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By Bengt Helmerson

A new tankhouse was started in January 1959 at the Copper Refinery of the Boliden Co., Skelleftehamn, Sweden. In early 1961 a semiautomatic machine for looping and straightening of starting sheets was introduced to substitute previous manual operations. The machine as well as consequent, racking and handling is described. Finally, economic benefits achieved and new constructions for the future are discussed. HISTORY Tankhouse operations at the Boliden Co. 's Smelter in Skelleftehamn started in 1932 on a scale that since then has been gradually increasing. In order to rationalize the operations, a new tankhouse was erected. It went into production in January 1959 and was designed for a yearly production of 35,000 metric tons at a current density of 16 amps per sq ft. Already from the beginning, however, the tankhouse has been run with a current density of 21.5 amps per sq ft, corresponding to a maximum capacity of 50,000 tons a year. During the time of planning of the new tankhouse, due consideration was given to the possibilities of mechanizing the operations. New ideas could be and were actually tested on full or pilot plant scale in the old tankhouse. In that way we developed a system for the cathode handling including washing, weighing, and transportation. A system using forklift trucks in combination with trailers and overhead cranes has been developed for transportation and racking of anodes and also for handling of anode scrap. With respect to the electrolyte, circulation and temperature control are partly automatic. Special attention was paid to the production of starting sheets, which operation normally requires a great number of man hours, and it was made the object of a particular survey as to the best ways of straightening starting sheets, attaching loops to the sheets, and so forth. As a result, a machine was designed during 1957-58 and built in our own shops. After a period of tests, the new equipment was put in operation commercially on the 10th of April, 1961. Since this date the machine has produced about 2 million starting sheets without interruption and has been the only source of looped starting sheets for the tankhouse. GENERAL DESCRIPTION Fig. 1 shows all the major parts of the system. These parts are: slitting machine with feeding table (I), standard roller leveler, type Ungerer (2), tilting roller table (3), conveyors for sheets and suspension bars (4, 7), storage of suspension bars (51, punching and stitching machine (6), two lift-turn-tilt tables (8) for discharging the starting sheets, two rack conveyors (9) for sheet assemblies. Included are a hy-daulic pump station and panels for pneumatic and electric controls. SLITTING AND STRAIGHTENING The machine is fed by hand by a man sitting in front of the slitting-machine table, Fig. 2. This operator inserts one sheet at a time into the slitter. After being trimmed, the sheet is automatically conveyed to the following step of handling, straightening. The slitting machine cuts away about 8 mm of the upper and lower parts of the sheet (in relation to its original position in the stripper section) for two reasons. The first one is to give the machine sheets of uniform dimensions; the second one is a matter of quality. Normally the starting sheets as stripped have a thick edge at the bottom end. This part would collect anode slimes and might also cause short circuits when inserted in the cells without trimming. The straightener used is of German construction

Jan 1, 1967

By M. C. Smith, W. V. Green, D. M. Olsen

The creep-rupture behavior of commercial powder-metallurgy molybdenum rod is reported in the temperature range 1600" to 250O°C, at stresses up to 9000 psi and times up to 1 month. The effects of temperature, stress, and grain growth are discussed. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher-stress results reported by pugh.1 BECAUSE of its high melting point, molybdenum should retain useful strength to relatively high temperatures. Combined with its ready availability in the United States, this makes it attractive for many applications in missiles, rockets, and so forth—wherever its susceptibility to oxidation can be tolerated or overcome. The mechanical properties of molybdenum rod in the temperature range —200" to 1540°C have been reported by pugh,' Bechtold,' Parke,3 and Carriker and Guard.4 Madden and chen5 have measured the tensile properties of molybdenum single crystals in vacuum up to about 2500°C. As one further step in evaluating its mechanical usefulness, the constant-load creep-rupture properties of commercial powder-metallurgy molybdenum rod have been investigated in the range 1600" to 2500°C. MATERIAL TESTED Creep specimens were machined from 1/2-in. round commercial molybdenum rod, manufactured from powder by pressing, sintering, and swaging. Spectrochemical analysis of the rod showed "traces" (less than 0.01 pct) of silicon, aluminum, chromium, iron, and zirconium, and "faint traces" (less than 0.001 pct) of manganese, magnesium, cobalt, and nickel. Carbon content was 130 to 200 ppm, nitrogen was 110 to 180 ppm, and oxygen 30 to 35 ppm. A typical microstructure of the as-received rod is shown in Fig. 1. Room temperature tensile properties for five specimens strained at about 0.015 in. per in. per min are shown in Table I. CREEP SPECIMENS USED The specimens used for creep-rupture testing are illustrated in Fig. 2. The 1/4-in.-diam gage section was 3/4 in. long, and terminated at shoulders 5 mils high. These shoulders served as fiducial marks for optical strain measurements. Surface finish on the gage section was 16pin. r.m.s. One specimen, for a "long-time" test described below, was modified by dividing the 3/4-in. gage length into three 1/4-in. long sections with individual diameters of 0.250, 0.230, and 0.210 in., each terminating in a pair of fiducial shoulders. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.6 In it the specimen is held vertically on the axis of a cylindrical tantalum or tungsten heater tube by threaded molybdenum or tungsten grips. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. The bottom specimen grip is held at its lower end by a clevis pin. The testing load is applied to the specimen through the upper grip by means of hanging weights, a constant force-multiplication lever system, and a pull rod sealed to the chamber lid by a bellows. The incandescent specimen is viewed by an external optical system through slots in the heater-tube and radiation shielding, and an enlarged image of it is projected on a ground-glass screen. Gage-length measurements are made on this image with a pair of cathetometers. Thorium oxide coatings were applied to the threaded ends of most specimens, to prevent diffusion-welding of specimens to grips during testing. Without such a coating welding usually occurred, and grips were often broken by subsequent efforts to remove the tested specimens.

