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By A. Satter

Studies of wellbore heat transtnission during the injection of a hot fluid, as either gas or liquid, have appeared in he literature. The present investigation takes into account the effect of condensation, which is of practical sig-nificance when considering steam injection operations. Calculation procedures are given for superheated and for saturated and undersaturated steam. Effects of injection rate, time, pressure, temperature and depth of a well on heat losses have been analyzed. The benefits of using a packer are discussed. Also presented are correlations for estimating heat losses involved during injection of saturated steam. INTRODUCTION Studies of wellbore heat losses during the injection of a hot fluid have appeared in the literature. Ramey' has presented a useful solution for calculating temperature of a heated gas as a function of depth and injection time. Ramey and others have also presented solutions for the hot liquid case.'. ' No method is available to take into account the effect of condensation, which is of practical significance when considering steam injection operations. This paper presents a method of estimating the quality of a condensing fluid as a function of depth and time. The approach is basically the same as that used by Ramey. The following injected fluids and conditions are considered in this study: 1. Injection of superheated steam A. Decrease in temperature until cooled to the saturated state B. Condensation until condensed completely into hot (saturated) water 2. Injection of saturated or undersaturated steam; condensation until condensed completely into hot (saturated) water. Although this investigation does not include cooling of water after steam is completely condensed, Ramey's solution for the hot liquid case can be used for this purpose. The effects of various process variables on heat losses During the injection of steam into a well are investigated. THEORY QUALITY OF CONDENSING STEAM Predicting the behavior of condensing steam flowing down the injection wellbore requires an estimate of the quality of steam, i.e., the mass fraction of vapor in the mixture. Let us divide the total depth of the injection well into several segments which might be, but do not have to be, of equal magnitude. Consider condensation within a given depth interval AZ, the bottom of which is located at a depth Z from the surface (Fig 1). The following equation, derived in the Appendix- relates the quality of steam at the bottom of an interval to that at the top of the interval:

Jan 1, 1966

By A. L. Fentress, P. R. Bucky

The purpose of this paper is to present a scientific method for determining the proper span and shape of roof for safe and economical mining; at present, these two vital factors wherever pillars are left to support the roof are determined by local practice or general experience. To develop the method described here, experimental laboratory work was done. The arch adopted was a segment of a circle, a flat roof being considered an arch with an infinite radius. Hitherto, arches have been used underground without the background of stress analysis that generally precedes arch construction on the surface. In many cases results have not been as expected, because of the lack of knowledge of the factors affecting its strength and behavior. A theoretical and experimental study of arches should furnish information that will make it possible to design safe and economical surface structures as well as underground openings. For example, on the subject of mine drifts and tunnels, the present idea is that arching their backs increases their strength; this paper will indicate that this is not always true, and if it can be shown that under certain conditions arching becomes unnecessary an economic saving will result. In room-and-pillar work a question may arise as to whether arching the roof and gobbing the excavated material will result in timber saving, and a decrease in the dangers from falls of roof. It is to be distinctly understood that each mine must be treated as an individual problem, and that answers to these questions and many others can now be found after experimental laboratory data have been obtained. Mine-Arch Structure Fig. 1 shows the elements that affect the strength or behavior of the experimental arch. They are the span, crown thickness, radius of curvature, rise and restraint. The restraint in all cases was made sufficient to cause the arch to fail without displacing the restraining sides. Fig. 2a is a photograph of a model arch prepared for testing in the centri-

Jan 1, 1934

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By Strathmore R. B. Cooke, Iwao Iwasaki, C. S. Chang

