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By H. A. Wriedt

Zinc-vapor pressures in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C were measured by an isopiestic method. Thermody-na?nic properties of zinc in these solutions were derived directly and those of iron with a Gibbs-Duhem integration. Zirzc and iron exhibit large, positive, and moderately temperature-sensitive deviations from ideality. Excess enthalpies and Gibbs energies are positive in the ranges studied. It has been establzshed in relating published phase equilibria to the Gibbs energies of forming solid solutions that positive departures from ideality also exist in the fcc solutions. Tlze stability, as defined by Darken, of the bcc solutions is small but positive at 703.5"C. Its decrease with decreasing temperature indicates that a miscibility gap may exist in the stable or metastable bcc solutions at lower temperatures. The changes of thertnodynanlic properties relatable to changes in magnetic state are minor compared to other changes due to alloying. The accuracy with which the relation between lattice parameter and composition of the bcc solutions is known has been improved. Zinc increases the lattice parameter of a iron by O.ZOZA per unit atom action zinc to at least NZn = 0.25. TO our knowledge, only Ciganl has previously investigated thermodynamic properties of the bcc solutions of the Fe-Zn system. He measured zinc-vapor pressures in the temperature range from about 320" to 360°C by an effusion technique. We have measured the vapor pressures of zinc in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C by an isopiestic technique. This investigation and the pursuant thermodynamic computations are part of a program for studying several properties of these solid solutions. In the appendix we report a remeasurement of the relation at room temperature between the lattice parameter and zinc content. Related work not reported herein embraces measuring the diffusivity2 of zinc in ferrite at 700" to 900°C and the Curie point temperature3 as functions of composition. EXPERIMENTAL METHOD AND APPARATUS Purified iron at a series of constant temperatures was saturated with zinc at a series of constant zinc-vapor pressures, the range of conditions being so limited that the equilibrated solid solutions were ferri-tic. The equilibration was conducted in long capsules, Fig. 1, that had been evacuated, gettered with titanium, and sealed. The purified iron, part of a vacuum-melted ingot of electrolytic-iron stock (Glidden Co. 1044-grade), had the impurity contents listed in Table I. It was used in the form of millings about 0.001 in. thick. A zinc of 99.999 pct purity (United Mineral and Chemical Corp.) and later one of 99.9999 pct purity (Cominco Products, Inc.) were used, with no observed difference in results. Sufficient zinc was placed in the capsule (separate from the iron and kept at a different temperature) to supply the vapor phase and the iron alloy, while leaving a pool of pure liquid zinc throughout the run. The imposed temperature of the residual zinc pool fixed the vapor pressure of zinc throughout the capsule; condensation was avoided at other locations by making this the lowest temperature in the capsule. Two common complications of nonisothermal systems were, we believe, effectively absent from ours: first, molecular species other than monatomic have no appreciable concentration in zinc vapor at 700" to 900~~: second, the development of zinc-pressure differentials in the capsules was suppressed by use of relatively large-diameter tubing and the absence of diluents in the zinc vapor other than desorbed impurities. The specimens and zinc pool were located at two isothermal zones (each ranging within 1°C over several inches) of a wire-wound, 37-in.-long vertical-tube furnace. The required temperature distribution was achieved by external adjustment of the currents in three electrically isolated windings. The temperatures of the isothermal zones were controlled independently by ther-

Jan 1, 1968

By A. G. Metcalfe

THE failure to detect any change in the thermal properties of cobalt at the Curie point would appear to indicate that the apparatus may have a limited sensitivity. The Curie temperature has been determined by direct methods to be 1121+3°CP and 1131°C.3 The specific heat has been determined many times'.' and weighted values are given in Table I. The allotropic transformations in iron and titanium, used by the authors to test the experiment method, involved a volume change of the order of 3 pct on going from the close-packed to the body-centered-cubic lattice. These energy changes are likely to be much larger than those involved in a diffusionless transformation from a hexagonal to a cubic-close-packed lattice. However, it has been pointed out that thermal observations are unreliable in the detection of phase changes when these are near a Curie point.' James 0. McCaldin and Pol Duwez (authors' reply)—The sensitivity of the present technique is limited to first-order transformations, so that gradual changes in specific heat, e.g., in the vicinity of Curie points, are not detected. Furthermore, the existence of first-order transformations with latent heats much smaller than those occurring in the known allotropic transformations of iron and titanium is, we agree, still pending.

Jan 1, 1956

By R. D. Pehlke, J. V. Gluck

The limiting activity coefficient of zinc in a "binary " solvent has been described for several dilute ternary solutions by combining literature data from recent interaction studies in the terminal regions with thermodynamic data for the central regions. Results are discussed in terms of the Alcock and Richardson random solution model. The observed behavior agrees semiquantitatively with predictions using the model. RECENT efforts in the thermodynamics of dilute ternary liquid metallic solutions have been mainly concerned with the interactions between two dilute solutes, that is, the terminal region at an apex of the composition diagram.'-' A more general case is that of the behavior of a dilute solute over the full range of a ternary system, or, more specifically, the limiting activity of solute i as projected to the k-j binary side of the i-j-k composition triangle. An implication of this is that the interaction between i and j at the k apex should connect in some way to the interaction between i and k at the j apex. A model to characterize various types of expected behavior has been discussed by Alcock and Richardson.9,10 Such behavior can range from a simple linear relation for In yi over the 1-k binary to more complex curved relations which depend on various assumptions regarding the heat of solution in the j-k binary system and the presence or absence of clustering with solute i. Quantitative data to assess these concepts have been limited primarily to the cases of nonmetallic interstitial solutes in ferrous solutions. Alcock, Richardson, and various coworkers9-13 have discussed the behavior of oxygen, sulfur, silicon, or hydrogen in dilute solution over the range of iron + metal systems; however, the only data considered by them for substitutional nonferrous metallic solutions were the results of Elliott and Chipman concerning the activity of cadmium in the Pb + Sn, Pb + Bi, and Pb + Sb systems.9 These data were limited and did not cover the terminal regions in detail. An opportunity to extend the Alcock and Richardson considerations to the dilute solution of zinc in various "binary" solvents has been afforded by combining results of several of the recent investigations of ter-minal-region interactions with previous data from the literature for the same more concentrated solutions. RESULTS AND DISCUSSION The results of the analysis are shown in Figs. 1 to 5 where the log activity coefficient, (In yZn)xzn--o, is plotted vs the composition of the "binary" solvent. In these plots the end points are the values for In yzn in the appropriate binary solution with Bi, Pb, Sn, Cd, or In at the indicated temperature—usually 550°C (823°K). For the terminal regions the slopes were drawn using the first-order interaction parameters taken from various studies reported in the literature. The data points shown in the central regions were obtained by the short extrapolation to infinite dilution of the logarithm of the activity coefficient calculated from thermodynamic studies reported in the literature for the same systems. The sources of the data are indicated on each figure. Second-order effects were not considered. Reasonably smooth curves can be drawn to connect the central region with the terminal regions for the Zn-Pb + Bi system, Fig. 1, the Zn-Pb + Zn system, Fig. 1, and the Zn-Bi + Cd and Zn-Bi + Sn systems, Fig. 2. As shown in Fig. 2, where central region data are available from two independent investigations, the agreement is quite good. The Zn-Pb + Cd system does not appear to be as well behaved as the previous four, Fig. 3; however, this type of behavior has also been