Jan 1, 1960

By C. H. Lee, R. Maddin

The diffusion rates of Ag110 in cylindrical single crystals of 99.99 pct pure silver, which were twisted to a total surface strain of 0.91 during the diffusion anneal at temperatures of 700°, 750°, and 800°C, were measured by sectioning and counting as a function of the strain rates. The ratio of the diffusivities while strain ing occurred (Ds) to those of the unstrained specimens varies linearly with the rate of twisting and attains values of near 100 for some of the rates used. The enhancement of diffusion by straining is inversely proportional to the temperature at which diffusion occurs. The activation energy for diffusion determined from the data plotted as a function of the rate of twisting decreases from 44,090 cal per mole for zero strain, to an asymptotic value of 21,000 cal per mole for the strain rates of 22 x it)"5 see-l. Qualitative explanation for the observations based on the generation of nonequilibrium number of defects by plastic deformation will be discussed. The initial research of Buffington and cohen1 on self-diffusion in a iron under compressive stresses contributed the first quantitative information concerning the effect of applied stresses on diffusion. These results were obtained from radioactive Fe55 plated on one of the horizontal surfaces and compressing the large-grained specimens while the diffusion-anneal was occurring. Enhancement of diffusion of a maximum of seventeen times was observed provided the strain was in the tertiary stage of creep and the rates of straining were at least as fast as rates used in the normal creep test. On the other hand, Darby, Tomizuka, and Balluffi,2 extending silver single crystals up to 30 pct elongation at rates of straining about equal to those used by Buffington and Cohen observed no effect. For the past two and a half years at the University of Pennsylvania, we have been investigating the effect or torsional strains on self-diffusion in silver single crystals. If enhancement is observed as has been reported1 a possible explanation may be based upon the generation of fairly large numbers of point defects and their role in the diffusion process. Hence, since torsion should produce an abundance3 of point defects, an increase in the diffusivity while the crystal is being twisted should easily be measured. EXPERIMENTAL PROCEDURE Our research uses single crystals of silver prepared from 99.99 Ag by the Bridgman method in a dynamic vacuum of less than 25 µ. As grown, they are about 25 cm long by 1.3 cm in diam. The crystals are cut into 7.5 cm lengths with a jeweler's saw and machined to the shape shown in Fig. 1. The test length of the crystal is machined to a 0.6 cm diam after which the ends are masked and the test section etched heavily in HNO3, and KCN:(NH4),S2Os , solution to remove the effects of machining. The specimen is then annealed in vacuum for 8 to 12 hr at 800°C to remove any residual stresses and also to recrystallize the end sections. The recrystallized ends are necessary since experiments showed that single-crystalline end sections are too soft to transmit the desired torque. Occasionally, recrystalliza-

Jan 1, 1960

By Tell Ertl

The term oil shale is defined. Foreign oil-shale developments are outlined briefly. The richest and most extensive oil-shale deposits in the United States lie in western Colorado. The Bureau of Mines is opening two adjacent areas for underground mining. in western Colorado. From the first area the oil shale is mined selectively as required by the retorting plant. The second area is being developed as a unit of a full scale oil-shale mine to ascertain the most practical methods of mining oil shale and to determine costs. In both of these mining areas, research will be carried on to develop new and improved practices for mining oil shale. Introduction Oil shale is a sedimentary rock containing a solid mineraloid of indefinite composition known as kerogen. On heating oil shale, the kerogen undergoes thermal decomposition and some of the vapor products of the decomposition can be condensed as shale oil. Oil from shale can be a major source of liquid fuels since extensive deposits of oil shale are known to exist throughout the world. The United States considers the establishment of an oil-shale industry only when doubt exists of the adequacy of the domestic supply of crude petroleum. On the other hand, oil shale is not strange to foreign oil men. The industry is an old one in other parts of the world. The French industry has been in existence since 1838, the Scottish since 1859, the Australian since 1860, the Estonian and Swedish The since World War 1, and the Manchurian industry since 1929. The most highly exploited oil-shale deposits are the Carboniferous shales of Scotland. About 20 seams ranging from 4 to I2 ft in thickness are worked. The yield during recent years in scotland has been 18 to 25 gal of shale oil per ton, from 3&"30'000 tons per year' The French and Swedish oil-shale deposits are of lower grade than the Scottish. The Estonian oil-shale deposits are 7 ft thick, and the oil yield averages 50 gal per ton. Over 1,000,-ooo tons are mined each year, half of which is used directly as fuel to substitute for coal and the other half is used for the production of oil. Immense deposits of oil shale that will yield 10 to 15 gal per ton exist in Germany. Because of the impending loss of the Rumanian and Polish oil fields and the bombing of synthetic liquid fuel plants, the Nazis in 1943 started a large-scale oil-shale program in Germany. By V-E Day, it is said, oil-shale production had reached the rate of 2500 tons per day and rapid expansion of the industry was imminent. Australian oil shale, known as torbanite, occurs in beds 2 to 6 ft thick. It is of a very high grade and on retorting yields 80 to 160 gal per ton. The oil-shale industry of Manchuria was the largest in the world during the past decade. The well-known Fushun coal deposit in Manchuria has an overburden of 500 million tons of oil shale about 450 ft thick that will yield 10 to 15 gal of shale oil per ton. The oil shale is

