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By Colman Goldberg

IT is customary to plot crystallographic planes or axes on a Wulff stereographic net which is ruled with parallels of latitude and meridians of longitude. If a single crystal is placed at the center of a sphere, the coordinates of a crystallographic plane or axis are the coordinates of the point where the axis intersects the sphere. The standard (HKL) projection is the projection for which the sphere is rotated so that the (HKL) pole is at the center of the projection. Schiebold and Sachs' and many others have published standard projections for the more important planes of a cubic crystal. With Tables I and 11, it is possible to plot any plane (HKL) of a cubic crystal on a standard (001) projection if the absolute values of the individual H, K, and L are nine or less, which is almost always the case. Using the methods outlined by Barrett,' the standard (001) projection can be rotated so that any arbitrary plane is at the center of the projection. The tables are believed to be important for two reasons: 1—The heretofore published standard projections usually are not of the proper size to fit the stereographic nets available. With these tables a standard projection can be made which will be of exactly the proper size for the available stereographic net. 2—With the tables, planes that do not appear on the previously published standard projections can be easily plotted. For these reasons, the tables are especially useful in the study of optical reflections from etched surfaces and can also be used to make a standard projection for the axis which is normal to the macroscopic surface. (This axis can be found by X-ray or optical methods.) Then if the crystal is etched, the effect of the etchant can readily be determined by comparing the latitude and longitude of the reflecting planes (as determined with an optical goniometer) with the standard projection that has been prepared. Use of the Tables Fig. 1 shows the meridians and parallel which have been designated as zero longitude and latitude. The tables themselves are self-explanatory. The

Jan 1, 1953

By D. J. Carney, J. Chipman, N. J. Grant

SINCE the beginning of this century it has been known that hydrogen contributes to the porosity of steel and that it is harmful to its mechanical properties. The evidence for this has been largely qualitative. Steel to which hydrogen was purposely added. in sufficient .amounts was shown to be either porous or brittle or both, whereas similar steel of low hydrogen content was shown to be free of porosity and to possess normal physical properties. There have been a considerable number of qualitative experiments of this type. Also, early in this century, a few attempts were made to measure the amount of hydrogen normally dissolved in commercial steels. This was usually done by placing the sample under an inverted liquid column such as mercury and collecting the evolved gas. These attempts, while not successful in measuring actual amounts of dissolved hydrogen gas, were able to prove that this gas will diffuse out of steel at room temperature, and that the amount of hydrogen dissolved is normally very small. On the basis of such qualitative evidence, hydrogen has been and still is blamed for a great number of the troubles encountered in the steel industry. In recent years, partial solutions for many steel-working problems have been obtained. These have led to increased interest in accurate quantitative work on hydrogen in steel, with the expectation that the results might possibly answer a few of the remaining unsolved problems. Commercially, two of the obvious questions which are in need of an answer are: (1) what are the most important sources of hydrogen, and (2) what quantity of hydrogen can be tolerated in various steels? There are many other unanswered questions. To begin to find the answers it seemed logical to start at the beginning of steel production with the liquid metal. Further, it seemed almost imperative to solve first the problems of analysis and sampling of the metal for hydrogen. Once these problems have been solved, it would be possible to answer more of the important commercial problems mentioned above. As a consequence, it was decided to design an analytical apparatus and, upon satisfactory completion of this, to develop an accurate method of sampling liquid metal for hydrogen.

Jan 1, 1951

By B. Alexander, G. Derge W. Peifer

This is part of a research project in the Metals Research Laboratory of Carnegie Institute of Technology, sponsored by the Carnegie-Illinois Steel Corporation. In organizing our program it became apparent that the problem of analyzing molten steel for hydrogen must be divided into two parts: (I) the correct analysis of a given sample, and (2) the correct sampling of the bath. Emphasis has been placed upon these divisions in the order named because methods of sampling cannot be evaluated until a satisfactory method of analysis is available. Vacuum fusion was selected from the list of possible analytical methods because it seemed to us to offer the best possibilities for giving rapid, accurate results on solid steel samples. A number of objections have been raised against this method as usually practiced. We have sought to meet some of these by proper design of the apparatus. Experiments will be described which show that others are not valid. In the conventional apparatus the sample is held under high vacuum for a period of several hours before it is actually analyzed and one might expect considerable hydrogen to escape during this period. We have provided a means of introducing the sample to the vacuum just before analysis. Another difficulty has been that the entire apparatus has been designed primarily for the purpose of analyzing for oxygen, which constitutes upward of go per cent of the total gases evolved from the sample The volume and pressure measurements have therefore been insensitive to the relatively small amounts of hydrogen present. This difficulty obviously can be taken into account in any apparatus designed especially for the amounts of hydrogen expected. Analysis in Vacuum-fusion Apparatus A number of experiments were carried out to determine the importance of several factors that have been stated as possible sources of error or uncertainty in vacuum-fusion analysis for hydrogen; namely, that hot graphite will absorb some of the gases, that metal vapor will cause discrepancies, and that low results may be obtained as a result of the water vapor (produced by the oxidation of the hydrogen) dissolving in the butyl phthalate of the manometer, or that the blanks obtained from the apparatus are so great as to make the method inaccurate. The experiments also checked on the accuracy and feasibility of using differential freezing as a method of gas analysis in a vacuum-fusion apparatus.

