity have been limited in scope because of their costliness and the great amount of time required. Studies of the structure of small steel ingots have not been very satisfactory because of the rapid rate of freezing of the ingots. Their structures are thus difficult to resolve and to interpret. Medium sizes of steel ingots in the ranges of 150 to 500 lb. do offer opportunity for study, but their cost also becomes greater and their use less expeditious. Experimental models for the study of steel-ingot structure have been made of nonferrous metals. Gathmann2 used lead-tin alloys and reported that they were satisfactory for determination of the location of the major shrinkage cavities and the Liplanes of weaknessv resulting from the pattern of crystallization. Certain features of mold design have been illustrated by these results. Bezdenezhnihk3 has used copper and aluminum ingots similarly and has shown the effect of mold-wall thickness on the depth of columnar grains. These studies of nonferrous models have been useful, but their results have been limited because the analogy with steel ingots obviously is not a close one. Model wax ingots have also been useful in pointing out important features of mold design. Gathmann4 watched the solidification of wax ingots, through a glass-walled mold, and has reported the effects of mold type on the location of the shrinkage cavities. Segregation was simulated by using a mixture of paraffin and stearine and adding a red dye that on freezing segregated preferentially to the stearine. Brearley5 also used wax models to determine the effects of some of the principal features of mold design. Carlsson and Hultgren6 dsed stearic acid to show that the columnar crystals of ingots tend to slope upward progressively from the mold wall toward the center of the ingot. As with the nonferrous ingots, the wax ingots have

Jan 1, 1943

By Margaret Dienes, Karl L. Fetters

It is recognized that ingot structure is important in determining the quality of finished steel. Such elements of ingot structure as the size, shape and distribution of primary crystals; the size, shape and distribution of shrinkage cavities; the degree and kind of segregation (both macro and micro); the distribution of nonmetallic impurities and gas cavities are each the result of solidification phenomena. 'These structural features vary with variations in ingot practice. Their control requires a knowledge of their correlation with the variables of ingot practice. The structures of full-sized commercial steel ingots have been studied extensively by the Steel Ingots Committee of the Iron and Steel Institute.l This work has contributed much to our knowledge of ingot structure and the factors that control it. These investigations of necessity have been limited in scope because of their costliness and the great amount of time required. Studies of the structure of small steel ingots have not been very satisfactory because of the rapid rate of freezing of the ingots. Their structures are thus difficult to resolve and to interpret. Medium sizes of steel ingots in the ranges of 150 to 500 lb. do offer opportunity for study, but their cost also becomes greater and their use less expeditious. Experimental models for the study of steel-ingot structure have been made of nonferrous metals. Gathmann2 used lead-tin alloys and reported that they were satisfactory for determination of the location of the major shrinkage cavities and the Liplanes of weaknessv resulting from the pattern of crystallization. Certain features of mold design have been illustrated by these results. Bezdenezhnihk3 has used copper and aluminum ingots similarly and has shown the effect of mold-wall thickness on the depth of columnar grains. These studies of nonferrous models have been useful, but their results have been limited because the analogy with steel ingots obviously is not a close one. Model wax ingots have also been useful in pointing out important features of mold design. Gathmann4 watched the solidification of wax ingots, through a glass-walled mold, and has reported the effects of mold type on the location of the shrinkage cavities. Segregation was simulated by using a mixture of paraffin and stearine and adding a red dye that on freezing segregated preferentially to the stearine. Brearley5 also used wax models to determine the effects of some of the principal features of mold design. Carlsson and Hultgren6 dsed stearic acid to show that the columnar crystals of ingots tend to slope upward progressively from the mold wall toward the center of the ingot. As with the nonferrous ingots, the wax ingots have

