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By S. G. Gibbs

A new method for predicting the behavior of sucker-rod pumping systems is presented. The pumping system is described by a flexible mathematical model which is solved by means of partial diflerence equations with the aid of computers. Polished rod and intermediate-depth dynamometer cards can be calculated for various bottom-hole pump conditions. The technique permits simulation of a wide variety of operating conditions, both normal and abnormal. The data generated with the new technique are useful in refining the criteria for design and operation of sucker-rod systms. INTRODUCTION Sucker-rod pumping systems are used in approximately 90 per cent of artificially lifted wells. In view of this wide application, it behooves the industry to have a fundamental understanding of the sucker-rod pumping process. Oddly enough, our understanding has been rather superficial. This is evidenced by the semi-empirical formulas which have been used as the basis for design and operation of sucker-rod installations. Thoueh- we have realized the limitations of our methods for many years, it has not been computationally feasible to use more refined techniques. With the advent and widespread use of digital computers, it is now possible to handle the mathematical problems associated with sucker-rod pumping. This paper summarizes a computer-oriented method which can provide greater insight into the sucker-rod pumping process. It is hoped that this technique, and techniques which may evolve from it, will prove to be the tool needed by industry to obtain the most efficient use of rod pumping equipment. THE MATHEMATICAL MODEL Prediction of sucker-rod system behavior involves the solution of a boundary value problem. Such a problem includes a differential equation and a set of boundary conditions. For the sucker-rod problem, the wave equation is used, together with boundary conditions which describe the initial stress and velocity of the sucker rods, the motion of the polished rod and the operation of the down-hole pump. Of these items, the wave equation, the polished rod motion condition and the down-hole pump conditions are of primary importance. Discussion of the mathematical model centers about these factors. ROD STRING SIMULATION WITH THE WAVE EQUATION The one-dimensional wave equation with viscous damp- is used in the sucker-rod boundary value problem to simulate the behavior of the rod string. This equation describes the longitudinal vibrations in a long slender rod and, hence, is ideal for the sucker-rod application. Its use incorporates into the mathematical model the phenomenon of force wave reflection, which is an important characteristic of real systems. The viscous damping effect postulated in Eq. 1 yields good solutions, even though nonviscous effects such as coulcomb friction and hysteresis loss in the rod material are present. Fortunately, the nonviscous effects are relatively small, so the viscous damping approximation used in the wave equation is adequate. The coefficient v is a dimensionless damping factor which is found in field measurements to vary over fairly narrow limits. For mathematical convenience the gravity term is omitted in Eq. 1. The effect of gravity on rod load and stretch can be treated separately, as will be noted later. Since Eq. 1 is linear, the legitimacy of this procedure is easy to demonstrate. POLlSHED ROD MOTION SIMULATION The motion of the polished rod is determined by the geometry of the surface pumping unit and the torque-speed characteristics of its prime mover. By determining the motion of the polished rod, we formulate an important boundary condition. From trigonometrical considerations it can be shown that the position of the polished rod vs crank angle 0 is given by (see Fig. 1) These equations are obtained from the general solution of the "four-bar" linkage problem and can be used to describe the kinematics of any modern beam pumping unit.' If prime mover speed variations are disregarded, the angular velocity of the crank is constant, and Eq. 2 can be used to predict the position of the polished rod vs time. However, the constant-speed condition leading to constant crank angular velocity is only approached in practice: hence, it is better to make provisions for prime mover speed variations in the mathematical model. The speed at which the prime mover runs is determined by its torque-speed characteristics and the torque imposed upon it. The torque that the prime mover "feels" is the net torque arising from the polished rod load and the opposing torque from the counterbalance effect. The

By P. B. Baxendell, R. Thomas

Work on the calculation of vertical two-phase flow gradients by Cia. Shell de Venezuela has been based mainly on the "energy-loss" method proposed by Poett-mann and Carpenter in 1952. The "energy-loss-factor" correlation proposed by Poettmann and Carpenter was based on relatively low-rate flow data. This correlation proved inapplicable to high-rate flow conditions. In an attempt to establish a satisfactory correlation for high rates, a series of experiments was carried out at rates up to 5,000 BID in Cia. Shell de Venezuela's La Paz field in Venezuela, using tubing strings fitted with electronic surface-recording pressure elements. As a result of these experiments a correlation between energy-loss factor and mass flow rate was established which is believed to be applicable to a wide range of conduit sizes and crude types at high flow rates (e.g., above 900 BID for 27/8-in. OD tubing). It is anticipated that the resulting gradient calculations will have an accuracy of the order of % 5 per cent. At lower flow rates the energy-loss factor cannot be considered as constant for any mass rate of flow, but varies with the free gas in place and the mixture velocity. No satisfactory correlating parameter was obtained. As a practical compromise for low flow rates, a modification of the curve proposed by Poettmann and Carpenter was used. In practice this was found to give gradient accuracies of approxirnately ± 10 per cent clown to flow rates as low as 300 B/D in 27/8-in. tubing. INTRODUCTION Production operations in Cia. Shell de Venezuela's light- and medium-crude fields are principally concerned with high-rate flowing or gas-lift wells. Under these conditions the analysis of well performance, the selection of production strings and the design of gas-lift installations are vitally dependent on an accurate knowledge of the pressure gradients involved in vertical two-phase flow. Initially, attempts were made to establish the gradients empirically as done by Gilbert,' but the results were not reliable due to scarcity of data over a full range of rates and gas-oil ratios. Several methods of calculation based on energy-balance considerations were attempted, but the computations were cumbersome and the results cliscouraging. In 1952 a paper was published by Poettmann and Carpenter' which proposed a new approach. Their method was also based on an energy-balance equation. but it was original in that no attempt was made to evaluate the various components making up the total energy losses. Instead, they proposed a form of analysis which assumed that all the significant energy losses for mutiphase flow could be correlated in a form similar to that of the Fanning equation for frictional 1osses in single-phase flow. They then derived an empirical relationship linking measurable field data with a factor which, when applied to the standard form of the Fanning equation, would enable the energy losses to be determined. The basic method was applied in Venezuela to the problem of annular flow gradients in the La Paz and Mara fields" This involved establishing a new energy-loss-factor correlation to cover high flow rates and, also, some adaptation of the method to permit mechanized calculation using punch-card machines. The final result was 1 set of gradient curves for La Paz and Mara conditions which proved to be surprisingly accurate. With the encouraging results of the annular flow calculations, several attempts were made to obtain a corresponding set of curves for tubing flow. Here, unfortunately, little progress could be made. The original correlation of Poettmann and Carpenter was based on rather 1imited data derived from low-rate observations in 23/8- and 27/8-in. OD tubing. It did not cover the higher range of production rates, and extrapolation proved unsuccessful. A new correlation covering high flow rates was required, but this proved to be extremely difficult to establish since tubing flow pressure measurements at high rates did not exist—due to the difficulty of running pressure bombs against high-velocity flow. The necessity for reliable tubing flow data increased with the development of the new concessions in Lake Maracaibo, where high-rate tubing flow from depths of 10,500 ft became routine. Thus. it was decided to set up a full-scale test to establish a reliable energy-loss factor for tubing flow conditions. A La. Paz field light-oil producer with a potential of approximately 12,000 B/D on annular flow was chosen. To obtain full pressure gradients, a special tubing string was installed which was equipped with electronic surface-recording pressure measuring devices,