Jan 1, 1945

Apparatus and a method for determining the volumetric behavior of hydrocarbons at pressures up to 10,000 psia and at temperatures between 0° and 460°F are described. The equipment is suitable for measuring the total volume of the system and the volume of a liquid phase as functions of state within these ranges of temperature and pressure. Introduction During the past two decades there has been a marked increase in the ranges of temperature and pressure encountered in underground hydrocarbon reservoirs of commercial interest. In addition, greater interest in the intensive characteristics of the fluids found in these reservoirs has developed. Apparatus Several types of apparatus have been developed in the authors' laboratory for volumetric measurements of hydrocarbon systems. The earliest equipment described1 was characterized by constant volume, and the weight of material present was varied systematically in order to attain the different pressures desired in the study. Later another apparatus2 was built in which the effective volume of the cylindrical cell, which confined a hydrocarbon sample of constant weight was varied by injection or withdrawal of mercury. The effective total volume of the equilibrium cell was measured by ascertaining the position of the mercury surface but no measurement could be made which gave knowledge of the volumes of individual phases existing within the hydrocarbon system. A third apparatus3 was designed for use at higher pressures and temperatures than the earlier equipment would tolerate. This apparatus was of the variable volume type but was built in the general form of a U-tube, the mercury level being measured at the surface which was not exposed to the hydrocarbon system. This arrangement avoided the need of subjecting measuring equipment to the extremes of temperature at which studies were made, but it gave no provision for measurement of the volumes of individual phases. Although this last apparatus was satisfactory as to accuracy and convenience for many purposes, need was felt for measurements of the volume of the liquid phase of the hydrocarbon system. For this reason a fourth equilibrium apparatus was designed and constructed, and it is the purpose of the present paper to describe it. The equilibrium cell has a working range of temperature from 0° to 460°F at pressures up to 10,000 psi. Provision for measurement of both total volume and liquid-phase volume makes it particularly suitable for the equilibrium study of heterogeneous systems consisting either of simple mixtures or of complex field samples of hydrocarbons. The general arrangement of the ap-

Jan 1, 1948

Apparatus and a method for determining the volumetric behavior of hydrocarbons at pressures up to 10,000 psia and at temperatures between 0° and 460°F are described. The equipment is suitable for measuring the total volume of the system and the volume of a liquid phase as functions of state within these ranges of temperature and pressure. Introduction During the past two decades there has been a marked increase in the ranges of temperature and pressure encountered in underground hydrocarbon reservoirs of commercial interest. In addition, greater interest in the intensive characteristics of the fluids found in these reservoirs has developed. Apparatus Several types of apparatus have been developed in the authors' laboratory for volumetric measurements of hydrocarbon systems. The earliest equipment described1 was characterized by constant volume, and the weight of material present was varied systematically in order to attain the different pressures desired in the study. Later another apparatus2 was built in which the effective volume of the cylindrical cell, which confined a hydrocarbon sample of constant weight was varied by injection or withdrawal of mercury. The effective total volume of the equilibrium cell was measured by ascertaining the position of the mercury surface but no measurement could be made which gave knowledge of the volumes of individual phases existing within the hydrocarbon system. A third apparatus3 was designed for use at higher pressures and temperatures than the earlier equipment would tolerate. This apparatus was of the variable volume type but was built in the general form of a U-tube, the mercury level being measured at the surface which was not exposed to the hydrocarbon system. This arrangement avoided the need of subjecting measuring equipment to the extremes of temperature at which studies were made, but it gave no provision for measurement of the volumes of individual phases. Although this last apparatus was satisfactory as to accuracy and convenience for many purposes, need was felt for measurements of the volume of the liquid phase of the hydrocarbon system. For this reason a fourth equilibrium apparatus was designed and constructed, and it is the purpose of the present paper to describe it. The equilibrium cell has a working range of temperature from 0° to 460°F at pressures up to 10,000 psi. Provision for measurement of both total volume and liquid-phase volume makes it particularly suitable for the equilibrium study of heterogeneous systems consisting either of simple mixtures or of complex field samples of hydrocarbons. The general arrangement of the ap-

Jan 1, 1948

By C. M. Nickerson

The possibility of deeper production in the Buena Vista Hills was first considered in 1933. At that time, however, the heavy state curtailment program served to deter any operator from drilling test wells, which, if successful, might upset the proration schedules. Because most of the acreage was held by several major operators and the remainder by substantial independents, the adoption of a plan of cooperative development was considered desirable. Such a plan was formulated for the development of any deeper oil and gas horizons that may be found to exist. This plan, which was signed by the Secretaries of the Navy and of the Interior on behalf of the United States on July 9,1936, is now effective for the development of lands within the area shown on Fig. 1. Unlike most unit plans, the present cooperative development plan permits each operator to drill and produce his own wells. For the purpose of this plan the Buena Vista Hills field is divided into two pools. The present production is classed as the " old pool,"' while any future production below a certain marker which roughly coincides with the bottom of the Santa Margarita formation is included in the "pool" to which the provisions particularly apply. Naval Petroleum Reserve No. 2 lies within the area and constitutes the major portion of the Federal leases subject to the plan. There are 39,040 acres and 27 operators within the area. Twenty-six operators controlling 99.5 per cent of the acreage have signed the agreement. Geology oF the Buena Vista Hills The Buena Vista Hills consist of a low range in the southern portion of the San Joaquin Valley, and are roughly parallel to the adjacent Temblor range to the south. The Elk Hills oil field parallels the Buena Vista Hills a few miles to the north. The subsurface structure is a re-entrant anticline upon the major Midway-Sunset monocline. This anticline is divided into two minor

