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By J. S. Kennedy, G. L. Simard, A. A. Lefrew, C. M. Judson, R. B. Booth

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from these laboratories.'* These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pct Zn for ZnS); and the quartz from Klondike, Mo., analyzed as 99.97 pct SiO,. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from SS supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1953

By J. S. Kennedy, A. A. Lefrew, C. M. Judson, R. B. Booth, G. L. Simard

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from these laboratories.'* These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pct Zn for ZnS); and the quartz from Klondike, Mo., analyzed as 99.97 pct SiO,. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from SS supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1953

By K. A. Jackson, J. D. Hunt

The discussion by Tammann and Botschwar of the transition from eutectie grouth to denrdritic plus eu-tectic growth is reviewed and applied to metallic eutectic systems. Using expevimental data on the geowth rate of the Pb-Sn eutectic, and an extrapolalion of dendritic growth rate in tin and Sn-Pb alloys , qlcantitatice prerlictiotls of the extent of the eutectic region in tin-vich Sn-Pb alloys are made. There are no experimenta1 measuvements available for detailed comparison with these predictions. EUTECTIC structures form over a small range of compositions. The theory of lamellar growth presented by Jackson and Hunt' indicates that it is in principle possible to have eutectic growth over almost the complete range of compositions between the two solidus lines. This does not occur in practice. Alloys far from the eutectic composition grow dendritically followed by a eutectic as shown in Fig. I. The transition from a eutectic to a dendritic plus eutectic interface cannot be predicted from constitutional undercooling arguments because constitutional undercooling always exists ahead of the eutectic interface.' Reasonable predictions can, however, be made using arguments originally put forward by Tammanl. and Botschwar.3 These and later workers'"*6 carried out extensive experimental investigations of the extent of the eutectic range in organic materials. They concluded that the structure formed, eutectic or dendrites plus eutectic, depended on which structure grew faster at the given undercooling. This is, of course, equivalent to the structure which grows with the smallest undercooling at a given growth rate. In this paper, we will discuss these ideas briefly and then apply them to predict quantitatively the range of eutectic growth in tin-rich Pb-Sn alloys. The temperature dependence of the growth rates of dendrites and eutectic for a typical metal alloy of eutectic composition is shown schematically in Fig. 2(a). The growth rate for the eutectic increases more rapidly with undercooling than those of the dendrites because of the short diffusion path maintained in the eutectic, see Fig. 1. For an alloy off the eutectic composition on the A-rich side, the growth rates shift as shown in Fig. 2(b). The liquidus temperature of the a phase increases, that of the 3 phase decreases, and the temperature of zero growth rate for the eutectic does not change. The curves, particularly the dendritic ones, change shape as well, but for our purposes the principal effects occur because of the change in liquidus temperatures.3-6 In an isothermal system, only a dendrites will grow above TE, Fig. 2(b). If the temperature is below TE, and both phases have nucleated, a dendrites will grow ahead of the eutectic at