By D. D. Dunlop, J. R. Welker

The growing interest in the use of CO, in crude oil recovery increases the need for data on the effect of CO, on hydrocarbon physical properties. Data are presented on the solubility of CO, in various dead oils, the swelling changes in CO2-oil solutions and the effect of CO, on dead oil viscosity. This latter property shows the most pronounced effect, with viscosity reductions up to 98 per cent of the uncarbonated viscosities. An empirical method of estimating the viscosity of carbonated oils is presented. The apparatus and procedures used are described in sufficient detail to allow others to make similar studies. INTRODUCTION The effect of dissolved carbon dioxide on the swelling and viscosity reduction of specific hydrocarbon oils has been observed and recorded by a number of investigators.'- me object of this paper is to offer a means of predicting these effects for crude oils free from natural gas, using the dead state viscosity and gravity of the crude oils. The CO, solubility and swelling of numerous crude oils were determined in a visual cell at various pressure levels. The viscosity of the oils carbonated to various pressure levels was then determined by measuring the pressure drop across a capillary tube. From these data, the physical properties were correlated empirically. The resulting correlations allow the prediction of CO, solubility, swelling and viscosity reduction if the dead state gravity and viscosity of the oils are known. SOLUBILITY AND SWELLING MEASUREMENT EQUIPMENT AND PROCEDURE A high pressure visual cell was installed in a constant temperature cabinet. A test gauge was attached at the top of the cell for pressure measurement, and a line was run through the cabinet wall to a wet test meter which was used for volumetric measurement of the gas. The first step in making a test run was to put the oil in the cell up to a level about half to two-thirds of the total volume. This required about 50 to 65 ml of oil. carbon dioxide was then bubbled up through the oil for a time during which the pressure of CO2 in the cell was kept above 800 psia. Saturation of the oil with CO2 at this pressure and ambient temperature was confirmed by slowly bleeding CO2 through a valve to the atmosphere. If the oil was completely saturated with CO2, bubbles of gas would form in the oil at the first small decrease in pressure. If the oil was under-saturated, no bubbles formed until the pressure was decreased to the saturation pressure existing in the oil. If this saturation pressure was lower than that desired, more CO2 was bubbled through the oil until the desired level was reached. After saturation at ambient temperature was completed, the cabinet temperature was adjusted to the desired level and the cell was allowed to reach temperature equilibrium. After temperature equilibrium was reached, the pressure was again decreased slightly, and the oil again checked for full CO2 saturation at the cell pressure. The pressure now had changed because of the difference in solubility of the CO, in the oil at higher temperatures and the expansion of CO2 as the temperature increased. The outlet tube from the cell was then connected to the wet test meter and the CO2 was allowed to flow slowly out of the cell and through the wet test meter at ambient temperature and pressure. The water in the wet test meter had previously been saturated with CO2 at ambient temperature and pressure by allowing CO2 to flow continuously through it lor a period of several hours. The gas flow was stopped at several pressures during the run and the cell was allowed to come to equilibrium; this made possible the measurement of solubility and swelling data at the intermediate pressures. The volume of the oil in the cell was recorded at each of the equilibrium pressures in order to obtain swelling data. DATA AND RESULTS The solubility of CO2 in the oil was calculated by the relationship V — V, where R. = solubility of CO, in crude oil, cubic feet of CO, measured at 60F and 1.0 atm/ bbl of dead state oil at the temperature under which solubility was measured, V, = volume of gas released from the cell between the saturation pressure and zero pressure, corrected to 60F and 1.0 atm, cu ft, V, = volume of CO: contained in the gas space above the oil, corrected to 60F and 1.0 atm, cu ft, and V, = volume of the dead oil in the cell in bbl at the temperature of the run. The volumetric data of Sage and Lacey' were used to calculate V., from the volume of CO2 at high pressures. The swelling factor was calculated as where V, is the volume of the C0,-

By R. C. Davis, R. F. Berry, G. W. White, B. T. O’Connell, L. A. Stacha

The formation density logging tool provides a radioactivity measurement that yields formation densities in situ. The relationship between bulk density and porosity is well understood. With knowledge of grain and fluid densities, porosity may be computed from the indicated formation bulk densities in shale-free formations. The porosities thus determined may be used with a resistivity log for water-saturation determinations. One technique utilizes a density vs resistivity plut. A plot of density vs Sonic-log transit time is used for porosity determinations in shaly sands. This method is particularly suited to wells drilled with oil-base or salt muds. In shale-free formations, comparisons of density values nnd neutron-log readings are used to identify lithologr and, thus, to select appropriate values of grain density for porosity computations. Through the use of Formation Density, Sonic and neutron logs, the interpretation problems caused by complex matrix lithologies are simplified. Other applications of the Formation Density log are found in the identification of minerals in evaporite deposits and in yield determinations of "oil shales". INTRODUCTION Widespread field application has demonstrated that the measurement of formation density is a useful and revealing technique for well logging. Responding to the bulk density variations of the formation, the Formation Density log affords valuable data on the porosity, lithology and fluid content of the formations. Although not without its own limitations, the Formation Density tool may provide effective interpretation under conditions that hamper or preclude the use of other porosity devices. When used in conjunction with other devices, such as the Sonic or neutron, complex matrix conditions may be better understood, defined and evaluated. A previous paper' described the valuable contribution of the Formation Density tool in the logging of empty, or gas-filled, holes. The purpose of the present paper is to describe applications of the device in liquid-filled holes. THE FORMATION DENSITY TOOL The Formation Density tool was devised to measure the bulk densities of formations in situ. Actually, the device responds to electron density, but in the overwhelming majority of cases of interest, the electron density is very closely proportional to the bulk density. In other cases appropriate corrections can be made if necessary. Comparisons of log-derived densities with true densities for the more common matrix minerals are shown in Table 1. The tool consists of a gamma-ray source and detector mounted in a skid which, during the logging operation, is in contact with the borehole wall (see Ref. 1 for schematic). Gamma rays are emitted by the source and diffused through the formation. The number of diffused gamma rays reaching the detector at a fixed spacing from the source are counted. An increase in counting rate by the detector indicates a decrease in bulk density in front of the skid. Conversely, a decreased counting rate signifies an increase in bulk density. A measurement of hole diameter, between the face of the skid and that of the eccentering arm, is recorded simultaneously with the measurement of diffused gamma rays. Since the tool is a wall-contact device, the size of the borehole has little influence, provided good contact is maintained with the wall of the hole. Only in extremely large or small boreholes does the actual diameter become significant. However, for most accurate measurements the borehole size should be taken into account. Fig. 1 presents the departure curves for the conversion of counting rate to bulk density for liquid-filled holes of various sizes. It is of utmost importance that the skid maintain good contact with the wall of the hole. If, due to roughness or caving, there is mud between the skid and the formation, the tool will include in its response the relatively low-density mud, and the apparent density reading will be too low. Normally, permeable beds do not cave appreciably, so that reliable readings are usually available for zones of interest. Nevertheless, the caliper reading over the zone of interest should be examined for any wall roughness. When mud cake exists between the skid and the formation, the Formation Density log sees it as part of the formation. When thick mud cakes exist, a correction is required. For best results in wells having thick mud cakes,