The effects of aeration on an aqueous suspension of pyrrhotite were studied and their results correlated with flotation tests using xanthates as collectors. The effects of copper activation and of pH variation were determined and possible mechanisms postulated. PYRRHOTITE has long been considered a gangue mineral to be eliminated as tailing in the treatment of various sulphide ores. However, in recent years the world-wide lack of sulphur resources has called attention to this mineral as a potential source of both sulphur and iron. Its importance as an economic mineral, however, has not been particularly emphasized. For this reason very little is known about its response to flotation, except that it can be depressed easily in alkaline circuit, by long aeration,1,2 addition of oxidizing agents,3 or by starch.' The object of this work was to study the floatabil-ity of pyrrhotite. This includes the effect of oxidation by aeration, of copper activation, and of change in pH. Preparation of the Pyrrhotite Sample: It was desirable that the highest grade of pyrrhotite obtainable be used for this experiment, since the presence of other minerals could affect the surface properties.5 However, no pyrrhotite was available as crystals, and massive deposits of hydrothermal origin commonly contain considerable amounts of chalcopyrite. Pyrrhotite concentrate was, therefore, prepared from a sulphide deposit occurring near Aitkin, Minn. The deposit is of pyrometamorphic nature consistirlg mainly of pyrrhotite and pyrite with graphite, silicates, and carbonates as gangue. The ore, already crushed through 3 mesh when received, was screened at 65 mesh and the undersize discarded. The oversize was crushed through rolls, and then stage-ground dry in an Abbe porcelain mill, the —65 mesh portion being screened out after every 15 min of grinding until all the material passed through this size. The ground product was then concentrated with a drum-type dry magnetic separator. The rougher concentrate was cleaned twice and then demagnetized. The final product was split in a Jones splitter and stored in air-tight bottles. Microscopic examination of the concentrate showed that it was relatively clean and free of pyrite, locked particles, and gangue. By means of the krypton gas adsorption method," the specific surface was determined to be 3000 cm2 per g. The chemical and screen analyses of the final concentrate are given in Tables I and II respectively. It is a well-recognized fact that the oxidation of some sulphide ores during stockpiling, grinding, and conditioning affects their flotation behavior. The problem of oxidation may become serious in the case of pyrrhotite, since this is known to be more easily oxidized than many other sulphides. To ascertain the extent of oxidation, an experiment was carried out by aerating an aqueous suspension of pyrrhotite with air, oxygen, and nitrogen as follows. A 300-g sample of pyrrhotite in 2700 ml of water was agitated and simultaneously aerated in a Fager-gren-type laboratory flotation machine. A Precision wet test meter was connected to the air inlet valve, the flow rate of the gas being kept constant at 0.3 cu ft per min throughout the experiment. Samples of approximately 30 ml each were taken from the cell at 0, 4, 10, 20, 35, 60, and 90 min. After the pH was taken, each sample was filtered and the filtrate was analyzed for total iron and sulphur. The iron was determined colorimetrically by the thioglycolate method using a green filter.' The filtrate was oxidized with bromine to convert all of the soluble sulphur compounds into sulphate and this was determined with a Parr turbidimeter." When aeration tests were made in alkaline circuit, calcium hydroxide or sodium hydroxide was added at regular intervals to maintain a constant pH. A similar procedure was followed in an experiment to determine the abstraction of copper. ion by pyrrhotite. In this case various quantities of cupric chloride were added. The filtrate from each sample taken was analyzed for copper, total iron, and sulphur. The carbamate method with a green filter was used for the copper analysis,' since this method could tolerate a considerable amount of iron in the solution. A pneumatic cell, made from a 350-ml fritted glass Buechner funnel, was used for this experiment. The detail of the assemblage has been described elsewhere." In the present work a stainless steel baffle was inserted in the cell. This baffle overcame the tendency for the coarse pyrrhotite particles to be swirled around the wall of the cell and thus fail to collect in the froth. A 50-g sample of pyrrhotite was added to the cell which contained 260 ml of water. When pretreat-ment of the sample was desired, reagents, such as activator and pH regulator, were then added and the pulp was conditioned for a specified conditioning time. Prior to the addition of the collector approximately 15 ml of the solution were removed for pH measurement and for iron and sulphur analyses. Copper when used as activator was also determined. Collector and frother were then added and the pulp was conditioned for an additional 2 min. Air was admitted to the cell and the froth removed. The separation required from 4 to 6 min, depending on the characteristics of the froth. The float and non-float products were filtered, dried, weighed, and assayed for iron.

Jan 1, 1955

By Frederick Laist

THE object of the construction and operation of the 80-ton leaching plant was to test out the leaching of sand tailings on a large scale and, if possible, determine a definite method of operation, and the best construction for the larger unit which is now being built. It was also of importance to obtain some practical data as regards cost items. The 80-ton plant was not expected to be a commercial success. A leaching process on such low-grade material necessitates the treatment of a very large tonnage.. Such a cost item as labor, for instance, is entirely out of proportion in such a small plant. The amounts of acid, salt, scrap iron, and fuel for roasting, however, are the same per ton in an 80-ton plant as in a 2,000-ton plant. These costs were definitely established. Also the percentages of extraction and grade of tailings were definitely determined for a large-sized unit. Following will be found the description of the plant, the method of operation and the results obtained. A -general view of the plant is given in Fig. 1. The bins consisted of one coal bin with a capacity of 30 tons, one salt bin with a capacity of 20 tons, and a "mill tailings" or feed bin which held 70 tons. The coal and salt bins were placed with their floor level even with the firing floor of the roasting furnace. The feed bin, to give it greater capacity, discharged about 12 ft. below this point, to a 12-in. conveyor belt, which, in turn discharged into a pug mill. This fed another conveyor belt, which discharged into the top hearth of the furnace. The furnace was an ordinary six-hearth MacDougall roaster, .20-ft. in diameter. It was equipped with two fire boxes, on opposite sides, the flames entering on the third hearth. An induced draft was obtained with a Buffalo blower, worked as an exhaust fan. Just above the top hearth was an annular flue around the whole circumference of the furnace. Slots at intervals of about 18 in. led from this flue down into the top hearth. The slots were 2 in. wide by 6 in. long. This annular flue proved rather unsatisfactory, as it tended to fill up with flue dust and choke the slots, thus cutting down the draft. The volume of gas through

