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By J. F. Pierce, S. M. Enterline

Since January 1959 a zinc refiner of novel design has been in operation at Blackwell, Okla., producing 99.995+ zinc from the output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyro-metallurgical unit with principal dimensions horizonhl permitting one floor operation. It is very ruggedly constructed. Furthermore it is not subjected to deterioration from high concentrations of iron in the feed metal because the boiling units are separate from the rectification columns and constructed with silicon carbide brick arches through which the heat is transferred radiantly to the zinc. A zinc refiner of novel design has been in operation since January 1959 at the Blackwell, Okla. plant of the Blackwell Zinc Co., Inc., a wholly owned subsidiary of American Metal Climax, Inc. Developed by the company's technical and operating staffs, the new refiner produces special high-grade zinc (nominally 99.995+ pct Zn) from the prime western1 slab output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyromet-allurgical, high-capacity unit employing fractional distillation to separate zinc from its impurities, consisting principally of lead, cadmium, and iron. In prime western slab, these elements may vary in concentration from 0.005 to 1.6 pct. Table I shows the impurities usually encountered in the Blackwell prime western metal fed to the refiner together with their boiling points and vapor pressures at 907oC. The commercial pyrometallurgical smelting processes for extracting zinc from ore include distillation from retorts and a limited degree of refining can be accomplished by redistillation in similar retorts. To achieve special high-grade purity, an impractical number of batch redistillations would be required, however, with an accompanying loss of much metal. A continuously operated and integrated unit is required in which fractional vaporization and condensation can take place in a large number of stages. The first commercial continuously operated unit was developed by the New Jersey Zinc Co.4 In the separation of any two substances the degree of separation is limited if a mixture exists having a constant boiling point. The Zn-cd5 and Zn-pb6 systems contain no constant boiling points and hence these metals may be separated to any degree of purity. Basically, the pyrometallurgical refining of zinc involves three steps: a) iron, copper, and other metals having no appreciable vapor pressures at 907ºC concentrate in the bath when the impure zinc is boiled, b) lead, bismuth, antimony, and other metals having boiling points above but closer to that of zinc are selectively condensed from the vapor boiled from the bath, and c) cadmium and other metals having lower boiling points than zinc are fractionally distilled by reboiling and subsequent condensation of the zinc from the vapor. The boiling and condensation of zinc must be conducted in vessels constructed of materials which are refractory at the temperature involved (907 ºC) and it is highly desirable that they also be resistant to attack by the various metals. This requirement dictates construction from relatively small, simply shaped pieces which limits the pressures which may be employed to avoid leakage through the numerous joints. Stresses induced must be limited essentially to compressive ones and suitable provision must be made to permit thermal expansion of the components in order to minimize these stresses. Where heat is to be added for boiling or removed for condensation, refractory material through which the heat flows must have a high thermal conductivity. Silicon carbide is highly conductive but is subject to attack by iron and is expensive compared to other commonly employed refractories. A hard, dense aluminous fireclay is well suited to contain these metals where high thermal conductivity is not required. Zinc will penetrate the pores of fireclay brick but only to a limited depth in an exterior wall and has little effect other than an increase in weight and conductivity. The design objectives of the Amax refiner were: a) to achieve a long life by heavy, rugged construction and by employing silicon carbide refractories only where required for heat conductivity and not in contact with liquids of high iron concentrations, b) to simplify operation, manning and control by essentially horizontal construction, and c) to obtain high capacity in a single unit. DESCRIPTION Flow of metal through the Amax refiner is shown diagrammatically in Fig. 1 and schematically in Fig. 2.