Jan 1, 1943

By J. M. Adams

It is my purpose to give some of the results obtained by an experience of nearly seven years in working ores by the method frequently called the Washoe Process, and in several mills of which I have had charge, but principally in the Owyhee Mill, at Silver City, Idaho, which had twenty 650-pound stamps, and sixteen pans. I shall discuss here merely the mechanical details for working ores generally, subdividing the subject as follows : 1. Preparation of the ore for the stamps; 2. The crushing in the battery; 3. The settling of sand or pulp in vats or tanks; 4. The treatment in the pans; 5. The results obtained in settlers, agitators, and concentrators; 6. The straining of quicksilver, cleaning of amalgam, and retorting; 7. The saving of slimes and their subsequent treatment; 8. The loss of quicksilver. For descriptions of the various kinds of orebreakers, stamps, tanks, pans, settlers, etc., I must refer to the various works on these subjects, prominent among which are the reports of the United States Commissioner of Mining Statistics,and the volume on "Mining Industry," the third volume of the United States Geological Survey on the Line of the Fortieth Parallel through the gold and silver bearing regions of the great West, undertaken under the able guidance of Clarence King, assisted by Mr. James D. Hague and others. In this discussion it will be assumed that the general arrangement of the quartz mill is understood; and the question will be treated how to secure, from such a mill, the greatest economy in working, combined with the largest results. This place seems fittest for a single preliminary suggestion—namely, that there should be double "floors" throughout the mill, so that nothing can sift through and be lost.

By R. T. Hukki

THE accepted basis of comparisons between mills of different diameter is the percentage critical speed. If n = actual mill speed, rpm, nc = calculated critical speed, rpm, np = calculated percentage critical speed, and D == inside diameter of the mill in feet, then n, In the following analysis capacity, T, is expressed in short tons per hour, tph, and power consumption, P, in kilowatts, kw. Accordingly power consumption per unit of capacity, P will be expressed in kilowatt hours per short ton, or kw-hr per ton. In all equations D refers to the inside diameter of the mill in feet and v to the peripheral speed of the mill in feet per minute inside the liners. ' Comparison between separate mills must be based on equivalent grinding conditions, i.e., same feed, same size distribution of feed, same size distribution of product, and same percentage of solids. In addition, comparisons between separate rod mills must be based on the same rods, same type of liners, and same percentage rod load. Comparisons between separate ball mills presuppose the same balls, similar liners, and same relative ball load. The practical np-range through which the equations apply varies, being narrower for fine grinding in ball mills and wider for coarse crushing in rod mills. The Relationship between Capacity and Speed It is the general belief that the capacity, T, of a tumbling mill is directly proportional to the speed of the mill, other things remaining constant.' Mathematically this is represented by the equation T - c¹ n tph [4] where c, is a factor related with the grinding characteristics of the ore, method of reduction, and the units chosen. It is proposed here that the general equation relating mill capacity and speed should be of the form T = c¹ nm tph [5] In other words, the capacity should be proportional to the mill speed raised to power m, the numerical value of the exponent being 1 5 m 5 1.5, depending on the circumstances. Eq. 5 can also be written in the following forms: T = c, (np)m tph, and [6] T=Ca vm tph, [71 where v = peripheral speed of the mill in feet per minute. If the observed capacity of a mill at speed n¹ is = T¹ tph, the capacity T² of the same mill at speed n² should be T² = T¹ (n²/n¹)tph [8] The Relationship between Power Consumption, Mill Diameter, and Speed The only well known theoretical deduction relating power consumption, P, and mill diameter appears to be the formula of duPont introduced by Gow, Guggenheim, Campbell, and Coghill.' According to duPont, the power required to operate a mill is a function of the mass of the balls, of the lever arm of the ball mass, and of the speed of the mill. The ball mass per unit of mill length is proportional to the square of the diameter, the lever arm is directly proportional to the diameter, and the critical mill speed or any percentage thereof is inversely proportional to the square root of the mill diameter. Following this reasoning, the original duPont formula is of the form P = c4D² c D • c6D-0.5 = c7D2.5 [9] If the mill speed in the above equation is expressed in terms of Eq. 3, the duPont formula may be written as follows: P=f1(D2) f2(D) f³(—np) or [10] vD P = c np D2.5 kw [11] Eq. 11 may also be derived from the mechanical principle of force, which is equal to mass x acceleration. Power necessary to operate a mill may be considered to be an homogeneous linear function of the force developed. Ball or rod mass per unit of mill length is a function of D2. The acceleration factor of the ball or rod mass is a function of the peripheral speed of the mill. Thus P = f4(F) = /x(D2) f5(v) Indicating that v = nDn, and n = c9 np /vD, the above equation becomes P = f2 (D2) -fa (D ca np/vD