Jan 1, 1937

By N. H. Murlenberg, T. M. Drown

It is often a tedious matter to get a solution of pig iron or steel, for the determination of phosphorus, which is absolutely free from silica. Where pig iron rich in silicon is dissolved in hydrochloric or nitric acid in the usual procedure, it is necessary, not only to evaporate the solution to complete dry ness, but to heat the dry residue for some beam in an air-bath to a temperature of about 120° C. The oxide of iron is thus rendered insoluble in nitric acid, and is only slowly dissolved by hydrochloric acid. In the method of determining silicon by nitric and sulphuric acid, described in the Transactions of the Institute, Vol. VII, page 346, arid Vol. VIII, page 508, we obtain in one or two hours a solution of the iron in the form of ferric sulphate entirely free from silica, and containing free sulphuric acid. It occurred to Us that this solution might be made available for the determination of the phosphorus by the molybdate method. The following experiments mere tried with unsatisfactory results. 1st. The iron was precipitated by ammonia, the precipitate filtered, washed, and dissolved in nitric acid. 2d. The iron was precipitated as basic acetate and dissolved in nitric acid. 3d. The solution was neutralized by ammonia, and nitric acid added in small excess. In all these cases the phosphorus obtained by precipitating by ammonium molybdate and magnesia-mixture was too low. The following method was then tried with success. The filtrate from the silica and graphite was evaporated to small bulk and heated in a porcelain dish on a sand-bath. until fumes of sulphuric acid ceased to escape. The dry residue was taken up with dilute nitric acid and the solution precipitated by ammonium molyldate. The phosphorus was weighed as magnesium pyrophosphate. The results were satisfactory. To save time, the original solution of the iron in nitric and sulphuric acids was evaporated to dryness and heated as before until

Jan 1, 1882

The 116th Meeting of the Institute is being held in New York as this Bulletin goes to press. A full account of the proceedings, together with a report of the discussion of technical papers, will be printed in the April Bulletin.

Jan 3, 1918

By Bryon W. Cheever

The greatest objection to be brought against the present methods for estimating phosphorus in iron and steel, is the time consumed in the operation. The following method, originated and perfected by Mr. E. D. Campbell, assistant in the chemical laboratory of the University of Michigan, will, 1 think, if carefully followed out, give results that are sufficiently accurate for technical purposes, and will give them in less time than they can be obtained by any other process. The process consists in comparing the color obtained by the action of stannous chloride upon a solution of the phospho-molybdate precipitate obtained from the solution of iron or steel, with that obtained from a standard solution of molybdie acid which represents a given amount of phosphorus. The operation is as follows : Take of ordinary steel 1 grm. and treat as in any of the wellknown processes until the phosphorus is precipitated as ammoniumphospho-molybdate. When precipitated, the phospho-molybdate precipitate is filtered out, thoroughly washed with an acid solution of ammonium nitrate, and, finally, twice with water, to remove most of the ammonium nitrate. The precipitate is then dissolved in about 1 c. c. of 10 per cent. potassium hydrate, which is let fall drop by drop on the filter till the precipitate is dissolved ; the filter is now washed with about 25 or 30 c. c. of water, and the potassium hydrate solution, which now consists of 25-32 c. c. of solution, is boiled until the peculiar frothy appearance, which first appears on boiling, is entirely gone. The solution is then cooled until perfectly cold, and about 10 or 15 c. c. of strong hydrochloric acid added ; if the solution is kept cold this will form no precipitate, but a light yellow or colorless solution. The solution is now ready for the addition of stannous chloride, and the subsequent comparison of color produced with that obtained from the standard molybdie acid. The comparison is made in tubes that are calibrated like carbon-tubes, but which are larger, about 5/8-inch bore, and graduated to 100 c. c.; this makes them about 18 inches long. To make the comparison of color, first transfer the now acid solu

Jan 1, 1886

By Louis E. Toth, Alan W. Searcy

A modification of Le Claire's microscopic model for self-diffusion is developed in a form suitable for prediction of activation energies for diffusion in disordered substitutional solutions as well as in pure metals Bonding is considered as a localized interaction, and the energy of bonding between atoms of different types is taken as the arithmetic mean of the energies in the pure elements. The activation energies for vacancy formation and migration in substitutional alloys are shown to depend on the empirical constants developed for self-diffusion when the equations are adjusted for the mole fractions of the two elements. The differences in activation energies between alloys and pure metals are calculated and compared with the experimental differences. MaNY different correlations have been proposed for use in predicting activation energies for self-diffusion or diffusion in dilute alloys. Usually theories for self-diffusion cannot be applied to alloys nor can theories for dilute alloys be satisfactorily adapted to self-diffusion. We present here a correlation scheme which can approximate activation energies for diffusion, vacancy formation, and atom migration in substitutional-alloy systems of any concentration. The activation energy for self-diffusion QD has been correlated to the melting temperature Tm,1, 2 the sublimation energy L,,l the heat of fusion Lf,3 crystal structure, and valence.4 Working with mechanical parameters Le claire5 proposed that the activation energy for vacancy migration Qm could be related to appropriate shear moduli. He also proposed that the activation energy for vacancy formation 62, is proportional to Ls. THEORY We consider that Le Claire's expression for 4, is satisfactory. But an alternate expression for Qm in terms of the bulk modulus is just as satisfactory from a theoretical point of view for the prediction of the energy of vacancy migration in pure metals and can more easily be used for alloys. In order for Qm to be a minimum, not only the moving atom but also adjacent and nearby atoms must undergo distortions. These distortions are neither isotropic as is implied by a correlation with the bulk modulus nor unidirectional as implied by a correlation with a shear modulus, but are complex and multidirectional. A complete analysis in terms of the bulk modulus and all the shear moduli is not yet available. In a first approximation in which only one parameter is used, there is no obvious theoretical reason to prefer the shear modulus over the bulk modulus. The bulk modulus is a much more convenient parameter for use in predicting Qm. Shear moduli are known for less than half of the metallic elements while bulk moduli are usually available. Furthermore, because of the directional dependence of shear moduli, their estimation for alloys appears inherently more difficult than is the estimation of bulk moduli. We assume that the bulk modulus Bs reflects an average value of the shear moduli such that the strain energy at the point of maximum distortion of the lattice during vacancy migration can be expressed as