Jan 1, 1963

By Tibor Stefansky, John E. Dorn

MOTT and Nabarro1-5 were first to illustrate the importance of the flexibility of dislocations in accounting for the strengthening that metals undergo due to the presence of internal-strain centers. Such strain-centers might arise from a number of causes such as radiation damage, the presence of semicoherent and coherent precipitates and clusters, as well as individually dispersed interstitial and misfit substitutional solute atoms. Each strain-center induces positive and negative shear stress fields on the slip planes of the surrounding alloy matrix. In order to effect plastic deformation, therefore, the alloy must be subjected to sufficiently high applied shear stresses to push dislocations past all such internal stress fields. If dislocations were inflexible and moved as rigid lines, they would be equally pushed and pulled by internal stress fields. At this extreme the strengthening would be vanishingly small. Dislocations, however, are not rigid; they are flexible and extensible. They wiggle between positive and negative strain-centers, thus increasing their line energy at the expense of their interaction energy with strain-centers. cottrel16 and Friedel7,8 have independently presented lucid reviews of the significance of the Mott-Nabarro dislocation-flexibility concept to the strain-center strengthening of alloys. Their analyses however were only semi-quantitative. There is evidence in the recent literature of renewed interest in a more rigorous analysis of flexibility. Thus, Gleiter9 and Gerald" have shown that the calculated strain-energy interaction between a dislocation and the stress fields of coherent precipitates can be seriously in error if the flexibility of the dislocation is not taken into account. This report will be concerned with a more detailed analysis of the problem based on the following approximations: 1) Although many types of strain-centers exist, the following analysis will be limited to the case of solute-atom strain-centers in fcc substitutional alloys. 2) To facilitate the analysis by avoiding statistical considerations, the strain-Centers are assumed to be in regular arrays on the slip plane. Although the quantitative results are somewhat dependent on the type of array that is assumed, the qualitative trends are similar for various arrays that were studied. 3) An adjustment of the results from those for square arrays to those for the more realistic case of a random distribution of strain-centers is accomplished by adopting the interesting statistical theory first introduced by Kochs,11,12 elaborated on by Dorn, Guyot, and stefansky,13 and analyzed by Foreman and Makin14 in their computerized experiments. 4) For simplicity the dislocation lines are taken to wiggle about their edge orientation and no correction is applied to their line energy for deviations from edge configurations or for the elastic interaction between segments of the now curved dislocation. It will be shown that for extremely low concentrations of atomic strain-centers the strengthening increases with the square root of their concentration. For slightly higher concentrations the strengthening rate becomes less rapid. At a critical concentration a maximum strength is obtained and a decrease in the strengthening takes place as the concentration of solute atoms is further increased. These trends are a direct consequence of dislocation flexibility. They arise from changes in the amplitude of the waviness of the dislocation line at the yield stress with solute atom concentration. Despite the simplifying assumptions that were made, the results agree qualitatively with appropriate experimental data. I) STRESS FIELDS ON SLIP PLANES Internal stresses are introduced in a lattice whenever a host atom of radius ro is replaced by another that has a different atomic radius. According to the classical theory of linear elasticity,15 the stress field about a solute atom at the origin of a spherical coordinate system is given by arr=-4G€(?_0)3 ffflfl ="W =2G€{t) f°rr^ro(l+e) UJ where G is the shear modulus of elasticity and Y, = ro(l + E) is the radius in situ, of the substituted atom. As shown by ~shelb~,'~ this approximation assumes that the bulk modulus of elasticity of the substituted atom is identical with that of the host species. ~abarro'~ suggested that the strain E can be deduced

Jan 1, 1970

By R. A. Breitrick, J. N. Swinderman, J. J. Cooper, H. L. Bauer Jr.

The Robinson Mining District, near Ely, Nev., is one of the major porphyry copper districts in the world. Within the district is an eight mile long east-trending zone of altered porphyry, metamorphosed sedimentary rocks, and sulphide mineralization surrounded by Paleozoic limestone, dolomite, shale and sandstone, Tertiary volcanics, and Quaternary alluvium. Six major disseminated ore deposits have been exploited in this zone. About 20% of the district production has come from disseminated ore in metamorphosed sedimentary rocks found adjacent to altered quartz-monzonite porphyry. The following brief statements summarize some of the relations between porphyry alteration, metamor-phism, and mineralization: 1) Disseminated copper ore does not occur in unaltered porphyry or in m-metamorphosed sedimentary rocks. 2) Sedimentary rocks have been only weakly metamorphosed where intruded by unaltered porphyry. 3) Intensely metamorphosed sedimentary rocks are found only adjacent to altered porphyry. 4) Many hydrothermal minerals are common to both altered porphyry and adjacent metamorphosed sediments. 5) Disseminated ore is found in altered porphyry and adjacent metamorphosed sedimentary rocks. 6) In general, there is a direct correlation between grade of ore in porphyry and copper content in the adjacent rocks. 7) Chemical changes in the altered porphyry and metamorphosed rocks appear to be related. The foregoing relations support a hypothesis that the porphyry alteration, the metamorphism of the sedimentary rocks, and the ore deposition were all part of a continuous hydrothermal process which probably closely attended the porphyry intrusion. The Robinson Mining District, most often referred to as the Ruth or Ely District, is located in eastern Nev. and is one of the major porphyry copper districts of the world. Production from 1908 through 1962 was nearly 250 million tons of ore averaging a little over one percent copper with a total metal value of nearly one billion dollars. The ore has been produced from six major disseminated-type deposits with the Liberty Pit deposit accounting for 70% of the total district production. Less than one million tons of base metal and gold ores have been produced from the replacement-type deposits of the district. Approximately 20% of the district production has come from underground mining operations; the pit ore has been mined with shovels and removed by train haulage, truck-train haulage combinations, truck haulage, and presently by a combination truck-skip system. Many of the ore deposits formerly worked by underground methods have been and are being exploited by open pit methods. (See Fig. I.) Two co.'s have accounted for virtually the entire production from the district. In 1958 Kennecott Copper Corp. acquired the district assets of Consolidated Coppermines Corp. and is now the sole ore producer in the district. Present operations are confined to the Liberty Pit where 22,500 tons of ore averaging a little less than 0.8% copper is mined per day. Cutoff grade is 0.4% copper, and the stripping ratio is three to one. The ore is hauled by rail 23 miles to the McGill Reduction Plant where it is concentrated to about 20% copper. Molybdenite is recovered as a by-product in the mill. The copper concentrates are smelted in McGill, and the blister copper is shipped for refining to Balt. where gold, silver, platinum and palladium are recovered. The Robinson Mining District has been well known as a porphyry copper district for the past fifty years, but many geologists are unaware of the fact that a large portion of the production has come from disseminated ore found in metamorphosed sedimentary rocks. The scope of this paper describes the occurrences of disseminated ore in the various metamorphosed sedimentary rocks, and presents evidence for the hypothesis that these ores are genetically, spacially, and coevally related to the disseminated ore in the porphyry rocks. Publication of this paper was granted by the management of Kennecott Copper Corp. A. H. James suggested and encouraged the writing of the manuscript. Special mineralogical and spectrographic analyses were performed by the Kennecott Research Center. The deposits of the district have been studied by many geologists since the turn of the century, and

