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By John S. Alexander

DURING the past few years the block coal of Indiana has been talked about and written upon to such an extent, that almost every one at all interested in such subjects, has been made acquainted with the area and geographical position of the field, the quality and peculiar properties of the coal, the thickness of the veins, the manner of mining, etc. The writer, therefore, taking for granted that, to those present all this is familiar ground, desires more especially to call attention to the position this coal takes in the market, and at those points of consumption where it is brought in direct competition with rival fuels. Chicago, thus far, has been the chief consumer of Indiana block coal, the distance from the mines at Brazil, via Terre Haute and the

By L. R. Woodyatt, H. J. Beattie, C. T. Sims

Theories correlating the formation of u and related intermetallic compounds to the electron-per-atom density of binary and ternary alloys have appeared regularly in recent technical literature. These same principles can be modified and applied to complex precipitation-strengthened alloys such as the iron-, cobalt-, and nickel-base superalloys and the stainless steels. Since these complex alloys contain carbides and other phases that normally precipitate before the U-type phases, the nature and amount of the precipitated phases must be calculated first. The following general formula is then applied to the residual matrix composition of the alloy: element. The magnitude of the resulting number is indicative of whether the alloy will form a a -type phase. When these calculations (which are computerized) are systematically applied to alloys of knoun phase analysis, a breakoff in average electron-vacancy number is noted between U-free and U-prone alloys. Alloys with an average electron-vacancy number higher than the breakoff form a-type phases, while those with lower ones do not form these phases. This method could then be used to eliminate from consideration all experimental compositions that would precipitate undesirable phases. It also is useful in evaluating analyzed heats of alloys where minor heat-to-heat variations determine whether the alloy is o-free or o-prone. THE highly significant development of strong, ductile superalloys to provide reliable construction materials in the 1000" to 2500° F temperature range has been due principally to unremitting application of Edisonian techniques and logic by the dedicated physical metallurgists who have shouldered this responsibility. Tools such as the electron microscope, phase analysis, and computers to accomplish regression analyses have been used heavily, but the effort has been essentially practice of an art, rather than a science. The objective of this paper is to describe and illustrate application of some relatively fundamental principles to certain of these alloy systems in an attempt to remove some of the empiricism from the technology. Specifically, the work presented here deals with the use of periodic-group relationships to predict the formation of intermetallic phases which can occur in primarily austenitic (fcc) structures. Calculations that have been developed might be applied in the design of new alloys and the evaluation of known alloys, and thus have the potential of eliminating vast areas of unnecessary alloy preparation and evaluation. ALLOYING CONCEPTS AND STRUCTURAL FEATURES OF SUPERALLOYS Strength is produced in austenitic superalloys by three principle mechanisms: 1) precipitation of y'; 2) formation of carbides; 3) solid-solution hardening by soluble refractory metals. The first mechanism requires the addition of aluminum and titanium, the second requires carbon and carbide-forming elements, while the third calls for the addition of molybdenum and/or tungsten. A considerable concentration of chromium is usually maintained to resist oxidation/corrosion, but it is also an important carbide-forming element. Fig. 1 shows a sketch and electron micrograph of the structure of a typical wrought nickel-base super-

Jan 1, 1967

By C. R. Hayward, H. O. Hofman

The aim of instruction in a metallurgical laboratory is to make real the principles on which metallurgical processes and operations are based, and to foster the spirit of investigation. The materials with which experiments are carried out are ores, metals, and metallic compounds. The method varies with the end sought. A class may work as a whole, each member contributing his share to the solution of a problem, or the students may carry on investigations independently; the former exemplifies class-research; the latter, individual research. It is with a branch of the former, with special reference to ore-treatment, that the present paper deals. In smelting an ore by a well-established process, the result is shown by analyzing the products to see whether their compositions correspond to those calculated in making up the charge; by taking account of stock to show the distribution of metal in the different products made and the losses from dust and volatilization; by casting a thermal balance to find the distribution and losses of heat; and by making a cost-sheet to ascertain, as far as possible, the necessary outlay of money. In lixiviation and amalgamation, the mode of operating has to be varied to adapt a process to the individual ore. Here a number of tests become necessary. Each will consist of a series of experiments with one variable, in order to find the conditions under which the variable gives the best result; a summary of several tests will give the best method of operating. Working a number of charges with the best method will furnish the data desired for ascertaining the recovery of metal,