Jan 1, 1970

By H. W. Mead, C. E. Birchenall

The rates of growth of graphite nodules in cast irons are calculated for a model of a growing graphite sphere surrounded by a shell of austenite through which carbon and iron are diffusing. The carbon is supplied by a cementite-austenite mixture at the outer edge of the shell. The calculated rates from carbon diffusion agree fairly well with the measured values, but the rates based on iron self-diffusion are much too low. Because the iron must be removed for the process to continue, o plastic deformation mechanism is suggested. THERE has been an unfortunate tendency in the literature of growth and dissolution reactions to identify the slope of a plot of the logarithm of the growth or dissolution rate vs reciprocal of temperature with the activation energies determined by diffusion measurements in chemically similar systems. If the solubility limits at the growing or dissolving phase interfaces change appreciably with temperature, such procedures may lead to serious errors in specifying the mechanisms controlling the rates of these processes. A reaction involving the simultaneous growth of graphite from and dissolution of cementite in austenite will be discussed here to show that substantial oversimplifications have been made in earlier studies of this process. From a dilatometric study of the overall y-range graphitization process, Bunin and Danil'chenko' found an apparent activation energy of 90 kcal per g-atom. They concluded that, since this value was much nearer the approximately 68 kcal per g-atom observed for self-diffusion in pure iron than it was to 32 kcal per g-atom for diffusion of carbon in iron, the rate-controlling process must be the diffusion of iron away from the growth interface to provide space for graphite to grow. Bunin and Salli' bolstered this agreement with the observation that graphite forms preferentially at surfaces, cracks, and pores where free volume is present initially. Ziegler, Meinhart, and DeaconQ ad found an apparent activation energy for graphitization of 98 kcal per g-atom. This value, like that of Bunin and Danil'chenko, applies to nucleation and growth occurring simultaneously. It is not generally assumed that nucleation is entirely diffusion-controlled. Treatments such as prior cold-working and prequenching, which strongly affect the rate of graphitization, would be expected to have little effect on diffusion processes occurring at the graphitization temperature. In any case 90 kcal per g-atom is not particularly close to the 54 kcal or lower to be expected for diffusion of iron which is carbon-saturated.' The presence of silicon in iron is said to reduce the activation energy for diffusion,' so its presence in cast irons would be expected to have a similar effect. The growth rates of nearly spherical graphite nodules have been studied by Brown and Hawkes." The initial rate of growth before impingement of adjacent carbon-depleted areas was found to be parabolic, and rate constants were measured at several temperatures. Their apparent activation energy for the growth process only was roughly 45 kcal per mol. Burke and Owen' made growth-rate measurements on several alloys, recording appreciable induction periods, initial nucleation rates, and average radial growth rates based on an assumed linear rate of radial growth. They found that increased silicon content increases the ovel-all reaction rate and the initial rate of nucleation, and decreases the induction period. Assuming 1) spherical nodules. 2) constant volume rate of nucleation, 3) austenite in equilibrium with cementite at positions where the cementite is not depleted, and 4) a constant diffusion distance during the growth of a nodule, they calculated an apparent overall activation energy of 68 kcal per mol, which was related to an activation energy for nucleation of 79 kcal per mol and activation energy

Jan 1, 1957

By W. van der Knapp

A theoretical and experimental ana1ysis is given of the change in volume of a porous medium due to changes in external and internal pressures. The result enable one to deduce directly the effect of large increlents in stresses. It is shown that the three-dimensional representation of the volume of a nonlinear porous system is a cylindrical rules surface, the generating lines of Which have a slope according to the solid rock compressibility. Analytical expression for such a ,surface is very simple. It follows that the bulk and pore compressihilities depend only on the difference between pore fluid and external hydrostatic pressure, i.e., the effective rock frame pressure. From measurements on a number of sandstones as well as limestones it can be conduded that for practical values of this effective frame pressure the pore compressibility falls in the range between the compressibility of water and that of undersaturated crude oil. In general, pore compressibility is found to be higher the lower the porosity. For a particular limestone reservoir pore compressibility and porosity could he related by means of a simple empirical formula. Results from the described study find a direct applicxtion in material balance calculations and in prob1ems of liquid flow through porous media. Since the elastic constants of the rock bulk material enter into equatiorls for velocity of acoustic waves, the results are also of importance for calculating rates of wave propagation in these media. It is shown for sandstones with 1.5 to -10 prr cent porosity that laboratory measured porosities may differ from those lender reservoir conditions by about I per cent of their value. The difference for low porosity limestotnes can be of the order of 10 per cent. The subsidence caused by elastic deformation of reservoir rock is shown to he very small. General formulas relating pore and bulk volume to external and internal pressure can be derived, as has been shown by Biot1, Gassmann2 and Geertsma.2 Their theories describe the differential change in volume caused by a variation in pore fluid tension and external hydrostatic tension. It has been known for a long timei that the stress-strain relations of a packing of spheres are essentially noninear. Our experiments show that for almost all reservoir rocks which arc elastically deformable the relation between volume and loading is also a nonlinear one, resembling that of a packing of spheres very closely. The behavior of these media is often described by using the linear stress-strain relations for small incremental stresses and strains in the vicinity of a pre-stressed condition." The present study differs from these considerations in that it enables one to deduce the effect of large increments in the stresses directly. In analogy to the stress tensor for a homogeneous body the stress tensor for a porous body can be written in the conventional way: where the tensor components, o, and t, represent the total forces acting on the faces of a unit cube of porous material. This tensor can be split into two parts. a hydrostatic and a deviatoric part, as follows2,3,1 where the component of the hydrostatic stress system, a. equals The hydrostatic stress causes a change in volume whereas the deviatoric stress system gives rise to a change in shape only. One of the difficulties in describing changes of volume occurring in reservoir rocks is that the relations connecting these volume changes with external and internal stresses are essentially non-linear. A complete description requires the bulk volume, V,,, as well as the pore volume,V,,. to be known as a function of both the changes in pore fluid tension (v) and the hydrostatic tension on the outer boundary.

