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By P. M. Robinson, M. B. Beaer

The heat of formation at 0°C of the intermetallic compound AgMg as a function of composition has been determined by tin-solution calorimetry. In this technique, the heat of formation is determined as the difference in the heat effects, at infinite dilution, on dissolution of the compound and a mixture of its components added alternately to liquid tin from a reference temperature, such as 0°C. The experimental technique and method of calculation have been described elsewhere.' The compound AgMg is a 0 electron compound with a CsCl structure.2 In nonstoichiometric compositions of the compound, atoms of the excess component are substituted on the AgMg lattice.3,4 The homogeneity range is approximately 43 to 52 at. pct Mg at room temperature and 38 to 65 at. pct Mg at 500Oc.2 Single-phase alloys outside the homogeneity range at room temperature can be prepared by quenching. The specimens used in this investigation contained from 39.0 to 54.8 at. pct Mg. They were made available, together with analyses, by the Research Laboratory of the General Electric Co. Metallographic examination of the quenched specimens containing 39.0 and 54.8 at. pct Mg gave no indication of the presence of a precipitated phase. The measured heats of formation are listed in Table I. In a calorimetric run, four to six additions each of a specimen and the corresponding mixture of the components were made. One or two calorimetric runs were carried out with each composition depending on the amount of samples available. The limits stated in the table represent the experimental precision and not the absolute accuracy of the measurements. Thermodynamic investigations of the compound AgMg have been made by Trzebiatowski and Terpilowski 5 and Kachi.6,7 The heats of formation at 500°C derived from the combined electromotive-force values of these investigators8 are more exothermic than the heats of formation at 0°C reported here, Fig. 1. The differences cannot be explained by the difference in temperature. This is shown by the published heat capacity of the stoichiometric compound, which obeys the Kopp-Neumann rule from 0" to 500oC.9 The heats of formation derived from equilibrium data are generally considered to be less accurate than those determined by calorimetric methods because small errors in the change of the equilibrium values with temperature have a large effect on the calculated value of the heat of formation. The heats of formation derived from the combined published electromotive-force values reach a maximum at 56.0 at. pct Mg.8 Kachi reports a maximum of -4.7 kcal per g-atom at the stoichiometric composition.7 The present results also indicate a maximum at or near the stoichio metric composition, Fig. 1.

Jan 1, 1964

By F. C. von der Weid

The mining district of Sao Fidelis, in the northern part of the State of Rio de Janeiro, is situated on the Paraiba River, where it crosses the Serra do Mar (Mountain of the Sea), in the center of a mountainous country having numerous graphitic outcrops. For a long time, these outcrops were irregularly explored by local people, who had little means and no technical advice. A few years ago, the Cia. Brasileira de Mineracao de Grafite took over the control of some of the more important outcrops and entrusted to me the task of studying the ores and establishing a flowsheet for a pilot plant to be situated in Sao Fidelis—the ore to be concentrated being mostly of a very high grade. Mineralization and Ores The rocks of the district are mostly gneiss and crystalline schists, with occasional interstratification of dolomitic limestone belonging to the Archean Brazilian Fundamental Complex. The general direction of the beds is roughly between 60' and 80°E., with variable dip, generally nearly vertical. Mostly, direction and dip of the graphitic outcrops is concordant with the embanking gneisses or schists. These outcrops seem to be aligned in two or three parallel zones (Padua, Sao Fidelis, Mac- abu), the Sao Fidelis zone being the best known and the most important to date. Two outcrops of the Silo Fidelis zone, Saudade and Sao Benedito, are now being exploited. Mining has beer] carried out, so far, on a small scale. The mineralization consists of a vein of nearly massive graphite in a very compact, partially granitized gneiss, with vertical dip. The vein is most irregular, nith nests and lenses irregularly distributed along the fracture plane. The ore consists chiefly (particularly in Sao Benedito) of massive graphite appearing and disappearing along the main direction of the vein, forming a succession of irregular lenses in a sort of rosary design. The average width is more or less one foot, with variations from zero to 6 feet. The lode minerals are quartz, a little feldspar and garnet (the latter having its origin perhaps in the embedding gneisses), with rare ferruginous clays on the outcrops. In Saudade a little pyrite, pyrrhotite and chalcopyrite is found occasionally, as well as a carbonaceous mineral, very light, black and shiny, with conchoidal fracture, looking like a sort of jet. The composition of this mineral has not yet been established, but it seems to be very complex. The mineralization seems to be hydro-thermal at a rather low temperature, perhaps mesothermal. The paragenesis, according to samples from Saudade, seems to be as follows, the earlier minerals being listed first: pyrrhotite, pyrite, chalcopyrite, with quartz concomitant to the three and graphite formed later. Age of the mineralization is still uncertain, owing to the very in-