Jan 1, 1964

By G. A. Crowe, W. T. Bishop

WHILE the literature in the United States on general polarographic technique is extensive, very little appears to be directly applicable to the analysis of flotation tailings. For this reason, it seemed worth while to present a few polarographic methods of ore analysis that have been in constant use in the laboratories of the Hercules Experiment Station for the past few years. At the time of our initial investigation of the polarographic method, there was little or no mention of its specific application to flotation tailings. It was therefore necessary for us to establish suitable conditions for the analysis of our flotation tailings and to consider possible interfering constituents. The polarograph, or dropping mercury electrode, method was discovered in 1925 by J. Heyrovsky and M. Shikata,1 of the Charles University, Prague. This method has since received extensive development and the literature contains many articles on the use of the polarograph for the quantitative determination of metals as well as anions, oxygen in solution, and reducible organic compounds. Kolthoff and Lingane,2 by the publication of their book, "Polarography," in 1941 did much to advance the knowledge and use of the polarograph. In chapter 25 of that book, methods for the polarographic analysis of brass, steel and iron products, alloys, and zinc ore are given. Aluminum,3 cadmium,3.4 cobalt,4 copper,3-9 gold,10 iron,3,11 lead, 3,12,13 molybdenum," nickel,4.8,9 tin,15 and zinc3,4,5,7 in ores have been analyzed by the polarograph. However, most of the work on tailing samples has been published in Russian journals and translations are not yet readily available. In this paper we will describe the method that was developed and used in our laboratory for the determination of copper, zinc, and lead in flotation tailings. PRINCIPLE OF THE METHOD The polarograph is an instrument for applying a potential to a mercury pool and a dropping mercury electrode separated by a solution, and for measuring the resultant electrical current. The procedure is essentially a small-scale electrolysis, in which the voltage required to reduce or oxidize the material identifies it qualitatively and the current measures the concentration quantitatively. Different constituents in a sample may often be determined simultaneously provided they reduce at sufficiently different voltages. An example is the determination of copper and zinc in the same solution. The reduction potentials are quite far apart, as shown in Fig. I. The polarographic method is particularly useful in the range of concentration between those normally determined by spectographic and chemical methods. In

Jan 1, 1946

By C. Wachmann

The theory presented ill this paper makes possible examination of the phenomenological aspect of secondary oil recovery by alcohol flooding. Limitutions of the theory are contingent on three primary assumptions: (1) chemical equilibrium, (2) no fingering, and (5) no dispersion. The second assumption implies one-dimensional flow. In a geometric sense the theory extends the Buckley-Leverett construction to systems of two slightly miscible fluids and to systems of three components. This is made possible by considering single-phase fluids to be made up two phases, namely of an excess of one phase and a negative amount of the other phase. The procedure is discussed in the paper. The theory also permits direct determination of the relationship between the aqueous phase saturation and the concentration of water in the aqueous phase in a zone of variable composition. The velocity of planes of constant water concentration and of constant saturation can be computted likewise and the existence of saturation discontinuities inferred. Consequently the behavior of such a Zone, which may exist at some time between a displaced and a displacing fluid, May be determined. mathematical details are given in Appendices. Problems of experimental verification are pointed out on the basis of a supporting experiment. Implications of the theory and effects of violations of primary assumptions are discussed briefly. The major conclusion is that, if the primary assumptions are met, with pure alcohol and alcohol-rich .slugs piston-like displacement of oil and water is possible. INTRODUCTION The recovery of oil from porous media by alcohol displacement has been studied for several years. Extensive experimental investigations into alcohol flooding have been carried out in the laboratory although little has been done in the field. A large amount of practical information is available, the extent being indicated by the first three papers cited 1-3 and their respecrive bibliographies. This has permitted the Formulation of inferential theories. A more analytical approach in which theories are developed primarily by reasoning from known physical principles and relationships has, however, lagged behind. In fact, an analytically derived theory of alcohol displacement has not been available. The theory presented in this paper on oil and water displacement by alcohol from a porous medium is a result of the analytical approach. The theory is idealized, as certain assumptions had to be made to make the mathematics tractable and reduce complexity of argument. In particular, major assuptions concerning conditions of equilibrium, interfacial stability, longitudinal mixing, etc., led to the exclusion of fingering, for example, from all considerations. In many laboratory experiments reported in the literature fingering could not be avoided. There is, therefore, disagreement between theories based on experimental evidence available and the analytically derived theory presented here. This theory presented is based on known physical data and makes use of the Buckley-Leverett construction and its suggested extension. The mathematical derivation of the theory is given in Appendices. Three examples relevant to alcohol displacement are discussed to explain the use of this theory: (1) system of two immiscible fluids (the Buckley-Leverett case); (2) system of two slightly miscible fluids involving an extension of the Buckley-Leverett construction; and (3) system of three components, including injection of pure alcohol or alcohol-rich fluid as a special case, which involves a more general extension of the Buckley-Leverett construction. In these discussions strict assumptions were made to impose equilibrium conditions and exclude mixing and fingering. Effects of relaxing these assumptions and consequent extensions of the theory are indicated. The complexity of the alcohol displacement process makes experimental verification of the theory essential. Some relevant evidence is offered in this paper.