Jan 1, 1964

By M. Garfinkle

LITERATURE data1'3 have suggested that the resolved shear stress necessary to initiate slip in a particular slip system in tungsten single crystals is strongly dependent on the tensile orientation of the crystals. This orientation dependence is contrary to the critical resolved shear stress criterion. Because the Schmid factors for slip on particular {110}( I l l), {112}(Ill), or {123}(111) slip systems in a (100) oriented tungsten crystal are virtually identical to the respective Schmid factors for a (110) oriented crystal, slip should initiate on the same system in both orientations, independent of the values of the critical resolved shear stresses. Thus, it would be expected that, for a critical resolved shear stress model to hold, the proportional-limit stress for these two orientations must be similar. The expectation of similar proportional -limit stresses has not been borne out by reported experimental observations. Rose et nl.' reported that the proportional-limit stress for crystals near the (110) orientation was 92,000 psi, approximately three times that of (100) oriented crystals (31,000 psi). Garlick and probst2 reported greater than a fourfold difference. Most recently, Beardmore and ~ull~ examined tungsten crystals with orientations along the edge of the standard stereographic triangle and showed a gradual increase in proportional-limit stress from 28,000 psi for the (100) orientation to 93,000 psi for the (110) orientation. Again, the difference was more than threefold. As has been emphasized by these investigators, the apparent gross variation of proportional-limit stress with orientation precludes any meaningful analysis of slip mechanics using a simple critical resolved shear stress relation. The purpose of the present communication is to report that, by use of refined strain-measuring techniques, the proportional-limit stresses for the (100) and (110) orientations are quite similar. Obviously, to determine accurately the value of the proportional-limit stress, which is by definition the stress at which nonlinear stress-strain behavior first occurs, the method of measuring strain must be capable of high accuracy. The investigators cited used as the measured elongation the crosshead displacement of the tensile machine. This method, however, introduces extraneous strain contributions from the load train. Because these extraneous contributions are considerable in the initial portions of loading (as has been well-documented in the literature) the proportional-limit stress measurement, dependent on the deviation of a line from linearity, can be significantly affected. During the course of a recent study, room-temperature strain was measured directly on several (100)-and (110)-oriented tensile specimens axially oriented within 5 deg of the desired direction. Each specimen was fitted with two foil strain gages mounted on opposite sides of the 0.08-in.-diam reduced section. The tensile specimens were loaded at a crosshead speed of 0.01 in. per min on an Instron Universal Testing Machine. Strain was monitored through an external bridge circuit in which the specimen strain gages comprised two arms. The bridge output was recorded against the applied load. A strain of 2 x 10"" could be readily detected by this method. Some specimens were subjected to conventional loading while the load for others was cycled between zero and continually increasing values until the first deviation from linearity was observed. The results of these methods were similar, and the stress at which nonlinear behavior occurred was considered the proportional-limit stress. The proportional-limit stresses measured in this study are approximately 5000 and 6500 psi for the ( 100) - and ( 110) -oriented crystals, respectively, a range of values almost a magnitude less than those reported previously. Representative curves are presented in Fig. 1. Because of the nature of the measurements made, the point of departure of a line from linearity is often debatable. While the load-strain curve for the (100) -oriented crystals made a relatively abrupt deviation from linearity, the curve for the (110) -oriented crystal was more gradual, so that the actual point of tangency may be at a lower load than reported. Thus, the difference in values for the proportional-