Jan 1, 1947

By F. C. von der Weid

The mining district of Sao Fidelis, in the northern part of the State of Rio de Janeiro, is situated on the Paraiba River, where it crosses the Serra do Mar (Mountain of the Sea), in the center of a mountainous country having numerous graphitic outcrops. For a long time, these outcrops were irregularly explored by local people, who had little means and no technical advice. A few years ago, the Cia. Brasileira de Mineracao de Grafite took over the control of some of the more important outcrops and entrusted to me the task of studying the ores and establishing a flowsheet for a pilot plant to be situated in Sao Fidelis—the ore to be concentrated being mostly of a very high grade. Mineralization and Ores The rocks of the district are mostly gneiss and crystalline schists, with occasional interstratification of dolomitic limestone belonging to the Archean Brazilian Fundamental Complex. The general direction of the beds is roughly between 60' and 80°E., with variable dip, generally nearly vertical. Mostly, direction and dip of the graphitic outcrops is concordant with the embanking gneisses or schists. These outcrops seem to be aligned in two or three parallel zones (Padua, Sao Fidelis, Mac- abu), the Sao Fidelis zone being the best known and the most important to date. Two outcrops of the Silo Fidelis zone, Saudade and Sao Benedito, are now being exploited. Mining has beer] carried out, so far, on a small scale. The mineralization consists of a vein of nearly massive graphite in a very compact, partially granitized gneiss, with vertical dip. The vein is most irregular, nith nests and lenses irregularly distributed along the fracture plane. The ore consists chiefly (particularly in Sao Benedito) of massive graphite appearing and disappearing along the main direction of the vein, forming a succession of irregular lenses in a sort of rosary design. The average width is more or less one foot, with variations from zero to 6 feet. The lode minerals are quartz, a little feldspar and garnet (the latter having its origin perhaps in the embedding gneisses), with rare ferruginous clays on the outcrops. In Saudade a little pyrite, pyrrhotite and chalcopyrite is found occasionally, as well as a carbonaceous mineral, very light, black and shiny, with conchoidal fracture, looking like a sort of jet. The composition of this mineral has not yet been established, but it seems to be very complex. The mineralization seems to be hydro-thermal at a rather low temperature, perhaps mesothermal. The paragenesis, according to samples from Saudade, seems to be as follows, the earlier minerals being listed first: pyrrhotite, pyrite, chalcopyrite, with quartz concomitant to the three and graphite formed later. Age of the mineralization is still uncertain, owing to the very in-

Jan 1, 1947

By R. S. Busk, E. G. Bobalek

THE relation between gases and metals has been a subject of increasingly active investigation during the past years, principally devoted to the study of metal-hydrogen systems. It has been found that hydrogen is soluble in most molten metals to an appreciable extent and somewhat soluble in most solid metals.1,2 In every known case there is a sudden decrease in solubility at the melting point. Thus a freezing mass of metal containing hydrogen in excess of the solid solubility must in some way expel that excess during the freezing process. This leads to internal blowholes, and such effects as pinhole porosity. Gas trapped in metal that is to be fabricated by a working process such as extrusion or rolling may be the cause of blisters. For some cases, notably in copper and iron alloys, the presence of hydrogen can lead to extreme embrittlement of the metal. The aluminum-casting industry has long recognized the importance of hydrogen in its techniques. Excess gas in molten aluminum alloys often leads to the formation of "pinhole porosity" in the solid casting.3 To prevent this hydrogen pickup it is necessary to avoid overheating the melt and to protect it from such sources of hydrogen as water. In spite of all precautions, it is sometimes necessary to extract hydrogen from the melt just before pouring by bubbling with a gas such as chlorine or nitrogen. Recently it has been found that somewhat similar effects are possible with magnesium alloys, in that the presence of hydrogen can induce or aggravate microporosity.4-6 This paper is primarily concerned with a presentation of some facts concerning the solubility of hydrogen in magnesium and its alloys, with some discussion of the significance of these facts in a practical sense. In any study of gas-metal systems it is important to bear in mind a clear distinction between adsorption on surfaces and absorption within the lattice.1 Considerable attention has been directed toward determining whether hydrogen is truly soluble in any solid metal, or whether the gas extracted from a sample was present at surfaces (external and internal) only.7 Most present day evidence supports the idea of true solution in addition to adsorption. A second important factor when dealing with gas solubility is the dependence of such solubility on external pressure. For diatomic gases such as H2, solubility in both liquid and solid metals apparently is proportional to the square root of the pressure, indicating a breakdown to a monatomic gas before diffusion into the lattice .2 For true equilibrium values of solubility, therefore, the pressure at the metal surface must be constant and, preferably, known. Very little has been published concerning the hydrogen-magnesium system. Winterhager has presented the most