By C. D. Hall, F. E. Dollarhide

Conventional static tests of fluid-loss agents do not realistically simulate conditions in a fracturing treatment. The dynamic tests reported here show that fluid-loss volume is better represented as proportional to time, rather than as the square root of time. This leads to a different equation for fracture area. The leak-off rate increases with increasing shear rate at the fracture wall, but appears to approach a limiting value. Pressure effects are minor. Spurt loss ordinarily is not affected by the flow velocity in the fracture and is inversely proportional to concentration of agent. The filter cake, once it is well established, is resistant to damage by the flow of plain fracturing liquid (without fluid-loss agent). The latter two findings indicate that a treatment employing a high-concentration spearhead followed by plain fluid can offer a more economical treatment under suitable conditions. INTRODUCTION The successful design of hydraulic fracturing treatments depends on accurate knowledge of the fluid-loss properties of the fracturing fluid. Howard and Fast,' in giving the basic equation relating fracture area to fluid and treating parameters, described three mechanisms which might control the rate of fluid leak-off from the fracture. One mechanism usually is dominant in a given well treatment. For each mechanism, the leak-off velocity is inversely proportional to the square root of time, and the proportionality constant is designated as the fracturing-fluid coefficient. For the wall-building type of fluid-loss agent, the coefficient is determined by a filtration test in a pressure cell, usually with a rock wafer or core as the filter medium. In these static tests, the cumulative volume generally is proportional to the square root of time, after an initial spurt volume. The static-fluid-loss test is not representative of the con,-&tions under which a fluid-loss agent performs in a fratturing treatment. The marked difference between the dynamic- and static-fluid-loss behavior of drilling fluids reported in the literature2,3 implies that dynamic testing is also needed with fracturing fluids. We have therefore undertaken a study of the dynamic-fluid-loss behavior of fracturing fluids. The testing apparatus has also afforded opportunity to evaluate the resistance of the filter cake to removal or damage by flowing fluid containing no fluid-loss agent, with and without sand. The results of these studies offer a means for more accurate evaluation of fluid-loss agent performance, and point the way to a "spearhead" fracturing technique which may offer more economical treatment for some wells. EXPERIMENTAL METHODS The dynamic-fluid-loss testing method is applicable to any type of wall-building fracturing fluid. The present study aimed first at finding what phenomena are involved, and therefore has been limited in the number of materials tested. All of the results specifically reported herein are for kerosene containing a commercial solid fluid-loss agent, which is commonly used at 50 lb/1,000 gal of oil. Another agent in liquid form, used usually at 20 ga1/1,000 gal oil, has shown all the same phenomena in dynamic tests, and generally the same level of fluid-loss control as the solid agent. The dynamic-fluid-loss core cell used in all tests is shown in Fig. 1. The fracture was simulated by the an-nulus between a 2.03 in. OD sandstone core and the surrounding pipe. Annulus widths of 0.234 and 0.117 in. were used, and the core was 3.5 in. long. The annular geometry provides a uniform fluid velocity and a well-defined shear rate over the entire filtering surface, and permits a large filter area (144 sq cm) in a reasonably compact cell. The leak-off fluid passed into a 0.5 in. diameter axial hole in the core. A hollow steel rod through this hole was threaded into a rounded "streamliner" upstream of the core, and into a mounting stud downstream. The streamliner and the stud had the same outside diameter as the core. In all tests except those where sand was circulated, the mounting stud had protruding rings which constricted the annulus, to minimize any tendency for channeling of the fluid to the side exit port. The ends of the core were sealed by Neoprene, steel and Teflon washers. The leak-off fluid was conducted from the hollow rod to an exit tube, through a metering valve (a fine-pitched needle valve) and a quick-opening toggle valve in series, and into graduated cylinders for volume measurement; Two separate circulating systems were used in the experimental program. The extensive initial testing was done at 50 to 150 Psi. The fluid was circulated by a variable speed Moyno pump, and the flow rate was read by a rota-meter flow meter. The filtration Pressure was supplied by holding a back-pressure with a throttling valve. The discharge streamcould be diverted into any of four sections

Jan 1, 1965

By G. P. Conard, R. C. Hall, J. F. Libsch

The 50 pct Fe-50 pct Co alloy undergoes a transformation from disorder to an ordered structure of the CsCl type reportedly in the vicinity of 732OC. During this process, the coercive force goes through a maximum, apparently as a result of strains associated with the coherent nucleation and growth reaction. This magnetic alloy also shows a marked increase in the ratio of residual to saturation induction, which is associated with annealing to a high degree of order with the continuous application of a magnetic field. The increase in ratio can be explained on the basis of a decrease in 90' domain boundaries and, perhaps, by an increase in anisotropy resulting from lattice distortion. THE 50 pct Fe-50 pct Co alloy undergoes a disorder-order transformation which has been reported to occur in the vicinity of 732°C1,2 The ordered structure is the CsCl type.' This magnetic alloy also shows a marked increase in the ratio of residual to saturation induction as a result of heat treatment in a magnetic field, sometimes called a response to magnetic anneal.'-' The purpose of this investigation was to study the course of the ordering reaction, the nature of the response to .heat treatment in a magnetic field, and the relation, if any, between ordering and the response. Procedure The method of approach in this investigation was to produce an initial structure as completely disordered as possible and then gradually to order the alloy by isothermal anneals at various temperatures under different conditions of the applied magnetic field. Magnetic, magnetostriction, and X-ray analyses were of primary importance in determining the property and structural changes resulting from the isothermal anneals. Rings of the 50 pct Fe-50 pct Co alloy were prepared from the elemental powders by a powder metallurgy technique, further details of which may be found in ref. 7. The initial structure was produced by annealing the specimens for ½ hr at 1000°C, cooling to and holding for ½ hr at 900°C (in the a range above the ordering temperature), and water quenching. Isothermal anneals were performed at 600°, 675°, 720°, and 740°C. For example, rings were heated to 600°C, held for a predetermined period of time, and cooled by natural cooling at a rate slightly slower than an air cool (average of 20" to 25°C per min). The tests (magnetic, etc.) were made after each heat treatment. All high temperature treatments were performed in a purified hydrogen atmosphere. The treatments at the various temperatures were carried out under one or more conditions of an applied field including 1—no field, 2—field of 20 oersteds applied on cooling only, and 3—field of 20 oersteds applied continuously during heating, holding, and cooling. Magnetic measurements were made using the standard Rowland ring technique8 with a maximum field strength of 100 oersteds. The magnetization curve, induction at 100 oersteds (B.), residual induction (Bt), and coercive force (Hc) were determined. All magnetic analysis data were based on an average of the results from three rings. A strain gage technique9 as used for the measurement of magnetostriction. The X-ray determination of the relative amount of ordered phase present was made on the ring specimen used for magnetic measurement. This was done by the back-reflection method using a rotating specimen (because of the large grain size) with unfiltered CoKa radiation and a 7 hr exposure time. Intensity measurements of the ordered line (300) were made by comparing visually the films so obtained with standard films prepared by exposing for different lengths of time a specimen given a long time anneal (high degree of order). Results In all instances the saturation induction (induction at 100 oersteds) was found to increase slightly with annealing time. This effect was small and appears to be the increase in saturation induction to be expected on ordering.10-13 The residual induction behavior was markedly influenced by the field condition during annealing, Figs. 1, 2. For the condition of no applied field, the ratio of residual to saturation induction remained essentially constant for short annealing times but showed a significant increase at longer times. With increasing annealing temperature, less time was required to produce this increase in the ratio. In the case of the 600°C anneals, the increase did not occur until approximately 20 hr, Fig. I, while on annealing at 740°C the increase was immediate, Fig. 2. Slight decreases in the ratio may be observed at 100 hr for specimens treated at 720°C and at 1 hr for those treated at 740°C. Specimens annealed in a field of 20 oersteds showed a residual to saturation induction ratio consistently higher than that for the specimens annealed without the field. The first anneal with the field (¼ hr) caused an abrupt increase in the ratio at all temperatures; thereafter, the increase in the ratio was generally similar for specimens annealed