Jan 1, 1910

By C. Schlumberger

LAST year the authors presented a paper that discussed the various electrical measurements they perform in drill holes, which they name "electrical coring."' The object of the present paper is to give a brief account of the points of scientific interest that have been elucidated by further field work and laboratory research, as well as the economic results that have been attained recently. The practical examples given in this paper are drawn, for the most part, from the field work performed in Russian oil fields during the years 1931 and 1932. This is due to the fact that, thanks to the comprehensive cooperation of the Russian geologists and scientists, the authors are allowed to make public a large amount of recent information. In other countries in which the authors are engaged in similar work, the competi-tion between private companies makes it imperative, for a considerable lapse of time, to avoid publication of the results obtained. The following points will be discussed successively, under sepa-rate headings: 1. Electrochemical phenomena in drill holes. 2. Stratigraphic correlations and tectonic studies. 3. Relations between the productivity of oil horizons and their electrical resistivity. 4. Location of coal seams. 5. Summary and conclusions.

Jan 1, 1933

By H. H. Podgurski, J. C. M. Li, Y. T. Chou, F. N. Davis, R. A. Oriani

When an Fe-2 pct A1 alloy is nitrogemted at 500ºC with a gus tnixture (NH3-H2) in which the nitrogen activity has been kept Lou] enough to avoid the formation of iron nitride, a two-phase alloy is generuled which consists of AlN particles and a ferrite phase cotaining a heavy network of dislocations. The amount of nitrogen contained in such an alloy, when equilibrated with the nitrogenating atmosphere, far exceeds both that needed to satisfy the normal solution requirements of a Fe and that needed to convert all of the aluninuwi to AlN. This excess nitrogen is accounted for as being trapped on dislocations, adsorbed at the ferrite -AlN interface, and as an en-Iuznced lattice solubility in strained ferrite. This excessive uptake of nitrogen had previously been attribuled by other investigators to the formation of a nonstoichiornetric aluminum nitride. Isotope exchange experiments revealed various amomts of exchargeable N14 present in the originally nitrided samples that could not be removed by reduction with HS at 500ºC. This exchangeable nitrogen has been identified us that bound to the AlN -ferrite interface. Estimates of inter facial areas in alloys containing -3 pct by weight of A1N are as high as 10 sq m per g of alloy. ThE first1 of this series of papers described the experiments forming the basis for the elucidation of the mechanism of the formation of aluminum nitride particles within an Fe-A1 alloy. It was found that not only are dislocations necessary for the nucleation of the AlN particles but also the nitriding reaction in turn produces a dense network of dislocations in the ferrite matrix. It was also observed that nitrogen in excess of that needed for the formation of stoichiometric AIN is taken up by the alloy without the formation of an iron nitride. The present paper is an analysis of the excess nitrogen sorbed by the nitrided Fe-A1 alloy which considers the structure generated by the formation of the aluminum nitride particles. Because of the high density of dislocations, this system has proved to be quite useful in studying nitrogen-dislocation interactions. Wriedt and Darken2 have already reported such studies in a cold-worked ferritic steel. EXPERIMENTAL Nitrogen Sorption. The specimens of this alloy were cold worked (50 pct reduction) to 0.011 in. thickness and chemically cleaned in a 2:1 concentrated phosphoric acid-50 pct hydrogen peroxide solution before nitrogenation. The flowing nitrogenating atmosphere (11 pct NH3-89 pct H2) was established before the ni- trogenating temperature was reached. The same gravimetric and gas-flow equipment described in an earlier paper1 was also used in this investigation. Changes in nitrogen concentration were followed gravimetrically when establishing the isotherms. In the isotope exchange experiments, concentration changes were followed volumetrically. In some instances chemical analyses (Kjeldahl method) were used to check for material balances in both the gravimetric and volumetric procedures. Our objective was to obtain reversible nitrogen sorption isotherms for alloys equilibrated with NH3-H2 gas mixtures over a large range of nitrogen activity* and temperature. The *Defined as equal to PN H /P3/2 ,where P corresponds to partial pressure in atmospheres. Actually the nitrogen activity, aN, in the alloy equals K PNH3 /p3/2H2, where K is the equilibrium constant for the reaction NH3 = N + 3/2H2. upper limit for nitrogen activity was below that which would produce iron nitride; for reasons which will become apparent later, most of the sorption studies were made in the temperature range between 400" and 500'C. The alloy sample studied most extensively in this investigation was given a series of successive reductions (100 pct H2) and nitrogenating treatments at 500°C to attain a stabilized structure. Presumably some dislocations were lost during these treatments. Throughout most of the sorption studies, temperature was held at ± 1°C and the gas-phase composition was held to k0.2 pet NH3. Based upon the results of numerous diffusion experiments with this alloy* the 'Results to be published in a third paper of this series. times chosen for equilibration were considered more than adequate, Nitrogen Isotope Exchange. The first exchange experiments were carried out by circulating a measured quantity of H2 and NH3* (with a predetermined isotopic *The NH3 was synthesized over a synthetic ammonia iron catalyst using H2, and N2, enriched with N15. AS the NH3 was formed it was removed continuously from the gas phase by circulating the mixture through a refrigerated (78ºK) trap. When most of the nitrogen had been converted to NH3, it was distilled from the trap into a glass storage vessel. composition, N15/N14) over a nitrided specimen at 450°C in a closed glass system. Attempts to reach the exchange limit isothermally, i.e., an isotopic ratio (N15/N14) in the gas phase identical with the extractable nitrogen in the nitrided alloy, were futile. The exchange rate between the gas phase and the alloy was too slow, involving many days. To circumvent the slow exchange with the gas phase, measured amounts of N15 and N14 were introduced into the alloy by nitrogenating with an NH3-H2, mixture at 500°C containing an N15/N14 ratio of 7.76; the charged specimens were then sealed by allowing an oxide film to form over them in air, and in this final condition the specimens were subjected to 500°C in vacuum for various times during which isotope exchange was allowed to proceed within the specimen. It was estab-