Jan 1, 1968

By Guillermo V. Borquez

INTRODUCTION The basic factors that influence the selection of a mining method are the geometry of the ore deposit and the strength of the ore and surrounding rock. These factors usually determine the ore recovery and dilution of the deposit under analysis. For the purpose of this paper we will consider a generalized case of a block caving system and the sequence of the analysis needed to optimize ore recovery. The analysis presented is intended for the preliminary planning stage. The critical factors involved in the caving process are identified and the methods for evaluating the suitability of a particular deposit to the caving method of mining are outlined. The mine design is approached by identifying the two most important, dimensions: the size and spacing of the draw points. These dimensions are estimated from a simulation model which takes into account the ore recovery, the incremental value of the ore recovered, and the safety conditions of the operations. The model estimates the number of draw points required to extract efficiently and safely the broken ore from the caving area. This number is found in the range where the net incremental value of the ore is maximized and the probability of pillar failure does not exceed the limit which is acceptable for a safe mining operation. A mining method and its design are in a continuous process of optimization. This process is unique for each deposit because of the many parameters involved; therefore, a back analysis of the operations should be performed when possible. These analyses will indicate if the ore body responds in a predictable manner to the parameters contained in the geological, fragmentation, and draw point models. SELECTION OF ALTERNATIVE MINING METHODS The selection of a mining method best suited to define the minable ore reserves of a given deposit involves consideration of the geometry of the ore deposit and the strength of the ore and surrounding rock. These two factors are usually sufficient to determine the ore recovery and dilution of the deposit. After analyzing the geological reserves and defining the limits of the deposit, either an open pit or an underground mining method can be selected to define the minable ore reserves. The sequence of steps to follow in the selection of a mining method is presented in Figure I. From an economic point of view, the strip- ping ratio is the determining factor for the selection between an underground or open pit method. In turn, the stripping ratio is a function of the grade distribution and con- figuration of the ore body. In order to obtain a preliminary estimation of the stripping ratio, a parametric analysis could be applied, such as the approach used by Professor E. P. Pfleider (1972) and summarized in Table 1.

Jan 1, 1981

By J. S. Kennedy, A. A. Lerew, C. M. Judson, G. L. Simard

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from. these laboratories." These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that, are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren, machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as. the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite. flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the. selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pet Zn for ZnS) ; and the quartz from Klondike, Mo., analyzed as 99.97 pet SiO2. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from S82 supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1952

By T. J. Nowak

The heat flow processes determining the injection and shut-in temperature logs in a water injection well have been analyzed and the theoretical basis for determining the water injectivity profiles from the temperature logs has been presented. Both the injection and the subsequent shut-in logs are necessary to resolve the injection interval into relative water intake strata; the former, to provide an accurate estimation of the thicknesses of the strata, and the latter to indicate the major and minor intake rates into the strata. A procedure is described for estimating the injectivity profile from the temperature logs and is applied to several temperature logs. For a water injection well, a comparison is made of the injectivity profiles obtained from the core analysis, the spinner survey, and the temperature logs. INTRODUCTION In secondary recovery of oil by water flooding, the injectivity profile is needed to obtain diagnostic evaluation of water intake distribution over the injection interval. If the distribution is unfavorable among the various strata, corrective measures can be taken to provide better control. Numerous methods have been developed for determining the injectivity profile from water velocity measurements in well bores. Often, dependence is placed upon core analyses and/or electric logs for estimating the relative water intakes over the injection interval. In many cases, the temperature log method described herein will give results more diagnostic than those obtained through use of the other available methods inasmuch as it is based upon the study of temperature disturbances in and around the well bore as a function of water flow in the well bore and in the formation. This method is the result of analyses of a number of temperature surveys made in water injection wells to determine the point of entry of the water into the formation. The material in this paper is presented in two sections: the first deals with the theoretical study of temperature survey data, and the second deals with the field application. PART I — THEORETICAL TREATMENT OF TEMPERATURE LOG DATA Before discussing the various aspects of heat flow relative to temperature log data, the phenomena that give rise to well bore temperatures — namely, the indigenous formation temperature and the associated rates of heat flow — will be considered. Geothermal Gradient The geothermal gradient is defined as the increment of depth at which the indigenous subsurface temperature increases by l°. It is caused by the continuous flow of heat outward from the interior of the earth. The flow of heat is an equilibrium process between the heat sources, the thermal conductivities of the formations, and the mean surface temperature. Therefore, there is no accumulation of heat energy in the path of heat transmission, and the geothermal gradient for a given formation will depend upon its thermal conductivity.