Jan 1, 1949

By C. G. Dunn, W. W. Martin

Various X ray diffraction techniques have been developed for determining orientations of crystals. Transmission and back-reflection Laue methods1,2,3 in particular have been found to be very useful. In many applications, however, a need still exists for a simplification of the details of analysis so that orientations can be determined more rapidly, and operators with little or no training in crystallography can be easily instructed in the necessary procedures. Filling this need in part is a system of analysis that has been in use for several years in the Metals Section of the Laboratory, General Electric Co., Pittsfield, Mass. This method is an extension of the one of Majima and Togino,4 which uses fifty-five indexed standard transmission Lauemams to cover the entire range of crystal orientations. Greater rapidity in determining the orientation of a crystal is achieved by using a slightly larger set of standard Lauegrams and by systematizing the steps followed. This system of analysis in its present form constitutes the subject matter of the present paper. Although the method uses transmission X ray Laue patterns, many of the operations are applicable to the analysis of back-reflection Lauegrams. Very briefly the method is based on the fact that Bragg and azimuthal angles for two or more identified Laue diffraction spots completely determine the orientation of a crystal, and standard Laue photographs of the Majima and Togino type provide a ready means for identifying Laue spots. After a preliminary analysis, which consists of identifying the pattern in terms of one of the standard patterns, a correctly marked Lauegram is selected to carry out the final analysis. From measured Bragg and azimuthal angles, the normals (poles) of the reflecting planes for the selected Laue spots are located on a stereographic projection and the orient.at.ion of the crystal determined (in terms of the positions of cube poles for example) by a few additional operations on a \I1ulff net. The actual procedure followed will be illustrated in detail after a brief treatment or X ray problems connected with orientation determinations and a discussion of useful principles and techniques. X Ray and Plotting Problems RELATIVE ADVANTAGES OF BACK-REFLECTION AND TRANSMISSION LAUE DIFFRACTION METHODS In the back-reflection Laue method it is easy to make a direct measurement of the tilt of a zone of Laue spots. Specimen thickness also is generally no problem. In the case of thin specimens, however, the time of exposure is less for the transmission Laue method. For example, with silicon ferrite this advantage holds up to a thickness of 0.6 mm if tungsten radiation at 40 kv peak voltage is used. Furthermore, the transmission photograph represents the entire thickness of the crystal whereas the back-reflection picture represents only a surface layer (a thickness of less than 0.05 mm for silicon ferrite), the deeper layers supplying a negligible amount to the diffraction pattern. If a crystal is distorted, the transmission Laue pattern gives more information particularly with regard to the orientation of the crystal and the overall amount of spread in orientation. Finally a 3 1/4 X 4 in. film suffices for transmission photograms; a 4 X 5 in. or 5 X 7 in. film with a central hole is needed for back-reflection patterns Not only is the manipulation of film easier because of the size of film, but

Jan 1, 1950

By A. W. Ruff

In the last ten years large gains have been made in the field of blasting. These gains have been both in the theoretical and in the practical application of explosives. One of the most publicized changes in the practical application of commercial explosives is the now-prevalent use of ammonium nitrate and fuel oil. The new water-compatible mixture of ammonium nitrate and TNT should also have a large field of application. Most of the theoretical gains have been concerned with the actual rock breakage obtained with explosives. In the last ten years, large gains have been made in the field of blasting. These gains have been both in the theoretical and in the practical application of explosives. One of the most publicized changes in the practical application of commercial explosives is the now prevalent use of ammonium nitrate and fuel oil. The new water-compatible mixture of ammonium nitrate and TNT should also have a large field of application. Most of the theoretical gains have been concerned with the actual rock breakage obtained with explosives. EXPANDING-GAS-BUBBLE THEORY There has been an outstanding change in the conception of how an explosive produces rock failure. The early theory which explained rock breakage was correct for some of the first force-producing agents such as quicklime. When a drillhole was filled with quicklime and water added, the material expanded and steam was generated. The expanding material and the steam exerted a slowly increasing pressure on the sides of the drillhole. The force broke the rock by splitting. Because a great quantity of gas was produced by the deflagration of gunpowder, the same process of the gas pressure splitting the rock was assumed to take place. Even after 80 years of use, the rock-breaking action of all high explosives was thought to be caused entirely by the expanding gas bubble which tore and split the rock. Fig. 1 shows a vertical section through an exploding spherical charge of high explosive. It illustrates the early theory which attributed the entire breakage to the expanding gas bubble. The basic idea of this theory is that the breakage started at the explosive charge and progressed toward the free face. REFLECTED-WAVE THEORY me expanding-gas- bubble theory has gradually been replaced by the reflected-wave theory. The reflected-wave theory explains rock failure by explosives in the following manner: The enormously high gas pressure in the drillhole produces fracturing of the rock on the sides of the drillhole. The fracturing around a 1 1/2-in. diam drillhole is usually confined to an area with about a 6-in. diam. In the fractured area, the pressure of the gas is reduced until the force on the walls is no longer capable of fracturing the rock. Although the gas pressure does not continue to fracture the rock, the pressure imposes a high impact stress on the wall rock. In addition, a pressure or seismic pulse is produced in the rock. The pulse is probably entirely a compression pulse when originally produced in the rock. But, with distance, part of the energy of the compression pulse is transformed into a tension pulse which follows the compression pulse. The explosive charges and burdens used in conventional mine blasting are such that the tension pulse of the original wave is probably too small to be considered in a practical evaluation of the theory. The compression pulse is transmitted through the rock with no associated fracturing.