Jan 8, 1914

By John R. Low

A number of cases of low-temperature, intergranu2ar brittle fracture of metals containing small amounts of certain impurities, have now been identified. Some degree of understanding of this phenomenon exists for the simpler binary systems of a metal and a single impurity, but the profound effects of other impurities and alloying elements in modifying this type of behavior remain unexplained. Current research in this area is reviewed and some of the newer techniques of investigation which should make possible a more quantitative study of the structure and composition of grain boundaries in impure metals are described. To indicate the subject matter of this lecture, we may begin by reviewing the experimental observations concerning low-temperature intergranular brittleness in impure metals, particularly those examples in which the embrittlement appears to result from what has been called "equilibrium grain boundary segregation."' These are the systems in which it has been impossible, at least up to now, to detect the presence of any second phase film at the brittle interfaces. When second phase films are present they are usually readily detectable by fractographic methods, often appearing as epitaxial films in geometric or dendritic patterns. An example is shown in Fig. 1 for the case grain boundary carbides in a sensitized stainless steel which failed by intergranular brittle fracture at 78?k2 In contrast to this type of embrittlement there are numerous examples of low-temperature intergranular embrittlement in which the fractographs are essentially featureless, for example, that of an oxygen-embrittled iron shown in Fig. 2. The only second phase particles visible are the small, widely separated, round oxide particles typical of the bulk material. The fracture surface is extremely smooth and the fracture path appears to follow the intergranular interface without deviation. This type of fractograph also implies that crack propagation has occurred without plastic deformation at the crack tip, since localized slip or twinning ahead of the crack would be expected to distort the interface and be readily visible in the fractograph. Such indications are occasionally seen in these fractographs, but are not characteristic. A second example of this type of fractograph is shown in Fig. 3, which is from a temper-embrittled, carbon-free, Fe-Cr-Ni alloy containing Sb, broken at 1OO?C.3 The similarity to the oxygen embrittled iron case will be apparent. In the case of the temper embrittled Cr-Ni ferrite containing antimony, it is possible to remove the embrittlement by suitable thermal treatment. The grain boundaries may then be examined by thin film transmission in the electron microscope for the material in both the nonembrittled condition and in the embrittled condition. Two boundaries are shown in dark-field transmission in Fig. 4, one in the nonembrittled

Jan 1, 1970

By Roy J. Greenfield, Charles H. Stoyer

A geophysical survey was made in Kylertown, Pa., in an area where the ground water is polluted with acid mine drainage. Since acid mine water is a good electrical conductor, both direct-current electrical and electromagnetic loop methods were examined for their ability to determine the subsurface electrical conductivity structure and from this to imply the location of the acid water. Consistent results were obtained with the two methods and the interpreted subsurface resistivities were consistent with the electrical resistivity measured for water samples. It was demonstrated that fracture traces which act as conduits for ground water flow can be located with electromagnetic surveying methods. Thus geophysical methods for measuring subsurface electtrical resistivity can be used to advantage for monitoring the environmental impact on the ground-water system of acid mine water.

Jan 1, 1977

By Arthur Notman

SacRamento Hill is a mass of granite porphyry intruded along a fault between Paleozoic sediments and pre-Cambrian schists in the Bisbee district, Cochise County, Arizona. The intrusion invaded both walls of the fault to a large extent, and the accompanying extensive mineralization of the Paleozoic limestones is the locus of the great high-grade copper orebodies of the Bisbee mines. Prior to 1909, although the presence of ore in the masa of the hill itself had long been suspected, systematic exploration had not been attempted. A few shallow pits on the surface here and there had disclosed some chal-cocite with associated carbonates as stringers in a mass of strongly brccciated, silicified, and iron-stained porphyry. The workings in the surrounding limestones had penetrated the porphyry in a dozen or SO places for some distance from the contact but had disclosed no ore. However, the rock had been largely altered to quartz and sericite and very thoroughly impregnated with pyrite and traces of the copper sulphides. A close geological study of the conditions, both surface and underground, strengthened these suspicions, and plans for prospecting the hill were made in 1909. Reference to the accompanying illustrations, Figs. 1 and 2, will give an idea of the general appearance of the surface. The mineralization is more intense in two main zones, one at the west end and the other at the east end of the hill. The outcrop of the hill is elliptical and approximately 3,000 ft. long by 1,400 ft. wide. The Sacramento shaft, which is the main hoisting shaft of the mine and situated at the east end of the hill, as shown by the accompanying map (Fig. 3), offered a convenient base for prospecting that end of the hill, while the workings from the Holbrook shaft offered a similar opportunity at the west end. The choice of level for the first work was determined by analogy with the most favorable depth for enrichment below surface obscrved in the other disseminated deposits of the Southwest.