Jan 1, 1953

By William A. Johnson

The mathematical analysis of diffusion curves in solid metals is carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. Experimental Procedure If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By G. E. McElroy

Though air jets occupy only a minor role in the ventilation of mines and other enclosures, their importance in this respect is greater than is commonly recognized and may be considerably increased as our conception of their modes of operation becomes clearer. The object of this paper is to discuss some of the ways in which air jets are involved in mine ventilation and some possible applications to the ventilation of mines and other enclosed spaces. The mention of air jets ordinarily suggests the use of some form of an air injector, such as the Venturi blower occasionally used for auxiliary ventilation in mines, or the Saccardo (injector) system used to a limited extent for ventilating railroad tunnels. Actually, the term covers such common phenomena as the discharge of air from fan pipes and coal-mine line brattices, and even from smoke stacks and fans. A knowledge of the general mode of air entrainment by jets also helps to explain certain phenomena—some mine-gas explosions, for instance—that otherwise would remain obscure. Jet action has been involved in three recent series of Bureau of Mines experi-ments in which the author has participated: experiments on fan-pipe discharge, On the dilution of gases discharged from a stack and On the ventilation of a ship's hold. Available data on the discharge of jets into large openings and on the design and performance of air injectors have been analyzed in considerable detail and supplementary experiments are planned for after the war. The results of the fan-pipe experiments have been combined with the analyses of data on jet discharge into large spaces, and have been published.' The results of the stack-gas dilution tests, which refer to a jet discharged into a crosswind, have also been published2 and a paper on the design and performance of injectors has been prepared for publication.3 These technical experiments and analyses form the background and the documented evidence for the following nontechnical discussion of the use of air jets in mine ventilation. Jet Characteristics The jets commonly encountered are those in which the air is in turbulent— as opposed to laminar, or streamline-— motion. The characteristics under discussion apply only to such turbulent jets and have their basis in theories of the mixing of turbulent air currents. Such jets have basic characteristics that are present, though variable in form, regardless of whether the jet expands freely in space, whether the expansion is limited by adjacent walls, or whether the jet propels air through a flow circuit. They expand at definite angles and entrain the surrounding air, even though the entrained air must be obtained by recirculation of their own air streams. As the quantity of air in motion in the mixed stream increases, the average velocity of the stream decreases.

Jan 1, 1946

By William A. Johnson

The mathematical analysis of diffusion curves in solid metals is carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. Experimental Procedure If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By S. F. Urban, G. Derge

At the time this investigation was initiated variations were observed in the quality of different heats of basic electric-furnace steels, although they had been made under purportedly similar conditions. This indicated that these variations were related to normally unobserved variations in the character of the bath, especially during the "refining" period. Although the slags used for this operation are commonly referred to as "reducing" slags, and are regarded as having a "deoxidizing" action on the bath, no reliable measurements of this action were available. It was decided, therefore, to study the behavior of oxygen in the metal for ' large enough number of heats to learn its normal variations and to relate these variations to regularly observed conditions of operation. The most important general conclusion reached was that the time a heat is held under a reducing 'lag should be reduced to a minimum, which was about an hour and a half under the conditions studied. Beyond this time no observable beneficial effects are obtained from the reducing slags, insofar as oxygen and sulphur content of the bath are concerned. It is likely that added time may increase hydrogen content as well as heat costs. The oxygen content of the bath is never reduced below the amount in equilibrium with the carbon. Concurrently with this work, J. S. Marsh1 presented data that supplement and support many of the results of this paper. Procedure The work was done in two different electric-furnace shops of the same plant. The selection of heats was made primarily with regard to the convenience of heat schedules. companion slag and metal samples were taken just prior to slag-ofi and throughout the refining period for an initial set of 17 heats, and before slag-off and near tap for an additional I3 heats. slag Sampling presented no particular problem; a spoonful of slag was poured onto a metal plate and when sufficiently cool was sealed in an airtight container. Sampling the metal for oxygen presented a more complex problem. Because of the lack of previous experience in sampling electric-furnace baths, a number of methods were compared. Chilled Wedge Samples2 An unkilled metal sample is removed from the furnace in a well-slagged car-bometer spoon and poured immediately into a heavy copper mold designed to provide rapid freezing. Three different types of molds were used to determine the optimum for electric-furnace hats. The Big wedge Mold (a) was a 4 by 4 by 4-in. split copper mold, yielding a wedge-shaped casting I in. wide, 1 1/2 in. long, and 34 in. maximum thickness, and was finally adopted as the most satisfactory design.