Jan 1, 1961

By E. R. Morgan

A series of manganese-rich ferromagnetic alloys has been studied. The alloys are based upon an interstitial solution of carbon in manganese. In each of the systems investigated, the ferromagnetic phase was found to be face-centered-cubic in structure. This magnetic phase is based upon the composition (Mn, X)4C; where X is a metallic element which has both a positive size factor with respect to manganese and a high positive valence. Typical elements of this type are aluminum, indium, and tin. Preliminary magnetic measurements indicate that the effective magnetic moment of manganese in the alloys is at least 1.0 Bohr magneton per atom. It is emphasized that the critical atomic separation beyond which ferromagnetism can occur will be governed by the electronic configuration of the manganese atoms. Lattice parameter measurements show that the ferromagnetic condition in the present alloys is associated with an increased atomic separation of only 3 to 6 pct compared with a hypothetical face-centered-cubic lattice of pure manganese. MANGANESE which is paramagnetic and not ferromagnetic in the pure state can become ferromagnetic if suitably alloyed. Under favorable conditions manganese can have an effective ferromagnetic moment of the order of 3.41,2 or even 4.0 compared with a moment of 2.2 Bohr magnetons for iron. The incidence of ferromagnetism is believed to be controlled by the degree of atomic separation.4,5 This is consistent with the fact that the atomic separation, when considered in terms of the ratio of the atomic diameter R to the diameter r of the 3d-shell, is larger in the ferromagnetic metals. The values of R/r calculated by Slater,' for metals of the iron group are given in Table I, and Slater has suggested that the critical ratio of R/r is 1.5. Consideration of the criterion of atomic separation alone would suggest that there are three classes of possible ferromagnetic manganese alloys: 1— Ordered structures, of either solution or compound types, such that manganese atoms are not near neighbors; 2—Structures in which the separation of near-neighbor manganese atoms is sufficiently increased by the presence of suitable solute atoms; and 3—Dilute solutions of manganese. Typical ferro- magnetic alloys of types 1 and 2 are the Heusler alloys and Mn4N, respectively. There are no recognized ferromagnetic alloys of type 3. In view of the proximity of the ratio R/r for manganese to the critical ratio of 1.5, the present work was concentrated on manganese-rich alloys rather than on ferromagnetic alloys of low manganese content, several examples of which are already known. Calculation of the distance of closest approach of manganese atoms in each of its allotropic forms, Table 11, indicates that the high temperature ? phase provides the most suitable basis for ferromagnetic alloys of high manganese content. However the high temperature forms of pure manganese cannot be retained on quenching, although a face-centered-tetragonal form apparently can be produced by electrodeposition. Since the critical separation which must be exceeded in order to obtain ferromagnetism is dependent upon the number of electrons in the d-shell, no exact critical value of R/r can be assumed. Not only will this separation vary from one pure metal to another, but it will also vary with the valency of the given type of atom when it is in an alloy. Raynor8 has shown that metals of the iron group probably

Jan 1, 1955

By W. O. Philbrook, K. Natesan

A mathematical model was derived for the temperature change in a particle undergoing heterogeneous chemical reaction and heal exchange with a stream of fluid. The model has been applied specifically to the exothermic oxidation of spherical particles of zinc sulfide. Very good agreement was obtained between the theoretical prediclion and experimental observation. It was found that at no stage of the reaction was the particle subjected to a state of thermal instability. In studies of gas-solid reactions, it is generally assumed that the gaseous and the solid phases are at the same temperature throughout the reaction period. This is not strictly true since most of the reactions are either exothermic or endothermic in nature. This paper deals only with heterogeneous gas-solid reactions of noncatalytic type. In the case of exothermic reactions (e.g., roasting of sulfides), there may result an increase in temperature of the particle due to the release of the heat of reaction, and this increase in temperature may enhance the reaction rate and thus cause further release of heat. Such a "spiralling" effect may lead to a thermally unstable situation within the particle. On the other hand, in the case of endothermic reactions (e.g., calcination of limestone), there may occur a decrease in temperature of the particle as the reaction proceeds, leading to a virtual "quenching" of the reaction front. A general discussion of autothermic processes with emphasis on properties and reactor design is given by Van Heerden. 1 Levesque and cubicciotti 2 observed self heating of the sample in the oxidation of thorium. Anous et al. 3 observed self cooling of the sample in their dehydration studies on chrome alum. Cannon and Denbigh, 4 and Ong et al.5 reported self heating of the sample in their studies of the kinetics of oxidation of zinc sulfide. A typical plot of heat generation and heat loss rates with reaction temperature is shown in Fig. 1.'14 The Sigmoid curve represents the heat generation rate while the straight lines represent the heat loss rate. The main objectives of this analysis are to estimate the temperature increase of a single particle undergoing an exothermic reaction and to study the possibility of a thermally unstable situation within the particle. Also, a study of the dependence of the tempera- ture increase on different process variables has been attempted. A "she ll-by-shell" method has been proposed to analyze the problem. The shells may be made as small as necessary, and equations may be set up for heat transfer by various mechanisms. Such equations will have to be solved for each shell, with the boundary conditions for ith shell being obtained from the (i - 1)th shell, using a high speed digital computer. The oxidation of spherical particles of zinc sulfide is considered for this analysis, but the treatment is general enough to be applicable to other reactions and particle shapes. The oxidation reaction can be written as AH =« -115 kcal/mole ZnS [1] Such a reaction has been found to proceed in a topo-chemical manner; i.e., as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,4-6 that the particle retains its original dimensions. Therefore, at any given time, the particle may be