Jan 1, 1967

By Shozo Saito, P. A. Beck

Mettrllographic and X-ray diffraction study of Cb-Co alloys in the Composition range of 7 to 33 nt. pct Cb, after annealing at 1175 °', showed that near 25 al. pct Cb on MgNi,-lype hexagonal Laves Phaseexists in a narrow composition range, and that an MgCl- type cubic Laves Phase occurs between approximately 27 and 32.6 ut. pd Cb. Lattice parameter and density measures indicated that, in both phases. the deviations from proper Loves sloichimetry result from the substitution of cobalt atoms for some 0f the columbium atoms. Tlle same phases occurant 1000'C, together with an additional phase of unknown structure, which appears between the hexagonal Laves phase and the cobalt-bose terminal solid solutions KOSTER and Schmid' identified a phase corresponding to the composition VCo,, and more recently the crystal structure of this phase has been determined.' In the Ta-Co system Korchynsky and Fountain recently found two intermediate phases at the composition Taco,, one of them metastable. In contrast to the V-Co and the Ta-Co systems, in the Cb-Co system no intermediate phase has been found4 at the composition CbCo,. The present investigation was undertaken in order to reexamine the question of the existence of such a phase. EXPERIMENTAL PROCEDURE Twelve alloys were prepared by arc-melting in a water-cooled copper crucible under helium atmosphere. Electrolytic cobalt and 99.9 pct pure colum-bium powder have been used as starting materials. It was found that melting losses can be reduced by compressing the colunlbium powder in the form of thin pellets before melting. For the alloys used the melting losses were not higher than 1 pct. The intended compositions of all alloys and the chemical analyses of three of them are given in Table I. Specimens from all alloys were annealed in evac- uated fused silica tubes at 1175°C for 3 days and quenched in cold water. A second set of specimens of most alloys was annealed at 1000°C for 7 days and then quenched in cold water. The annealed and quenched specimens were examined metallographically, using the following etchant: 60 pct glycerine +20 pct H,NO, + 10 pct HF + 10 pct water. Powder specimens for X-ray diffraction were prepared by crushing annealed solid specimens in a mortar. Alloys containing 27.3, 28, 29.7, and 32.6 at. pct Cb annealed at either 1175" or 1000°C were very brittle and it was found unnecessary to reanneal the powders. However, alloys containing 24.8 at. pct Cb, or less, especially those annealed at 1000°C, were much less brittle and re-annealing was required to remove the strains present in the crushed powders. In each case reannealing was done at the same temperature at which the corresponding solid specimens were annealed and it, too, was followed by quenching in cold water. In many instances X-ray diffraction patterns were also taken of the polished and etched solid specimens and compared with the corresponding X-ray diffraction patterns obtained with powders. The X-ray diffraction patterns were taken with an asymmetrical focusing camera, using CrK radiation. For precision lattice parameter measurements some X-ray diffraction patterns were taken with a symmetrical focusing camera, again using CrK radiation. EXPERIMENTAL RESULTS A microscopic examination of the alloys annealed at 1175°C revealed that the alloy containing 25.5 at. pct Cb was composed of a single phase, but that the 24.8 at. pct Cb alloy did contain a small amount of a second phase, identified by means of X-ray diffraction as having a fcc structure, undoubtedly the terminal solid solution based on cobalt. Apart from the few very weak lines corresponding to this minor phase, the X-ray diffraction patterns of these alloys could be well interpreted in terms of a MgNi,-type hexagonal Laves phase structure. The indexing of the X-ray diffraction pattern, Table 11, yas based on the lattice parameter values a, = 4.740A and c,