Jan 1, 1948

By M. T. Simnad, G. Derge, Ling Yang

STUDY of diffusion in molten substances is important in at least two respects. Diffusion data, combined with thermodynamic and kinetic information, throw light on the structure of the liquid state. Moreover, a knowledge of diffusion coefficients and their temperature dependence is useful in ascertaining the controlling step in many metallurgical reactions. Although diffusion measurements have been made on a number of molten salts, slags, metals, and alloys,'-'" the results available are still limited and widely scattered, especially for the high temperature melts. It is the purpose of this investigation to establish reliable procedures for the measurement of self-diffusion coefficients in high temperature melts and to use these procedures to determine the self-diffusion coefficients of iron in molten Fe-C alloys of different carbon contents. Experimental Measurement of self-diffusion coefficients in high temperature melts is usually carried out by using one of two methods. In the first, diffusion takes place between two cylindrical samples of the same material, one of which is made radioactive. The diffusion coefficient is calculated from the radioactivity penetration curve in the solidified sample after the diffusion. In the second method, samples contained in capillaries of an inert substance are immersed in an infinite reservoir of the same material. Either the material in the capillary or that in the reservoir is made radioactive and the diffusion coefficient is calculated from the change of the radioactivity of the sample in the capillary after the diffusion. The second method is simpler because a radioactivity penetration curve is not needed for the calculation of the diffusion coefficient; however,.it is valid only when no convection has occurred in the capillary during the diffusion. A radioactivity penetration curve is therefore always useful in indicating that the required conditions for the diffusion are ful- filled. Towers and Chipman" recently studied the self-diffusion of calcium and silicon in CaO-Al,O,-SiO, melts by using the capillary method. Instead of measuring the change of the radioactivity of the sample in the capillary, they autoradiographed the sample after the diffusion and calculated the diffusion coefficient from the intensity distribution of the autoradiograph. Their method is useful when the radioactive isotopes are weak ß-emitters, but is very difficult, if not impossible, to apply to cases involving strong ß or y-emitters. For such cases, sectioning of the sample according to the method of Morgan and Kitchener' may be used for the construction of the radioactivity penetration curve. The self-diffusion of iron in molten Fe-C alloys has been studied in this manner and the experimental procedures are described as follows: The diffusion apparatus is shown schematically in Fig. 1. The bath consisted of about 200 g of an Fe-C

Jan 1, 1957

By Frank C. Appleyard

Gypsum, the dihydrate form of calcium sulfate, has a history of usefulness to man dating back several thousand years, and a worldwide industry has been built on the mining and processing of this versatile industrial mineral. However, anhydrite, the other principal calcium sulfate mineral has very limited use, so much so that separate statistics for it are not always kept, but are usually included with those for gypsum. Although often found in close association, the two minerals have important chemical differences in that anhydrite is the anhydrous form of calcium sulfate (CaSO,) whereas gypsum is the dihydrate (CAS0;2H20). These two molecules of combined water result in significant differences in hardness, density, and solubility of the two minerals. However, of most importance is the difference in thermal properties wherein gypsum, upon the application of a modest amount of heat, can be converted to the hemihydrate of calcium sulfate (CaS0;Vi H,O) or plaster of paris, an intermediate product upon which is based over 90% of the value of all calcium sulfate end products. Anhydrite, on the other hand, is inert at these temperatures and its uses have been limited to only those few cases where calcium sulfate in the anhydrous form may have an advantage. The earliest known use of gypsum plaster dates back some 5000 years to the time of the Pharaohs of Egypt who had discovered that gypsum rock, when exposed to fire, broke down into a powder which when mixed with water would form a putty that could be "plastered" on a rough mud brick or stone wall to make a smooth finish. It was used down through the centuries in a limited way for ornamental purposes, but did not achieve wide acceptance because of its quick (25 to 30 min) setting or hardening time which made it difficult to use. The first real understanding of gypsum chemistry was developed in France about 1755, and the gradual growth of its present utilization dates from that time. In the United States, the first utilization of gypsum was to grind it to a fine material for use as a soil conditioner at about the time of the Revolutionary War, and the term "land plaster" for ground gypsum has remained in use. Another cementituous material-lime or calcium oxide-had become the usual plastering material, but by about 1870 a method for retarding the set of gypsum plaster was discovered and it has today almost completely replaced lime as a plastering material. In recent years, gypsum products sold in the United States have reached a total valuation of approximately $500 million per year as illustrated in [Table 1].