Jan 1, 1916

By Richard L. Ash

7.3-1. Introduction. All phases of mining competent materials are affected directly by the results achieved from primary blasts. It is imperative that their design suit each particular set of mining conditions. In general, the round design must provide an adequate tonnage of material, properly placed with suitable fragmentation, to ensure that loading, haulage, and subsequent disposal or processing are accomplished at the lowest possible cost. Blasting rounds are designed by the proper application of cratering relationships developed for the single, concentric, confined explosive charge. Blasting for surface mining and most open-cut heavy construction, however, is characterized by the use of rounds, composed of a number of explosive charges with relatively long lengths, which are placed in benches with specific finite dimensions. Therefore, modifications must be made to the classical, single point-charge cratering concepts. It is the purpose of this discussion to outline the basic principles, significant variables, and procedures for their integration in the design of rounds that are applicable to conditions characteristic of surface mining. Because relatively insensitive blasting agents will be used in most instances, particular attention must be given to priming, control of confinement, and selection of charge diameters that ensure complete explosive-reaction execution. 7.3-2. General Considerations. The primary requisites for any blasting round are that it ensure optimum results for existing operating conditions, possess adequate flexibility, and be relatively simple to employ. It is important that the relative arrangement of blastholes within a round be properly balanced to take advantage of the energy released by the explosives and the specific properties of the materials being blasted. There are also environ- mental and operational factors peculiar to each mine that will limit the choice of blasting patterns.

Jan 1, 1968

By C. B. Clark, W. H. Bruckner

Since the end of World War II interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Mun-roe more than 50 years ago (in 1888). Details of their design have been explained elsewhere.1,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense Pressures exerted when the explosive charge is detonated. Among the conclusions reached in research On shaped explosive charges, the following have been established concerning cavity liners:1'2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the 'One as well as On the base diameter of the charge. Acute apex angles require thinner walls for optimum perfmnance and more obtuse angles require thicker walls for the same base diameter' 2. Cones were more effective in forming a penetrating jet when the walls were tapered; that is, the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical properties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, tensile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2, Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45° cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1949

By C. B. Clark, W. H. Bruckner

Since the end of World War II interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Mun-roe more than 50 years ago (in 1888). Details of their design have been explained elsewhere.1,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense Pressures exerted when the explosive charge is detonated. Among the conclusions reached in research On shaped explosive charges, the following have been established concerning cavity liners:1'2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the 'One as well as On the base diameter of the charge. Acute apex angles require thinner walls for optimum perfmnance and more obtuse angles require thicker walls for the same base diameter' 2. Cones were more effective in forming a penetrating jet when the walls were tapered; that is, the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical properties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, tensile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2, Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45° cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1949

By R. J. Wasilewski

THERMAL expansion of rhenium data have been reported by Agte et al.,&apos; and Medoff and cadoff,&apos; respectively, while the linear expansion coefficient was determined by Sims et Al.3 Denoting expansion coefficients parallel and at right angle to c axis by all and Al respectively, their weighted mean should be equal to dilatometric linear coefficient of a random polycrystalline specimen. The values reported for these coefficients are tabulated below: Since these values are in poor agreement, and because of anomalous expansion behavior observed in titanium 4 and chromium, a rede termination of the axial expansion was carried out. A Unicam 19-cm-diam high-temperature camera was used, with unfiltered CuK radiation. Camera calibration was carried out using at Pt wire standarde at temperatures up to 1100oC, the variation between indicated and true temperature being within the experimental error (estimated at <3oC) above 750o C. Rhenium Johnson Matthey spectrographic standard) was vacuum annealed at 1000 oC prior to X-ray diffraction experiments. Lattice parameters were obtained by least-squares solution using the reflec- tions (1232), (1015), (2024), and (3030) for all the patterns, and the additional reflection (2133) for higher temperature (400°C and above) patterns. The relative expansion data obtained are shown in Fig. 1, lengths of the vertical bars indicating the spread in the parameter values obtained by using various combinations of three spacings from the four or five measured. The data calculated from the equation of Ref. 2 are included for comparison purposes. Several specimens were used to obtain the above data, neither of them showing a significant parameter change after completion of the high temperature runs. Some parameter data and the corresponding expansion coefficients between 25 oC and the measurement temperature are tabulated below. The comparison of the present data with those previously reported shows reasonable agreement with the results of Medoff and cadoff2 within the temperature range covered by them (up to 1000 oC). The a values are appreciably higher throughout most of the investigated temperature range. The basal expansion is—in agreement with their findings—appreciably higher than that in the direction of hexagonal axis. The expansion coefficient, al, however, decreases rather more slowly with temperature than previously reported. The expansion along the c axis up to nearly 1000°C appears in excellent agreement. However, at higher temperatures there is a marked deviation towards higher expansion, reproducible between different specimens. Furthermore, there seems to be some irregularity in the variation of all with temperature, the apparent local minimum and maximum values at 510o and 1024o C, Table II, being well outside the experimental error limits. It must be stressed that the apparent discontinuity in the c parameter expansion is still insufficient to account for the expansion value reported by Agte et al.&apos; since a total expansion of close to 2 pct would