Jan 1, 1961

By V. Koump, T. F. Perzak, R. G. Olsson

The rate of dissolution of recrystallized alumina in molten iron oxide in equilibrium with iron at 1450°C was studied by rotating alumina disks in the melt. The samples were rotated from 1 to 12 min at speeds from 54 to 3270 rpm. It is concluded from the experimental results that the process is limited by diffusion in the liquid boundary layer. The interdiffusion coefficient for the dissolution of alumina disks in pure molten iron oxide was estimated to be about 3 xl0-5= sq cm per sec. THE erosion of refractory materials is of considerable importance in iron- and steelmaking processes. Since many refractories contain alumina, this investigation was undertaken to develop a further understanding of the erosion mechanism. Shurygin et al.1-3 have investigated the rate of dissolution of alumina in molten silicates and molten fluorides by rotating alumina disks in various melts. The rates were reported to be limited by diffusion in the liquid boundary layer. In the present investigation the rate of dissolution of alumina in molten iron oxide in equilibrium with iron was studied in a similar manner; alumina disks were rotated at different speeds in molten iron oxide at 1450°C. The relationship between the rate of dissolution of the flat surface of the disk and the speed of rotation was used to determine whether the process is limited by diffusion in the liquid boundary layer or by some chemical reaction mechanism. APPARATUS AND EXPERIMENTAL PROCEDURE A schematic diagram of the experimental apparatus is shown in Fig. 1. The iron oxide melts were contained in 2-in.-diam high-purity iron crucibles that were centered in a cylindrical graphite susceptor. Prior to each sequence of experiments, sufficient reagent-grade ferric oxide was added to a crucible to form approximately 350 g of molten iron oxide; the depth of the melt was about 11/2 in. To prevent excessive erosion of the crucible, about 70 pct of the required iron was added to the crucible in the form of iron powder. The mixture was melted in an atmosphere of purified argon by induction heating with a 250-kc generator. After the oxide was molten, a Pt/Pt-10 pct Rh thermocouple at the exterior of the crucible was calibrated against an iron-sheathed thermocouple immersed in the melt and was thereafter used to regulate the melt temperature. All experiments were conducted at 1450°C with a probable error of 10°C. The alumina disks were constructed from pure re-crystallized alumina having a density of 3.7 g per cu cm (porosity approximately 6 pct). For each disk sample a 1-cm-diam alumina cylinder of known length (0.9 to 1.0 cm) was cemented into a ground seat at the end of a 1.27-cm-OD centerless ground alumina tube. The ends of the tube and cylinder were flush and served as the disk surface. When mounted in the apparatus the alumina tube was guided by tungsten carbide bearings and rotated by a variable-speed motor. The bearing and drive assembly could be raised and lowered in order to allow the sample to be quickly moved in and out of the melt. At the start of an experiment, a sample was preheated for several minutes directly above the melt, and then immersed in the middle of the melt to a depth of a in. and rotated for 1 to 12 min at speeds of 64 to 3270 rpm. The speed of rotation was measured by a hand tachometer. At the start and completion of each experiment, a melt sample was withdrawn with a cold copper rod and the alumina content was determined by chemical analysis. During individual experiments the alumina concentration of the melt changed by the order of 0.25 wt pct. Average melt compositions for individual experiments were used in the subsequent computations and were in the range between 0.12 and 4.3 wt pct alumina. The extent of dissolution was determined by sectioning the end of the sample and measuring the final length of the alumina cylinder with a microscope. Since the exposed end of the cylinder, i.e., the disk surface, was etched in a manner characteristic of this geometry, a number of measurements were made on

Jan 1, 1969

By T. A. Pollard, C. R. Sandberg, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By C. R. Sandberg, T. A. Pollard, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By Y. Kondo, S. Yamazaki, Z. Asaki