Jan 1, 1946

By H. C. Stumpf, L. A. Willey, V. L. Fink

Very few studies of the aluminum-sodium system have been reported. Heycock and Neville1 were unable to detect any solubility of sodium in liquid aluminum. Mathewson2 prepared an equilibrium diagram consisting of two horizontal lines at the melting points of the two metals. He was unable to detect solubility at either end of the system. Scheuer3 first developed a method for the chemical determination of sodium in aluminum and then studied the solubility of sodium in liquid aluminum. His method involved heating aluminum with excess sodium under hydrogen until the two liquids were at equilibrium, chilling the melt, and analyzing the aluminum-rich layer. He reported the solubility to be 0.10 pct sodium at 700°C, 0.115 pct at 750°C, and 0.128 pct at 800°C. This paper on the aluminum-sodium system is the twenty-first in a series from the Aluminum Research Laboratories describing equilibrium relations in aluminum alloy systems. Materials The alloys for this investigation were prepared from electrolytically refined aluminum (99.99 pct) and sodium of reagent quality conforming to specifications of the American Chemical Society. Chemical analysis of the aluminum showed the fol- lowing impurities: 0.002 pct Si, 0.002 pct Fe, 0.002 pct Cu, <0.001 pct Mn, 0.002 pct Mg and 0.001 pct Na. The sodium content of all alloys was determined by either chemical or spectro-graphic standard procedures5 No. IIA and No. SI I respectively. Determination of Miscibilitv The boundary of the miscibility gap was determined by a modification of the method of Scheuer3 and of that used by Henry and Cordiano. As finally developed the method was as follows: A fused alumina crucible 25 mm id with 75 mm depth and 1.5 mm wall thickness was placed on the bottom of a container made from a 4-in. length of 1 1/2-in. iron pipe and pipe caps. ?&apos;he space around the sides of the crucible was filled with 40 mesh crystalline alun-dum. A charge of 60 g of aluminum and 10 to 15 g of sodium was placed in the crucible, the sodium first being trimmed and rinsed with iso-pentane to remove kerosene. The container was tightly capped, filled with argon (99.6 pct pure), and heated to the desired temperature (between 670 and 800°C). A positive pressure of argon (about 8 mm of mercury) was maintained through a small pipe to the upper cap. After soaking for from 2 to 5 hr, the container was quenched by directing a stream of water onto the base, so that solidification of the aluminum-rich layer was rapid and essentially unidirectional. Analyses were made on drillings taken from the bottom of the ingots after machining off the surface layers. Pre-

Jan 1, 1949

By J. E. Breen, J. Weertman

The creep rate of polycrystalline tin was studied as a function of temperature and stress in constant stress experiments. The temperature was varied from room temperature to almost the melting point of tin. Activation energies were calculated from tests run at the same stress. It was found that on a log creep rate vs inverse temperature plot the experimental points did not fall on one straight line but on a line which changed its slope in the 90° to 160°C region. Two activation energies for the creep of tin can be calculated from the data: a value around 26,000 cal per mol at high temperatures and a value around 11,000 cal per mot at low temperatures. It is suggested that the discrepancies between the creep activation energies and those of self-diffusion can be accounted for if self-diffusion takes place predominately by Zener&apos;s ring mechanism rather than through vacancy or interstitial movement. SHERBY, Orr, and Dorn&apos; and Dorn&apos; have recently reviewed some of the data on high temperature creep of metals. -The data show that the activation energy of high temperature creep is approximately equal to the activation energy of self-diffusion. This same correlation has also been successfully made between the activation energy of grain boundary relaxation and that of self-diffusion.3,4 The metal tin does not fit into this simple picture. Its activation energies of self-diffusion differ appreciably from that of grain boundary relaxation and of creep. Fensham,5 from a precisely performed experiment, has determined that the activation energies of self-diffusion of tin are 10,500 and 5,900 cal per mol along the C and A axes, respectively. There are two energies because of the anisotropic nature of tin. Rotherham, Smith, and Greenough6 have shown that the grain boundary relaxation activation energy is 19,000 cal per mol (measurements made from room temperature to 100°C). Puttick and King7 found the same activation energy for grain boundary slip in bicrystals of tin (180° to 225°C region). Until recently, there was no high temperature large strain creep data on tin suitable for activation energy calculations. At rather small strains (up to 0.01), Tyte8 had made a series of measurements on tin from which activation energies can be calculated. In Fig. 1 are plotted some of his data on a log creep rate vs inverse temperature graph. It can be seen that Tyte&apos;s work indicates that at a relatively low temperature the activation energy is around 7,400 cal per mol but at higher temperatures the activation energy increases. Since Tyte measured the creep only for small strains, it is doubtful if a