Jan 1, 1970

By Frank M. Brooks

Endeavoring to meet the requirements of more oil created by the war effort, the oil industry of Kansas in 1944 maintained a level of exploratory and development work well above the average of previous years. During the year, 1866 test wells were drilled, of which 838 were completed as new oil wells, 89 as new gas wells and 939 as dry holes. These figures compare with 895 new oil wells, 32 new gas wells and 834 dry holes for a total of 1761 tests in 1943. Thus, there was a marked decrease in the number of new oil wells, and an increase in the new gas wells and dry holes. The total daily initial potential of production discovered by the successful wells amounted to 494,689 bbl. of oil as compared with 736,297 bbl. in 1943. The increase in unsuccessful tests and decrease in the daily initial potential of production has caused considerable comment and speculation among the oil operators of the state. This tends to confirm the fact that each year it is becoming harder to find the remaining oil fields. The total number of wildcats drilled in Kansas was 651 in 1944, including the so-called "extension wildcats" (more than 1/2 to I mile from known production). Of this number, 410 are classified as "rank wildcats," being more than one mile from production. The total of 651 compares with the total of 577 for 1943, showing an increase in wildcat drilling of 74 test wells: Of these tests, 81 were successful in finding new oil fields or substafitially extending known areas of production, and 20 either found new gas pools or extended old ones. The ratio of dry holes to producing wells among the "rank" wildcats was approximately 10 to I (372 dry and 38 successful). This compares with a ratio of 10 to I in 1943, 11 to I in 1942, and 6 to I in 1941. A compilation of the results obtained by 34 active companies, including all of the major companies, reveals that their efforts accounted for 286 rank wildcat wells, of which-37 found oil or gas, making a dry-hole percentage of 87. Approximately 55 per cent of all, tests (pool and wildcat) were failures. Thc Kansas Nomenclature Committee of the Kansas Geological Society named and classified 43 new oil fields and 8 new gas fields during the year. The discovery wells of the new oil fields had a total initial potential of 18,358 bbl. for a per well average or' 427 bbl. The average initial potential per well in 1942 and 1943 was 894 and 419 bbl., respectively. With nearly all wells producing at their economic capacity, the total production for Kansas during 1944 totaled 101,896,704 bbl., which compares with total runs of 107,709,679 bbl. in 1943. Production of natural gas during 1944 reached a new high record of 135 billion cubic feet. This compares with 122 billion cubic feet for 1943, and 98 1/2 billion cubic feet for 1942. The large Hugoton field of Southwestern Kansas accounted for about half of the total gas produced. Highlights OF the Year Although 51 new fields were found in the state during 1944, it is apparent that the

Jan 1, 1945

By John Johnston

When I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in I9I6—that is, about 25 years ago—in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father— Dr. Samuel Gridley Howe, his mother— Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature, is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-clrbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable. tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass ... by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half-initiated from misusing it and the uninitiated from being misled by these misuses," he writes—and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration: It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. it tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works of the watch was the best butter. If the reader learns no more than to beware of attempts to dccipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

By John Johnston

When I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in I9I6—that is, about 25 years ago—in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father— Dr. Samuel Gridley Howe, his mother— Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature, is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-clrbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable. tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass ... by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half-initiated from misusing it and the uninitiated from being misled by these misuses," he writes—and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration: It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. it tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works of the watch was the best butter. If the reader learns no more than to beware of attempts to dccipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

By F. G. Miller, T. D. Mueller, L. B. Davidson

A mathematical model of reservoir behavior during one cycle of the intermittent steam injection process is presented in this paper. A cycle of the process is considered to be composed of three stages: injection, condensation and production. The model concentrates on behavior during the production stage. The influence of several parameters on production improvement is described, using the results obtained with a numerical equivalent of the model. Reservoir system parameters considered are thickness, reservoir thermal conductivity, oil viscosity, solution gas-oil ratio and the change in oil effective permeability with temperature. Operating parameters investigated are heat injection rate, steam temperature and cumulative injection time. In the face of considerable uncertainty, the model appears to give a fair prediction of the behavior observed during an actual test. This makes the model a useful means of selecting projects. It is shown that the model may also be utilized to select an optimum set of operating conditions for a particular project. Results of this study show the extent to which production improvement depends on each of the parameters investigated and give an indication of the range of system conditions within which the process would be effective. INTRODUCTION In recent years the intermittent steam injection or steam soak process of oil recovery has become a popular method of improving recovery in reservoirs bearing high-viscosity hydrocarbons. Production improvement due to the process results from heating the reservoir near the wellbore. The process is applied on an individual well basis and is executed in a series of cycles, each consisting of three stages: injection, condensation (the soaking period) and production. During the injection stage, high-pressure steam is injected into the reservoir surrounding the well-bore. This study assumes that injection is carried out over the entire vertical section of the reservoir rock that can be exposed to fluid injection. The condition of steam entering the reservoir is considered to fall within the following limits: (1) steam pressures less than 1,000 psig, (2) steam temperatures between 300 and 700F and (3) steam quality less than 90 percent. The last restriction is due to equipment limitations. Normally, injection re maintained for less than 3 weeks. After termination of injection, the condensation stage begins. The well is shut in for several days, supposedly to make certain that the injected steam condenses. This condensation would insure the retention of injected heat. The production stage is initiated when the well is opened again. Reservoir response during this stage determines the effectiveness of the process (response is defined as the oil production rates, the water production rates and the wellbore temperatures observed during the entire production stage). The immediate response of the reservoir is sometimes quite good. Sets of case histories by Longl and by Owens and Suter2 give some typical figures for response. Duration of the production stage is equal to the time needed for the oil production rate to decline to some predetermined value. This usually requires 4 to 6 months. Termination of the production stage coincides with the start of the next cycle. The process is continued, cycle by cycle, until it becomes unprofitable to continue. One simple model2 and two more sophisticated models3,4 of the process have been presented. These are based on fundamentally different assumptions than those used in this investigation. Although the three models might be modified to fit the assumptions used in this study, it is felt that greater rigor would result by developing a

By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide 'pest' ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,' comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