Jan 1, 1975

By C. Burton Clark, J. Spotts McDowell

Refractories are defined as "materials having the ability to retain their physical shapes and chemical identities when subjected to high temperatures," or as "nonmetallic materials suitable for the construction or lining of furnaces operated at high temperatures." While resistance to "high" temperatures is thus the primary requirement for refractory materials, it is by no means the sole requirement. They must be able to withstand thermal shock resulting from rapid heating or cooling; other stresses induced by temperature change; pressures from the weights of furnace parts or contents; mechanical wear (abrasion) resulting from movement of furnace contents; and chemical attack by heated solids, liquids, or gases. Refractories of many kinds are needed for the many and widely diversified industrial applications. Those in greatest demand are classified on the basis of composition or properties into a few main groups, known as alumina-silica, silica, basic and insulating refractories. In each of these groups there are several classes. In addition to those included in the main groups, there are various special refractories, including silicon carbide, carbon, zircon, zirconia, alumina, and several others. Alumina-silica refractories comprise two main divisions: fire clay and high-alumina. The alumina content of fire-clay refractories covers the range from about 45 pct to 18 pct, and the silica content from 50 pct to 80 pct. The alumina content of fired high-alumina refractories ranges from about 99 pct to 45 pct, and the silica content from about 0.5 pct to 50 pct. Silica refractories of the different classes contain 94 pct to 97 pct silica. Basic refractories include periclase (magnesite), chrome spinel, forsterite, and dolomite. Refractory materials, including insulating firebrick, are supplied mainly as preformed shapes. Other products include bonding mortars and high temperature cements, ramming mixtures, plastic firebrick, hydraulic setting castables, dead-burned grain magnesite, and dead-burned dolomite. Refractory brick are classified on the basis of their physical form as Standard Sizes and Special Shapes. The Standard Sizes are brick of certain definite sizes and relatively simple design which are used in sufficient amounts to permit quantity production. The brick most widely used are the standard 9 in. X 4 ½ in. X 2 ½in. and 9 in. X 4½in. X 3 in. straights and corresponding series of sizes. All brick of nonstandard dimensions are regarded as "special shapes." They include a wide variety of brick regularly used for specific services, such as baffle tile for boilers, checker brick for regenerators, and others; together with shapes of special design manufactured on particular orders from designs submitted by the user. Not included in the broad classifications of Standard Sizes and Special Shapes are several specific-service refractory products, usually made by companies which specialize in their manufacture, or in some cases by the consumers themselves. These products include