Jan 1, 1955

By W. W. Gorr, R. Smith, E. H. Wyche

THE combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W? and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. DEVELOPMENT OF THE NEW STEEL For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield 18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators 'then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, o.58; Ni, 7.28; Cr, 17.6o; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1946

By C. H. Benedict

1. Shaking Tables 2. Fine Grinding 3. Hydraulic Classification 4. Mechanical Thickeners 5. Flotation ENTERING the profession of minerals beneficiation (it was plain garden variety "ore dressing" . in those days) I was fortunate that at that time the first major innovation in modern ore dressing practice was being introduced. I refer to the Wilfley table. You youngsters that came into the game only 30 years ago or even more recently, with flotation machines and reagents as your very ready tool in time of trouble, do not realize what the invention of the Wilfley table meant to us. We had but one physical property of ores to reckon with-specific gravity- and when there was but little difference in specific gravity between the mineral and the gangue, we were in trouble. The jig and the revolving table were our only mechanical equipment for recovering values and so that we might make even a reasonably satisfactory extraction, we had to classify and reclassify, and jig and rejig, and worry about the laws and advantages of free settling vs hindered settling and just tire the minerals out.

Jan 10, 1954

By J. M. McKenzie

p-n junctions to detect and measure the energy of single quanta of electromagnetic radiation are described. Useful energy range is from 1 kev to several Meu. Achieved energy resolution varies from 30 pct at 6 keu to 0.12 pct at 2 Mev. Parameters affecting the perfornzance of the present detectors and desired of a new material are discussed. DURING the last 6 years semiconductor detectors have been used extensively to detect and to measure the energy of charged particles. These detectors are made from reverse-biased p-n junctions. Electron-hole pairs are created in the depletion region of the junction, Fig. 1. The carriers are separated by the electric field and give rise to a pulse of current in the external circuit. This current pulse is proportional to the number of carriers and hence to the energy deposited in the depletion region by the ionizing event. More recently the discovery of the lithium drift process, first in silicon' and then in germanium,2 has extended the use of semiconductor detectors to the detection and the energy measurement of single quanta of electromagnetic radiation. These detectors now have a useful measurement range extending from the soft X-ray region, about 6 kev, to the hard y ray region of several Mev. Surface-contoured avalanche diodes can be used to extend this range down to 1 kev. There is however a desire for other materials suited to higher operating temperatures, and particularly for those materials with high y ray stopping power. The most important advantage of the semiconductor detector over gaseous and scintillation detectors is the average energy, E, required to form an electron-hole pair. Fig. 2 shows the quantum efficiency for germanium as a function of photon energy.3 At the band-gap energy, 0.7 ev, an electron-hole pair is generated by the absorption of the photon and the quantum efficiency is unity. The quantum efficiency remains constant at unity between 0.7 and 3 ev. It then increases as additional electron-hole pairs are formed by secondary ionization of the initial photoelectron. The rate of increase is about 1 electron-hole pair per 3 ev (actually 2.9 ev for germanium and 3.6 ev for silicon). This figure is constant irrespective of the particle type (electron, proton, a particle, heavy ion) and energy. In an ionizing event an incident particle of energy E will create N = E/e ion pairs. The statistical fluctuation in this number is proportional to &. The fractional energy resolution is therefore proportional