Jan 1, 1956

By J. G. Thompson

Determinations of the hydrogen content of irons and steels invariably are subject to two serious difficulties: (I) the determination of amounts of 0.001 per cent or less of any constituent requires an analytical procedure of unusual precision and accuracy, and (2) the hydrogen content of many samples is dccidedly not stable; i.e., there is no assurance that the content at the time the analysis is made is the same as it was when the sample was taken or at some previous time in the history of the piece. In respect to both the precision and speed of the determination, the vacuum-extraction procedure for the determination of hydrogen possesses advantages over the vacuum-fusion procedure, which has been the recognized standard for the detcrmination of other gaseous elements in sted-— oxygen and nitrogen for example. The basic facts upon which the vacuum-extraction procedure is based—i.e., the evolution of gas from solid steel when it is heated in vacuum, and the fact that the evolved gas is rich in hydrogen—were observed by Graham1 many years ago. Subsequent investigations have shown that hydrogen exists in steel chiefly as interstitial solid solution (i.e., in atomic dispersion) and perhaps to some extent as hydridcs that are unstable and decompose to form atomic hydrogen. In either case practically all of the hydrogen in steel at elevated temperatures exists in the atomic condition and consequently is able to diffuse readily through the metal. In contrast to this, other gaseous elements, such as oxygen and nitrogen, normally are present in steel chiefly in the form of relatively stable compounds such as oxides or silicates and nitrates; i.e., the oxygen and nitrogen atoms are fixed in stable combinations and are not free to migrate. The only oxygen or nitrogen that can diffuse in steel is the small amount in solution (atomically dispersed) and the rate of diffusion of these atoms is much less than that of hydrogen because of their greater atomic volume and lower mobility. Consequently, it is possible to extract most or all of the hydrogen from solid steel in a reasonable time at moderately elevated temperatures, but the procedure is not applicable to the determination of oxygen or nitrogen. It is only within the last decade that these observations have been developed into an analytical procedure for the determination of hydrogen. Apparatus and Procedure The apparatus used at the National Bureau of Standards,6 for the determination of hydrogen by the vacuum-extraction procedure, is shown schematically in Fig. I. The specimen, freshly cleaned and dried,* is suspended on a fine wire within the quartz furnace tube that is connected to the reservoir system and analytical train.

Jan 1, 1945

By H. l. Burghoff, C. H. Mathewson

THE study of the creep of metals under conditions of prolonged loading has received the attention of many investigators for several years and almost innumerable papers have been published on the various aspects of the subject. As it appeared that much could still be learned from a study of single crystals, the present work was carried out to study the effects of temperature and conditions of loading upon the properties and deformation in tension of single crystals of alpha brass containing about 70 per cent copper and 30 per cent zinc. In particular, it was hoped to obtain information from tests below and above the recrystallization temperature of the material, so that properties such as elastic limit, yield point or critical stress, and manner of deformation might be compared for tensile tests at an ordinary loading rate and for prolonged. loading. Accordingly, short-time tensile tests and creep tests were made at room temperature, 300º, 500° and 700°F. The two latter temperatures are above the lowest possible recrystallization temperature of polycrystalline 70-30 brass. PREVIOUS WORK Clarke and White1 have made creep tests of some copper-zinc alloys, including 70-30 brass, and copper-zinc-tin alloys at temperatures both below and above the recrystallization temperature of the materials considered. Hanson and Wheeler have studied the flow and fracture of single crystals of aluminum for short-time and prolonged tensile loading over a range of temperature extending from room temperature to 400°F., their experiments being made without consideration of the orientations of the test specimens. Extensive creep and fracture tests on single crystals of lead at room temperature have been made by Betty3 and by Baker, Betty & Moore.4 Results of the last-named investigation were published while the present work was in progress. Millers examined the elastic limit of zinc single crystals at and above room temperature by means of creep tests, while Miller and Milligan6 reported the results of tests designed to show the influence of temperature on elastic limit of single crystals of aluminum, silver and zinc. The behavior, of iron crystals under static tensile loading at room temperature was reported by Gensamer and Mehl7 while the present investigation was in progress. Their specimens exhibited a well-defined yield point, below which no appreciable creep could be detected. The manner of yielding proved interesting, as the shape of the creep-time curve for the iron crystals differed from the common type of creep curves. Elongation did not begin immediately, or at least was initially very slow. The rate of elongation then increased continuously and finally decreased to zero. This S-shaped type of elongation-time

Jan 1, 1941

By L. G. Sprague

The fact that this latest and most modern of the Universal Atlas Cement Company&apos;s plants at Northampton, Pa., is the fifth to be built on these same properties, and their development has been coincidental with the development of the portland cement industry in the United States, makes it appropriate to sketch briefly the history of the successive steps. In 1889 the original Atlas Portland Cement Co. started its first plant at Coplay, Pa., which is just across the Lehigh River from the present operation. Here the first successful rotary kiln was operated. These kilns were 6 ft. in diameter and 60 ft. long; they used oil for fuel until 1895, when the company developed the first burner for pulverized coal. Shortly thereafter the Atlas company acquired property on the Northampton side of the river and built its plants Nos. 2, 3 and 4 within the following 10 years. During the same period the production of portland cement in the country was increasing rapidly; owing largely to the development of the rotary kiln and improved grinding machinery, which lowered the cost and improved the quality of cement. The general tendency has been to increase the length of the kiln and grind both raw material and finished product Liner. In 1930 the Atlas Portland Cement Co. and the Universal Portland Cement Co. united to form the Universal Atlas Cement Co., and the same policy of improving the product has been continued. Because of the large amount of research carried on by manufacturers and consumers, including government agencies, there is a demand for cement of different chemical and physical characteristics for different kinds of structures. Hence many engineers in recent years have been asking for cements of certain definite chemical analyses, which they think are best for their particular jobs. This has compelled the manufacturer to make several different types of cement by variations of chemical composition. These are generally made by adding silica, iron and lime to the standard mixture, which necessarily increases the cost of the product. Therefore the Universal Atlas Cement Co., in planning the modernization of its Northampton plant, gave this particular phase of the problem considerable study. Research and experimentation have developed the practicability of making a wide variety of differently proportioned raw materials for cement by a process of subtraction rather than by addition. With such process, it is possible to discard the undesirable aluminates and silicates from the ample supply of impure limestone available from the company&apos;s property rather than by adding high-grade limestone obtained from distant sources. This procedure requires mineral separation by centrifugal sedimentation and froth flotation. Since the chemical and mineral constituents of Lehigh Valley "cement rock," together with the methods of separating them, have been thoroughly described in published