By J. T. Norton, N. J. Grant, I. S., Servi

Coarse grained high purity aluminum was tested in creep at temperatures of 400° to 1200°F to develop subgrain structures. Measurements of subgrain size, distribution, and rotation were made from X-ray diffraction patterns. Subgrain size and distribution were checked metallographically and the size was compared with average slip band spacing. The slip family was determined for several specimens. THE interest and research recently evident abroad in the role of subgrain formation and polygon-ization as a contribution to the creep of metals at elevated temperatures is deserving of greater attention in this country. Such metallic subgrains can be defined as macroblocks existing within the grains. The general observation has been that the macro-blocks which belong to the same grain have a maximum difference in orientation of a few degrees. In spite of the considerable amount of work that has been done since Jenkins and Mellorl observed the "division of existing crystals into smaller units when deformation occurs at an annealing temperature," the subject of subgrain formation is only now receiving truly active discussion and investigation. The existence of subgrains has been revealed by metallographic methods, as in the work of Jenkins and Mellor,1 and by X-ray methods, first applied to this problem by Homes.' Hirst3 and Calnan and Burns4 applied the back-reflection Laue technique to the study of coarse grained specimens. Wood et al.5 and Greenough and Smith' examined the ring obtained with a back-reflection camera for the study of fine grained specimens. In addition to the above, the transmission technique was used by Wood.6 A special technique was developed by Guinier and Tennevin8 in order to improve the resolution. Metallographically, the subgrains have been observed directly on the surface of deformed specimens by Wood et al.,3 or have been made evident on repolished surfaces by applying a suitable etching reagent. The latter technique, first suggested by Lacombe and Beaujard,9 was then improved by Wyon and Crussard.10 Subgrains can be formed in single crystals after small amounts of bending followed by heating after this cold work, or during deformation at elevated temperatures. The first phenomenon was analyzed by Cahn11 for the simple case of pure bending followed by annealing. Cahn suggested a mechanism of subgrain formation based on the dislocation theory and called this phenomenon "polygonization." He extended this mechanism to the more complex case of local bending, such as the bending which may occur when a polycrystalline specimen is deformed in tension. Cahn's suggestion was later found quite consistent with the results obtained by Dunn and Daniels." An explanation has been presented recently regarding the formation of subgrains during deformation at elevated temperatures by Chang and Grant.'" In general, there are two schools of thought on the subject. One, according to Wood et al.,5 is that subgrain formation is a mechanism of deformation which is operative under certain conditions in the same way that the slip process is the mechanism of deformation which is operative under other conditions. The boundaries between the subgrains undergo a viscous flow which contributes substantially to the deformation of the material. The second, according to Cahn,13 Wyon and Crussard,10 and Chang and Grant,18 is that subgrain formation is the effect of simultaneous deformation and annealing and is,

Jan 1, 1953

By L. G. Jones

An approximate method of calculation is developed in this paper which allows duplication of radial unsteady-state gas flow computer results where Darcy's law applies, such as those reported by Aronofsky and Jenkins and Bruce, Peaceman, Rachford, and Rice. Moreover, the new calculation method can be used to obtain results for radial unsteady-state gas flow obeying the quadratic flow law proposed by Duwez and Green. Means are discussed for predicting well behavior at single or superimposed flow rates in finite or infinite reservoirs, determining reservoir rock properties from well-test data, reproducing and interpreting back-pressure test data, and determining the radial extent and reserves of gas reservoirs from well-test data. Example calculations are presented for gas flow following both Darcy's law and the quadratic flow law. INTRODUCTION Since the publishing of U. S. Bureau of Mines Monograph 7,1 most gas-well testing methods have been based on the equation q = y (pl2 - pw2)a, where q = production rate, pl and pw, are formation pressure and sandface pressure, respectively, and y and a are constants to be obtained from test data. These methods, used for predicting both deliverability and "open-flow" capacity of gas wells, have been useful and accurate in many cases but unsatisfactory in others. Even at best, however, they do not supply information about the formation or lead to an understanding of nonsteady-state gas flow in porous media. Many theoretically based studies2-4 of gas flow obeying Darcy's law have been made.' Since the partial differential equations which result from combining Darcy's flow law with the continuity equation are nonlinear, most of the published research consists of either numerical solutions or analytical solutions for linear approximating equations. Such solutions have been of limited value in field work due to their unhandy form and their failure to correlate most field data. There is evidence5,6 which indicates that Darcy's law is inadequate to describe gas flow at some flow rates of practical interest. A quadratic flow law: which reduces to Darcy's law at low rates, is more successful in accounting for experimentally observed behavior. This flow law has been applied successfully to a few hypothetical reservoir cases in work which has recently been published.10 However, these numerical solutions of the equations involved have been successful only on a special analog computer. Routine applications to field cases would be awkward and have not been attempted. The present paper describes an approximate method for computing nonsteady-state gas flow solutions which has been completely successful in predicting the results for both Darcy flow and quadratic flow obtained by elaborate numerical methods. The new calculation method allows determination of the observable variables in gas-well testing at constant rates. It is similar to the scheme of using a succession of steady states suggested by Muskat7 in that it makes use of steady-state and material-balance equations. It also is similar to the work of Aronofsky and Jenkins2 in that the new method includes Aronofsky and Jenkins' stabilized flow equation as a special case. It improves upon both of these calculation schemes in that it accurately describes all portions of reservoir history and suggests means of determining reservoir rock properties from well-test data. This paper deals only with production from a reservoir, in which case the rate is defined as being negative. The reservoir studied here is a homogeneous, disk-shaped porous body of uniform thickness, with all boundaries sealed except the inner radial boundary of the well.