Jan 1, 1956

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.'' The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-' "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

By R. I. Jaffee, E. S. Bartlett, D. N. Williams

The oxidation resistance and fabricability of molybdenum powder-metallurgy alloys containing up to 20 wt pct nickel in the form of a fine dispersion were studied. The effects of dispersion distribution and of amount and type (pure nickel or nickel compounds) of additive were considered. A definite improvement in oxidation resistance was observed, but the amount of improvement fell far short of requirements for an oxidation-resistant alloy. Fabricability by hot-rolling was limited. INVESTIGATIONS at Ohio State university1 and Battelle Memorial institute2 have indicated that the attainment of a truly oxidation-resistant molybdenum-base alloy for high-temperature service, with the coincident retention of high-temperature strength and toughness, will be a difficult, if not impossible, feat. Among the most promising alloy systems studied was the molybdenum-nickel system shown in Fig. 1. Alloys in this system show good oxidation resistance at temperatures well above the normal melting point of molybdenum trioxide because of the regenerative formation of protective nickel-molyb-date (NiMoO4) on the surface of the alloy during exposure at high temperatures. Unfortunately, the required alloy content to obtain oxidation resistant molybdenum-nickel alloys far exceeds the limits of the narrow terminal solid-solution boundary, and closely approaches the peri-tectic composition involving the brittle intermetal-lic compound, MoNi. Because of the peritectic reaction, fusion alloys are characteristically brittle, since the MoNi phase, being the last to form, tends to occur as a continuous grain-boundary network around each molybdenum grain. An added problem with this system is that the protective nickel-molybdate layer formed at high temperatures is unstable, undergoing one or more allotropic modifications upon cooling. The volume changes associated with this modification during cooling are such as to cause violent expulsion of the protective molybdate coating from the surface of the piece. This is, of course, quite detrimental in material exposed to cyclic temperature during service. The research reported here resulted from an attempt to overcome the aforementioned problems associated with the molybdenum-nickel alloys primarily by controlling the amount, size, and location of the MoNi phase. By using powder-metallurgy techniques of alloy preparation and sintering the blended molybdenum-nickel powder mixtures at a temperature below the peritectic reaction temperature, molybdenum-nickel alloys with a randomly dispersed MoNi phase were produced. MATERIALS The molybdenum powder used in the preparation of alloys for this study was commercial hydrogen reduced, minus 325-mesh (Tyler) material. Master alloys, by which nickel was added, consisted of elemental carbonyl nickel powder (12 average particle size), an alloy of 50 wt pct Ni-50 wt pct Cr, and compounds of MoNi, Ni,Si, and Ni2B. The nickel-chromium powder was prepared by filing a vacuum-arc-melted ingot, separating impurities magnetically, and screening to minus 200-mesh. The MoNi powder was prepared by pulverizing a hydrogen-sintered powder-metallurgy compact to minus 325-mesh material. Further sizing of this powder for study of effects of dispersion distribution was accomplished by air classification of the minus 325-mesh powder. The Ni2Si and Ni2B powders were prepared by crushing vacuum-sintered powder-metallurgy compacts to minus 200-mesh material. EXPERIMENTAL PROCEDURE Specimen Preparation—The general procedure followed in the preparation of alloys for testing is described as follows: 1) Blending. Either hand-blending of the powders in a ceramic mortar and pestle for X 1/2 or mechanical blending was used. Hand-blending seemed preferable for optimum homogeneity. 2) Compacting. Most of the blended powders were pressed to green compacts at pressures of 15 tons per sq in. in a single-action die, although some were pressed at 80 tons per sq in. A 1 X 11/4 X 1/4-in. green compact was the standard size for oxidation test material, and 7 X 1/2 X 1/4-in. compacts were used for fabricability test specimens. 3) Sintering. All green compacts were sinteredat