Jan 1, 1948

By L. G. Sprague

The fact that this latest and most modern of the Universal Atlas Cement Company&apos;s plants at Northampton, Pa., is the fifth to be built on these same properties, and their development has been coincidental with the development of the portland cement industry in the United States, makes it appropriate to sketch briefly the history of the successive steps. In 1889 the original Atlas Portland Cement Co. started its first plant at Coplay, Pa., which is just across the Lehigh River from the present operation. Here the first successful rotary kiln was operated. These kilns were 6 ft. in diameter and 60 ft. long; they used oil for fuel until 1895, when the company developed the first burner for pulverized coal. Shortly thereafter the Atlas company acquired property on the Northampton side of the river and built its plants Nos. 2, 3 and 4 within the following 10 years. During the same period the production of portland cement in the country was increasing rapidly; owing largely to the development of the rotary kiln and improved grinding machinery, which lowered the cost and improved the quality of cement. The general tendency has been to increase the length of the kiln and grind both raw material and finished product Liner. In 1930 the Atlas Portland Cement Co. and the Universal Portland Cement Co. united to form the Universal Atlas Cement Co., and the same policy of improving the product has been continued. Because of the large amount of research carried on by manufacturers and consumers, including government agencies, there is a demand for cement of different chemical and physical characteristics for different kinds of structures. Hence many engineers in recent years have been asking for cements of certain definite chemical analyses, which they think are best for their particular jobs. This has compelled the manufacturer to make several different types of cement by variations of chemical composition. These are generally made by adding silica, iron and lime to the standard mixture, which necessarily increases the cost of the product. Therefore the Universal Atlas Cement Co., in planning the modernization of its Northampton plant, gave this particular phase of the problem considerable study. Research and experimentation have developed the practicability of making a wide variety of differently proportioned raw materials for cement by a process of subtraction rather than by addition. With such process, it is possible to discard the undesirable aluminates and silicates from the ample supply of impure limestone available from the company&apos;s property rather than by adding high-grade limestone obtained from distant sources. This procedure requires mineral separation by centrifugal sedimentation and froth flotation. Since the chemical and mineral constituents of Lehigh Valley "cement rock," together with the methods of separating them, have been thoroughly described in published

Jan 1, 1948

By R. T. DeHoff

A new approach to the measurement of the size distribution of particulate structures imbedded in opaque bodies is developed. The method is based upon the assumption of a general two-parameter distribution curve, and the estimation of these two parameters from three well-known counting measurements made upon metallogvaphic sections. The total number of particles in the system is also a product of the analysis. Application of the method with the assumption of the logarithmiconorma1 disfribution function is developed in detail. A complete description of the geometry of a particulate structure requires the determination of the size distribution of particles. The problem of estimating the size distribution of particles of a particular phase in a multiphase system, or the grain-size distribution in a homogeneous system, has been approached by many investigators.&apos;-&apos;0 All of the solutions proposed by these investigators share the following characteristics. a) A minimum of several hundred particle sections in the microstructure must be examined, and some characteristic dimension recorded, such as area,3&apos;5 intercept length,6"9 or diameter.1&apos;2&apos;4&apos;10 b) The resulting data must undergo a series of fairly complex calculations to generate the empirical histogram which describes the size distribution in three dimensions. c) In order to manipulate the result, the histogram must be fitted to some assumed mathematical formula, using the attendant statistical procedures. d) With two notable exceptions,8,10 the particles must be spherical. The measurements and calculations involved are in general very tedious and time-consuming, with the logical result that much effort has been expended in the development of equipment which will perform these tasks automatically and semiautomati-cally.9,11-15 considerable success has been achieved in this area, but the equipment is in general expensive, and usually places stringent requirements On the quality of microstructure which can be reliably analyzed. In laboratories which do not possess such equip- ment, the analysis of geometry is usually limited to measuring total properties of the microstructures, such as volume fraction and interfacial area, because the measurements required are much simpler to make. The determination of size distributions rarely is undertaken. The development which is presented in this paper permits the estimation of size distributions of three-dimensional structures from the same simple counting measurements which are required to determine the surface area and volume fraction of the particulate structure, and one other counting measurement. The basic approach that is used is to assume a general mathematical form for the distribution, which is described by two parameters (as the normal distribution is described by assigning values to the mean and the standard deviation), and then estimate these two parameters from the results of the counting measurements. The introduction of a third counting measurement also permits the evaluation of the number of particles per unit volume, Nv.