Thermal deco7nposition of Pyrite particles in a fluidized bed with inert gas stream was studied. Assuming that heat transfer from the surroundings to the fluidized particles controls the overall decomposition rate, rate equations for the batch process and for the continuous process were derived. In the batch experiment, a linear rate equation satisfies the experimental results and the overall heat transfer coefficient calculated from the rate constant agrees fairly well with that obtained by Leva.l1 For the continuous process, two rate equations were derived, one on the assumption of complete mixing of particles and another on the upward piston flow of particles in a fluidized bed. The former holds for a bed containing a higher fraction of decomposed pyrite realized at lower feeding rates. The latter can be applied for a bed at higher feeding rates. Thus, segregation of particles in the fluidized bed was indicated at higher feeding rates. Bed temperatures also correspond to these conditions. ThERMAL decomposition of pyrite may be represented by Eq. [I]. The pressure of diatomic sulfur gas reaches 1 atm at about 690°C. The thermodynamics,' kinetics,2'3 composition, and properties3-5 of decomposed products of such a reaction have been studied. Pyrite is a very common sul-fide mineral and is often accompanied with other sul-fides. It is of basic interest in nonferrous metallurgy to clarify the behavior of pyrite in the pyrometallur-gical processes of sulfide minerals of metals such as copper, lead, zinc, nickel, and so forth. Interest in this reaction increased recently because of possible elimination of arsenic from pyrite in processing highly purified iron oxide pellets. Producing elemental sulfur from pyrite, instead of sulfuric acid, also aroused interest in this reaction. It is indicated that the thermal decomposition of solid particles, such as calcium carbonate, proceeds through three major sequential steps: heat transfer, interfacial chemical reaction, and mass transfer.637 It is known that the decomposed product of pyrite is very porous2, 3 and the diatomic sulfur gas evolved can easily escape through this layer of decomposed product. It depends upon the circumstances, therefore, whether the heat transfer to the interface within particles or the chemical reaction at the interface determines the overall decomposition rate. The enthalpy change in the decomposition of pyrite is about 33 kcal per mole FeS2 which is comparable to that of calcium carbonate. The decomposition of calcium car- bonate becomes more and more dependent on the rate of transport of heat when reaction temperature increases, such as occurs in a fluidized bed.6'7 It is reasonable to presume, therefore, that the thermal decomposition of pyrite, an endothermic process, carried out in a fluidized bed may be analyzed according to the heat transfer controlling model. This work intends, first, to propose a mathematical model that determines the overall rate in a fluidized bed for the decomposition process and, second, to investigate a few characteristics of the fluidized bed based upon the experimental results obtained. KINETICS OF THERMAL DECOMPOSITION IN A FLUIDIZED BED It is intended in this section to obtain rate equations for thermal decomposition of pyrite in a fluidized bed by assuming that the overall rate is determined by heat transfer from the surroundings to the particles. Both batch and continuous processes are considered. 1) Batch Process. To obtain the rate equation in the batch process, the following two additional assumptions are made. First, the temperature of preheated inert gas, tg, blown into the fluidized bed is assumed to be the same as the temperature of the fluidized bed, tf. Thus, no heat exchange occurs between the gas and particles in the bed and only the heat transfer from the reactor wall kept at tw to the particles is to be considered. Second, the decomposition is assumed to start at the outer surface of the particles and to proceed toward the center. At any given time during decomposition, undecomposed pyrite remains in the tori at a temperature: td. The decomposed shell is composed of FeS1+x whose outer surface is at tp Diatomic sulfur gas evolving at the interface is heated to tf during its escape through the decomposed shell. This is illustrated in Fig. 1. With the above-mentioned assumptions of heat transfer, we have:

Jan 1, 1969

By T&apos Ke, ing-sui

NUMEROUS investigators have observed that internal friction accompanies cold-working of metals and the effect of annealing is to reduce this internal friction.1,2 However, - most of the experiments were made at high stress amplitudes and the principal purpose was to study the increase of internal friction as a result of the applied cyclic stress during measurement. In order to study the internal friction introduced by cold-working applied prior to the measurement, the stress level applied during the measurement of internal friction must be sufficiently small. The results of measurement are significant and can be used for a base of comparison only when the applied cyclic stress is so small that the internal friction is independent of stress amplitude. Internal friction of cold-worked metals under small stress level has been studied by a number of workers8 -" he internal friction was measured around room temperature with a frequency of vibration of the order of kilocycles per second. The purpose of this paper is to report a study of the change of internal friction when severely cold-worked aluminum was annealed at successively higher temperatures until it was completely recrys-tallized. The measurements of internal friction were made over a range of temperature extending from room temperature up to the temperature of prior anneal. The frequency of vibrations used was about one cycle per second. The apparatus used for the internal friction measurements to be reported in this paper was a torsion pendulum with the specimen in wire form as the suspension fiber. The description of this apparatus and the method of measurement have been previously given.7,8 The applied stress was sufficiently small SO that the magnitude of internal friction is independent of stress level at each temperature range concerned. Corresponding to this stress the maximum shearing strain on the surface of the specimen is of the order of l0-5 and lower. The in- ternal friction (Q-1) is reported as 1/p times the logarithmic decrement. Internal Friction Versus Temperature of Anneal: Fig. 1 shows the internal friction measurements performed upon 99.991 pct aluminum subjected to 95 pct reduction in area. The final diameter of the wire is 0.033 in. This figure gives a general survey of the effect of temperature of anneal and of temperature of measurement. The internal friction of the cold-worked specimen was first measured at room temperature. It was then annealed at 50°C for one hour and the internal friction measured at 50°C and at room temperature. The same wire was successively annealed at higher temperatures for one hour and measurements were taken at the annealing temperatures and lower temperatures as before. Such a procedure was followed in order to stabilize the internal friction at the temperature of measurement so that during the measurement which generally takes about half a minute, there is no detectable change in internal friction. This series of measurements .was made up to 450°C. After each annealing a short test piece of the specimen, which had received the same past thermal and mechanical treatments, was taken out for metallographic examination. It is seen from fig. 1 that up to the annealing temperature of 250°C we have the following observations: for any given temperature of measurement, the internal friction is lower the higher the temperature of prior anneal. When the annealing temperature is 290°C or higher, the internal friction at the annealing temperature drops abruptly to a value which is much smaller than that for the previous curve. Metallographic examinations showed that the recrystallization of the specimen was completed after the annealing at 290°C. Fig. 1 shows that, as far as internal friction is concerned, there is no abrupt transition between the processes of recovery and recrystallization. Averbach has also reached the conclusion that recovery may be a process analogous to recrystallization on the basis of X ray extinction measurements in brass." The effect of annealing temperature upon the internal friction at room temperature is shown by curve I of fig. 2. In this figure the internal friction at room temperature was plotted as a function of annealing temperature. It is seen that the internal friction decreases rapidly at first with an increase