Jan 1, 1959

By D. Weinstein

The high temperature mechanical properties of stainless steels after fast neutron irradiation are discussed in the light of effects caused by lattice dattmage and effects caused by helium generated from n,a transmutations. Embrittlement at high temperatures is due to helium accumulation at grain boundaries and to cavity formation and proPagation along grain boundaries. Following from the embrittlement mechanism, it is suggested that when deformation occurs by mechanisms associated with super plasticity, helium ac-curnulation at boundaries should be attenuated and cavities, if formed, should be nonpropagating. As the mean free Path between interphase boundaries of a two-phase Fe-Cr-Ni alloy was decreased, the degree of superplastic deforrnation at 870°C increased, as vneaszired by total elongation and by the expottent m = a log 'a/a log 'i. This alloy and type 304 stainless steel were cyclotron irradiated in an a-particle beam to a helium concentration of -1 x 10 atom He per atom. The stainless steel specimen was embrittled, but the ductility of irradiated two-phase Fe-Cr-Ni alloys correlated with the values of. m during 'defor-malion. The .finest grained, helium-injected specimens that deforrned with highest m values exhibited the largest elongations to ,fracture. These results could be correlated with metallographic observations of cavity behavior: the propensity for intergranular propagation was lessened as the m value increased. It is concluded that superplastic deformation is ef-fectizle in attenuating helium embrittlement at elevated temperatures. One of the principal problems associated with development of fast breeder reactors is application of alloys such that suitable fuel cladding results. Stainless steels and other Fe-Cr-Ni alloys, because of highly acceptable nuclear characteristics, represent the primary materials for this component, and an exhaustive research and development effort is being conducted. The main deficiency of these materials has been a severe loss of ductility at high temperatures after fast neutron irradiation. An extensive body of mechanical property data and microstructural observations has provided an adequate phenomenological description of embrittlement; in conjunction with transmission electron microscopy studies, a reasonably acceptable embrittlement mechanism has been obtained. Following from this mechanism, it is suggested in the present work that ductility would be enhanced if deformation could occur by mechanisms associated with the phenomenon of superplasticity. Experiments to test this hypothesis have been conducted, and the results are presented and discussed in this paper. IRRADIATION EMBRITTLEMENT AT HIGH TEMPERATURE Austenitic stainless steels have been irradiated to accumulated fast neutron fluences of 1020 to 1022 nvt at temperatures between 60" and 600°C. Specimens that have been exposed to these conditions and subsequently tensile tested at temperatures between 600" and about 900°C exhibit approximately 5 pct total elongation to fracture.'-3 For unirradiated specimens receiving a nearly identical thermal exposure, total elongation at these test temperatures is about 45 pct. Examination of irradiated specimens has shown that fracture propagation is entirely intergranular. These phenomenological aspects of irradiation embrittle-ment at elevated temperatures are well known and are not generally disputed. Although the explanation of this phenomenon has been controversial, a mechanism for ernbrittlement has emerged that accounts reasonably well for the observed mechanical behavior. The controversy resulted primarily from an indeterminate role of neutron-in-duced lattice damage, if any, and a presumed, but experimentally unverified, contribution to embrittle-ment from helium generated by n,a transmutations. Recently, Holmes and coworkers4 have conducted experiments that separate these effects, and the results are instructive in formulation of the ernbrittlement mechanism. Holmes el al.4 irradiated type 304 stainless steel in EBR-I1 to a fluence of 1.4 x 1022 nvt (E > 0.18 mev); the irradiation temperature was 538" * 48°C or, in terms of absolute melting point, 0.49 * 0.03 T,. After irradiation, tensile tests were conducted at temperatures of 21" to 870.C, the specimens first being annealed for 30 min at each test temperature. In addition, thin sections of irradiated specimens were annealed for 1 hr at identical temperatures, electro and examined by transmission electron microscopy. Thus, for a given temperature, it was possible to correlate mechanical properties with the defect structure. At room temperature, the yield stress of irradiated specimens was a factor of 2.5 higher than unirradi-ated specimens exposed to an equivalent thermal history. Electron microscopic examination of the irradiated specimen revealed a high density of lattice damage in the form of Frank sessile dislocation loops and polyhedral voids. Holmes et al.4 concluded that the presence of this defect substructure caused the increase in yield stress and that after irradiation in a fast neutron flux at 0.49 Tm, substantial lattice dam-age persists. Annealing at progressively higher tem-

Jan 1, 1970

By W. L. McMorris, A. H. Brisse

IN the last several years the coal industry has intensified its effort to solve the growing problem of cleaning and recovering fine mesh coals. On one hand these has been increasing civic pressure for cleaner streams, and on the other hand there has been increasing production of fine mesh coal, resulting directly from adoption of the modern mining methods so essential to the economy of the coal mining industry. Cleaning fine coal with the same precision possible with coarser coals is a difficult task, and for coals finer than 200 mesh it has been impractical. Furthermore, the inclusion of —200 mesh material in the final product markedly increases costs of de-watering and thermal drying, which are necessary steps if coal is to meet market requirements. Consequently these extreme fines have generally been wasted. As a result, problems have been created in many districts because there has not been enough area for adequate settling basins. Wasting of coal in the -200 mesh slimes may account for a loss in washer yield equivalent to 2.0 to 2.5 pct of the raw coal input. With rising mining costs the value of such a loss is constantly increasing and a need for a better solution to the fines problem becomes more pressing every day. From an operating viewpoint, also, continuous removal of extreme fines from the washing plant circuit permits good water clarification practice, improving significantly the overall cleaning efficiency. The obvious desirability of recovering a commercially acceptable coal from washery slimes prompted U. S. Steel Corp. to investigate the merits of the Convertol process developed in Germany." Although this process has been used commercially in Europe for some time, little if any consideration has been given to its possible adoption in the U. S. until very recently. Fundamentals of the Convertol Process: In the Convertol process, droplets of dispersed oil are brought into intimate contact with the solids suspended in the coal slurry to be treated. This contact causes oil to displace the water on the surface of the coal by preferential wetting, or phase inversion, after which the coal particles are allowed to agglomerate in a manner permitting their re- moval from the slurry by centrifugal filtration. The clay and other particles of mineral matter suspended in the slurry do not have the affinity for oil the coal particles have. Consequently the oil treatment is preferential to coal to the extent that more than 95 pct of the oil used reports with the clean coal recovered. Figs. 1 through 3 will clarify the steps involved in the process. Fig. 1 shows the suspended material in the slurry to be treated, which is a thickened product containing 40 to 45 pct solids. Oil is now injected into the slurry under vigorous agitation to produce good oil to coal contact conditions, which result in preferential oiling of the coal particles. These coal particles are then permitted to agglomerate by gentle stirring in a conditioner to form flocs, as shown in Fig. 2. At this point in the process the agglomerated oiled coal can be washed and partially dewatered on a vibrating screen, as shown in Fig. 3. Finally, the washed flocculate can be further dewatered in a high-speed screen basket centrifuge or in a solid bowl centrifuge. Commercial Application of the Convertol Process in Germany: The original Convertol process was developed by Bergwerksverband zur Verwertung von Schutzrechten der Kohlentechnik, G.m.b.H., a German research organization controlled by the Coal Operators Assn. of the Ruhr Valley. The process as reduced to commercial practice in Germany' is shown in Fig. 4. In this process a thickened slurry (40 to 45 pct solids) mixed with a predetermined percentage of oil is fed from a surge tank to the phase inversion mill. After the phase inversion step, the slurry is usually discharged directly to a highspeed screen centrifuge. From 3 to 10 pct oil is used, depending on type of oil, size consist of coal to be recovered, and operating temperature. The top size of fine coal cleaned in Germany by the Convertol process is limited by the size of the openings in the centrifuge screen basket. Any mineral matter coarser than the basket opening, which is generally 60 to 80 mesh, must remain with the oiled coal. If the coal fines have been effectively cleaned down to about 80 mesh, the cleaning performance of the process is practically unaffected by the presence of coarse coal particles. However, since recovery of coal much coarser than 80 mesh is mow economical by conventional methods, it normally becomes more costly to allow substantial percentages of this coarse coal in Convertol process feed. Where the general plant layout does not permit effective cleaning of coal sizes down to 80 mesh or lower. there is some justification for a coarser Con-