Jan 1, 1965

By Marston G. Fleming

CRITICAL pH has been defined by Wark1 as that pH value below which a mineral will float and above which it will not float in solutions containing a given concentration of collector but free from other depressants or activators. - The relationship between mineral, collector concentration, and pH is expressed in the form of a critical pH curve determined by the captive bubble method and is generally regarded as being fundamental to the system involved. The mechanism of alkali depression is currently in dispute, two general theories having received authoritative support. The view expressed in Taggart&apos;s chemical theory of flotation2 is that in the presence of a critical concentration of hydroxyl ions, all the metal ions available at the surface of the mineral are present as anions of the form [M (OH)x]-y. The formation of the necessary metal xanthate is thus precluded and, furthermore, any metal xanthate coating previously formed, at a lower pH, will be dissolved. Gaudin3,4 and the Melbourne school under Ware hold that alkali depression is caused by the preferential adsorption of hydroxyl ions by the mineral surfaces. This paper describes an investigation of the mechanism of alkali depression in each of the three systems: cerussite-aqueous carbonate-xanthate, cerussite-xanthate, and galena-xanthate. Alkali Depression of Cerussite by Control of Carbonate Ion Concentration Wark and Cox6 have shown that in the presence of Na2CO3 a higher concentration of xanthate is required to effect bubble contact with a cerussite surface than in carbonate-free solutions. To examine this depression of cerussite by sodium carbonate, a series of captive bubble tests was carried out on cerussite specimens in solutions containing 100 mg per liter of potassium ethyl xanthate and varying concentrations of sodium carbonate. The pH was adjusted by the addition of dilute hydrochloric acid. For purposes of comparison a standard critical pH curve was determined for cerussite with potassium ethyl xanthate in solutions containing no added carbonate. In the latter case pH adjustment was made with sodium hydroxide. The experimental method employed in both series was broadly similar to that described by Wark and Cox;7-9 a number of refinements suggested by Sutherland10 were adopted, and the procedure was further developed and modified to suit the particular requirements of the investigation. The relationship between pH and the concentration of potassium ethyl xanthate necessary to induce bubble contact at cerussite surfaces is shown in Fig. 1. The relationship between pH and the concentra- [ ] tion of sodium carbonate necessary to prevent bubble contact at cerussite surfaces in the presence of 100 mg per liter of potassium ethyl xanthate is shown in Fig. 2. Comparison of the. two curves shows that at a collector concentration of 100 mg

Jan 1, 1952

By R. J. Teitel

FOUR or five years ago an investigation was initiated to study and develop basic information on llquid metal fuels for future power nuclear reactors. The objective was to find fluid forms of uranium (solutions or dispersions) in low melting alloys. A summary of the different fuels was presented in a recent article by Teitel, Gurinsky, and Bryner.&apos; The combination of uranium and bismuth, with its low thermal neutron cross section and low melting point, is of basic interest to the development of these fuels. Most of the previous effort on the U-Bi phase diagram was done under security regulation. Ahmann and Baldwin&apos; reported their findings on the U-Bi system in 1945. Their results indicated that the phase diagram had at least two compounds and possibly one more. UBi, and UBi were established by chemical analyses of residues after high temperature centrifugation of alloys. UBi, decomposed peritectically at1980°C and there were signs of another reaction above that. UBi melted at a very high temperature, and there were also signs of a monotectic at high temperatures in high uranium alloys. The solubility of uranium in liquid bismuth has received attention by three groups of authors: Bareis,X ayes and Gordon,&apos; and Ahmann and Baldwin.&apos; The latest and most widely accepted data is that of Bareis, and it is included in Fig. 1 along with new data at higher temperatures. Brewer et al." and Ferro"&apos;&apos; have used X-ray diffraction to determine the number and crystal structure of the compounds. Brewer identified the structure of UBi to be a simple NaCl cubic structure having a cell edge of 6.364A. The density of the compound was calculated to be 11.52 g per cu cm. Two other unindexed patterns were presented as possibly belonging to two other compounds. Ferro agreed with Brewer on the crystal structure of UBi and identified the structure of UBi, and U,Bi,. The intermetallic compound UBi, has a tetragonal cell with a = 4.445A and c = 8.908A. The density of the compound was determined and the number of atoms per cell (six atoms) was calculated. The X-ray density reported was 12.35 g per cu cm. The compound UsBir was treated in a similar way and it was reported to have a cubic structure 9.35A on an edge and to contain 28 atoms per cell. The density was given as 12.59 g per cu cm. Teitel reported that there was a compound UaBi, and no UBi, compound. (The difference in the compositions is 3.3 pct U.) This conclusion was based upon the extrapolation of some 20 tie lines in the

Jan 1, 1958

By M. D. Hassialis

THE claim is made in a number of patents1,2,3,4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S¬R[=]-R’ (where x = r,2, . . . ), with the restriction that if the aromatic radicals R, R&apos; contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using Biphenyl sulphide, ditolyl disulphide and dinapthyl disulphide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed was that of Moses, Hess, and Perkins. A sample of ore weighing 500 grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a 2-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8: 1. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of 12: 1. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. CONTACT-ANGLE TESTS In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcocite, chalcopyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By R. W. Fenn, H. A. Lepper, W. R. Hibbard