By Ihor A. Kunasz

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

Jan 1, 1975

By S. J. Rothman, J. J. Hines, D. Rokop, R. Bastar

Self-diffusion has been measured along each principal axis of mosaic-structured and relatively perfect a uvaniuln single crystals. The anisotropy reported before,' D[loo] = D[001] » D[010 , has been confirmed. and is shown to represent volume diffusion. Diffusion along the dislocations in the imperfect crystals increases the measured value of D significantly without changingr either the shapes of the penetvation plots or the anisotropy. SINCE a uranium is orthorhombic, the diffusion coefficients along the principal crystallographic axes need not be equal. A previous measurement of self-diffusion in three mosaic-structured a uranium single crystals1 showed that Dil00| =D[001 >>D[010 This result was deduced from penetration plots similar to those in Fig. 1. That is, the plots for diffusion along [loo] and [001] were the straight lines expected from the solution of the diffusion equation for the boundary and initial conditions of the experiment, while the plot for diffusion along [010] was curved so that the part near X = 0 had a much steeper slope than the straight lines did. The observed anisotropy could have been due either to volume diffusion or to diffusion along the very large number of dislocations in such crystals, according to the model proposed by aart.' The authors of Ref. 1 argued that the latter possibility was unlikely, but did not exclude it. To settle the question, a simultaneous measurement of self-diffusion in mosaic-structured and mosaic-free crystals was carried out. This paper reports the results, as well as a measurement of the temperature dependence of self-diffusion in a uranium. EXPERIMENTAL The single crystals of a uranium used in this experiment are listed in Table I, together with other experimental details. '(Mosaic structured" here means crystals grown by solid-state phase change.3 The Laue spots from such crystals spread over about 6 deg of arc, which indicates that the density of dislocations is very large. "Perfect" crystals are ones grown by Fisher's grain-coarsening tehnique; the Laue spots from these are quite sharp,4 which shows that the dislocation density in these crystals is much lower. All of the crystals were made from high-purity uranium; a typical analysis is given in Ref. 1. The actual diffusion directions were within a few degrees of the nominal. The thin layer-sectioning method was used. The experimental techniques were similar to those described in Ref. 1, except the sectioning. Crystals Za, 2b, 2c, 4a, 4b, and 4c were sectioned on a lathe. Crystals 3a, 3b, and 3c were sectioned by grinding on glass plates, with 1 p diamond powder in butyl alcohol as the abrasive. The use of glass plates eliminated the crowning noted in Ref. 1, and the use of butyl alcohol as a lubricant simplified the chemical processing of the sections. Material from the sides of these three crystals was removed by spark machining before sectioning. The sectioning of crystals 4a and 4c was botched. A small cylinder of metal was extruded from the center of crystal 4a while turning off material from the side of the sample. Crystal 4c was misaligned by 2.1 x 10"3 cm because the dial gage jammed during the alignment. Notwithstanding these errors, useful data were still obtained from these crystals. The points

Jan 1, 1967

By H. H. Rachford

This work presents a first-order analysis of the instability underlying viscous fingering in adverse viscosity-ratio water floods. It extends previous analyses of frontal instabilities, which were carried out with equations for parallel plate models, by including effects of the saturation transition zone observed behind the front in water floods in water wet systems. This zone tends to insulate incipient fingers from the high-mobility watet;. thus conditions for the onset of fingering differ from those in the parallel plate theory. Finite-difference solutions of the two-dimensional equations of displacement in porous media exhibited the predicted stability characteristics in six hypothetical field- and laboratory-scale floods in rectangular reservoirs. In contrast to results with parallel plate systems, this paper concludes that for waterwet reservoirs, laboratory models scaled by the usual criteria are also correctly scaled for frontal instability. Further, fingering in the systems studied can occur in any saturation range behind the front, and may occur at an intermediate saturation even though stability obtains both at the saturation corresponding to the Buckley-Leverett front and near residual oil saturation. Other points of contrast are that the likelihood of occurrence of fingering may not increase as flow rate or viscosity difference increases, but my be sensitive to changes in he relative permealdlity and capillary pressure functions. INTRODUCTION The recovery of oil by water flooding frequently involves displacing the oil by water of a lower viscosity. Displacement of a fluid by a less viscous one may lead to gross channeling or fingering like that observed in solvent floods, in which it severely lowers recovery efficiency.1 In addition to adverse effects on recovery, it has been suggested that the unstable move- ment causing fingering may interfere with interpretation of scaled model studies of proposed water floods, since the instability in the model might not be faithfully scaled to that in the reservoir prototype. In view of the serious implications of this possible breakdown of widely used scaled model techniques4-6 it is the purpose of this paper to examine the question further. Instabilities in the solutions of systems of differential equations imply a loss of smooth dependence on initial and boundary conditions. Thus, the possibility exists that in using models whose scaling is based on the differential system there may arise size- and rate-dependent factors which are not properly scaled. This possibility was examined in detail by Chouke et al., who analyzed the instability of frontal advance in a related problem, water-oil displacement in parallel plate models,2 in which a moving interface separates two regions of constant, unequal mobilities. First-order perturbation theory predicts the existence of a critical wave length for the growth of perturbations: and a wave length of maximum instability of A, = The interpretation is that wave lengths in a perturbation which are longer than A, will grow. Thus, if the width of a two-dimensional channel is greater than A,, fingers will grow, and the spacing of the fingers which grow at the maximum rate will be approximately It is important that the higher the velocity and/or the difference in flow resistance, the lower is A,, and thus the greater the number of fingers that can grow in a given model. In applying these conclusions to porous media, a pseudo-interfacial tension, , was assumed for the invasion front. Since this would not necessarily be equal to the liquid-liquid interfacial tension, an unknown constant was substituted for the foregoing expression for A, This was determined