Jan 1, 1965

By R. H. Schnitzel

Internal-friction peaks have been observed in tungsten single crystals at about 300° and 400°C. The characteristics of these peaks are similar to interstitial peaks observed in other bee metals; therefore, the origin of these peaks appears to he the Snoek mechanism. The interstitial responsible for the peak at about 300°C has not been identified. Carburizing increases the magnitude of the peak at about 400°C; consequently, it appears reasonable to suppose that the specific interstitial associated with this peak is carbon. The activation energies associated with the 300° and 400°Cpeaks are about 35,000 and 45,000 cal per mole, respectively. INTERNAL - friction peaks resulting from the stress-induced diffusion of interstitials (Snoek relaxation peaks) have been frequently observed in bee metals.1-5 Attempts to detect Snoek relaxation peaks in tungsten have, however, not been fruitful.' Failure to find Snoek peaks in sintered tungsten can perhaps be attributed to one or more of the following difficulties: a) the relatively low purity of the sintered tungsten; b) the lack of extensive metallurgical knowledge about tungsten-interstitial alloys, such as suitable interstitial dosing and quenching procedures; and c) the inconsistency of some of the interstitial analyses of tungsten, which reflects itself in one's inability to be sure of the nature of the specimens. This present investigation did not overcome all of these difficulties for successful tungsten internal-friction measurements. Some of these difficulties still persist and new difficulties were encountered during the course of this investigation. Nevertheless, the use of electron-beam tungsten single crystals having somewhat greater purity levels than sintered tungsten combined with appropriate carburizing and quenching procedures permitted a reasonable attempt to be made. As a consequence, internal-friction peaks were observed in these tungsten single crystals at about 300° and 400°C. These peaks were found to be unstable, since they annealed rapidly away during a sequence of internal-friction measurements. Hence, it was necessary to construct an apparatus having a faster heating rate to study some of the details of these peaks. From the behavior of these peaks as well as our knowledge of similar peaks in other bee metals, one can reasonably conclude that these peaks are caused by residual interstitial impurities within these crystals. Further investigation of these peaks after the application of various metallurgical treatments lent credence to this supposition. EXPERIMENTAL TECHNIQUE The internal friction of tungsten single crystals was measured using two different pieces of apparatus both of which are of essentially the same conventional design, namely the KE type of torsion pendulum. The important difference between these two types of apparatus was in the attainable heating rate and method of protection of the specimen from atmospheric contamination. The apparatus designated "number 1" was enclosed in a vacuum chamber which was heated by an externally mounted furnace. It had a slow rate of heating which was estimated to be about 4°C per min from room temperature to about 350°C and then about 1°C per min to 600°C. The internal friction of tantalum was measured with this apparatus and the established Snoek peaks were found.' These tantalum peaks in the temperature range from room temperature to 400° C served as a check for the apparatus. The apparatus designated "number 2" having a faster heating rate than number 1 was not elaborate. It consisted of a mounted nickel tube to which split heating elements were attached. Argon was used as the protective atmosphere. The measured heating rate was about 12° to 15°C per min whereas the cooling rate was somewhat slower at about 10° C per min because of the increased difficulty encountered in stabilizing the temperature. No surface oxidation of the specimen was noted after any test. This apparatus was also checked with the known peaks of tantalum.1 The preparation of the single-crystal specimens for internal-friction measurements consisted of centerless grinding the crystals from an approximate 0.200 in. diameter to 0.030 to 0.040 in. in diameter, and then electropolishing them to about 0.020 in. in diameter. Single crystals processed in this manner are designated as being in the virgin condition. Since the length of crystal varied from 3 to 9 in., the test frequency varied from about 1 to 2 cps. The frequencies of measurement, axial orientations, and chemical analyses for the various crystals are listed in Table I. The controlled addition of carbon into tungsten is a difficult problem. Attempts to find the critical conditions necessary for an equilibrium treatment were not fruitful. Therefore, a simple nonequi-librium method was used. The addition of carbon to these crystals consisted of appropriately combining three treatments—carburizing to achieve a case, annealing to partially dissolve the carbon into the