Jan 1, 1968

By D. R. Wieland, A. N. Barron, A. R. Hendrickson

A definite relationship has been found between the reactivity of flowing hydrochloric acid and its shear rate in a carbonate fracture. Both flow velocity and fracture width affect the acid reaction rate. Laboratory studies were conducted on acid reactivity at different flow velocities through horizontal-linear fractures, using 15 per cent hydrochloric acid at 80' F and approximately 1,100 psi. Fracture width varied from 0.02 to 0.20 in. These data provide a new basis from which the spending time and penetration of the acid can be estimated. Equations were derived expressing the relationship between injection rate, fracture width, acid concentration, time and fracture height, for linear and radial fracture systems. Because the penetration of the acid before spending is closely related to the extent of productivity increase resulting from an acidizing treatment, these data provide a valuable insight into some of the controlling factors that must be taken into consideration during treatment preplanning. INTRODUCTION Acidizing of carbonate reservoirs to improve production characteristics has been widely practiced since 1932. Originally, it was assumed that the acid uniformly penetrated natural formation pores and flow channels, enlarging them and thereby increasing their flow capacity. Little consideration was given to the reaction rate of the acid, or how far it would penetrate away from the wellbore into the formation, before spending. It has been shown recently' that, unless fractures are present in the rock, very little penetration is attained before spending, and the benefits of the acidizing treatment are largely confined to the immediate vicinity of the well-bore. Therefore, acid treatments may be classified into two categories: (1) matrix acidizing, in which the acid flows through multiple: formation pores; and (2) fracture acidizing, in which the bulk of the acid travels through fractures in the rock, whether natural or induced. When acidizing treatments are conducted at pressures of sufficient magnitude to open and extend such fractures, it is often desirable to inject a propping agent to hold the fracture open after the treating pressure has been released, thus providing a highly conductive flow channel through the rock. In some cases where acid attack produces surface irregularities, the resulting flow passages can be sufficient to provide high conductivity without use of a propping agent. During injection, the acid dissolves the carbonate rock with which it comes in contact until it is spent. Deeper penetration of the spent acid into the formation produces no appreciable benefit (if no propping agent is used) because the unetched fracture faces will rejoin when treating pressures are released and the fracture will "heal", with negligible resultant conductivity. The spending time of the acid thus becomes important in determining how far from the wellbore the improved-conductivity zone extends. The spending time of acid after injection into carbonate rock depends on the rate at which the acid reacts with the rock. This in turn is controlled by a number of factors, as previously reported. 2-4 These include temperature, pressure, acid concentration, rock composition, injection rate and the area-volume relationship between the acid solution volume and the surface area of the formation flow channels through which it penetrates. Thus, in matrix acidizing, where an extremely large area is exposed to the acid, spending is rapid. In contrast, spending time is prolonged in open fractures, where the area-volume ratio is much lower. Thus, greatest penetration of the acid before spending will be achieved in acid-fracturing treatments where fractures are held open by hydraulic pressure. Perkins and Kern5 have presented equations for fracture-width determinations which, for hard formations such as limestone or dolomite, indicate that high injection rates and viscous fluids are required to create wide fractures. Increasing the injection rate will, in itself, produce faster reaction rates. Because this type of reaction can be considered to be first-order diffusion-controlled, '-' the rate of movement of fluid past the rock surface affects the thickness of the diffusion layer, in turn affecting the reaction rate. Staudt, et al,10 report the results of tests in which a rotating marble cylinder was immersed in acid, and the weight loss at different speeds determined. Such test conditions, however, are not truly indicative of the situation in a formation during an acid-fracturing treatment. This paper reports reaction-rate data obtained under

By L. J. Murphy

The production of crude oil in the United States is exceeding consumption by one-quarter million barrels per day and, with the possibilities of West Texas, this condition of overproduction, unless controlled, is likely to continue for some time. The resulting low price of oil has caused the operator to observe closely his lease operating costs. The installation of more efficient and reliable machinery has followed and it can well be said that the art of producing oil is on the threshold of a new era. In this advancement electricity has played a leading part. This paper covers only the problem of electricity as applied to lease operation and does not consider other phases of the industry, such as drilling and pipe-line pumping, in which electric power has been utilized economically. In considering electrification of pumping wells, the first question the operator asks is whether or not his costs will be reduced and the second question is whether or not the production will be increased. The third question, although in effect it is closely allied to the first, is the cost of power. The last question can be answered only after a thorough analysis of operating conditions and a study of the power rates prevailing in the particular field under consideration. Within the past few years, the power companies have realized the desirability of a steady 24-hr, pumping load, have made their rates for oil-field service particularly attractive, and in general have shown splendid cooperation in assisting the oil companies in the satisfactory application of electric power to their leases. When everything is taken into consideration, the first cost is practically the same for electric drive as for gas engines when pumping on the beam with individual motors. This cost, at prevailing prices, should aver-age approximately $2200 to $2400 per installation when using 15 to 35-hp., two-speed pumping equipment, including motor and control, countershaft, motor house, belt, installation charges, and a prorated portion of the cost of transmission lines and transformers for serving a number of wells. Since there is practically no difference in the cost of the two installations, it is evident that electricity, to justify its consideration, must have a lower operating cost or produce more oil.