By J. H. Scaff, H. C. Theurer, E. E. Schumacher

The microwave region of the radio spectrum was effectively utilized in radar designs during the recent war and it has become of increasing interest in the field of communications. Work in this field has led to an important use for silicon—that of the point contact rectifiers†1 in the frequency converter of microwave (radar or radio) receivers—and has stimulated considerable interest in the electrical properties and preparation of silicon and its alloys. Silicon is an electronic semiconductor. Its conductivity at room temperature results principally from the presence of certain impurities. While for metals an increase in impurity content increases the resistivity, for semiconductors such as silicon the opposite occurs and, in general, the addition of impurities lowers the resistivity. Silicon materials may be classified into one of two groups depending upon the manner in which the impurities contribute to electrical properties. These have been termed for convenience p-type or n-type. P-type silicon develops a very large positive thermal emf against metals, has a Hall coefficient of positive sign and a low resistance direction in point contact rectification with the silicon positive with respect to the point. N-type silicon, on the other hand, develops a negative thermal emf against metals, has a Hall coefficient of negative sign and a low resistance direction in rectification with the silicon negative with respect to the point. Impurities which produce n-type silicon are called donors inasmuch as these elements contribute to electrical conductivity by donating electrons to an unfilled energy band in the silicon. On the other hand, elements which produce p-type silicon are known as acceptors as these impurities contribute to the electrical conductivity by accepting electrons from a filled energy band permitting what is known as conductivity by "holes" in which the sign of the carriers appears to be positive. A general treatment of the mechanism of conduction in semiconductors from the viewpoint of modern band theory has been given recently by Pearson,2 by Becker, Green and Pearson,3 and by Torrey and Whitmer.4 In this investigation boron and aluminum have been found to be acceptors, and phosphorus, arsenic, and antimony to be donors in silicon. Data on the effect of boron and phosphorus on the electrical properties, when present singly and in combination, have been acquired. These data are discussed in the present paper. Raw Materials Used and Methods for Adding Seeond Constituents Silicon from two sources was used in this work and these will be referred to as A and B respectively. Silicon A is a material of high purity supplied by the Electro Metallurgical Co. It is prepared by chemical purification of "commercial" silicon obtained from the arc furnace reduction of SiO2. It contains 99.8 pct silicon, minimum, with small amounts of calcium, iron, aluminum, boron, and phosphorus as the principal impurities. This material was extensively employed in these studies as well as in the commercial preparation of rectifier materials. Silicon B is a material of high purity from the du-Pont Co. It is prepared by a pyrolytic reduction of Sicl4 and is free of analytically detectable amounts of boron and phosphorus. Its use permitted study of the effect of boron and phosphorus individually on the properties. This material contains, however, spec-troscopic traees of a number of metals, some of which affect electrical and rectification properties. Typical analyses for the two grades of silicon are given in Table 1. To make controlled additions of boron to the charge it was necessary to employ a low boron content master alloy since the quantity of boron to be added was usually only a few thousandths of one percent. The alloy containing nominally one percent boron was prepared by melting chemically pure boron with silicon A using the melting techniques for 320 g silicon

Jan 1, 1950

By J. H. O’Dette

BLISTER formation on wrought aluminum products has been a matter of concern to aluminum fabricators for many years. The fact that blisters make their appearance during the final stages of fabrication means that much time and effort have been expended before it is evident that the material must be scrapped. This and the loss of production are ample reasons for embarking on a research program to find out more about blistering and possible methods of control. Many excellent papers on this subject have appeared in the technical literature in the last few years. In one of the more recent papers, Kostronl gives a fairly complete review of the problem of gas in aluminum and blistering in general. From the work of the various investigators, a general mechanism for the formation of blisters has evolved and may be summarized briefly as follows: Hydrogen gas is usually present in the cast ingot, in the atomic or ionic state, in excess of the solid solubility. At room temperature the gas atoms are relatively immobile, but at elevated temperatures they become mobile and diffuse to free surfaces where they associate to form molecules. If these free surfaces are discontinuities within the ingot then the associated gas molecules collect and build up considerable pressure until equilibrium is reached with the dissolved gas around the discontinuity. Since the solubility of the gas is proportional to the square root of the partial pressure it is evident that large pressures may be built up at the discontinuities. When the metal is rolled to sheet the pressure of the gas in these, discontinuities is sufficient to deform the surface of the sheet and form a blister, particularly when the strength of the material is reduced during the annealing. Although the mechanism of the formation of blisters was fairly well known, the actual impor- tance of the individual roles played by the gas and the discontinuities was not so well established that positive methods for control of blistering were at hand. It was the object of the investigation to learn more about the nature of the discontinuities giving rise to blistering and to develop methods of control. The investigation was carried out in three stages as follows: a) A study of the more commonly used methods of removing hydrogen from aluminum, such as fluxing and holding, and their effects on blistering. b) Location of the discontinuities giving rise to blistering. c) A study, by indirect methods, of the movement of gas in the metal and its effect on blistering, and the development of methods of blister control during fabrication. Removing Gas and Reducing Blistering by Fluxing or Holding-—The work of removing gas and reducing blistering by fluxing or holding was carried out on metal of Alcan 2s (1100) composition with an artificially high gas content. The high gas content was obtained by introducing water into the melt prior to casting; the water reacted with the aluminum forming A12O3 and hydrogen. The procedure was to raise the gas content by introducing water into an aluminum melt and using half the melt to cast one ingot immediately. The remaining metal was treated again with water to make up for the reduction in gas content during holding, while the first ingot was being cast, and then given a fluxing or holding treatment and cast into an ingot. Samples for gas determination were cast from the molten metal before and after the gassing operation; before, after, and during fluxing, and while casting. Samples were also cut from sections of the ingots. Gas determinations were made on these samples using the well known vacuum fusion technique. All ingots were hot rolled at 500°C to 0.250-in. slab which, in turn, was cold rolled to 0.040 in. sheet. The sheet was coiled and annealed for 2 hr at 500 °C and then cut into 5-in. squares which were inspected for

Jan 1, 1958

By W. J. Carlson, I. Iwasaki

A previous article reported a combination process for recovering both metallic iron and metallic manganese from the manganiferous iron ores of the Cuyuna Range in Minnesota.' In this process, the iron was recovered by direct reduction and magnetic separation and the manganese was recovered from the nonmagnetic tailing by leaching and electrolysis. The current efficiency during the electrolysis of manganese is quite low, in the range of 60 to 70%, due to the simultaneous plating of hydrogen.2,3 The parameters that affect the current efficiency are (1) the concentrations of the manganese ion and the ammonium sulfate buffer, (2) the effect of autoxidant, (3) temperature, (4) pH, and (5) current density. To study the plating characteristics of manganese metal.