Jan 1, 1962

By J. P. Myers, A. H. Flagg, E. S. Mardock, J. L. P. Campbell, J. M. Terry

The development process for the use of radioactive tracers as a means of locating zones of permeability is discussed. The general techniques for the safe handling of radioactive materials is given as developed by the Lane-Wells Co. and Well Surveys, Inc. The prob1em and. successes with tracers in waterflood systetns, oil and gas injection profiles, fracture sand tracing, squeeze (ement tracing. lost circulution, and cement top localion are discussed and illustrated. INTRODUCTION The exact location of the permeable zones lying within the productive horizon has been a major problem faced by the petroleum engineer for decades, and it has been a problem which has seldom been solved with certainty. Reservoir engineers usually have to incorporate a question mark in their estimates of future reservoir performance because of blanks in the core data. Although the use of radioactivity or electrical logs for the estimation of porosity has been of great assistance in furnishing a record for the reservoir engineer, this application of logging data has not completely solved the problem. In short, the industry needs an in-situ well surveying method which can locate and estimate the permeability of the zones existing within a given pay section. The initial development work with radioactive tracers has been towards filling the need for permeability information. Progress to date permits the location of permeable zones with a qualitative estimate of their relative importance with respect to permeability. The calibration of the method is still incomplete. but present development work on tracer preparations, borehole effect correction factors, and instrument limitations give a promise of quantitative "permeability profiles" in the near future. The development work on the radioactive tracer method discussed here began several years ago in the laboratories of Well Surveys, Inc., in Tulsa. At the outset of this work, three approaches to the problem were visualized as follows: 1. A fluid carrying a soluble, chemically inert, gamma ray emitting isotope is pumped down the borehole and out into the permeable zones of the formation. The greater gamma activity of the permeable zones thus permits them to be differentiated from the impermeable zones which contain no active tracer. It was found difficult to obtain a tracer material which was chemically inert. Absorption to some degree was noted in all experiments. Also, it proved impossible to hold the tracer near the horehole where it could be logged. 2. A fluid carrying a soluble, gamma ray emitting isotope is pumped down the borehole into the permeable formations. In contrast with proposal 1, above. the tracer is chemically active with the fluids and materials in the pore spaces of the permeable zones. The permeable zones are thus indicated by their higher radioactivity level. The main difficulty in this proposal was finding a tracer material which would not be absorbed by shale as well as in the permeable porosity. Very little field work was done with this system. 3. Radioactive particles suspended within the injection fluid are pumped down the well. As the fluid enters the permeable formations, the radioactive particles are filtered out on borehole wall. The permeable zones are differentiated from the impermeable by the gamma ray activity deposited on the formation wall.

Jan 1, 1956

By A. H. Willis

In this paper the results of an exploratory study conducted by personnel of the Knolls Atomic Power Laboratory on 18.6, 22, and 40 wt pct uranium-zirconium alloy will be presented. LARGE power output and long life or endurance from small, compact nuclear reactors require the use of enriched uranium for a fuel material. However, the ability to remove heat from the element, the tolerable fission product concentration, or some physical limitation of the system can limit the allowable fuel enrichment, or the volume of the fuel. In such an event, the fuel-element designer must find a suitable diluent for the uranium. Zirconium is an attractive material for such a purpose as it has good nuclear properties and a low absorption cross section. Because it has a good corrosion resistance in water, zirconium is a suitable cladding and the uranium-zirconium alloy makes a good core material. The alloy has a high thermal conductivity, a low elastic modulus, and a low thermal-expansion coefficient, all of which tend to minimize the thermal stresses in the core. Furthermore, the unirradiated material is reasonably ductile and has adequate strength. DESCRIPTION OF SAMPLES Two types of cylindrical samples were used in this study 1) short, 1/2-to 1-in.-long samples to test the irradiation stability of the alloy and 2) 2-ft-long samples to investigate the resistance of an element to longitudinal deformation. Composite samples having 0.060-to 0.140-in. core diameters and clad with a 0.010-in. thick zirconium jacket were fabricated by coextrusion and by hydrostatic pressure bonding of the cladding to the preformed core material. Both fabrication processes produced the uniform metallurgical core-to-cladding bond which was felt necessary to minimize the uncertainty of the central core temperature. Both consumable-arc and induction-melting techniques were used to melt the uranium-sponge zirconium core alloy. Since a graphite crucible was used in induction-melting this alloy contained more carbon impurity, which resulted in a finer grain size than the arc-melted alloy. The core to cladding interface was uniform in elements coextruded from the fine-grain, induction-melted core material, while those elements fabricated using arc-melted core material had very irregular interfaces because of the coarser grain size. Both cold-worked and heat-treated fuel materials were irradiation tested. Cold-worked alloys were swaged to about a 5 pct final reduction in area without subsequent annealing. The heat-treated alloys were heated to 800°C, held at temperature for 15 min and furnace-cooled to about room temperature. This