Jan 1, 1965

By J. B. Newkirk

IN 1939 Bitter and Kaufmann1 suggested that iron, precipitating from a copper-rich, Cu-Fe solid solution, appears initially as coherent particles of r-Fe which transform to the body-centered-cubic form of iron when the alloy is cold worked. Since then there has been considerable discussion, supported only by indirect evidence, regarding the validity of the concept. For example, Reekie, Hutchison, and Hether-ington2 interpreted the changes in electrical resistance accompanying the aging of Cu-Fe specimens in terms of a coherent 7-Fe precipitate which transformed to the incoherent a-phase during long aging or cold working. Greninger- ound that Cu-Fe alloys which had been water quenched from 1050" and then held at 650°C for 3 hr changed from weakly to strongly ferromagnetic as the aged wire was subsequently cold worked. He also found diffraction lines corresponding to body-centered-cubic iron in Debye-Scherrer patterns given by aged and worked specimens but lines corresponding to only one face-centered-cubic phase in specimens which had been aged but not worked. Knoppwost,' and later Cech and Turnbull,5 found that aged Cu-Fe specimens showed a slight increase in ferromagnet-ism after they had be? cooled in liquid nitrogen. Very recently Denney6 followed the kinetics of the precipitation reaction as indicated by the saturation magnetization, hardness, and diffuse X-ray effects. The experimental results reported by all of the authors mentioned above are readily explained in terms of the Bitter and Kaufmann concept. However, most of the evidence is indirect when used to define the structural changes involved. It was the aim of the present investigation to determine the mechanism of precipitation of iron from a Cu-Fe solid solution in the light of available published information and with additional new and more direct experimental data. Experimental Method At 1060°C copper will contain up to 3 atomic pct Fe in equilibrium solid solution.7 The solvus slopes rapidly toward lower iron concentration, so that at 600°C only about 0.5 pct Fe remains in solution at equilibrium. Below the eutectoid temperature (850°C), the iron-rich phase in equilibrium with the copper-rich solid solution consists of body-centered-cubic a-Fe. Above 850 °C the equilibrium iron-rich phase is face-centered-cubic r-Fe. The alloy to be studied was made by melting electrolytic iron and OFHC copper by induction under vacuum in an Alundum-lined crucible. The metal was held molten for about 5 min, after which time the power was turned off and the crucible was tipped about 70" to promote directional solidification. The resulting ingot, containing 2.5 wt pct Fe by analysis, was clean, large grained, and free of gross segregation. Slices % in. thick were cut from the ingot, rolled to 1/8 in. in thickness, homogenized in hydrogen at 1060°C for 24 hr and, finally, quenched in cold water. Specimens for all subsequent tests were made from these slices. Squares measuring about 1 cm on a side were cut from the slices to make specimens for studying hardness and microstructure. Wires (0.020 in.) for the Debye-Scherrer survey were drawn from 1/8 in. sq rods which had been cut from the homogenized slices. Large crystals for observing diffuse X-ray diffraction effects were prepared by mechanically

Jan 1, 1958

By P. E. Baker

Approximate solutions are presented for the heat-flow equations in a loss-free linear system with a moving source and with heat transfer by convection and conduction, representing in situ combustion in an oil reservoir. The rate of heat generation and the velocity vf of the source (flame front) are assumed constant. A cold front or convection front caused by the cooling effect of in-jected air develops behind the flame front and moves with velocity vc, which is determined by the thermal properties of the air and rock. Because of thermal conduction the fronts are not sharp; i.e., they do not represent temperature discontinuities. The following solutions apply after a sufficiently long time. where Q is heat generated per unit volume of formation, k is thermal conductivity, CF is volumetric heat capacity, a is thermal diffusivity, and subscripts 1 and 2 refer to values behind and ahead of the flame front, respectively. The parameter CF2 is contained in v . Te is initial reservoir temper- . C2 e ature and air-injection temperature. Other mathematically possible solutions are presented. The different solutions result from the use of different values for various physical parameters. The solution just presented is thought to be most commonly applicable. INTRODUCTION In this paper, approximate analytical expressions are derived for the temperature profile developed in the underground combustion method of oil recovery. A qualitative description of the process may be found in a paper by Tadema.1 The flame front is regarded as a moving source with a constant rate of heat generation. Heat transfer is by conduction and convection. Previous publications, of which a few are cited here, 2-5 have also attacked this problem and have presented solutions pertaining to different methods of approximating or idealizing the process studied. The present paper also treats an idealized case: linear flow is assumed for heat and fluids, and vaporization and condensation effects are neglected. The results obtained are similar to those derived by Bailey and Larkin,3 but are obtained by an entirely different procedure. The method used here should give considerably greater insight into the physics of the in situ combustion process. Four types of cases are considered, distinguished by thermal and fluid-flow properties of the system. A constant rate of heat generation and constant rate of flame-front advance are assumed. Flame-front temperature is determined for each case using a heat balance which involves the entire temperature profile. The applicability of the different solutions to real systems is discussed after they are all presented. Again, this is done for the purpose of understanding better the physics of the process. Consideration of the nonapplicable solutions and of the reasons for their not applying is significant. In a paper by Cooperman,4 the only case solved is one considered here as not applicable. Fluid flow, as such (pressures, saturations, oil recovery, etc.), is not treated. This subject has been covered in a paper by Wilson, et al.6 Also, we are not concerned with requirements for continuance of the process; we only attempt to determine the temperature history for cases where the process has continued for some time. PHYSICAL SYSTEM AND APPROACH TO PROBLEM A linear flow (heat and fluid) system is assumed and the x-axis is taken parallel to the flow direction. The combustion zone (flame front) is vertical,