Jan 1, 1959

By John S. Brown

IN 1925 the writer undertook a detailed statistical study of all producing areas in the Joplin district as a basis for evaluating programs and measuring objectives. For this purpose, the published figures in the yearly volumes of Mineral Resources were used, supplemented for earlier years by publications of the Missouri Geological Survey and other local and less official sources. When all else failed, the available data were projected backward to hazard a reasonable guess as to the unrecorded early output of important areas. Fortunately, the proportion of such prehistory production is not a large factor in any of the totals. These results were used during the next few years to measure the relative importance of various producing areas and to predict the peak period of development of the all-important Picher field. For the purpose of this review, the charts have been completed to the end of 1950. During World War 11, the U. S. Bureau of Mines became interested in a similar study and issued comprehensive statistical tabulations of data up to 1945 ( Info. Circular 7383), which have been checked against the figures used herein. This tabulation, however, does not include all the earlier data used by the writer nor does it offer any estimates of the wholly unrecorded era in the beginnings of the earlier camps. The area covered in this study is shown in Fig. 1 on which are indicated the relative location and approximate outlines of the principal producing camps. This also shows the approximate yield to date of each major camp in terms of combined lead and zinc concentrates. The output of zinc concentrates is roughly seven times that of lead. Hence, the economy of the district has depended primarily on the price of zinc, with lead as an important byproduct. Over much of the productive period, lead concentrates averaged about twice the value of zinc concentrates per ton, and in certain mines or areas the proportion of lead to zinc was substantially above average. The Joplin district is largely flat prairie but is partly moderately dissected, partially wooded land with a relief generally less than 100 ft. The rocks are almost flat-lying, nearly parallel to the surface, and the chief ore formation is the Mississippian Boone limestone, including its cherty phases. This formation either outcrops in the producing areas or is covered by a thin veneer of Pennsylvanian shales. Virtually all the ore occurs within 400 ft of the surface, and a large part at less than 300 ft in depth. Most of the land was divided into small farms or town lots before mineral development; tracts seldom exceeded 160 acres, and averaged considerably less. Mineral rights followed the surface ownership, segregation was rare, and a system of leasing for mineral development became well established early in the region's history, many landowners deriving small to sizable fortunes from royalties. Because of the shal-lowness of the ore and other factors, prospecting and mining was cheaper than in almost any comparable mining district in the United States. This situation, coupled with the widely divided land ownership, offered a fertile field for promoters and speculators and led to the rise of many small mining concerns. Only in its later history, under stern economic compulsion, has control tended to centralize in a few companies. Under these conditions, any important new discovery or successful development had much the effect of a gold rush or an oil boom. Every property in the area was leased quickly, promptly drilled, and, if ore was found, it was soon on the market. Many companies and individuals participated, and the average producing lease-hold probably was about 40 acres in extent. Any important field thus was attacked by anywhere from 10 to 100 or more producers. Production zoomed, eventually steadied or wavered, and ultimately subsided, leaving a desolation of tailings mountains, cave-ins, empty housing, and wreckage. The object of this paper is to depict the pattern of this process, so far as metal production is concerned, and to note the way in which it reacted to economic and political pressures. Production Charts In Fig. 2 is charted the production record, in tons of lead and zinc concentrates combined, of eight of the principal camps, which together account for approximately 99 pct of the total district production, over the years from 1870 to 1950. This period covers all but the very minor beginning of mining history. Two important camps are divided by state lines; hence, it has been necessary to combine production records for the two portions, based on estimates that may be slightly in error. Certain camps are sub-dividable into important units for which separate figures are available in whole or in part and have been charted as fractions of the major unit. The corresponding price of zinc is shown above all the charts. Three camps, Aurora, Neck City, and Galena, show a remarkably symmetrical graphic pattern, which is interpreted as the norm. The curves rise steeply to a peak, level off for an irregular interval, and then drop sharply to zero on a slope corresponding roughly to that covered by the initial rise. The three portions of these charts seem appropriately characterized by the designations of youth, maturity, and decline. On the whole, with some irregularities, the production in each of the three periods seems to be almost equal. A fourth camp, Granby, fails to conform to the normal pattern. It exhibits a very long period of reasonably uniform, stabilized production corresponding to maturity, followed by a rather precipitate decline. Its youth is hidden in the era of prehistory. This habit of steady, long-continued production at an even keel is attributable to the fact that this camp, more than any other, was controlled largely by a single principal owner at any given period over most of its history and this permitted the imposition

Jan 1, 1952

"Coulter's Rainbow and Crooked Falls are situated about five miles below the City of Great Falls. Coulter's, the first of the series in the course of the river, is unimportant and has been submerged by the Rainbow dam. Next below Coulter's is the Rainbow Falls, 47 feet in height. Following Rainbow Falls is the Crooked Falls, 21 feet in height. The power developed at this point is such that the one clam, power house and tail-race utilize the power from all three of the above falls.The development at Rainbow was started October, 1908, and completed July, 1910. It has a total capacity of 21,000 k-w. in generators, and 36,000 h-p. in waterwheels, and operates at 105 foot head. The general scheme of development is typical of what may be called standard practice in the west for plants of medium head, and consists of a low diverting clam, a double pipe line feeding into a balancing reservoir near the plant, and individual pen-stocks supplying the turbines from this reservoir.The dam is a rock-filled crib structure 1,146 feet long and 29 feet high, the up-stream side of which slopes at such an angle that the stability of the clam is assured even under the greatest floods, the weight of the water acting to hold it down, so that the higher the flood the greater the stability. The down-stream side is also sloping and tapers off into a long apron so designed as to take care of any overflow which may occur without shock or commotion. The clam is founded on solid rock throughout its entire length."

Jan 1, 1913

By R. D. Carnahan

The authors are to be complimented on their timely study of solution-hardening effects in a bcc metal. Unfortunately there are some misleading aspects of the paper that should be discussed and clarified which is the purpose of this letter. In particular the writer is concerned about the allusions to rate theory of deformation that are inferred by the authors. This position is taken on the basis first of the "weaker" temperature dependence of the yield and flow stresses of the alloy relative to pure niobium and second of the strong temperature dependence of the Young's modulus of elasticity. It is by now well-recognized that any collection of data points used to determine a flow-stress temperature-dependence relationship must be established under isostructural conditions, i.e., similar or identical sessile and mobile dislocation densities and arrangements. Admittedly this is a formidable experimental undertaking and not what would be expected in an exploratory investigation of the present kind. As an alternative to the former one can consider, however, the temperature dependence of flow stresses at comparable strains. In the present study the authors have elected to use the lower yield stress and ultimate strengths to exhibit the temperature dependence of their alloys except for the data points taken at liquid nitrogen temperature. Here they have used the proportional limit for the yield stress and the fracture stress for the ultimate strength. This seems to be an unrealistic choice particularly in view of the fact that this temperature is below the duc tile-brittle transition region for the alloy and no supporting data points were obtained between -55" and -196°C. If the authors' data in Fig. 2 are extrapolated and data points selected at a constant strain, for example a strain of 0.01, the reader can quickly verify that a temperature dependence exactly paralleling that of pure niobium is obtained.