Jan 1, 1970

By Max W. Bowen, A. J. Weinig

The important part that dissolved oxygen plays in the cyanide treatment of gold and silver ores is commonly recognized by most metallurgists and mill men. But heretofore there has been no simple method on which the mill man could rely for determining the amount of oxygen in the various mill solutions. A few methods are adaptable to the laboratory, such as the gasometric1 determination by actually measuring the oxygen, Winkler's2 iodometric method, and Schutzenberger's3 method, which depends on the reducing action of sodium hyposulfite on a blue solution of indigo carmine; but these are not readily adaptable to the needs of the mill man and cannot be applied to cyanide solutions without modification. The gasometric method is the most accurate but it takes too long to complete a determination. White's4 method (a colorimetric method that depends on the degree of coloration imparted to a solution of pyro-gallic acid in the presence of caustic soda) although much more rapid than any of the methods named, often gives misleading results on account of grading of colors of different solutions, which nearly always contain various kinds of salts. The method herein described was devised for the use of the mill man, the aim being to develop a simple, practical, accurate method. It is a modification of the Schutzenberger method and depends on the reducing

Jan 1, 1925

By T. Egleston

The importance of making analyses of gases in furnaces which are used for metallurgical purposes is every day growing more and more evident. It is the only method of understanding the reactions that take place in the furnace, and of economically conducting the operations both with regard to the fuel used and the reactions which take place on the bodies to be subjected to the influence of the heat and gases. As a knowledge of the composition of gases is becoming every day more necessary to the proper conduct of furnace operations, it seems desirable that furnace managers should generally know that the analysis of gas for commercial purposes is neither difficult, tedious, or expensive, and that it does not necessarily imply the use of corrections requiring difficult instrumental observations and long and tedious mathematical calculations. Any method, therefore, which will tend to render these analyses simple will also tend to having them made and repeated as frequently as the analyses of the ores and other materials charged in the furnace. They should be made even more frequently, as their composition is affected by any change in the condition of the furnace, and a knowledge of their composition will give a ready clue to the unseen and otherwise not easily detected changes which are taking place. The only practicable method of making industrial analyses of gas is that of measuring volumes in graduated tubes. The methods by