Jan 1, 1960

By N. J. Grant, D. S. Bloom

An investigation of the Cr-Mo-Ni ternary system and attendant binaries has been completed. Some changes in the binary diagrams are shown to be necessary. The 1250°C section of the ternary and the liquidus surface have been delineated. A system of invariant reactions existing above 1250°C has been suggested. BECAUSE chromium, molybdenum, and nickel are important not only as bases for alloying systems but also as major alloying additions for other refractory metals, a study of the phase diagrams is of great interest and importance. In addition there are interesting features of theoretical value, a number of which are of prime consideration in this work. The major aim was to determine the ternary phase diagram of these metals at and above 1250°C, with sufficient attention given to lower temperatures to permit an understanding of the conditions existing at 1250°C and above. To understand ternary systems it is essential that accurate information concerning the binary systems be available, which in turn presupposes thorough knowledge of the constituent elements. On the basis of this investigation not only were significant inaccuracies indicated in the binary systems but much consideration had to be given to one of the elements, that is, chromium. The observation has been made that chromium undergoes a crystal transformation at a temperature near its melting point. Much of the experimental data leading to the detection of this transformation and the effects of this hypothesis on the form of the Cr-Ni phase diagram have already been reported' . and will not be repeated here. The experimental methods employed in the investigation have also been covered.'-" he purity of the molybdenum utilized in this work showed by qualitative spectrographic analysis that chromium, copper, iron, silicon, and tungsten were present in quantities of 0.1 to 0.001 wt pct. During the course of the investigation more than 100 melts were made, weighing from 150 to 200 grams each. Each of these melts was sectioned for chemical analysis and for specimens for examination in the as-cast and various heat-treated conditions by X-ray and metallographic means. All X-ray diffraction patterns reproduced here were made using chromium Ka radiation although iron and copper targets were used on occasions during the investigation. Experimental Results Mo-Ni-System: The most recent comprehensive investigation of the Mo-Ni system was made by Ellinger' in 1942; the diagram as shown in the American Society for Metals Handbook is based on his work. The work done on the system in this investigation substantiated the general form of the diagram although some differences were observed. These are indicated by a comparison of Ellinger's diagram and Fig. 1, the latter showing the results of pertinent thermal analyses made in this research. It can be seen in Fig. 1 that the eutectic composition is

Jan 1, 1955

By William A. Johnson

THE mathematical analysis of diffusion curves in solid metals is Carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. EXPERIMENTAL PROCEDURE If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By S. Isserow

RECENTLY, a description of the wartime work in this laboratory on the U-Si phase diagram was published. This diagram was available earlier in the open literature; as were Zachariasen's crystal structure identifications for the compounds in the system. The uranium end of the phase diagram is shown in Fig. 1. The most recent work on this system has emphasized the peritectoid E phase, of particular interest for a number of reasons. The early work provided evidence of this phase's resistance to corrosion in water and of its slight ductility. Further information on these properties has been obtained here. Work elsewhere4 has provided evidence of stability under irradiation. This body-centered-tetragonal phase is relatively isotropic compared to the more usually applied a or ? uranium phases. Unlike the other compounds in this system, it contains no Si-Si covalent bonds.3 In addition, consideration on the basis of Pauling's concepts leads to the conclusion that in the E phase, uranium has a higher valence than in any of the other phases. Definition of the composition of the ? phase has been of prime concern in the study of this alloy. Evidence is presented below that its silicon content is slightly higher than that of stoichiometric U8Si, the composition frequently assigned this phase on the basis of Zachariasen's identification. This work on the composition required careful attention to the method of dissolving the alloy for analysis, since apparently low silicon contents could be found under certain conditions, see Appendix. Preparation: Melting, Casting, and Heat Treatment—Almost all the samples were from castings with a diameter of 13/4 or 2 in. and about 1 ft long, weighing 10 to 15 lb. The U-Si charge was melted by heating to about 1650°C in an induction heated vacuum furnace. Beryllia crucibles were used at first, but were replaced by zirconia-washed graphite as the technique of keeping the carbon content low enough (about 500 ppm) was mastered. The alloy was bottom-poured at about 1650°C into graphite molds. A few small buttons, weighing no more than 50 g, were prepared in a small arc melting unit.' Since cast material has a preponderance of uranium and U8Si2, heat treatment is necessary to ob-tain the ? phase by the solid-solid peritectoid reaetion. Once obtained, the ? phase is stable to room temperature, obviating the need for speeial attention to the method of cooling after epsilonization, see Fig. 1. It was found desirable to epsilonize at 800°C for a week. For some purposes, in which residual uranium and/or U8Si2 are tolerable, shorter periods may be adequate. The temperature of 800°C is not critical, since essentially the same results were obtained from 785° to 825°C. Further departure from this epsilonization range is inadvisable.