Jan 1, 1969

By Leonard R. Weisberg

The general properties of diffusion in GaAs are reviewed. A total of .fourteen atoms have been studied to date, and activation energies for eleven reported are (in ev): Ga (5.6), As (lo), Zn (2.49), Cd (2.43), Sn (2.5). Mn (2.75). S (4.0). Se (4.2). Ag (0.33), Cu (0.52). and Li (1.0). The dijfusion of the first eight atoms, as measured by Goldstein using radiotracer techniques, established the principle of sub lattice diffusion for both host and impurity atoms, since atoms substituting for gallium have lower activation energies than those substituting for arsenic. The diffusion constant of interstitial copper has been determined for the first time by Hall and Racette using heavily doped p-type samples in which interstitial copper predominates. The anomalous behavior of zinc, which has an abrupt diffusion front and a strong dependence on zinc concentration, has recently been quantitatively explained in terms of an interstitial-substi-tutional equilibrium-diffusion mechanism. Lithium and silver diffuse mainly interstitially, while the diffusion of phosphorus is complicated by the continual formation ofGap. Junction-migration measurements indicate diiferent results than radiotracer techniques, and this is one problem that still remains, together with discrepancies in cadmium-diffusion results, and an unexplained dependence of impurity diffusion on arsenic pressure. BESIDES the usual insights into the behavior of atoms in solids, studies of diffusion in semiconductors have additional importance for device applications. In fact, the amount of diffusion studies performed on a semiconductor might serve as a simple barometer of its technological importance. Thus, the information accumulated for GaAs is not yet quite comparable to that for germanium or silicon, but considerable knowledge is available. The diffusion of at least fourteen atoms has been investigated for GaAs, and the diffusion constants have been determined for eleven of these. Interesting results were found for GaAs that elucidated problems not previously solved for germanium or silicon. For example, the interstitial-diffusion constant for the very fast diffusant, copper, was first measured in GaAs. Also, solutions for interstitial-substitu-tional equilibrium diffusion in extrinsic material were provided first for GaAs, although they are ap- plicable to germanium, silicon, and other semiconductors. Studies in GaAs firmly established the concept of sublattice diffusion, which should have application in many different compound systems. The purpose of this paper is to review briefly the general state of knowledge concerning diffusion in GaAs. First some general aspects of diffusion will be covered, and next attention will be given to the results mentioned above. Diffusion in GaAs has been measured both by radiotracer and junction-penetration techniques, and some discussion will be given of differences in the two sets of results. The comprehensive work of oldsteinl-' has served as the primary reference for the diffusion of well-behaved substitutional atoms in GaAs. Since a review has recently been presented of many of these reults, details of the diffusion data will not be repeated. Neither will any discussion be given of the experimental techniques of diffusion measurements, except to note here, in passing, the simplicity and effectiveness of the precision lapping device employed by Goldstein.' I) EXPERIMENTAL RESULTS AND DISCUSSION A) Summary of Experimental Results. Diffusion constants D = Do exp(E/kT) have been determined for eleven atoms in GaAs: a,' AS,' n,'" Cd,'" n,' n,8 s, e,' Ag,O CU," and i." These results are summarized in Table I. In addition, diffusion was investigated for phosphorus,4'12 germanium,I3 and ilicon,' but Do and E were not determined. Radiotracer techniques were used for most of the studies except for lithium, where a combination of chemical and electrical techniques was employed, and germanium and silicon, where junction-migration techniques were applied. The diffusion of zinc, manganese, sulfur, and tin was also measured using junction migration.13'14 Goldstein demon-

Jan 1, 1964

By Fred H. Poettmann

An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of the compressibility factor of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. Comparison of calculated results with field measured results were made on 20 dry gas wells from a given field and 11 distillate wells from different fields. The agreement between calculated and observed results is good. In addition to their use in the calculation of sandface pressures of flowing wells, the factors can be used in the direct calculation of the static bottom hole pressure of gas wells, the capacity of gas transmission lines, and in the calculation of the theoretical isothermal horsepower necessary to compress a natural gas. Examples demonstrating the use of various equations are given. INTRODUCTION Many of the equations used to calculate the sandface pressures of flowing gas wells from well head data do not take into consideration rigorously the deviation of the natural gas from ideal gas behavior. For low pressure wells this error is not serious. For high pressure wells flowing at high rates this error call be serious. Sandface pressures are used to determine the producing capacity of gas wells as shown in the U. S. Bureau of Mines' Monograph 7.' An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of compressibility of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. In addition to their use in the calculation of sandface pressures, these "factors" can also be used to give a direct solution in the calculation of the static bottom hole pressure of gas wells, the calculation of the capacity of gas transmission lines, and the calculation of the isothermal horsepower necessary to compress a gas. CALCULATION OF SANDFACE PRESSURE OF FLOWING GAS WELLS The starting point in the derivation of any specific flow equation is an energy balance on the fluid flowing between any two points in the system. This energy balance based on one pound of flowing fluid is expressed by the well known general flow equation: jp~- vdP+ Ah + -— + wt + r. = o . . (i) P, 2 g. where V = specific volume of flowing fluid in cu ft/lb P = pressure in Ib per sq ft ah = difference in height above datum plane in, ft ------ = kinetic energy change of one lb of flowing fluid, v equals velocity in ft/sec and g. = 32.174 Ws = Work done by fluid while in flow (similar to shaft work in driving a turbine) W, = Znergy losses due to the irreversibilities of the flowing fluid This equation contains no limiting assumptions and can be made the basis of any fluid flow relationship by limitations or substitutions. The energy units are usually expressed in term* of foot-pounds of energy per pound of mass. Considering the vertical flow of gas through tubing or annu-lus, the external work W, done by the gas is zero. Let us also assume that the value of the kinetic energy function is small and can be neglected. Equation (1) is reduced to: /P: VdP + Ah+Wt = 0 .......(2) Pi The energy loszes PI can be expressed in terms of the well known Fanning equatinn: 4/Lf: rf = —— ............(3) 2g,D where L = the integrated average velocity in ft/sec of vertical flow in a uniform flow string -~h = L v = the integrated average velocity in ft/sec / = dimensionless correlating function