Jan 1, 1951

Sept. 3-8, AIME, Fall Meeting, Industrial Minerals, Minerals Beneficiation, Mining, Geology, & Geophysics, Iron and Steel, and Coal Div., Palmer House, Chicago. Sept. 3-13, AIME, Chicago Section, Centennial of Engineering, Chicago. Sept. 5-8, Engineers' Council for Professional Development, annual meeting, Hotel Sheraton, Chicago. Sept. 11-13, American Institute of Chemical Engineers, Palmer House, Chicago, Ill. Sept. 13, Columbia Section, AIME, Canadian Institute of Mining and Metallurgy, joint all-day meeting, Metaline Falls, Wash. Sept. 18, AIME, Utah Section, Newhouse Hotel, Salt Lake City. Sept. 20, Colorado Section, AIME, Denver. Andrew Fletcher, speaker. Sept. 22-25, American Mining Congress, Metal and Nonmetallic Mining Convention and Exposition, public auditorium, Denver. Sept. 23-25, Institution of Mining and Metallurgy, symposium on mineral dressing, Royal School of Mines. London.

Jan 1, 1952

By A. F. Crawley

THIS communication reports measurements of the densities of dilute liquid alloys of 0.1 and 0.5 pct Ag in Sn over temperature ranges of 170" and 210°C, respectively, above the melting point of pure tin (232°C). The work was earried out to provide accurate density data for some liquid diffusion studies performed by Davis.1 Densities were measured using a pycnometric technique established in this laboratory. Earlier papers2, 4 attest to the accuracy of ±0.05 pct and the reliability of the method. Tin, 99.999 pct pure, and silver 99.99 pct pure, were melted in a graphite crucible in a vacuum furnace and held at temperature for 10 hr to ensure homogenization. Ingots suitable for machining

Jan 1, 1970

By Per-Martin Sandgren, Alrik Anttila

LKAB's ores have specific mineralogical properties that make them especially suitable for the production of supergrade concentrates. Conditions are particularly good for this purpose at Malmberget, where a concentrate for high-purity sponge iron production has been produced for many years. This product assays approximately 71.5% Fe and 0.20% SiO2. Potential exists for still further improvement. In recent years, the production of fractioned concentrates has been started. The material lies within the size range 74-125 µm and the approximate chemical analysis is 71.4% Fe and 0.30% SiO2. Other special products are under discussion. Malmberget ores are also suitable for the production of high- purity direct reduction pellets with a SiO2 content below 1%.

Jan 1, 1983

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.' Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2'4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy's equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.' were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton' reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler' stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,' is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors' sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958