By William R. Rumbold

When I was in South Africa during the latter part of 1904, there were three known tin-fields, which may be called the Cape Town, the Bushveld, and the Swaziland fields. The Cape Town Tin-Field. This district is situated near Kuils river, 20 miles west of Cape Town, and 5 miles from Kuils River station on the Cape Town & Stellenbosch railway. The deposits are in granite, intrusive in the Malmesbury beds, which are supposed to be of Silurian or Cambrian age. The granite, resisting denudation better than the surrounding shales, has formed low-lying hills, the highest of which, the Bottlelary Berg, is 1,510 ft. above sea-level. The rock consists of quartz, orthoclase feldspar, and biotite mica; tourmaline is also present. The feldspar occurs in large crystals. The rock is generally decomposed on the surface, and the decomposition sometimes extends as deep as 100 ft. This formation—granite intrusive in Silurian shales— extends for many miles to the northeast, but so far as I know the Kuils River deposits are the only ones now known to occur in it, though probably further prospecting will reveal other deposits. This particular discovery was accidental; alluvial tin being found in the course of boring for oil. The Kuils River Deposit. This deposit comprises both lode and alluvial tin. The lode strikes N-S., and dips about 30' E. into the hill. It is 5 ft. wide, and composed of dense white quartz, in which pinkish-gray cassiterite is distributed in large crystals. The vein also contains considerable quantities of wolframite. Fig. 1 is a rough plan of the relative positions of the lode and the alluvial deposit, the latter, as shown, following the course of a stream, while the lode crops out on the hillside ,

Jan 1, 1909

By C. M. Weld

Attention has been turned recently to the exploration and development of certain large blanket-deposits of brown iron-ore in Cuba. The most conspicuous of these to-day, and the one upon which the most light has been shed, is the Mayari deposit, situated about 15 miles south of Nipe bag. Here the Spanish-Aniericau Co. has sole control over 18,500 acres of ore-bearing lands, reported by its engineers to contain 500,000,000 tons of ore. The necessary plant and equipment, with docks and railways, is now under construction for the early marketing of this ore. A similar deposit, and undoubtedly the next to be exploited, is the ore-field at Moa bay, where from 13,000 to 15,000 acres of ore-lands, immediately adjacent to the shores of an excellent harbor, have been generously covered by numerous mining-claims, practically all controlled by four large interests;. This deposit is now estimated to contain approximately 350,000,000 tons, on the basis of dried ore ready for shipment, a figure which may be increased when the western limits of the ore-deposit have been more accurately defined. Other deposits of the same type, but smaller and less accessible, are those at Cubitas, situated from 12 to 15 miles north of Camaguey city,

Jan 1, 1910

By Joshua E. Clayton

This remarkable gold and silver bearing district is situated on the middle fork of Boise River, in Alturas County, Idaho Territory, about eighteen miles north of Rocky Bar, and sixty-five to seventy miles, as the crow flies, east of Boise City, the capital of the Territory. This district lies in the very heart of one of the most wild and mountainous regions of Idaho. For many miles in every direction nothing can be seen but bold granite mountains, with deep narrow gorges cutting into their sides in every direction, rendering them almost inaccessible except to .the hardy mountaineer and adventurous prospector. The mountain sides are covered, in most part, by dense forests of pine, fir, and spruce timber. In every canon there are clear streams of pure running water that empty into the principal forks of Boise River. The only line of approach to this mountainous region at present is from the southwest, by way of Rocky Bar, the county seat of Alturas County, to which place there is a good wagon-road. From thence to Atlanta City, eighteen miles, the road, or pack-trail, passes over the high, steep range that separates the south and middle forks of Boise River. During severe winters this line of approach is closed up by deep snows for months at a time, thus leaving the district isolated, in the bosom of the grand old mountains. The geological formation is granite, of a coarse, friable texture, and in many places is traversed by numerous dikes of syenite, and three or four varieties of porphyry, which cut through the granite in easterly and westerly directions. The metal-bearing reins also have an easterly and westerly trend, bat are occasionally intersected by the dikes. The largest number of the gold and silver lodes are confined to a