Jan 1, 1960

By H. H. Klepfer, K. J. Gill, P. Chiotti

SOME observations relative to the U-Zn system have been made by other investigators. Chipman1 and Carter2 have reported the preparation of several U-Zn alloys and point out that these alloys are generally difficult to prepare. Chipman1 reported evidence for a high melting compound at about 90 atomic pct Zn and the possible existence of a eutec-tic between the compound and uranium. Raynor," in a theoretical discussion of the alloying properties of uranium, included zinc among the elements predicted to have little or no solubility in a, p, or y uranium. In the present investigation, thermal analyses, X-ray, metallographic, and vapor-pressure data were obtained to determine the phase boundaries. The relatively high zinc pressure over most of the alloys at temperatures of 900 °C and above proved troublesome and special techniques had to be employed in preparing suitable alloys. Materials and Preparation of Alloys The metals employed in this investigation were Ames Laboratory biscuit uranium containing less than 500 ppm total impurities and Bunker Hill slab zinc or Baker Analyzed reagent granulated zinc, both with a purity of 99.99+ pct. Due to the high vapor pressure of zinc and the high reactivity of both uranium and zinc with oxygen at only moderately high temperatures, alloys were prepared in closed containers which had either been evacuated or evacuated and filled with helium. High purity magnesia, magnesia containing 10 pct calcium fluoride, and tantalum proved to be suitable crucible materials. Tw-o different procedures, described below, were used to prepare alloys, the latter being the most satisfactory. The metals, uranium turnings and granulated zinc, were cleaned with dilute nitric acid, rinsed, dried, and placed immediately in a helium-fill&apos;ed dry box. The two metals were placed&apos; in a 10 mil Ta crucible. The charge was enclosed in the tantalum crucible by welding on a preformed tantalum cap. This assembly was enclosed inside a stainless steel (AISI 309) bomb. The bomb was made by welding a piece of stainless steel plate on each end of a stainless steel pipe. All these operations were carried out in a helium atmosphere. These assemblies were heated in a muffle furnace at temperatures between 1100" and 1200°C for 10 to 15 min or held as long as 15 to 20 hr in the 950" to 1000°C temperature range before quenching. Spectrographic and chemical analyses showed no tantalum pickup by the alloys, indicating no reaction between the alloys and the crucibles. However, some of these crucibles failed, probably due to imperfections in the welds of the stainless steel or tantalum crucibles. The second and most satisfactory method was to prepare the alloys by powder metallurgy techniques. The procedure was to press degreased and acid-etched uranium turnings with granulated zinc into 20 g compacts under 20,000-psi pressure. The compacts were placed in MgO crucibles, and sealed in evacuated Vycor or fused silica tubes. The alloys were then heated as long as two weeks at about 550°C in a muffle furnace. The pressed compacts were observed to expand by several volume percent during heating and it was necessary to make allowances for this expansion in order to avoid breaking the crucible and Vycor tube. This method was found very satisfactory for preparing alloys which were suitable for thermal analysis or vapor pressure studies. Experimental Methods and Results The phase diagram for the U-Zn system at 1 atrn pressure, shown in Fig. 1, is based primarily on vapor pressure measurements and on thermal analysis taken at temperatures below 950°C. Fig. 2 shows the U-Zn diagram at 5 atrn pressure, constructed on the basis of thermal analysis of alloys in sealed containers up to 1150°C and on the basis of metallographic, X-ray, and analytical data. The alloys sealed under vacuum were actually under their own vapor pressure and those sealed in an atmosphere of helium were under an additional pressure due to the helium. At temperatures up to 1100°C the zinc pressure is 5 atrn or less for these alloys; consequently the maximum pressure over the alloys sealed under a helium atmosphere was 10 atrn or less at temperatures up to 1100°C. Changes in pressure of this order of magnitude do not appreciably alter the position of most solid-solid or liquid-solid phase boundaries. In constructing the phase diagram for a pressure of 5 atm, the effect of pressure on all phase boundaries except those for liquid-vapor or solid-vapor regions was considered negligible.