THIS paper reports the results of static tension and torsion tests made on single crystals of alpha brass for the purpose of determining its elastic coefficients. 70-30 alpha brass was chosen because it has been used extensively in the study of the plastic deformation and because it has the following desirable characteristics: (1) face-centered cubic structure, (2) marked elastic anistropy, (3) low elastic modulus. In 1928 Masima and Sachs&apos; using static methods reported the following values for the elastic coefficients of 72-28 pct alpha brass: S11 = 19.4 X 10-13&apos; cm2 per dyne S12 = —8.35 X 10"&apos; cm2 per dyne S44 = 13.9 X 10-13= cm2 per dyne These values were obtained from the measurements shown in fig. 1. The experimental points for both tension and torsion lie consistently below the lines drawn to represent them. Fig. 2 shows the stress-strain curves for their specimens. Only a few points in the elastic range of these curves were available to obtain their values for Young&apos;s modulus. Therefore, it was considered that a re-evaluation of these data was desirable. In addition a variation of from 1.13 to 1.485 kg per mm2 was found in the values of the critical resolved shear stress for 70-30 alpha brass reported by Burghoff,² Treuting and Brick: Martin,4 Maddin, Mathewson and Hibbard5,6 and von Goler and Sachs.&apos; Therefore, it was desired to evaluate the conclusion of Boas and Schmid8 that a constant resolved shear stress and not a constant elastic shear initiates plastic deformation. Theoretical Considerations*: The elastic deformation of cubic crystals may be defined by three elastic coefficients (S11, S12, S44,) or three elastic parameters (C,,, C,, C,,). These coefficients or parameters are sufficient to define the stress and strain relations for cubic crystals in the generalized form of Hooke&apos;s law referred to Cartesian coordinates. Elastic parameters and coefficients in the cubic system are related by the expressions: C11 —S11+S12/(S11-S12)(S11+2 S12) C12=-S12/(S11-S12)(S11+ 2 S12) (S11 — S12) (S11 + 2 S12) [2] C44 =1/S44 PI It is possible to determine all the elastic coefficients for a cubic metal by measuring two of the three elastic constants: Young&apos;s modulus (E), torsion modulus (G), or compressibility (S). The following relations exist between crystallographic orientation and E, G and S for cylindrical crystals of the cubic system: 1/E = S11 — 2 [(S11 - S12) — Su] (?1² ?2² + ?2²?83 + ?3² ?1²) [4]

Jan 1, 1951

By Don B. Carson, Donald L. Katz

NATURAL gases under pressure form crystal-line hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methane-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbonrich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. INTRODUCTION Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villard1 and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies.2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Deaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on temperatures and pressures of hydrate formation for pure methane, ethane, propane, n-butane, methane-ethane mixtures, methane-propane mixtures, methane-butane mixtures, and some 15 natural gases, all in the presence of excess water. However, up to the present time no method has been available for predicting the temperature at given pressures or the pressure at given temperatures at which natural gases will form hydrates if saturated with water. This paper pre¬sents data on the methane-propane-water, methane-pentane-water and methane-hexane water systems in four phases, one of which is the hydrate. The application of the phase rule to the methane-propane-water data proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1941

By Thomas Fraser, H. F. Yancey

Prior to the war just ended, Germany was the greatest coal producer in continental Europe. In 1943 the production of coal, bituminous and higher in rank, together with brown coal calculated to the equivalent amount of bituminous coal, is estimated to have been about 240 million metric tons, according to the War Department. Before the war production in Germany exceeded consumption. No other country in continental Europe except Poland had a large surplus. However, England&apos;s surplus was the largest in Europe as a whole. Before World War II the Ruhr Basin normally supplied about 70 pet of the total production of high-rank coal, the Saar and Aachen about 6 pet each, Upper Silesia about 14 pet, and Silesia and Saxony the remainder. Nearly one third of the brown coal was produced in the Rhineland, a little less than one half in central Germany nest of the Elbe River, and about one fourth east of the Elbe. Bituminous coal and brown coal together constituted by far the most important energy resources of the old German Reich. Bituminous coal furnished nearly 70 pet of the total energy requirement, brown coal supplied about 25 pet, and water power, wood, petroleum and alcohol together aggregated only 7 pet. Because it was the most important single mineral resource of Germany, an excess of coal enabled the Reich to import nearly all the other mineral products that she lacked, such as iron ore from Lorraine. The area adjacent to the coal fields was supplied with gas from an interconnected grid. Similar electric grids are based on brown coal with the power stations at the mines. Coal tar provided the foundation for the development of the extensive German chemical industries as exemplified by the I. G. Farbenindustrie. For almost a century, German scientists have been adequately supported both by the State and by industry in studying improved methods of utilizing coal. In Germany the mineral rights were reserved by the State and ordered eatraction of coal was enforced. Each lease comprised a relatively extensive area. which accounts for the generally large size of the mines and mining companies In 1938 there were 160 mines in the Ruhr, with a total output of 125 million tons but 90 pet of the production was controlled by 20 companies. By far the largest single coal-mining company in Germany was the Gelsen-kirchener Bergwerke A. G., which produced nearly 27 million tons in the Ruhr in 1937. Second was Saargruben A. G. a State-owned company operating in the Saar, which produced &apos;lore than &apos;3 million tons. Third was Bergwerksgesellschaft Hibernia A. G., with 10 million tons, also in the Ruhr. Briquettes are made from both bitumillous coal and brown coal, but in 1938 some 44 million toils of brown-coal bri-