Jan 1, 1958

By S. F. Urban, G. Derge

At the time this investigation was initiated variations were observed in the quality of different heats of basic electric-furnace steels, although they had been made under purportedly similar conditions. This indicated that these variations were related to normally unobserved variations in the character of the bath, especially during the "refining" period. Although the slags used for this operation are commonly referred to as "reducing" slags, and are regarded as having a "deoxidizing" action on the bath, no reliable measurements of this action were available. It was decided, therefore, to study the behavior of oxygen in the metal for ' large enough number of heats to learn its normal variations and to relate these variations to regularly observed conditions of operation. The most important general conclusion reached was that the time a heat is held under a reducing 'lag should be reduced to a minimum, which was about an hour and a half under the conditions studied. Beyond this time no observable beneficial effects are obtained from the reducing slags, insofar as oxygen and sulphur content of the bath are concerned. It is likely that added time may increase hydrogen content as well as heat costs. The oxygen content of the bath is never reduced below the amount in equilibrium with the carbon. Concurrently with this work, J. S. Marsh1 presented data that supplement and support many of the results of this paper. Procedure The work was done in two different electric-furnace shops of the same plant. The selection of heats was made primarily with regard to the convenience of heat schedules. companion slag and metal samples were taken just prior to slag-ofi and throughout the refining period for an initial set of 17 heats, and before slag-off and near tap for an additional I3 heats. slag Sampling presented no particular problem; a spoonful of slag was poured onto a metal plate and when sufficiently cool was sealed in an airtight container. Sampling the metal for oxygen presented a more complex problem. Because of the lack of previous experience in sampling electric-furnace baths, a number of methods were compared. Chilled Wedge Samples2 An unkilled metal sample is removed from the furnace in a well-slagged car-bometer spoon and poured immediately into a heavy copper mold designed to provide rapid freezing. Three different types of molds were used to determine the optimum for electric-furnace hats. The Big wedge Mold (a) was a 4 by 4 by 4-in. split copper mold, yielding a wedge-shaped casting I in. wide, 1 1/2 in. long, and 34 in. maximum thickness, and was finally adopted as the most satisfactory design.

Jan 1, 1948

By John L. Lamont, Walter Crafts

STUDIES of the effect of composition of steel on hardenability by Grossmann,1 and as-quenched hardness by Field2 and by the authors,3 have made it possible to predict the results of quenching when the composition and cooling rate are known. In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tempered properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq. in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as- quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content- Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after lie heat-treatment, differ considerably in tensile strength. PROCEDURE In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08-to 0.65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc. The accuracy of the method was finally checked on a variety of carbon, low-alloy and high- alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from ¼ to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability specimens quenched from a normal temperature for austenitization were used to obtain a range of as-quenched Rockwell C

Jan 1, 1946

By A. V. Deforest, A. R. Anderson, C. W. MacGregor

ONE of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing of the A.S.T.M., 1938. The work of Mann,1 Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserve especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by [P OL, plotting So = Ao as a function of eo = Lo] where A o and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors' It was shown that the true physical behavior of the material in the tension test could best be represented [by plotting the average true stress, S = P as a function of e = q' = log o = log Log] where P, A, L, S, e, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximum load point to fracture. The construction of such- curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain difficulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece

Jan 1, 1941

By A. V. Deforest, A. R. Anderson, C. W. MacGregor

ONE of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing of the A.S.T.M., 1938. The work of Mann,1 Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserve especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by plotting [So = ooT as a function of eo =o] where A o and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors? It was shown that the true physical behavior of the material in the tension test could best be represented by plotting the average true stress, [S = P] as a function of [e = q' = log A-le = log Lo] where P, A, L, S, [e], and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximum load point to fracture. The construction of such curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain difficulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece

Jan 1, 1941