By N. H. Emmons

The work of a consulting engineer or manager, when controlling mining-operations, requires that he have all the information concerning the mine in as concise a form as possible, and as the ore-reserves and their depletion and enlargement are the vital points to be studied, it is well to have the records kept up to date and in some convenient form. The present paper describes a method adopted by me, which shows in a very clear manner the ore-reserves in a mine. The case illustrated is that of a vein near enough to the vertical for the vertical elevation of the mine to be the main working-map. A flat ore-body would be represented on a similar plat, but instead of the horizontal thickness of the vein being shown in the circles, the vertical thickness would be inserted. Fig. 1 represents an ideal longitudinal elevation of a mine, plotted in the ordinary way, using 100-ft. blocks and section-lines. In a mine where the block-numbers are posted by the engineer underground, the system of keeping the ore-tonnages extracted from the different blocks is easily maintained, and the actual tonnages of ore extracted can be kept so that the surveyor can have a check on his estim'ate from time to time. The ore-reserve sheet, Fig. 2, should be the same size as the map it is to accompany. Each square is used for the description of the ore-reserve in the block it corresponds to on the elevation. Where the section-lines cross the levels a circle is drawn, in which are written the midths of ore at that point, these widths being used in the calculations of each block cornering in the circle. It has been found convenient to show the figures in black in the lower half of the circle when the actual widths of ore are known, and when it is necessary to make up the figures of probable ore, as at the time of making

Jan 1, 1913

By D. O. Wyble

Five water-driver fields, for which pressure predictions had been made within a few years after discovery, were re-studied when four to five years of additional pressure and production data became available. It was fortnd that forecasts of the pressure in water-dri~fe reservoirs may be subject to considerable unccrtainty. Predictions car be erroneous when there is insufficient presswe history to define the cllaracteristics of the aquifer, and when there are errors in the pressure, production or geologic data. INTRODUCTION The efficient operation of an oil or gas reservoir requires that the important characteristics of the reservoir be determined soon after its discovery. It is especially desirable to evaluate the pressure-production relationship quickly, for this relationship provides a basis for deducing the type of production mechanism that is operative, and for making pressure predictions. The pressure predictions, in turn, provide a basis for calculating efficient rates of production, determining whether water or gas should be injected, etc. The importance of pressure prediction is such that forecasts should be made as accurate as possible, and the limits of error well defined. Historically, pressure forecasts for some fields have proved very accurate, while for others the forecasts were so erroneous that they resulted in the adoption of wrong, or at best, unnecessary production practices. Pressure predictions made for water-drive fields are especially subject to error. Accurate forecasting for these fields requires that much be known not only about the reservoir proper but about the adjacent water-filled rock as well. The water-containing rock, or aquifer, may extend for many miles, and often there is only meager data regarding its thickness, permeability and porosity. Much of the information must be inferred from the previous pressure behavior of the reservoir. A brief pressure history may provide little information about the characteristics of the aquifer. Hence, pressure predictions made early in the life of water-drive fields can be incorrect. The work described in this paper was done to determine the degree of reliability which can be expected of pressure predictions made within a few years after water-drive fields are discovered. Five fields, for which the original pressure predictions had been based on less than seven years' history, were re-examined with the aid of four to five years of additional pressure data. Where the predictions were inaccurate, the reasons for failure were ascertained. The studies were accomplished by use of the electric reservoir analyzer.' The analyzer was first adjusted to repeat the original pressure-production match using the same values for the various parameters as were used in the original study. Then, the actual production rates experienced during the time elapsed since the initial study were set into the analyzer, and the pressure behavior indicated by the machine for this period was compared with that which actually OCcurred. Where the pressure profile traced out by the analyzer deviated from the observed field behavior, the analyzer was readjusted to obtain a better over-all match. The old and the new solutions were compared to determine the reasons for any differences. COMPARISON OF PREDICTED RESERVOIR PRESSURE BEHAVIOR WITH ACTUAL PERFORMANCE Field A The original pressure-production match is entirely adequate as evidenced by the pressure match of the field's history subsequent to Jan., 1952 (see Fig. 1)'.