Jan 1, 1958

By A. K. Sinha

The market for thermal coal has recently been growing rapidly and it is projected to continue to do so in the foreseeable future. Both the national and international markets often demand high-Btu low-sulfur thermal coal in order to minimize the cost of utilization and meet the environmental restrictions. High quality thermal coal can be prepared to compete in the utility market by desulfurizing the high-Btu midwestern coal and blending it with low-sulfur western coal which is usually low in Btu content. The methods that can be used for optimizing the coal preparation plant operating parameters for physically desulfurizing coal are presented.

Jan 1, 1985

By B. Russell, J. R. Tuffley

The stability regions of the normal sulfate and the various basic sulfates of lead in 02-SO2 and PhS-SO2 gas atmospheres were calculated from available thermodynamic data over the temperature range 600o to 1200oC. Roasting experiments were carried out on samples of synthetic lead sulfide at various temperatures and for various roasting times. Compounds in the oxidized surface layers were identified by X-my techniques. The order in which the various reactions occurred was determined by considering the experimental results in conjunction with the thermodynamic calculations. The results of these investigations were applied to the sintering of lead sulfide concentrates, and the extent to which each of the various reactions occurred in a sinter bed was determined. PRODUCTS which may be formed during the roasting of PbS are PbS04, PbSO4. PbO, PbSO4 . 2PbO, PbSO4 . 4PbO, PbO, and Pb.1, 2 The formation of some sulfates has been studied by a number of investigators3-&apos; whose experiments have mostly been confined to the temperature range between 500" and 850°C. Culver, Gray, and spooner3 were able to isolate the reactions which formed PbSO4 and PbSO4. PbO by carefully controlling the compositions of the roasting gases. The kinetics of these reactions were studied within the temperature range 673" to 807°C. Gardner4 and Merrick5 also studied the kinetics of oxidation of PbS. Gardner disregarded the existence of basic sulfates and, as a result, misinterpreted some of his experimental data. Merrick recognized that most of the products of oxidation were mixtures of basic sulfates, but was unable to identify the individual components. Hoschek6 oxidized PbS in air at temperatures up to 800°C. The products were analyzed after roasting had proceeded for some minutes, but no attempt was made to follow the reactions in the initial stages. Consequently, no roasting mechanism was derived. He also showed that PbSO4 and PbSO4 - 4PbO decomposed slowly in air at temperatures in the region of 800°C. The stability regions of sulfates in the temperature range 500" to 850°C have been only partially determined, while practically no information is available for higher temperatures. In the lead sintering process, PbS concentrates are roasted at temperatures within the range 1000o to 1200°C. In order to investigate sulfate formation, it is necessary to determine the effects of temperature and gas composition upon the various oxidation reactions and upon the regions of stability of the various lead sulfates. Kellogg and Basu2 introduced an equilibrium diagram similar to those in Figs. 1 to 3 which provides a convenient medium for represent-