Jan 1, 1947

By Thomas Fraser, H. F. Yancey

Prior to the war just ended, Germany was the greatest coal producer in continental Europe. In 1943 the production of coal, bituminous and higher in rank, together with brown coal calculated to the equivalent amount of bituminous coal, is estimated to have been about 240 million metric tons, according to the War Department. Before the war production in Germany exceeded consumption. No other country in continental Europe except Poland had a large surplus. However, England&apos;s surplus was the largest in Europe as a whole. Before World War II the Ruhr Basin normally supplied about 70 pet of the total production of high-rank coal, the Saar and Aachen about 6 pet each, Upper Silesia about 14 pet, and Silesia and Saxony the remainder. Nearly one third of the brown coal was produced in the Rhineland, a little less than one half in central Germany nest of the Elbe River, and about one fourth east of the Elbe. Bituminous coal and brown coal together constituted by far the most important energy resources of the old German Reich. Bituminous coal furnished nearly 70 pet of the total energy requirement, brown coal supplied about 25 pet, and water power, wood, petroleum and alcohol together aggregated only 7 pet. Because it was the most important single mineral resource of Germany, an excess of coal enabled the Reich to import nearly all the other mineral products that she lacked, such as iron ore from Lorraine. The area adjacent to the coal fields was supplied with gas from an interconnected grid. Similar electric grids are based on brown coal with the power stations at the mines. Coal tar provided the foundation for the development of the extensive German chemical industries as exemplified by the I. G. Farbenindustrie. For almost a century, German scientists have been adequately supported both by the State and by industry in studying improved methods of utilizing coal. In Germany the mineral rights were reserved by the State and ordered eatraction of coal was enforced. Each lease comprised a relatively extensive area. which accounts for the generally large size of the mines and mining companies In 1938 there were 160 mines in the Ruhr, with a total output of 125 million tons but 90 pet of the production was controlled by 20 companies. By far the largest single coal-mining company in Germany was the Gelsen-kirchener Bergwerke A. G., which produced nearly 27 million tons in the Ruhr in 1937. Second was Saargruben A. G. a State-owned company operating in the Saar, which produced &apos;lore than &apos;3 million tons. Third was Bergwerksgesellschaft Hibernia A. G., with 10 million tons, also in the Ruhr. Briquettes are made from both bitumillous coal and brown coal, but in 1938 some 44 million toils of brown-coal bri-

Jan 1, 1947

R.. B. T. KILIANI, New York, N. Y.-I do not care to discuss Mr. Taggart&apos;s paper in the light of theory, as that has been very well done by Prof. Bell,1 but I should like to criticize some of his conclusions, in the light of actual operating practice at plants all over the country. 1. Mr. Taggart&apos;s first conclusion is that in crushing average ore, the character of the gangue has little effect on the efficiency of the mill. This, I believe, is not in accordance with the usual practice, since in crushing a hard ore the capacity will be much reduced below what it would be with a softer ore, while the power consumed will be practically independent of the character of the ore, being proportional only, to the load of ore and balls in the mill. 2. Mr. Taggart&apos;s second criticism is that the Hardinge mill is not suitable for grinding soft, tough material. In answer to this I might mention that the mill is being used for grinding tough, dnctile material, such as metallic aluminum, and also for grinding licorice root. 3. He says that the ball-mill works more efficiently on material of intermediate size, say 1/2 to 3/4 in., than on either coarser or finer feed.. This is true as to coarser feed. For the most efficient work, I believe that a ball-mill should be fed with material not coarser than 1 1/2 in.; it&apos; will handle material up to 3 and even 4 in., but the reduction from 3 or 4 in. to 1 1/2 in. can be done much more cheaply and efficiently by rolls or disk crushers than in the ball-mill. 4. As to Mr. Taggart&apos;s fourth conclusion, that a greater ratio of reduction can be expected with feed of an intermediate size than with a coarse feed, I have not enough information to express an opinion. 5. His next conclusion is that steel balls are much more efficient crushing media than pebbles. Steel balls are undoubtedly more efficient for crushing coarse feed. On fine material they are also more efficient as to tons per horsepower crushed to 10-mesh, but on fine material I think it will be found that flint pebbles are cheaper than cast-iron balls, per ton of ore, although there will be a saving in power per ton by using cast iron instead of flint. The increased cost of crushing with cast iron will be due to the higher cost of iron at the present time. 6. Mr. Taggart&apos;s sixth conclusion coincides with present practice, that steel balls will grind as fine or finer than pebbles when working on the same feed.

Jan 1, 1918

By J. H. Lightfoot, Stuart E. Buckley

DEEP drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.1 The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen4,5,6 and by others,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems.9-17 It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 lb. per sq. in. Thus, at pressures of 2500 lb. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 600°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduction. The combined effects of pressure and temperature on condensation and vaporization of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpretation of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate systems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21.22 it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has

Jan 1, 1941