Jan 1, 1928

Jan 1, 1967

By G. K. Manning, M. C. Udy, L. W. Eastwood

Those who have examined beryllium and beryllium-rich alloys under the microscope have noted the results of the difficulties encountered when preparing these materials for examination. Hard constituents are readily chipped and pulled out of the matrix, and the soft ones are easily gouged out or embedded with abrasive or other material. The matrix is easily deformed, which makes it very difficult to remove the effects of scratches. Furthermore, the matrix and some of the constituents are also readily pitted during etching, which makes the structure difficult to develop. The metallographic techniques designed to avoid these difficulties are neither radically new nor necessarily the best possible procedures. They were developed at Battelle to fill immediate requirements as part of a study of the preparation and pouring of beryllium melts as described in a separate paper. A part of the research program on the causes of gas unsoundness in beryllium castings entailed a study of the effects of such gases or gas formers as oxygen or oxides, nitrogen or nitrides, and carbon or carbides. These gases or gas formers, if dissolved in the melt, might be an important factor in the study of unsoundness caused by gas evolution in beryllium. Because it was necessary to be able to distinguish these gases or gas formers, if present as alloy constituents, from metallic phases also present as alloy constituents, a series of alloys was prepared with additions of the various possible metallic and non-metallic constituent formers. It should be emphasized that the constituents referred to as gases or gas formers are important in the study of gases in beryllium only if they form a part of the alloy, that is, if they dissolve in the liquid or solid metal. During the first part of the development of metallographic techniques, the Massachusetts Institute of Technology, unpublished report (TC 3315, Nov., 1945) by Paul Gordon, describing various microconstituents in beryllium, was quite useful. Of particular interest in this report is the confirmation of one of the conclusions drawn from the present investigation, that is, that a distinct oxide phase apparently does not occur in beryllium. The Preparation of Metallographic Specimens GRINDING PROCEDURE The original specimen is either sawed or cut on an abrasive wheel to a convenient size. For best results, the surface to be polished should not be more than about 1/4 in. square, and it is convenient to mount the specimens in bakelite to facilitate handling. Two alternative grinding procedures have been developed. As one alternative, specimens are ground successively on 120-, 240-, and 400-grit, wet-or-dry metallographic discs. The abrasive discs are revolved at 1750 rpm on a conventional pedestal grinder. The coarsest disc (120 grit) is used either wet or dry, and in most instances, it can be eliminated from the procedure. Grinding on the two finer discs (240 and 400 grit) is accompanied by the application of kerosene. The technique consists of holding an oil can, containing kerosene, in one hand and the mounted specimen in the other hand. While the grinding is being done, several drops of kerosene are applied every few seconds close to the center of the disc. Carbon tetrachloride serves at least as well as kerosene as a lubricant; perhaps it is slightly better, but it volatilizes so readily that an additional health hazard is involved. Light oils and water are not satisfactory for the finer grinding operations. The second procedure is perhaps slightly slower than the first and requires a more careful technique, but it eliminates the use of kerosene. The specimen is first ground wet on a 240-grit disc, followed by dry grinding on a 400-grit disc. Finer grinding does not appear to be necessary with either of the two alternative procedures. The pressures used throughout either grinding operation must be extremely light, that is, barely sufficient to hold the specimen in contact with the disc; otherwise, flow and chipping are almost certain to occur. In both procedures, it is essential that the discs be sharp and that they be discarded as they show evidence of becoming dull or loaded. In general, not more than four or five specimens can be ground on a disc before the disc becomes dull enough to warrant discarding it.