By G. A. Collins

Being much interested in efficiency-work in general, and an ardent reader of writings on this subject by Frederick W. Taylor and others, as applied to manufacturing-plants, and having served my apprenticeship from mucking to the engineering design of ore-dressing and underground plants, I hope that this paper will lead others to investigate the field more fully, to the improvement of general mine- and mill-operations, as well as the advancement, intellectually, physically, and financially, of the employee and his relations with the employer. If a man who is prepared to look closely and observe broadly starts in Canada and zig-zags from camp to camp to southern Mexico, taking time casually to inspect mines, mills, and smelters, he will be pitifully impressed by the great difference in customs, and the general waste of labor, time, and money throughout the country. He will so seldom observe a dollar's worth of results given in exchange for a dollar spent that he will form a poor opinion of operating-efficiency and management. This highly-scientific department, requiring an amount of skill and executive ability equaled in few, if any, of the professions, certainly falls short of the standard established in our greater manufacturing industries. It is easily said that this is due to the diversity of conditions in mining, milling, and smelting. But on second view it must be admitted that there is room for tremendous improvements in nearly every mining-organization. The proposal of such improvements is often met by the argument that any mine is but a temporary affair, yielding such profits as to make efficiency-work of no consequence; but any business which is profitable and worth doing at all is worth doing on a basis which gives the greatest return on the investment.

Jan 1, 1913

By S. Arthur Krom

ThE James diagonal-plane slimer is specially adapted to handle the finest slimes, but it will also handle sands as coarse as 40-mesh. The saving efficiency of this machine is due to the original construction ,of the deck, and to the rapid reciprocating movement imparted to it by the head-motion. The deck consists of a plurality of connected planes, having a certain fixed ratio of inclination one to another. These planes intersect each other diagonally to the stroke-line of the table and are arranged so as to give the pulp on the table a double treatment. This double concentration performed by the diagonal-plane deck produces cleaner concentrates and tailings than those obtained by the operation of two separate machines. The action of the diagonal planes settles, combines, and holds all the concentrates in one compact mass, sharply defined from the gangue, and easily cut away without loss. Many slime-concentrating machines distribute the feed-pulp for a distance of 4 or 5 ft. only, and upon a very limited settling-surface. This results in a thick, heavy deposit, from which it is impossible to stratify the values and wash away the gangue, the resulting products being dirty concentrates, and tailings carrying high values. The diagonal-plane slimer distributes the feed-pulp for a distance of 10 ft., and upon a settling-surface having an area of 40 sq. ft.; in other words, it spreads the pulp thinly on the table, which allows the metallic values to settle through the gangue quickly, forming a bottom stratum from which the thinly-distributed overlying stratum of gangue is easily brushed away by the feed-water without disturbing the underlying concentrates. Referring to Fig. 1, plane A is the main settling-section of the table. The feed pulp flows gently down this plane and is

Jan 1, 1913

By G. S. Brooks

The tendency of the oxides of such metals as aluminum, zinc, chromium, and calcium to form compounds at high tempera tures with iron oxide is well established by past investigation. Data of this reaction, as developed in laboratory research, have been contributed by Burleigh, Hofman, and Wells, in America, and by many others abroad. A partial bibliography of the subject is appended. From these authorities we learn that the ferric oxide here has the function of an acid, giving in the case of ZnO a zinc ferrite, with a normal composition of ZnOFe2O3 This formation of zinc ferrite particularly affects the success of such processes as leaching or magnetic separation, and thus becomes practically important to the metallurgist. But the meager existing data do not entirely agree; and quantitative results from muffle-practice are conspicuously absent. Furthermore, it being of some general importance to the zinc smelter in both roasting and reduction, the following few notes of operations oil a commercial scale are contributed: I. Physical Properties of Zinc Ferrite. As formed for the most part synthetically by investigators, zinc ferrite exhibits characteristic physical properties, such as octahedral crystals, dark color, and a density over 5, together with a slight magnetic attractability. In examining with the microscope many products of mechanical muffle-roasting kilns, it is, however, impossible to find individual grains which can be identified as consisting entirely of zinc ferrite. The variety of colors, especially where each grain of blende was mechanically free from marcasite, rather conveys the impression of a partial ferritization of the grain. One side or end, for example, may often have the hard, dense surface and dark red to black color of the ferrite, while the balance shows the usual light yellowish brown of a normal iron-free blende.