Jan 1, 1967

By A. Wahab Khair

This paper presents an analysis of fracture mechanisms in coal subjected to bi-axial state of stresses, indentation of laterally con- fined coal specimen. Coal specimens were loaded to failure by the straight wedge indenters at various lateral confinement pressures. Strain distribution and acoustic emission characteristics of coal specimens under stress were recorded. The influence lines of vertical forces acting on the horizontal straight boundary of the coal specimen for each type of wedge indenter have been established using holographic interferometry technique. The effects of wedge indenter angle, confinement pressure, and coal anisotropy on fracture types, failure modes, and post-failure conditions were studied. The results indicated that combined application of holographic interferometry and acoustic emission monitoring techniques is not only suitable for studying deformability of heterogeneous and microscopically discontinuous material under stress but it also enhances the mode of fracture during the post failure stage.

Jan 1, 1984

By THEODORE DWIGHT

Members of the Institute have already received a special pamphlet descriptive of the United Engineering Society building, and wilt doubtless be interested in the progress that has been made up to date-February 24th-in erecting this home for the engineering profession. The old buildings on lots Nos. 25 to 33 W. 39th St., New York, were,' removed many months ago, but final contracts for the new, building were not let until the summer of 1905. The size of the building is 115 ft. on 39th Street, and 88 ft. in, depth; the height from, the sidewalk to the top of the parapet is 220 feet. The cubic contents of the building from the. bottom of the basement floor, to the top of the roof, including the pent houses, is 2,290,000 cubic feet. The number of light's, in the building will be between 4,000 and 4,500. The air supply for Auditorium and Lecture. Halls will amount to nearly 10.0,000 cu. ft, per minute, and the exhaust. to 90,000 cu. ft. per minute. In excavating for cellar and foundations, the average depth where good rock was. found was 37 ft.-it varied, however,: from 27 to 65 ft., due to an old water-course having run through the center of the lot; this condition, and the presence of soft rock, which rapidly disintegrated when exposed to air and water, made the foundation-work very difficult. As two of the column-footings of the building have to sustain a weight of 3,000,000 11) each, the most substantial foundations are necessary; 13,000 cu. yd. of earth were excavated for the foundation and basement; and 1,600 cu. yd. of concrete were necessary, to build up the footings. In the completed building there will be about 3,500,000 bricks. Owing to the number of auditoriums, and their location, and the placing of the library on the top floor; where allowance will have to be made for the enormous weight of 300,000 books, the structural steel work has been unusually complicated in this building. For instance, over the auditorium there are two 60-ton plate-girders, made up

Mar 1, 1906

By F. W. Luerssen, J. F. Elliott

F LUSHING the early slag from a stationary open Fhearth having a high percentage of hot metal in its charge is necessary in order to remove silica from the system. The flush slag is strongly oxidizing and is somewhat acidic. It has, however, considerable capacity to extract phosphorus from the bath and it also removes considerable manganese. It seems probable that factors which control the distribution of phosphorus and manganese between slag and metal in the refining period also should be dominant in the flush and postflush periods. Several studies, as summarized elsewhere,1,2 support the viewpoint that conditions closely approaching equilibrium for these elements are rather readily established during the refining period. Over the years these studies have repeatedly demonstrated that 1—high slag v01ume, 2—low bath and slag temperature, 3—basic slag, and 4—strongly oxidizing slag favor rapid elimination of phosphorus from the bath to the slag. They also show that the following conditions favor retention of manganese in the bath: 1—low slag volume, 2—high bath and slag temperature, 3— basic slag, and 4—minimum oxidizing power of slag. When it is considered that the flush slag often carries as high as 75 pct of the manganese charged and only 25 to 60 pct of the phosphorus charged, it is evident that in removing silica much manganese is sacrificed but phosphorus removal is far from conplete. Because of overriding circumstances, this is accepted in most operations and actually it is considered to be inevitable. This may account for the fact that little attention has been paid to conditions affecting the elimination of phosphorus and manganese in the flush slag. A recent study of the behavior of various charge oxides has developed considerable information on the flush and postflush periods. Because the data are felt to be of general interest, they have been brought together and Presented in this paper. The object is to show the various factors in the flush and postflush periods which influence elimination of phosphorus and manganese. Physical Conditions During and After Flushing Physical conditions existing during the flush vary from plant to plant, from shop to shop, from furnace to furnace, and even from heat to heat. They are strongly influenced by the physical and chemical character of the charge oxide which is ordinarily necessary to provide sufficient oxidizing power early in the heat. Invariably the period is characterized by a vigorous reaction between the principal re-actants: the hot metal being added and the charge oxide. During the flush, it is probable that the slag acts to some extent as an oxidizer; but, because of the critical influence of the behavior of the charge oxid'e on flushing action, it seems apparent that the oxide itself is the dominant oxidizer. Fig. 1 shows the course of two heats which were selected as being typical of the group studied. Heat A was charged with 55 pet hot metal, based on the total metallics charged, and heat B had 57 pct hot metal. As indicated in Table I and Fig. 1, the melt-down slag, which is not usually voluminous and which is principally FeO, expands greatly in volume and will show rather high levels of SiO2, MnO, and P2O5 very soon after the beginning of the hot metal addition. Simultaneously, large volumes of CO are liberated which cause violent mixing of slag and metal. It is of interest to note that the time required to bring carbon down to a low level is very much longer than that required for the removal of silicon, manganese, or phosphorus. At the end of flush, carbon in the bath is still approximately 2 pct. When strongly reducing hot metal is brought into contact with strongly oxidizing conditions within the furnace! it is probable that the rate of mass transfer to the slag (and atmosphere) of silicon, manganese, phosphorus, and carbon initially depends principally on the rates at which the two participating phases are brought into contact That is, it depends on the nature of the various reactions. Later in the flush period, when the scrap is virtually all dissolved and the action of the bath has settled down to a steady and somewhat gentle boil, it is likely that other factors, such as the transfer of oxygen across the slag-metal interface, become dominant. The temperature of the slag-metal system is far from uniform. Heat is being driven by the flame down through the slag. Bubbling and surging of the metal also frequently brings portions of the bath in contact with the flame. At areas of contact between the ore and liquid metal, or slag and liquid metal, the oxidizing reactions generate much heat. On the other hand, scrap is being melted which tends to absorb large quantities of heat. Because the liquid bath is high in carbon, the steel scrap is brought into solution rapidly. This can proceed at a rather low temperature; and until much of the scrap has been taken into solution, the bath temperature would not be expected to increase appreciably. Consideration of these factors leads to the conclusion that during the flush period the slag should be rather hot and the bath relatively cold. Both observation and temperature measurements bear this out. Experimental Data The extended program of charge oxide evaluation permitted study of the widely varying conditions existing during the flushing period. Slag and metal analyses and bath temperatures reported herein (Tables I and 11) were obtained toward the latter portion of the work. Four different types of charge oxide, sinter, two types of hydraulic cement-bonded soft ores, and a pyrobonded agglomerate were used in the study. Although the heats reported were from only one 205 ton furnace, they show variations in flush slag analyses all the way from 25 pct FeO, which is typical with the use of a hard natural charge ore, to 45 pct FeO which resulted when a very poorly agglomerated fine ore was used. The physical behavior of the flushes showed a correspondingly wide variation from well controlled reactions to violent surges following periods of inac-