Jan 1, 1950

By George R. Mansfield

Interest in the reserves of phosphate rock in the United States and their proper conservation has recently been aroused by hearings held in different parts of the country by the "Joint Committee to investigate the adequacy and use of phosphate resources of the United States." This committee was appointed within a few days after a Presidential message to Congress on the same subject, dated May 20, 1938, and began to function almost immediately. Hearings were held in Washington, D. C., Pocatello, Ida., Wilson Dam, Ala., Knoxville, Tenn., and Lakeland, Fla. The resulting testimony, when published, comprised a volume of 1182 pages.l At the earlier hearings held in Washington and Idaho the seeming disparity between the great reserves of the West and the smaller reserves in the East led to some suggestions as to the desirability of curtailing or even prohibiting the exportation of phosphate rock so that eastern producers, becoming alarmed, cooperated in making available for the use of the committee information hitherto closely guarded. This information has provided an opportunity for new studies by official agencies, for a restatement of the reserves of Florida and Tennessee, and for some modification of figures for the Western States. The writer, representing the Federal Geological Survey, was given free access to the Florida material and has prepared for publication a report,² some features of which are summarized in this paper. The Tennessee material was studied by Dr. G. I. Whitlatch,³ of the Tennessee Division of Geology. Prof. J. Stewart Williams,* of the Utah State Agricultural College at Logan, has published a recent study of the phosphate resources of Utah and the writer has given some further study to reserves of western phosphate from the viewpoint of including material of lower grade than that hitherto considered. Technologic advances in the phosphate industry must be credited with a large share in the expansion of reserves by making available for

Jan 1, 1942

By George R. Mansfield

Interest in the reserves of phosphate rock in the United States and their proper conservation has recently been aroused by hearings held in different parts of the country by the "Joint Committee to investigate the adequacy and use of phosphate resources of the United States." This committee was appointed within a few days after a Presidential message to Congress on the same subject, dated May 20, 1938, and began to function almost immediately. Hearings were held in Washington, D. C., Pocatello, Ida., Wilson Dam, Ala., Knoxville, Tenn., and Lakeland, Fla. The resulting testimony, when published, comprised a volume of 1182 pages.l At the earlier hearings held in Washington and Idaho the seeming disparity between the great reserves of the West and the smaller reserves in the East led to some suggestions as to the desirability of curtailing or even prohibiting the exportation of phosphate rock so that eastern producers, becoming alarmed, cooperated in making available for the use of the committee information hitherto closely guarded. This information has provided an opportunity for new studies by official agencies, for a restatement of the reserves of Florida and Tennessee, and for some modification of figures for the Western States. The writer, representing the Federal Geological Survey, was given free access to the Florida material and has prepared for publication a report,² some features of which are summarized in this paper. The Tennessee material was studied by Dr. G. I. Whitlatch,³ of the Tennessee Division of Geology. Prof. J. Stewart Williams,* of the Utah State Agricultural College at Logan, has published a recent study of the phosphate resources of Utah and the writer has given some further study to reserves of western phosphate from the viewpoint of including material of lower grade than that hitherto considered. Technologic advances in the phosphate industry must be credited with a large share in the expansion of reserves by making available for