Jan 1, 1914

By Herbert H. Kellogg

Graphs representing the standard free-energy of formation as a function of temperature for 21 fluorides are presented, along with estimated values for the standard free-energy of formation of 20 atedadditional fluorides. A few of the many possible uses of these data in metallurgical calculations are discussed, including the fluorination of oxides, sulphides, metallurgicaland chlorides, and the reduction of metal fluorides. RECENT papers which have presented free-energy data for oxides, sulphides, chlorides, carbonates, sulphates, and silicates in the form of free energy vs. temperature plots,1-5 have found important uses in teaching and metallurgical development work. This method of presentation of thermo-dynamic data serves to make available in readily usable form thermodynamic constants which are scattered throughout the literature, and to show by graphical means the stability relations which exist between the compounds of a given type. It is certainly desirable to have these free-energy-temperature diagrams for as many types of compounds as are of present or potential use in metallurgical processes. Thus, even though there are but few uses of metallic fluorides in extractive metallurgy today, the potential uses of fluorine processes are of great importance and serve as the principal justification of this paper. Recent developments in the production of fluoro-carbons have resulted in vastly improved methods for the production and handling of fluorine and corrosive fluorides, with consequent reduction in costs.".' The extractive metallurgist should no longer overlook possible fluorine processes when development of a new process for a relatively high unit-price metal is being considered. In a previous paperv he author outlined in some detail the importance and use of free-energy data in metallurgical calculations and also discussed the properties of a standard free-energy vs. temperature diagram. The same method of presentation is adopted in this paper, and the reader is referred to the earlier work for explanations of the use of free-energy data. Thermodynamic Data This paper presents standard free-energy vs. temperature diagrams, Figs. 1 and 2, for those fluorides for which the major thermodynamic constants are known. In the calculations of the standard free-energy of formation (AGO), values of the enthalpy of formation at 298°K (?Ho,) were taken from "Selected Values of Thermodynamic Constants"8 most of the values of standard entropy at 298°K (S°298) were taken from "Selected Values"," but in a few cases the values given by Kelley9 ere preferred; data for the Phase changes came from "selected Values" and several of Kellley's publics- tions;0-12 and most of the specific-heat data were taken from Kelley.l0 The appendix gives a detailed list of the sources of the data. As explained in an earlier paper,6 he accuracy of some of the standard free-energy relationships is not high. An error of +1 kcal at 1000°C is expected in most of the curves of Figs. 1 and 2. The error may be as high as +3 kcal in some of the curves. Rather than attempt to estimate the reliability of each curve, the source of the data used is reported in the appendix, and the reader may compare these data with newer values as they become available. Figs. 1 and 2 fail to show values for the fluorides of many important metals. In most cases this is because the entropy of the metallic fluoride is unknown. For preliminary calculations it is often useful to have available the best estimate of an unknown datum, rather than no information at all. With this in mind, Table I lists estimated standard free-energy values for a number of important metallic fluorides not included in Figs. 1 and 2. The values reported in Table I were, calculated by Brewer et al.13 and are based on estimated entropy values. The estimated uncertainty of the values for each fluoride were calculated from the uncertainty values given by Brewer1' for ?H°, and the entropy function.

Jan 1, 1952

By E. Keller

Some years ago the writer's attention was called to the fact that rolling-mill scales from auriferous copper do not have the gold content proportional to the gold contained in the copper from which they are derived.' So, later, he made a few simple experiments, which are described herewith. In order to test the gold movement on the changing surface of a copper plate under the influence of oxidation, plates 6 in. by 8 in. by 1 in. (15.2 cm. by 20.3 cm. by 2.5 cm.) of converter copper, refined, of 99.29 per cent. purity, and leaded copper with a content of 95.65 per cent, copper, were obtained. Ten cuts were made through the thickness of the plates along the longitudinal center and the silver and gold content ascertained in each of the 10 samples in both plates, as shown in the accompanying illustration. The assay results, recorded in Tables 1 and 2, show that the gold distribution is relatively uniform in both plates, while silver has greater variations, especially in the leaded plate. The plates subjected to oxidation were placed in a red-hot muffle for about 2 hr., two small scarifiers being used as supports. Arranged alongside each other, they nearly filled the width of the muffle, and so were practically under equal conditions of heat and draft. The accurate observance of the time was not possible, however, because of other work, but the time of the exposure of each plate in a pair was identical. At the end of each period, each plate was plunged into water and completely freed of scale, which was carefully collected, dried, weighed, and analyzed. Samples of the plates had also been taken of the molten metal and duly analyzed. Table 3 contains the analytical data for the two plates and their several sheets, or layers, of oxide scales. These figures show that in the oxidations of the converter copper the silver is fairly uniform, while the gold is highly irregular and especially low in the first layer. In the oxidations of the leaded copper plate, the silver and gold contents are variable; however, this irregularity is due to two different causes. The