By E. S. Anolick, Joseph Singer

The magnetic after-effect, in the form of time decay of permeability (l/µ), has been used to obtain independent data on the solubility of' carbon in pure iron. The results differ slightly from the solubilities obtained through internal -friction experiments. The mechanism of the time decay being the magnetic analogue of internal friction, it appears necessary to explain the observed discrepancies, and some suggestions are made. THE purpose of this work was to establish the reliability of the time decay of permeability as a measure of dissolved interstitial in the body-centered-cubic lattice, and further, to establish techniques suitable for such measurements with samples of a form convenient for various other measurements. This particular sample form was the "epstein" strip, i.e., 25 cm by 3 cm by 0.035 cms. While the general conclusions are not limited by this geometry, there are two aspects of the samples that may be relevant: a) texture, and b) grain size, which ranged generally from 1 to 10 mm. Effects due to these two possible parameters were thought to be small and were not investigated. Calibrating the time decay technique and the other experimental procedures by measuring the solubility of carbon in pure iron suggested itself because of the accumulation of data on this subject through the related technique of the internal friction'; The essentials of this report have been published in a somewhat condensed form.5 Since then some additional data have been taken. It is the purpose of this paper to add these data and to provide more complete description of the experimental techniques than was possible then. The time decay of permeability is a form of the magnetic after-effect.6,7 Permeability is measured immediately after demagnetization (µº) and also long after (µ8). The time decay, ?(l/µ), is the difference 1/µ8 - 1/µ0 and has been considered to be proportional to the concentration of a dissolved interstitial6,8,9,12 The relaxation time! 7, is characteristic of a particular diffusion, and affects the permeability as follows: where he being the activation energy for diffusion of the interstitial. Reference is made to the works of snoek6 and Neel7 for a complete discussion. A brief exposition of the principal ideas may be in order here, as follows. On the basis of the simplest model, resistance against domain wall motion increases with time after demagnetization due to the diffusion of interstitials to preferred sites created by the magnetostrictive tetragonolization under the strong magnetic field. Thus permeability, measured with a small field after the abrupt removal of the large field, will continuously fall with the process of diffusion of the interstitials, and the total "time decay" (or "time decrease") should be proportional to the amount of interstitial in solid solution. In the present report, use is made only of the total time decay rather than of the nature of the progress of the decay; the only problem involved in this approach is the need for assurance that only one interstitial is contributing to the effect as used. It is felt that the special use made here of the total time decay warrants the conclusions. Other work has been going on elsewhere on the detailed study of the nature of the time decay.8'9 EXPERIMENTAL A) Materials—12-lb ingots were made in a vacuum furnace from high-purity iron and by a series of hot and warm reductions were brought down to 14-mil strip. This was cut into 25-cm epsteins. The pure iron was decarburized at 750 °C by hydrogen. The time decay measurement for the decarburized iron (see below) indicated a satisfactorily low starting level of interstitials. Grain growth to grain sizes of 1 to 10 mm was produced in the pure iron by a 700" anneal in hydrogen after a critical reduction of about 7 pct as suggested by previous trials. No measurement of texture in the pure iron was made. The grain size was taken to be large enough to be beyond any sharply critical size regarding solubility. B) Infusion of Carbon—Since the permeability measurement required about two dozen epsteins, a special method of carbon infusion had to be developed to ensure homogeneity of infused carbon. This was accomplished by setting the samples edgewise in a

Jan 1, 1961

By NEWTON B. KNOX

IN Bolivia, mining is still the principal economic activity, as it was before and during the Spanish Colonial period. Tin, tungsten, antimony, copper, lead, zinc, gold, silver, sulphur, and a little bismuth are produced. The Andes mountains are divided into two main ranges in Bolivia; the Western range marks the border with Chile and the Eastern range forms the backbone of the country; in the North it drops rather abruptly eastward, to the plains of the Beni, whereas in the South it splits and is separated from the Chaco flatlands by a series of folded mountain ranges. In general the mineral deposits are found within the Eastern range or in the hills that rise from the high plateau between the ranges - really parts of the Eastern range partly submerged by recent sediments. The mineral belt is thus over 500 miles long and about 100 miles wide and includes most of the principal centers of population and the most important means of communication. The region is mountainous and the roads are bad; furthermore labor is a serious problem, for the land is poor and the agricultural population is never far from hunger. The floating supply of miners is limited and soon exhausted in any emergency like the present.

Jan 1, 1945

By Daniel Bloomfield

ONE of the major problems of management is how to restore in some measure the personal relation-ship between employer and employed which, in the days of small concerns, meant better morale among employees. The complexity of industry today, the heterogeneous mass. of workers employed, many .of them new to this country and to its institutions, the inability of those whose task it is to get out production to spend much time on the problems of labor-all these and many other factors serve to make of great impor-tance the question of how to establish more satisfactory mutual good will. While there is no such thing as a sure cure for labor troubles, in spite of the fact that charlatans have been selling alleged cures to guileless employers, study and experience have brought to light methods of approach to the problems confronting management in its relation to labor that are well worth consideration. Labor problems must be approached with common sense and an open mind. Facts must be the basis of action. So it is with the question of morale in industry. What makes or breaks morale? What are the forces behind the actions of men? What is there in one man that makes him act differently from another man under similar circumstances? How are men affected by the actions of others in their own group or by the actions of those under whose supervision they work? These are questions that must be carefully studied if we are, to get at the bottom of industrial unrest. It is an easy thing to say that good will can be created by "treating men right." That involves so many things and points of view that it will hardly serve as a full answer to our problem; but it is a good starting point if we mean by right treatment the payment of wages consistent with the well being of the worker and his family as members of the community, and if we also mean the provision of sanitary, wholesome working conditions and a working schedule that does not overtax the worker physically, and mutuality-a give and take relationship. With this as a basis we can go a step farther and see what else can be done to promote better relations between management and the workers.

Jan 9, 1922

By D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.' and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~' have reported the structure of

Jan 1, 1965