Jan 1, 1964

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The ductile fracturing process was studied in single-crystal and poly cvystalline aluminum deformed in tension over a temperature range from 295° to 4.2°K. At temperatures as low as 77°K, the fracture of "inclusion-free" material, including zone-refined aluminum, was by rupture (-100 pct RA). At 4.2 OK, fracture was brought on by adia-batic shear. Metallographic examination did not disclose any voids or slip-band microcracks, thus negating for inherently ductile metals any mechanism of void nucleation by vacancy condensation or of cracking due to dislocation pile-ups. In Izigh-purity aluminum not treated to be inclusion-free, fracture at temperatures as low as 45°K was of the double-cup type and a result of void formation. The reduction-of-area decreased as temperature was lowered, corresponding to the earlier appearance of voids. Such behavior was rationalized in terms of a larger increase, with decreasing temperature, in the .flow stress relative to the strength of the inclusion-matrix interface. Evidence for low-temperature adiabatic shear was found in discontinuous flow at 4.2"K, in the transition to a localized shear fracture at low temperatures, and in the suppression of shear fracture with an elastically hard pulling device. A simple analysis for the initiation of adiabatic shew permitted a general correlation of the various contributing factors. It has been pointed out that the duration of shear depends upon effective mass and elastic stiffness of the deformation system. IT has long been recognized that fracture* may Throughout this paper, the term "fracture" is taken to mean any process that results in the separation of a material into two (or more) parts. Thus rupture as it may be encountered in a tension test leading to 100 pct reduction-of-area is included in this category. occur in a ductile mode, and that the process can be of great practical as well as general interest. Much information about ductile fracture has also been accumulated over this period, but only recently has an understanding of mechanism begun to appear. Ludwik,&apos; in 1926, first reported fracture in a tensile specimen starting with a central crack in the necked section. Since then, other studies have disclosed that such cracks may form by the coalescence of voids nucleated in this region where hydrostatic tension is highest.2-4 Rogers and Crussard et al.&apos; have emphasized void formation and reori-entation along localized shear bands as a mode of crack propagation. pines6 has considered the tensile rod as a bundle of fibers joined by weak interfaces, which subsequently separate to allow individual fiber contraction. The notion of cavity growth and coalescence by purely plastic processes was discussed by Cottrell: who added that the tensile reduction-of-area ought not to be sensitive to temperature. On the other hand, it has been observed that the reduction-of-area is greatly increased if tests are carried out at high temperaturesa or under high hydrostatic pressure.&apos; Fracturing anisotropy in wrought products lends support to the idea of void formation from preexisting flaws strongly aligned by earlier processing.&apos;&apos;-l2 There is evidence that many voids result from the fracturing of inclusions or separation at the inclusion-matrix interface Another possibility is that voids grow out of pore volume produced in the initial solidification and never fully removed in later working. In general, a structure 3f particles, pores, and weak interfaces can be expected, at least in materials of engineering interest. Vacancy condensation has been suggested as an alternative mechanism of void formation for materials considered to be inclusion-free.13 Yet experience has shown that tensile reduction-of-area increases with purity, to the extreme of rupture as so often observed in single crystals. Adiabatic shear has an important bearing on ductile fracture. It occurs when the decrease of flow stress, as a result of local temperature rise from heat generated during straining, becomes larger than the increase due to strain and strain-rate hardening. As demonstrated by experiments on punching of plates,14 a large temperature rise may be brought about by rapid straining. Adiabatic flow as a result of the high strain rate reached in an ordinary tensile specimen just prior to separation may account for the cone formation in cup-and-cone fracture;14 evidence of such local heating has been presented.15 For geometrical reasons, however, pure sliding along the conical surfaces is unlikely, and separation under tensile forces is probably an important accompanying feature of the shear.7 In deformation processing operations, a high shear-strain rate may exist at boundaries between plas-

Jan 1, 1964

By H. C. Howard

Reaction of oxygen and bituminous coal starts as soon as the coal bed is exposed to air and, with some coals, proceeds with significant velocity even at normal temperatures and at normal oxygen partial pressures of one-fifth of an atmosphere. At higher temperatures, the reaction is greatly accelerated and ultimately a condition is reached where the process is very rapid and we then speak of combustion. It is the purpose of the present paper to discuss the reactions of oxygen and coal at temperatures below those of active combustion. It is these low temperature oxidation reactions which are responsible for heating in storage and for marked changes in agglutinating proper-ties. These reactions may also be employed for the preparation of organic acids, which are of direct interest to the chemical industry. For convenience in discussion, the low temperature reactions of oxygen and bituminous coal can be roughly divided into three stages though there is, of course, overlapping. Stage I is a surface oxidation stage, characterized by the addition of oxygen, with the formation of oxygen containing groups some of which have acidic properties. Carbon dioxide, carbon monoxide and water may be formed con-comitantly and are always liberated at higher temperatures, and in cases where the oxidation is prolonged. Superficially, the coal is little affected by this primary stage of oxidation and usually only minor changes in ultimate composition result. There may be definite changes in coking and coking properties, and heat of combustion susceptibility to further oxidation. The presence of acidic groups can be demonstrated by specific reactions. These groups may show cation exchange properties like the mineral zeolites. The formation of oxalic acid has been reported. If the oxidation is continued, a large fraction of the organic material of the coal is converted ultimately into alkali soluble, acid insoluble products, which have been given the name "regenerated humic acids" and which are the characteristic products of Stage 2. These humic acids, in the solid stage, do not differ greatly in appearance from the original coal, but show large differences in chemical composition and chemical and physical properties. Along with the humic acids, carbon dioxide and some of the water soluble types of Stage 3, are also formed. If the oxidation is carried still further, the humic acids may be degraded completely to the simpler, lower molecular weight acids of Stage 3 which are characterized by solubility in acid as well as in alkaline media, and by their orange, yellow or white colors. Additional carbon dioxide is formed in the transformation from Stage 2 to Stage 3 and, for a number of American coals, a maximum yield of the water soluble types of acids is reached when about 50 pct of the carbon of the coal is converted to carbon dioxide. Primary Oxidation The initial step in the reaction of gaseous oxygen on coal, like that on carbon,

Jan 1, 1949