Jan 1, 1951

By Fred H. Poettmann

An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of the compressibility factor of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. Comparison of calculated results with field measured results were made on 20 dry gas wells from a given field and 11 distillate wells from different fields. The agreement between calculated and observed results is good. In addition to their use in the calculation of sandface pressures of flowing wells, the factors can be used in the direct calculation of the static bottom hole pressure of gas wells, the capacity of gas transmission lines, and in the calculation of the theoretical isothermal horsepower necessary to compress a natural gas. Examples demonstrating the use of various equations are given. INTRODUCTION Many of the equations used to calculate the sandface pressures of flowing gas wells from well head data do not take into consideration rigorously the deviation of the natural gas from ideal gas behavior. For low pressure wells this error is not serious. For high pressure wells flowing at high rates this error call be serious. Sandface pressures are used to determine the producing capacity of gas wells as shown in the U. S. Bureau of Mines' Monograph 7.' An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of compressibility of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. In addition to their use in the calculation of sandface pressures, these "factors" can also be used to give a direct solution in the calculation of the static bottom hole pressure of gas wells, the calculation of the capacity of gas transmission lines, and the calculation of the isothermal horsepower necessary to compress a gas. CALCULATION OF SANDFACE PRESSURE OF FLOWING GAS WELLS The starting point in the derivation of any specific flow equation is an energy balance on the fluid flowing between any two points in the system. This energy balance based on one pound of flowing fluid is expressed by the well known general flow equation: jp~- vdP+ Ah + -— + wt + r. = o . . (i) P, 2 g. where V = specific volume of flowing fluid in cu ft/lb P = pressure in Ib per sq ft ah = difference in height above datum plane in, ft ------ = kinetic energy change of one lb of flowing fluid, v equals velocity in ft/sec and g. = 32.174 Ws = Work done by fluid while in flow (similar to shaft work in driving a turbine) W, = Znergy losses due to the irreversibilities of the flowing fluid This equation contains no limiting assumptions and can be made the basis of any fluid flow relationship by limitations or substitutions. The energy units are usually expressed in term* of foot-pounds of energy per pound of mass. Considering the vertical flow of gas through tubing or annu-lus, the external work W, done by the gas is zero. Let us also assume that the value of the kinetic energy function is small and can be neglected. Equation (1) is reduced to: /P: VdP + Ah+Wt = 0 .......(2) Pi The energy loszes PI can be expressed in terms of the well known Fanning equatinn: 4/Lf: rf = —— ............(3) 2g,D where L = the integrated average velocity in ft/sec of vertical flow in a uniform flow string -~h = L v = the integrated average velocity in ft/sec / = dimensionless correlating function

Jan 1, 1951

By D. W. Duncan, A. Bruynesteyn

An ore containing chalcopyrite was microbiologically leached in 6 ft columns at particle sizes ranging from -2 +1 ½ inches, to -3/8 + 3/16 inches. The rate of leaching increased exponentially as the particle size decreased. The controlling factor was the active leaching volume made up of the particle surface area and the depth of penetration of the bacteria and leach liquor into the particle. This volume became an increasingly larger part of the total volume as the particle size decreased. The sample under test leached poorly at larger particle sizes and it was calculated that under commercial conditions, it would produce at best a pregnant solution containing 100 mg/l (0.2 lb/ ton) of copper per 100 ft of dump height.

Jan 1, 1974

By S. J. Im

Bupyung Silver Mines daily treats average 14 tons of concentrates containing 9,000 g Ag per ton. Bupyung Silver Refinery uses Merrill Crowe process to recover the silver from the leach solution containing 1.0 g/l Ag; Series of experiments were carried out to recover the silver from the solution by means of direct electrowinning in place of Merrill Crowe process. The recovery of the silver was 99% when the cell voltage and the retention time were 1.9 v and 3.0 hours, respectively. Power consumption was 3.2 Kwh/kg of Ag. It was found that impurity buildup was not significant during the recycling. The direct operating cost for the electrowinning was evaluated to be $ 0.35/kg of Ag.

Jan 1, 1984

By John T. Galey

The outstanding developments of the year in southwestern Pennsylvania were the establishment of the Summit Fayette County gas pool and the gas pool in Nicholson township, Fayette County, and Monongahela township, Greene County, as major producing areas, and the indication of four new shallow gas pools. Curtailment of drilling for shallow gas is expected to follow order M68 of the Office of Production Management. Gas completions were approximately 70 per cent higher, oil completions nearly 25 per cent lower, dry holes were unchanged and drilling wells as of Dec. 31, 1941, nearly loo per cent higher than last year. Shallow Development Oil.—Outside Butler County, only 11 producers were drilled, with a total initial of 221 bbl. The best of these was in a portion of Gilmore township, Greene County, which ordinarily produces gas. This well flowed 77 bbl. in 11 hr., along with about one million cubic feet of gas from the Fourth (U.Dev.) sand. Washington County had a 10.20 and a 25-bbl. well in Morris township and a 20-bbl. well in South Franklin township. These were all in the Fifth Sand. The price of oil to Jan. 27 was $1.80 per barrel, when a 15¢ increase was made. This was followed by a raise of 20¢ on Apr. 23, 15¢ on May 21, 20¢ on June 18 and 25¢ on Aug. 14. The last increase was canceled on Aug. 23 by the Office of Price Administration, which pegged southwestern Pennsylvania crude at $2.40 per barrel. Gas.—An almost doubled initial production of natural gas is the result of the large increase in number of wells drilled. The outstanding discovery of the year was in the vicinity of Armbrust, Hempfield township, Westmoreland County, where a well drilled to what at first was considered the Bayard sand, but what is now known to be the Fifth (U.Dev.) sand, at 2100 ft. found nearly 5 million cu. ft. of gas. Since this completion 14 wells have been finished, only one of which was dry, giving a combined total open flow of approximately 15 million cu. ft. The sand is 35 to 40 ft. thick and the saturation extends through most of that thickness. Rock pressure, which is 1040 lb. per sq. in., is abnormally high. An area of only about one square mile has been proven but some of the 24 new wells drilling as of Dec. 31 will no doubt extend it considerably. This development has taken place in an area heretofore considered to have had little prospect. There were three good wells in other parts of Westmoreland County. One well in Franklin township, which had 12 million cu. ft, of gas in the Fifth sand, was entirely surrounded by dry holes but is still pro- . ducing at a high rate. In Bell township a 1.6 million cu. ft. well was found in the Speechley (U.Dev.) sand and in Washington township the same sand produced 2.7 million cu. ft. with shut-in pressure of 970 Ib. at 2820 ft. This well is offset by two dry holes and one well with a capacity of only 10 M cubic feet.