Jan 1, 1965

By P. Pietrokowsky, T. E. Tietz, J. E. Dorn

The amount of solid solution hardening in aluminum alloys was found to be dictated by two factors: the lattice strain, and the change in the mean number of free electrons per atom of the solid solution. To obtain this correlation it was necessary to assume that aluminum contributes two electrons per atom to the metallic bond. WHEN the modern scientific method of analysis was first being formulated, Francis Bacon recorded in his "Essays" (circa 1600) that "an alloy . . . will make the purer but softer metal capable of longer life." During the intervening centuries voluminous data have been reported which demonstrate that the additions of alloying elements do in fact increase the hardness and strength of the pure metals. Nevertheless, the significant details of this problem on the unique effect of each element toward enhancing the mechanical properties of alloys only recently have been subjected to systematic scientific scrutiny. The major objective of this investigation is to determine how minor additions of alloying elements affect the plastic properties of polycrystalline aluminum alloys. By means of such studies it is hoped to provide not only data on the solution strengthening of aluminum alloys, but also a body of facts which will supplement the knowledge already available on the factors responsible for solution hardening in general. A review1"10 and analysis1' of the existing data on the effect of solute elements on the plastic properties of solid solutions reveal that our current knowledge on solid solution hardening is somewhat meager, inconsistent, and inconclusive. Many of the inconsistencies are undoubtedly attributable to the influence of unsuspected factors, such as purity; or uncontrolled factors, such as grain size, on the plastic properties of alloys. Nevertheless the following conclusions might be tentatively accepted: 1. Addition of solute elements invariably increases the yield strength, tensile strength, and hardness of the host element. 2. The rate of strain hardening, in general, increases with the concentration of the alloying element. 3. The strengthening effect in ternary alloys is the sum of the individual strengthening effects of the two solute elements as measured in their binary alloys. 4. The lattice strain is one factor that affects the strengthening of the alloy but it is not the only factor. 5. A second factor might be the difference in valence between the solute and solvent metals. All of the available evidence is in complete agreement with the first conclusion; the remaining conclusions, however, are not in agreement with all of the published data, but, in each case, the major weight of the existing evidence favors these deductions. Additional investigations will be required before most of these tentative conclusions can be accepted without reservation. In the following report an extensive investigation of the plastic properties of binary aluminum alloys is described. This work was undertaken in an attempt to shed more light on the general problem of solid solution hardening. Materials for Test: Aluminum was selected as the solvent metal for the present investigation on the effect of solute elements on the plastic properties of alloys. This choice was made for several reasons: (1) There appears to be little fundamental data in the published literature on the effect of solute elements on the properties of high-purity aluminum alloys. In view of the ever increasing economic importance of aluminum, such data would be of basic interest to the metallurgists concerned with the development of new aluminum alloys. (2) Aluminum is thought to be only partially ionized in the metallic state1' and consequently it might provide more complex relationships of the mechanical properties with the concentrations of the solute elements than more simple fully ionized solvents would reveal. (3) The data on aluminum alloys will provide a broader basis for correlations between the mechanical properties of metals in general and the concentration and atomic properties of the solute elements than is now available. Some complications, however, attend the selection of aluminum: The solubility of the various elements in the alpha aluminum phase are quite restricted, and not always well known. Consequently, only dilute solid solutions are available for study. This, however, may be somewhat advantageous because the dilute solution laws presumably are simpler than those applying to concentrated solutions. In addition, strain-hardened pure aluminum is known to recover at atmospheric temperatures. Very likely its alloys exhibit slower recovery rates. Thus, the secondary factor of effect of alloying elements on recovery might complicate the data. Such compli-

Jan 1, 1951

By W. C. Smith, P. J. Hickey

After a short historical background of the process evolution, this article descvibes present-day plant facilities and operating techniques utilized for high-purity bismuth production. The plant is one of the world's largest, with an annual output of some one million pounds of refined bismutlz. PREVIOUS papers1 written by staff members of Cerro de Pasco Corp. have referred briefly to the production of refined bismuth. Since the Corporation is one of the world's foremost producers of high-purity bismuth, a detailed description of the process for extracting the metal may be of general interest. Following a short historical background of the development of the actual process, this presentation will trace the progress of bismuth from its entry into the primary smelting circuits to its concentration in electrolytic lead cell slimes. Our facilities for the treatment of anode muds will be described and the extractive methods given in some detail, with particular emphasis on the techniques which result in the production of refined metal. HISTORICAL BACKGROUND Shortly after Cerro de Pasco began smelting operations at Oroya, Peru in 1922, it became apparent that the dust carried by copper converter gas contained appreciable amounts of bismuth. Although dust collection efficiency was poor prior to building of the 550-ft stack and installation of the central cottrells in 1938, a large stock of dust was accumulated during the intervening years, having the following approximate composition: Oz. per ton Ag - 11.0 Pct Sn — 0.5 Pct Pb - 49.0 Pct Zn - 6.5 Pct Bi - 2.0 Pct Insol. - 1.5 Pct Cu - 0.7 Pct Fe - 2.3 Pct Sb - 3.0 Pct S - 10.0 Pct As - 7.5 In the mid-1920's, experimental crucible melts of this dust with carbon indicated that most of the bismuth and silver, and some of the lead, could be reduced to a fairly clean bullion. Other products were a small amount of leady copper matte and a slag high in zinc, arsenic, antimony, and lead; this slag contained some tin but only small quantities of silver, bismuth, and copper. After the laboratory results had been confirmed by operation of a small reverberatory, a dust reduction furnace was constructed. The ±10 pct Bi-Pb bullion produced from this operation was stocked until 1930, when an Oroya-designed converter type furnace3 was installed for the elimination of arsenic, antimony, and some lead from the bullion. This process concentrated the bismuth from 10 to about 60 pct. By means of the bismuth process developed4 by W. C. Smith at East Chicago (1909-1914) and the discovery of a method5 for separation of lead from bismuth with chlorine gas in 1929, it became possible to begin production of refined bismuth. Unfortunately, bismuth deleaded with chlorine always contained residual chlorides, and the removal of the chlorides by caustic soda left a lead content of 0.02 to 0.04 pct. This final problem was solved6 by substitution of air-blowing for the caustic treatment, which effectively removed all excess chlorine and gave bismuth which was practically lead-free. In 1934, a pilot electrolytic lead refinery began operations at Oroya. Lead smelting was resumed in 1935 and two years later a 100-ton-per-day lead refinery was put into service. In conjunction with the latter, the present-day Anode Residue Plant was constructed. Until 1940, the plant treated both lead anode slimes and dust reduction bullion. The dust reduction furnace was shut down in that year, and all cottrell dusts (with the exception of the product from the arsenic cottrell) were mixed with pyrite and treated in a Wedge roaster to eliminate all possible arsenic. Calcine from this operation joined the sinter plant feed; hence the bismuth from the copper and lead circuits was collected in the lead bullion and subsequently in lead anode slimes from the electrolytic lead refinery. The latter source has been the only bismuth-bearing material of any consequence entering the Anode Residue Plant from late 1940 to the present. A copper refinery began operating in 1948, and the cell mud from this plant is mixed with lead slimes and processed through the same circuit, though only a small quantity of bismuth is present in electrolytic copper cell residues. BISMUTH INTAKE Present-day routes which are followed by the new bismuth feed from its entry into the primary smelting circuits to its arrival at the Anode Residue Plant are traced schematically in Fig. 1. As illus-