Jan 1, 1942

By Harold Margalin, Elmars Ence

M. H. Mueller, M. V. Nevitt, and H. W. Knott (Argonne National Laboratory)—We have reported1 the crystal structure of Ti2CU as body centered tetragonal with a. = 2.944A and co = 10.786A, six atoms per unit cell, and space groupl4/mmm(MoSi2 type). This cell is larger but definitely related to the unit cell reported by the authors. It permits definite positions for the titanium and copper atoms in the cell located as follows: 2 Cu (a) 0 0 0; 1/2 1/2 1/2 4 Ti (e) 0 0 z; 1/2 1/2 1/2 + z; 0 0z; 1/2 1/2 1/2- z where z = 0.341 The face centered tetragonal cell reported by the authors can be transformed to a small body centered tetragonal cell with flo (small bet) = ao(fct)v2 Both unit cells have the same CO. Neither the face centered tetragonal cell with four atoms per unit cell nor the small body centered tetragonal cell with its two atoms per unit cell lend themselves conveniently to an orderly arrangment of the 2 to 1 ratio of titanium to copper atoms. When the co of this small body centered cell is tripled, however, a large body centered tetragonal cell results with six atoms per unit cell as described above. We had also noted that the X-ray patterns of Ti2Cu indicated that the structure could be approximately described by the face centered tetragonal cell as reported by the authors; how- ever, there was evidence for a few additional very weak lines whose positions indicated a larger unit cell. Since the X-ray scattering amplitudes of titanium and copper are nearly equal, it is evident that it is difficult to distinguish their positions especially from X-ray powder patterns. It was therefore decided to look at a powder pattern obtained by neutron diffraction since the scattering amplitudes of the two elements are considerably different in magnitude and opposite in sign. The sample used for neutron diffraction was selected from a group of three alloys prepared by arc melting using crystal bar titanium of 99.92 pet nominal purity and 99.999 pet pure Cu. The alloys designated as A, B, and C had the following respective compositions: Ti-32.8 at. pet Cu, Ti-33.3 at. pet Cu, and Ti-33.8 at. pet Cu. On the basis of the melting losses incurred, it was established that the actual concentration of either component in any of the alloys probably did not deviate from the intended value by as much as 0.1 at. pet. The alloys were annealed for 5 days at 700°C in evacuated Vycor capsules and quenched in tap water. The metallographic structures of these alloys are shown in Fig. 1. None of the alloys contained sufficient second phase to permit its positive identification. Since alloy B contained the least amount of second phase and since its composition placed it closest to the ideal stoichiometry, it was chosen for the neutron diffraction study. The oxygen content of alloy B was found by chemical analysis to be 0.06 at. pet. This particular intermetallic compound is especially suitable for investigation with neutron diffraction since if the titanium and copper atoms have a random statistical distribution, a near null-matrix would result in which there would be practically no coherent scattering of neutrons, and hence no Bragg diffraction peaks. Such a condition could come

Jan 1, 1962

By W. A. Backofen, G. Mayer

Single crystals of iron, copper, and a Cu-7 wt pct A1 alloy were pulled through conical dies to simulate the constraint in a polycrystalline aggregate undergoing axisymmetric reduction. With Taylor-type hardening, dependence of the drawing stress, od, on the Taylor orientation factor, M, is predictable from the polycrystal stress-strain curve; in particular, for a power-law relationship, it should follow that d log od/d log M = (1 + n). A first-order agreement with analysis was found in the data from iron. For copper, the implied n from the observed d log od/d l°g M was -0, while for Cu-7Al it was negative. The trend was in the direction of random polycrystal behavior. Thus the idea of hardening only in response to the amount of prior slip loses validity as stacking fault energy (SFE) is lowered. Two possible explanations have been suggested: as stacking fault ribbons are widened, barriers from dislocation reactions become increasingly effective in dispersing slip and reducing the orientation dependence of the total glide strain dm that appears in alternatively, or conjointly, the polyslip shear stress, 7, acquires an orientation dependence of a kind which has the same leveling effect on M. The problem of relating the strain hardening of polycrystalline material to that of an isolated single crystal is still largely unsolved. In a new experimental approach from recent work, single crystals of different orientations have been deformed under the constraints found in an aggregate while measuring their deformation resistance. Procedures have involved drawing cylindrical crystals through conical dies1 and compressing slab-shaped crystals in plane strain.2'3 Predictions for the outcome of such experiments were made first by Taylor~ and later, in more general form, by Bishop and Hill.5'6 Taylor's example was the axisymmetric extension of an fcc crystal slipping on the usual {111}(110) systems or, equivalently, a bcc crystal undergoing 'kestricted" slip on {110}(111). In his solution, the deformation work supplied was equated to that dissipated internally in slip on all active systems. With o the single applied tensile stress, dc the resulting axial strain, and dyT the total glide strain on systems operating at resolved shear stress, 7: The orientation dependence of M was found by minimizing dyT for each orientation while activating five independent systems, Fig. l(a).? The Bishop and Hill analysis, based on a principle of maximum work, leads to essentially the same conclusion; the need for at least five active systems is recognized in the finding that either six or eight are actually brought into operation. The mean value from the entire stereo-graphic triangle in either case is M - 3.06. More recently, Hutchinson8 made a Taylor-type analysis for pencil glide in a bcc structure, from which piehlerg prepared Fig. l(b) as the counterpart in Fig. l(a); here M = 2.75. The obvious weakness in such analyses is the indifference to slip-system interactions. A condition of what might be termed "independent"

Jan 1, 1969