Jan 1, 1942

By John T. Galey

The outstanding developments of the year in southwestern Pennsylvania were the establishment of the Summit Fayette County gas pool and the gas pool in Nicholson township, Fayette County, and Monongahela township, Greene County, as major producing areas, and the indication of four new shallow gas pools. Curtailment of drilling for shallow gas is expected to follow order M68 of the Office of Production Management. Gas completions were approximately 70 per cent higher, oil completions nearly 25 per cent lower, dry holes were unchanged and drilling wells as of Dec. 31, 1941, nearly loo per cent higher than last year. Shallow Development Oil.—Outside Butler County, only 11 producers were drilled, with a total initial of 221 bbl. The best of these was in a portion of Gilmore township, Greene County, which ordinarily produces gas. This well flowed 77 bbl. in 11 hr., along with about one million cubic feet of gas from the Fourth (U.Dev.) sand. Washington County had a 10.20 and a 25-bbl. well in Morris township and a 20-bbl. well in South Franklin township. These were all in the Fifth Sand. The price of oil to Jan. 27 was $1.80 per barrel, when a 15¢ increase was made. This was followed by a raise of 20¢ on Apr. 23, 15¢ on May 21, 20¢ on June 18 and 25¢ on Aug. 14. The last increase was canceled on Aug. 23 by the Office of Price Administration, which pegged southwestern Pennsylvania crude at $2.40 per barrel. Gas.—An almost doubled initial production of natural gas is the result of the large increase in number of wells drilled. The outstanding discovery of the year was in the vicinity of Armbrust, Hempfield township, Westmoreland County, where a well drilled to what at first was considered the Bayard sand, but what is now known to be the Fifth (U.Dev.) sand, at 2100 ft. found nearly 5 million cu. ft. of gas. Since this completion 14 wells have been finished, only one of which was dry, giving a combined total open flow of approximately 15 million cu. ft. The sand is 35 to 40 ft. thick and the saturation extends through most of that thickness. Rock pressure, which is 1040 lb. per sq. in., is abnormally high. An area of only about one square mile has been proven but some of the 24 new wells drilling as of Dec. 31 will no doubt extend it considerably. This development has taken place in an area heretofore considered to have had little prospect. There were three good wells in other parts of Westmoreland County. One well in Franklin township, which had 12 million cu. ft, of gas in the Fifth sand, was entirely surrounded by dry holes but is still pro- . ducing at a high rate. In Bell township a 1.6 million cu. ft. well was found in the Speechley (U.Dev.) sand and in Washington township the same sand produced 2.7 million cu. ft. with shut-in pressure of 970 Ib. at 2820 ft. This well is offset by two dry holes and one well with a capacity of only 10 M cubic feet.

Jan 1, 1942

By J. E. Worthington, W. H. Spence, I. T. Kiff

Gold was discovered at the Haile mine in Lancaster County, South Carolina, in 1827 or 1828, and since that time the mine has been worked intermittently by both open-pit and underground methods until its forced closure in 1942 by World War II. Production figures are incomplete, especially for the early years, but the total gold produced is estimated to have been greater than 200,000 oz. Thus, the Haile mine has been the most productive gold mine in the eastern United States. The upper, residually enriched ores were relatively rich, but the bulk of the production has come from the mining of lower grade ores. General Geology The Haile mine is located in late Precambrian or early Paleozoic rocks of the Carolina slate belt at the edge of the Atlantic Coastal Plain [(Fig. 1)]. The metamorphic grade is lower greenschist facies and the rocks have been folded into a sequence of northeast-trending isoclinal folds. The gold is associated with siliceous, pyritic, and kaolinized felsic pyroclastic and tuffaceous rocks in an interbedded volcanic and volcanoclastic sequence of felsic to mafic tuffaceous rocks and argillaceous sediments [(Fig. 2)]. The ore bodies occur in two northeast trending zones approximately 500 m apart; each zone is 30-70 m wide and 600 m or more in length, with possible extensions to the east beneath the Coastal Plain sediments. Mineralogy. Gold in the Haile mine is always associated with siliceous and/or pyritic ores. The gold occurs in at least three states: As native gold as originally deposited; as residual gold derived from the breakdown of pyrite; and as gold included in pyrite. Major associated minerals in addition to quartz and pyrite are kaolinite, sericite, and iron oxides. Minor molybdenite, arsenopyrite, pyrrhotite, copper sulfides, sphalerite, rutile, and topaz are also present. Petrology. The gold-bearing ore zones vary from highly siliceous rocks to pyritic massive sulfide lenses. This variation is most easily seen today along strike from the Haile pit to the Red Hill pit. Ore grade material still exposed in the wall of the Haile pit consists of a highly siliceous and very thinly bedded rock containing minor pyrite. Along strike, the character of the mineralization changes to pyritic massive sulfide lenses occurring interbedded with siliceous horizons at the Red Hill pit. The siliceous rocks vary from the thinly-bedded material as just described from the Haile pit to silicified fragmental-appearing rocks to totally recrystallized cherty rocks lacking any recognizable primary features. Scattered, apparently at random, throughout the very thinly-bedded and very fine-grained ore face of the Haile pit are seemingly anomalous silica-rich clasts or concretions up to 5 cm in diameter which will be discussed later in this paper. Alteration. One of the most striking features of the Haile deposit is the alteration mineral assemblage which is intimately associated with the siliceous and pyritic ores. This altered material has been intersected in drill core at depths greatly exceeding the modern weathering profile and is, therefore, of hydrothermal origin rather than from supergene processes. This "sericite," actually a fine-grained mixture of sericite, kaolinite, and quartz, can be shown to stratigraphically underlie the gold- quartz-pyrite zone, and is well exposed in the open pit just southeast of the Haile and Bumalo pits. Relict textures indicate that this highly altered material was originally a felsic ash flow. Other similar alteration zones have been found in outcrop and drill core underlying the remaining ore bodies. Thus each of the mineralized zones consists of two parts: A siliceous and/or pyritic gold-bearing ore zone which is stratigraphically underlain by a zone of high alumina minerals, in this case sericite and kaolinite along with variable amounts of quartz. A green chrome mica, presumably fuchsite, is present in trace amounts in the high alumina zone. Genesis An adequate model to explain the origin and distribution of the gold deposits in the Carolina slate belt is presently lacking. Worthington and Kiff1 suggested a volcanogenic origin for certain gold deposits in the North Carolina slate belt from the waning exhalations of felsic volcanic piles. They also pointed out that such an origin has similarities to many epithermal precious metal deposits located in more recent volcanic piles in the western United States. A further key to the understanding of the genesis of the gold mineralization at the Haile mine is the close association of the mineralization in siliceous and sulfidic horizons to the genetically related and stratigraphically underlying high alumina alteration. Such high-alumina alteration is common around felsic volcanic centers in the Carolina slate belt and the mineralogy as seen today consists of some combination of kaolinite, sericite, pyrophyllite, kyanite, andalusite or sillimanite depending on the local prevailing grade of metamorphism. Accompanying the high-alumina alteration are large quantities of pyrite and iron-oxide minerals as well as characteristic minor accessory minerals often including base metal sulfides, fluorine-bearing minerals (topaz, fluorite, apatite), titanium-bearing minerals (ilmenite, rutile),