Jan 1, 1962

By Arthur Knapp

Oil-well depletion curves, to be of value, should show when a well or lease may no longer be operated at a profit. The difference, at any time, between the total expenditures and the total income of a lease or well may be called the lease status. Plotting this lease status against time will give a curve subject to more accurate and different interpretations than the barrels-time curves. According to the hypothetical barrels-time curves shown in Fig. 1, well A, at the end of 16 mo., is producing twice as much oil as well B and will continue to produce for another year whereas well B will cease producing in about 6 months. Data fob Lease Status-time or Dollars-timb Curve Time Lease Months Status Lease purchased for $3000.............................. 0 — $ 3,000 No expenses chargeable to lease for 3 mo................. 2 — 3,000 Well A is started; cost of drilling for month is $16,000..... 3 — 19,000 Well is completed at additional cost of $10,000............ 4 - 29,000 Well A is brought in and flows 10,000 bbl. first month (we Fig. 1). Necessary to invest in tanks, boilers, pipe lines, etc.; difference between expenditures and receipts gives profit for month of $5,000............................ 5 — 24,000 Investment is small, cost of operating well A is small, so profits are $15,000................................... 6 — 9,000 Well ceases to flow so there is additional investment for pumping equipment and additional operating expense; net earnings from 6,000 bbl. of oil produced is $4,000. 7 ... Lease operation nor becomes normal and curve becomes smooth........................................... 8 — 500 9 2,000 10 4,500 11 6,000 12 7,700 13 8,700 14 9,000 15 9,500 16 10,000 A hypothetical lease status-time, or dollars-time, curve of this lease is shown in Fig. 2. At zero time, the lease is purchased for $3000, which is plotted below the zero dollar line, All subsequent entries are plotted

Jan 1, 1921

By Enrique Touceda, Henry M. Howe

This paper gives the composition of the iron and slag at different stages in the " air-furnace" process of preparing " hard metal," or white castriron, for conversion into malleable cast-iron by annealing. The details of the process are given in an appendix. One of us had been trying for years to work some chemist of some of our malleable-iron plants up to a degree of enthusiasm which would lead him to make such an investigation. It would have had the advantage of the greater familiarity with the conditions which one habitually on the spot must have. Failing in this, he made use of an opportunity which presented itself of taking samples here represented, with such fairness as the conditions permitted, holding firmly that a rough approximation to the truth is better than the complete lack of data, or that a bird in the hand is worth two in the bush. We hope that this attempt may stimulate others effectively to duplicate this work, and thus correct or confirm it. Our results are shown in Table I. and graphically in Figs. 1 arid 2. Discussion.—At the time when the first two samples were taken, the metal and slag were still too sluggish to permit fair sampling, and not until sample 6 were the conditions really favorable, because at the time of the fourth sample the metal was not fully melted, and even at the time of sample 5 it was still sluggish. Indeed, the slag was probably very heterogeneous throughout, because it took up silica and alumina rapidly from the bottom, and because it was so siliceous as to be sluggish at this relatively low temperature. This hetero-geneousness is exaggerated in the two samples of slag 8, apparently by the great viscosity due to its extraordinary acidity. Note that the manganous oxide of one sample is about two and

Jan 1, 1909

By R. A. Feemster, C. M. Rader

Because of the necessity for taking regularly occurring open-flow tests in prorated high-pressure oil fields, much gas is turned to atmosphere by way of vertical vent lines leading away from the oil and gas separator. In the past, measurement of such gas has been accomplished by several methods, usually by use of the open-flow Pitot tube. The use of the closed-flow Pitot tube has been avoided apparently chiefly because the ordinary vent-line hook-up makes it necessary to apply the instrument closer to a bend, valve, or obstruction in the pipe than is recommended by rules of good practice. The many advantages that would result from the application of the closed-flow Pitot tube prompted investigation of the actual effect upon quantity rate of flow measurements computed from data obtained with the tube in a normal working position, which is closer to the tee at the base of the vent riser than is usually considered as giving highly accurate results. An effort Was first made to compare the results thus obtained to those under ideal conditions and at high velocities To make this comparison, knowledge of the characteristics of gas flowing at very high velocities is essential. Research for such information indicated that little or no work had been done that would give data necessary for such a comparison, therefore the problem was changed to a test designed to determine the relationship between quantity rates of flow as measured by an orifice meter and a Pitot tube placed at the center of a pipe eight diameters from a tee or ell at the base of a vent riser, through which gas is flowing under low pressures at very high velocities. To determine this relationship, a series of tests was run on a number of 8-in. iron-pipe vent riser., in which the Pitot tube data were taken at the position as stated above. Gas from a wet-gas gathering system was passed through an orifice meter setting and thence to atmosphere by way of the vents. Data were taken simultaneously from the orifice meter and Pitot tube from which computations for comparisons were made. The actual method of comparison is discussed later in this paper. Since Pitot-tube information is usually given in general terms, and not readily usable, it will be the purpose of this paper to discuss the applica-