Jan 1, 1956

By K. Brack, G. H. Schwuttke

Annealing properties of subszerface amorphous lavers produced through high-energy ion implantation in silicon are studied. The buried layers are produced through the implantation of ions (nitrogen), ranging in energy from 1.5 to 2 mev. X-ray interference patterns, transmission electron microscopy, and resistivity profiling are used to study the annealing characteristics of the ion damage. The annealing experiments indicate a low temperature (below 700°C) and a high temperature (above 700°C) region. Significant changes occur in the amorphous layer during the high-temperature anneal. Such changes are corre-lated with the re crystallization of the amorphous silicon and the formation of subsurface (buried) silicon-nitride films. TODAY'S main problems in the field of ion implantation are related to the accurate determination and prediction of 1) the distribution profiles of implanted ions, 2) the lattice sites occupied by the implanted ions, 3) the lattice damage produced through ion implantation, and 4) the annealing characteristics of damage centers in the lattice. This paper reports investigations concerned with the problems listed under 3) and 4). EXPERIMENTAL Our investigations cover the energy range of incident ions from 100 to 300 mev and from 1 to 2.5 mev. The emphasis of this study is on the energy range from 1.5 to 2 mev. The experiments are conducted with single charged nitrogen ions. To implant the ions a van de Graaff generator is used as described by Roosild et al.1 Accordingly, a gas containing the desired ion specie is passed through a thermome-chanical leak into a radio frequency activated source. The positive ions are driven into the van de Graaff with the help of a variable voltage probe. Emerging from the accelerator the ions drift into a magnetic analyzing system and here the desired ion specie is bent 90 deg into the exit port. The ion beam leaving the analyzer is defocused and drifts down a 4-ft long tube to hit the silicon target. At this position the 20 pamp ion beam has a circular cross-section of 2.1 cm. N2 is used as a source gas for nitrogen ions. The implantation target is silicon with zero dislocation density, 2 ohm-cm resistivity, (111) orientation, mechanically-chemically polished, and 1 mm thick. The target is mounted on a water-cooled heat sink and kept at room temperature. A fluence of 1015 to 1016 ions per sq cm is used. RESULTS 1) Silicon Perfection after Bombardment. High-energy ion bombardment of silicon has some striking effects on lattice perfection. Some results were reported in detail previously at the Santa Fe conference2 and are here briefly summarized for the benefit of the experiments described in the following. 1.1) Identification of Surface Films on Silicon. After bombardment all samples are found to be coated with surface films. The films on the silicon surface vary in thickness and color; they can be transparent, slightly brown, or opaque. The films are thicker and darker in the high-intensity area of the beam and they delineate the bombarded surface area of the crystal. The films produce electron diffraction patterns characteristic of carbon and of SiO2. Carbon is predominant. The presence of carbon in these films was confirmed by use of the electron microprobe. Formation of the films occurs independently of the ions used and is attributed to a contaminated vacuum of the high-voltage machine. The carbon is most likely the product of the pump oil which is cracked and polymerized under ion impact. The films stick tenaciously to the silicon surface and burn off in a low-temperature Bunsen flame. 1.2) Mechanical Perfection of the Silicon Surface. The mechanical perfection of the bombarded silicon surface was investigated through optical microscopy, electron microscopy in which the replica technique is used, and optical interferometry. No mechanical damage of the surface was visible after bombardment. However, if a bombarded sample is soaked for several minutes in hydrofluoric acid (HF), gas bubbles may develop in certain spots of the silicon surface. It is also noted that in these areas the surface film starts to peel off. Relatively large patches of film come off if the sample is soaked in HF during ultrasonic agitation. After HF treatment, pits may be present on the silicon surface. The pit dimensions are estimated to be as large as 50 µ. The pits appear in the region of most intense irradiation. 1.3) Lattice Perfection After Bombardment. No lattice damage is found on the silicon surface. Electron transmission micrographs and selected area diffraction patterns of the surface show no difference before and after bombardment. Measured approximately 2 µm down from the surface, the silicon lattice throughout this depth is of good perfection. Well-defined Laue spots and Kikuchi lines are obtained from the surface as well as from the indicated area below the surface. However, some radiation damage is dispersed in this top layer. A sharp boundary line separates this surface layer from a highly damaged layer which extends further downward into the silicon. Typical of this

Jan 1, 1970

By AIME AIME

THE American copper mining industry is threatened with disintegration and destruction. This threat is not one which may only materialize in the distant future. The destruction has already commenced. At present, many domestic mines have already closed down. .Others are operating on a greatly curtailed basis. Those operating are doing so only at tremendous loss-because the selling price of copper is below the cost of production and rapidly diminishing financial resources and credit clearly forecast the early suspension of operations in most of the industry. Unemployment in the mining districts is increasing by leaps and bounds. While this condition is due in some measure to the present unsatisfactory state of business in general, the copper industry, unlike other lines of business, sees no possibility of recovery without definite aid. The fundamental, underlying cause of present conditions in the American copper mining industry is the unprecedented rise in foreign production, and the basic change which has taken place in the world copper industry in the last three years. The American industry had begun to feel this change early in 1929 long before the general collapse of business in the fall of that year. While the distress in the industry is undoubtedly aggravated by the present economic depression, it nevertheless would have arrived and. have been present at this time, regardless of general business conditions.

Jan 1, 1932

By George H. Anderson

A CHAPTER of appealing interest was added to the industrial history of the Southwest early in June, when the War Production Board gave final approval to the erection of a blast furnace, a battery of coke ovens, an ore-beneficiation plant, and other facilities for the production of pig iron in northeastern Texas, just north of the East Texas oil field. For many years the people of Texas and adjoining states have cherished the ambition and desire that eventually an iron and steel industry drawing upon local mineral resources would be established to serve Southwestern markets. The existence in this vicinity of valuable deposits of iron ore, limestone, and coking coal has been known in a general way for many years, and efforts have been made from time to time to use them in the production of iron. The present development promises to bring to realization the dreams of the men who have visualized what the establishment of this basic industry would mean to the region.

Jan 1, 1942

A LARGE proportion of the steel that is melted and refined in the United States and poured into ingots is made in basic open- hearth furnaces. The capacity of these furnaces varies over a wide range with a large majority falling within limits of 50 to 200 tons (Fig. 1) The two general types of furnace design used are stationary [ ] and tilting furnaces, the former being much more common. The fuel burned in such furnaces is either one of several types of gas, or a liquid fuel such as oil or tar, or a combination of gas and liquid fuel. GENERAL FEATURES OF FURNACE CONSTRUCTION The design of a modern stationary furnace built to burn liquid fuel and with a capacity of 175 tons is shown in Figs. 2 to 4. The cross- section of the furnace at the tap hole is illustrated in Fig. 2, which shows the bottom construction, sloping back wall, and the rigid steel

Jan 1, 1944