Jan 1, 1981

By M. J. Marcinkowski, Gordon E. Lakso

An extensive investigation has been made of the deformation behavior associated with the Fe3Si super-lattice using transmission electron microscopy techniques. Above 243°K the stress-strain curve exhibits three stages. Stage I occurs at a very low stress level and is related to the generation of perfect superlat-tice dislocations. Stage II is characterized by an extremely rapid rate of work hardening and is associated with the Taylor type locking of these superlattice dislocations. Finally Stage III is related to dynamic recovery processes since the work hardening rate is very small. Below 243ºK, only Stage I is observed, but it occurs at a much higher stress level. This latter observation is related to the generation of imperfect dislocations in Stage I with the consequent production of second nearest neighbor antiphase boundaries. The reason for this is that insufficient thermal energy is available at these low temperatures to generate the complete and perfect superlattice dislocations. It has been shown that the fully ordered FeCo alloys, i.e., those possessing the B2 type structure, exhibit three distinct stages of work hardening whereas the corresponding disordered alloys show only one.&apos;" This difference in behavior between the disordered and ordered alloys has been attributed to the fact that dislocations in the former case travel only as ordinary 1/2ao(111) types whereas in the latter case the move through the lattice as coupled 1/2a0(111) dislocations separated by an antiphase boundary (APB), i.e., the so-called superlattice dislocation. Although some preliminary work has been carried out concerning plastic deformation in ordered alloys possessing the DO3 type superlattice,3 no detailed analysis similar to that described in Refs. 1 and 2 has been attempted. Specifically, it has been suggested that the superlattice dislocation in this particular type structure should consist of four ordinary 1/2ao<111> types bound together by first and second nearest-neighbor APB&apos;s. Fe3A1 and Fe3Si are the two classic alloys possessing the DO3 type lattice; however, because of the somewhat higher ordering energies associated with the FesSi alloy, which in turn assures that dislocations will travel through the lattice as perfect superlattice dislocations under at least some conditions, it was chosen for the present investigation. Because of the extreme brittleness of Fe3Si, all deformation was done in compression. Stress-strain curves were obtained using both polycrystalline samples as well as single crystals. In the latter case the crystals were oriented so that deformation could be controlled either by single or double slip. They were then wafered parallel to and at various angles to the operative slip planes. These wafers were in turn examined by transmission electron microscopy (TEM) techniques in order to determine the extent of the interaction from the dislocation configuration contained therein. EXPERIMENTAL PROCEDURE The alloys used in this investigation were arc melted under helium from electrolytic iron of greater than 99.90 wt pct purity and transistor grade silicon of 99.99 wt pct purity. A typical analysis of interstitial impurities showed 120 ppm 0, 15 ppm N, and 65 ppm C Because of the extremely low ductility of the Fe3Si alloys, it was necessary to spark cut 0.230-in. diam polycrystalline cylinders 0.400 in. long from arc-melted fingers using a thin-walled brass tube as a cutting tool. The polycrystalline alloys could not be recrystallized since very little strain was induced in preparation. However they were annealed at 1273°C for 15 min in evacuated vycor capsules to relieve any cooling stresses that may have developed during solidification and then air cooled. The resulting grain size of the alloy was 0.50 mm. According to warlimont4 1273ºC is just within the single phase field where FesSi possesses the DO3 type lattice. In addition because of this high critical ordering tem-ature, air cooling from this temperature was believed sufficient to fully order all of the Fe3Si samples used in the present investigation. For the same reason, no attempt was made to achieve any degree of disorder by quenching. In fact, rapid quenching from 1123°K caused cracking. Such cracking was first suggested by sato5 with respect to the experimental observations of Glaser and Ivanick.6 Single crystal compression specimens were spark cut from single crystal ingots grown in a Bridgman type furnace. The iron and silicon for the crystals was prealloyed by arc-melting two 130-g buttons which were cut into small pieces before remelting in the furnace. This procedure resulted in a long-range inhomogeneity of 0.5 at. pct Si between the top and bottom of the 2-in.-long single crystal ingot, which was assumed to be negligible in the present investigation. The single crystals, after orienting and spark-cutting, were about 0.37 in. by 0.37 in. in cross section and about 0.5 in. long. True stress-strain curves were obtained using an Instron Tensile Testing machine in conjunction with techniques described previously. 1,7 The strain rate was 0.05 in. per in. per min. Prior to testing, the ends of all the compression cylinders were hand polished using a special jig to insure parallelism after which the sides of the samples were electrochemically polished to eliminate stress risers and to facilitate slip line observations. Test temperatures between 77" and 823°K were obtained using various cooling and heating media as described in Ref. 7 while at the upper end of this temperature range, a mixture of equal