Jan 1, 1934

By J. M. Campbell, T. S. Buxton

The most widely used methods of predicting the volumetric properties of gas are based on the principle of corresponding states, which asserts that the compressibility factor is a universal function of reduced temperature and pressure. Previous studies have shown that the acentric factor, as proposed by Pitzer, l is an important addition to reduced pressure and reduced temperature as factors affecting the compressibility factor. Results of this study indicate that, if the pseudocritical temperature and pressure used to determine the reduced conditions are adequately predicted, characterization of natural gas-carbon dioxide mixtures with the acentric factor will allow reliable determination of the compressibility factor. Comparisons of predicted and experimental compressibility factors have shown that the pseudo-critical constant rules of Stewart, Burkhardt and Voo 2 are satisfactory for hydrocarbon mixtures. However, these rules fail to predict the pseduo-critical constants for hydrocarbon-carbon dioxide mixtures. Based on graphically determined pseudocritical temperatures for binary hydrocarbon-carbon dioxide mixtures, a correlation which gives the required correction to the Stewart, Burkhardt and Voo rules was prepared and a compressibility factor prediction technique was proposed. To test the proposed technique, compressibility factors for live mixtures of methane, carbon dioxide and either ethne or propane were experimentally determined at 100, 130 and 160F and pressures up to 7,026 psia. The predicted and experimental compressibility factors for these live mixtures had an average absolute deviation of 0.55 percent. INTRODUCTION Two-parameter generalized correlations based on the principle of corresponding states (PCS) are presently available for reliably predicting the compressibility factor of lean natural gas, i.e., natural gas with low concentrations of hydrocarbons heavier than methane. When these same correlations are used for mixtures of natural gas and carbon dioxide, large deviations between actual and predicted compressibility factors are observed. This study was undertaken to provide a means for accurately predicting the compressibility factor for such mixtures. In the past, two avenues of approach have been employed to extend the applicability of the PCS. The first has been to introduce additional parameters. The second has been to develop combination rules for predicting pseudocritical constants which do not suffer from the limitations of the commonly used molal average constants. In this study, both of these approaches have been considered and employed to arrive at a method for predicting the compressibility factor of mixtures of hydrocarbons and carbon dioxide. SELECTION OF A THIRD PARAMETER Failure of the original PCS to predict the compressibility factor for all pure gases, regardless of their mass, shape or polar moment, has led to the introduction of additional parameters into the PCS. Parameters have been introduced to correct for quantum deviations,3-5 non-spherical or globular shapes6-9 and for polar moments.8-12 In addition to these parameters which are based on some microscopic property and intended to correct for some specific cause of deviation, more general parameters based on some bulk property have also been introduced.1913-16 To use additional parameters to correct for each of the possible causes of deviation among the individual constituents of a gas mixture would require a rather complex form of the PCS. To maintain the PCS in as simple a form as possible, it is more desirable to have a single third parameter which is based on some bulk property influenced by several of the factors causing deviations. The third parameter selected for use in this study is a factor originally proposed by Pitzer.9

By F. F. Poland

The purpose of this paper is to describe a new process for the refining of secondary copper-base metals and a specially designed high-temperature electric-resistor furnace used in the process for the distillation of zinc from these metals. The process was used for the conversion of nickel silver to cupronickel and to recover the zinc content in metallic form. It also proved applicable and economical for the treatment of scrap brass for separating and reclaiming the copper and zinc. The relatively large furnace developed for the distillation of zinc is described in detail, for it made economically possiblc the direct recovery of metallic zinc from scrap brass, which is a new step in the processing of such material. Considerable interest has been shown in the utilization of the distillation furnace for other metallurgical processes, where it is of advantage to operate in a controlled neutral or reducing atmosphere, or to avoid having the processed metal in contact with refractories other than carbon, or to operate at temperatures between 3000 and 4000°F. Purpose of Development It was recognized early in the war effort that nickel would become a critical metal. therefore all nickel stock and alloys containing relatively high percentages of nickel were frozen immediately. Among these alloys were considerable quantities of various grades of nickel silver, an alloy containing copper, nickel, zinc, and in some grades lead, also minor amounts of iron, manganese and other constituents. At the time there was no existing plant or process to eliminate the zinc, lead, and minor constituents so as to convert this metal to cupronickel, one of the important alloys needed by the U. S. Navy for condenser parts. Therefore the Bureau of Industrial Conservation of the War Production Board requested the executives of the leading nonferrous metal companies to have their metallurgical staffs study the problem of converting this metal to cupronickel conforming to U. S. Navy Specification 44T40. The composition specified therein is as follows: nickel, 29 to 32 per cent; zinc, 1.00; iron, 0.00 to 0.60; lead, 0.05; tin, 1.20; manganese, 0.00 to 1.00; total of other elemcnts (maximum). 0.50; copper, remainder. The problem in converting these alloys to cupronickel was the elimination of zinc, lead, iron, manganese, and other elements without appreciable loss of nickel to slags or other by-products. Revere Copper and Brass Incorporated, through its Research and Development Department, undertook to solve this problem. A Government-owned plant was built at Rome, N. Y., and there the conversion was made successfully.

Jan 1, 1949