Jan 1, 1970

By C. W. Sherman, John Chipman

IN the mathematical statement of the law of mass action, the activity of each substance consumed or produced in a reaction is used to obtain a numerical constant which is characteristic of the equilibrium of that reaction at the given temperature. The activity in many cases is equal to, or proportional to, the concentration. If this is the case, any units denoting concentrations, such as weight percentage or mol fraction, may be substituted in the equilibrium expression. It is even permissible to use mixed units provided only that each unit is that used in defining the activity of the corresponding substance. The indiscriminate use of concentration units in writing equilibrium constants sometimes leads to very erroneous results. On the other hand, what appear to be contradictory results from similar investigations often might be resolved if the activity is the quantity that is used to determine the equilibrium constant for the reaction in question. De-sulphurization serves as an important illustration. Sulphur in lron and Steel The control of the sulphur content of the finished product is one of the oldest and broadest problems in the metallurgy of iron and steel. In general, this control must be exercised through the action of a slag, and for this reason experimental studies of the distribution of sulphur between slag and metal have assumed considerable importance. Under slags of the type found in the basic open-hearth furnace the ratio (% S)/[% S] does not in general exceed about 8. Under blast-furnace conditions, however, de-sulphurization ratios of 50 to 100 are readily obtained, and under laboratory conditions using similar slags, the ratio may be as high as 400. The fact that blast-furnace metal is much more readily desulphurized than is molten steel rests upon two distinct phenomena. The first of these is connected with the slag reaction. In the open-hearth furnace, the equilibrium in the following reaction places a definite limit on the sulphur content of the slag: S + 0-- = 0 + S- - where the symbols underlined indicate elements dissolved in the liquid metal, while slag constituents are represented as ions. The high oxygen content of the open-hearth bath prevents this reaction from proceeding far enough to effect good desul-phurization. In the blast-furnace process, however, the oxygen activity is limited by the presence of carbon in the metal and in the coke bed and the controlling reaction becomes: S_+O- + C_=S- + CO(gas) [2] The second phenomenon which contributes to the easier desulphurization of blast-furnace metal is the effect of high concentrations of other elements. These elements, notably carbon, silicon, and phosphorus, increase the thermodynamic activity of sulphur several fold. As a result of this increase, the escaping tendency of sulphur from the metal phase is increased and its removal facilitated. Previous Studies It becomes, therefore, a matter of importance to determine the effects of various elements upon the activity of sulphur in the melt. The experimental approach to this problem has been made through the equilibrium between sulphur in the melt and gaseous atmospheres containing hydrogen and hydrogen sulphide. The reaction and its equilibrium constant are written as follows: S + H2(gas) =H2S(gas);K1 = -- [3] Pn2 • as where the symbol a, represents the activity of the sulphur in solution in the metal. The understanding of the chemical behavior of sulphur in steel and pig iron rests on a firm knowledge of the binary system Fe-S. A number of studies of the equilibrium have given closely agreeing results from which the activity and free energy of the dissolved sulphur may be found. The recent paper by Sherman, Elvander, and Chipman1 includes a discussion and quantitative comparison of the results of several of the significant researchesr-" on dilute solutions of sulphur in iron. The results of this study indicate that the relationship between the ratio Ph,s/p+ and the percentage of sulphur in solution is not a linear one. This

Jan 1, 1953

Prof. Henry M. Howe, New York, N. Y. (communication to the Secretary*):—The results presented in Mr. Mathewson&apos;s paper are of very great interest. Perhaps the most interesting is that shown in Table I. and Fig. 1, in which the arsenic decreases in 10 min. from 0.22 to 0.07 per cent. This is such a large decrease that it is to be hoped that Mr. Mathewson will verify it by repeating his tests with a matte of similar composition. This is particularly to be desired, because the simultaneous removal of sulphur appears to be very small. All three blows further agree in showing that the removal of arsenic is in the very early part of the blow. The fact that the removal of arsenic then ceases abruptly cannot be explained completely by the fact that the arsenic has fallen so low as by its lowness to resist further removal, because in the first blow the arsenic becomes stationary at 0.06 per cent., whereas in the third blow it does not become stationary until it has fallen to 0.034 per cent. The abrupt ending of the removal of arsenic is more likely to find its explanation in the composition of the slag, and it is to be hoped that Mr. Mathewson will supplement these extremely valuable data with others in which the composition of the slag at the same time shall be given. The sudden rise of arsenic toward the end of the third blow I suppose must be referred to an error in sampling or analysis.

Jan 1, 1908

By E. I. Salkovitz, F. W. von Batchelder

DURING the last few years several papers1-&apos; have been published in which internal friction measurements have been used to determine the quantity of carbon or nitrogen dissolved in a iron. This method is based on the fact that, in pure Fe-N and Fe-C alloys, nitrogen and carbon cause peaks in the internal friction vs. temperature curve; at a frequency of 1 cycle per sec (cps) these peaks appear at $-200 and +360C, respectively, and if internal friction is expressed as Q-1, which is equal to times the logarithmic decrement, this figure will, by coincidence, give the weight percentage of nitrogen or carbon in solid solution.&apos; In most of the studies published, very pure iron (Puron) was used. In one case the influence of manganese on the behavior of nitrogen in a iron was mentioned.4 It would be of great value, especially for the study of aging and related phenomena, if this method could be applied to commercial mild steel with norrnal percentages of manganese, phosphorus, sulphur, etc. As a rule, in such steels carbon and nitrogen are present together, and the amounts of these elements in solid solution should preferably be determined separately. The fact that their internal friction peaks appear at different temperatures (+36° and + 20°C in pure iron) seems promising for such a selective determination. It is necessary, however, that the peaks are narrow enough not to interfere with one another, and further, that there is no effect from carbon on the behavior of nitrogen in stress induced diffusion, and vice versa. According to Fast,&apos; however, in the presence of manganese the nitrogen peak gets wider and appears at a higher temperature nearer the carbon peak, and thus the prospects for selective determination are reduced. (The carbon peak was not affected by the presence of manganese.) But even if fully quantitative de- terminations of the two elements are not attained, some relative figures on the sum of them and an indication of which one is the predominant one, would be of value. Some results from experiments along these lines will be reported here. An internal friction measuring device was assembled mainly following a description by KG." The measurements were also carried out as reported in that paper. Table I gives the chemical compositions of the four different materials used in this investigation. All materials were drawn to wires with diameter about 0.8 mm, and the analyses refer to these final shapes. Determination of Nitrogen Peak Wires from steels A, B, and C were decarburized in wet hydrogen (about 30 pct H2O) at 700°C until no carbon or nitrogen could be found by chemical analysis. No peak was then found in the internal friction. The wires were further annealed at 580°C for 16 hr in hydrogen bubbled through a solution of 6.8 pct NH3 in distilled water. Chemical analyses gave 0.04 pct N in A and C, and 0.06 pct in B. After annealing at 580°C for 15 min in a lead bath and water quenching, the internal friction was immediately measured. The resulting curves are shown in Fig. 1. At these high values of the internal friction the accuracy is comparatively poor; at Q-1 - 0.030 it is estimated to be 0.002. In order to make possible a calculation of the activation energy for diffusion of nitrogen, measurements were made at two different frequencies. Steel A shows rather broad peaks, and their temperatures can hardly be expected to be very accurate. Steels B and especially C are better in this respect. The finding of Fast&apos; that manganese broadens the nitrogen peak is con-

Jan 1, 1953