Jan 1, 1919

By W. C. Ellis

IN an ingot of germanium solidified progressively from the bottom by a method' devised by J. H. Scaff and H. C. Theuerer, examination discloses ex- IH. C. Torrey and C. A. Whitmer, Crystal Rectifiers. p. 364. 1948. New York. McGraw-Hill Pub. Co. tensive twin relationships. A slice taken about midway in a cylindrical ingot approximately 3/4 in. in diameter and 1 1/2 in. in length, after etching and polishing to delineate different orientations, is shown in fig. la. The orientations of the regions designated with letters were determined by Laue X-ray back-reflection methods and plotted on stereograms. The orientation relationships of the designated components were determined by comparing the values for the nine angles between the three respective cube poles of each orientation with the values calculated in a formal treatment of octahedral multiple twinning in cubic crystals. Germanium, diamond cubic in structure, has the octahedral twinning habit. I am indebted to K. H. Storks for the calculation of the angular relationships of cube poles in octahedral twinning to four orders. The set of values for the nine angles is distinctive of the order of twinning. Confirmation for a multiple twin relationship is obtained from the determined indices of the mirror planes. These exist for all orders of twinning through the third and for some of the fourth." If the orientations are not those for twinning, then the nine angles for the cube poles do not correspond in value and distribution to those formally calculated. Since all nine angles must correspond in values and distribution of values to the calculated ones, the Laue method with a precision of one or two degrees is adequate to establish or deny with confidence the existence of multiple twins. Regions of the same orientation can also frequently be identified by the optical reflections. For example, the narrow twin bands in A at 2: 00 o'clock have orientation B1. The interesting twin relationships shown schematically in fig. lb were found for the section in fig. la. Most of this slice was made up of orientation, A, appearing in widely separated regions. Of the four possible first order twins of A, three were present in this slice and are designated by B with subscripts. Four second order twins of A are designated by C with subscripts. It is worth emphasizing that two of these, C, and C,, are second orders of A through the first order missing in this section. Two regions, designated by D with subscripts are third order twins of A. D2 is a sixth order twin of D,. All orientations found were ascribable to multiple twinning, as if the orientations in this section originated earlier in solidification from a single nucleus. The presence of extensive multiple twinning to- gether with the absence of other orientations appears to be a characteristic result in many instances of solidification of germanium. Fertile conditions for twinning probably exist in the array of atoms in the diamond cubic structure. The high order twins in the section shown, it is reasonable to presume, are the result of progressive octahedral twinning through several generations in the material freezing earlier. Some of these generations do not appear in this section, it is suggested, because their orientations with respect to the growth direction were unfavorable for survival. The extensive twinning is probably promoted during solidification by constraint imposed by volume increase, and to an irregular growth front. Twinning may also be due, in part, to the attempt of the solidifying region to attain the orientation most favorable to the growth direction (maximum thermal gradient). The nucleus for a twinned orientation could have its origin in a "stacking fault" on the close-packed octahedral plane. Further work is being done in which the course of twinning throughout an ingot is being studied. The results appear to be important in the general theory of solidification.

Jan 1, 1951

By V.F. Marsters

Peru has produced petroleum since the early seventies, the first work being in the Zorritos field, in the Province of Tumbes, adjoining Ecuador. In the early nineties, the Negritos field, in the Department of Piura, came into prominence, and by 1905 had attained an annual production of 335,160 bbl. The early development of the field was under the general direction of the London & Pacific Petroleum Co., but it is now handled by the International Petroleum Co. In 1900 and 1901, the Lobitos field became the seene of marked activity. In 1905, its total production amounted to 75,000 bbl.; it has continued to increase, as has Negritos. From 1897 to 1902, there was prospecting in the region of La Brieta (or Fernandex), on the Mancora River, about 25 to 30 km. from the coast. Small production of a heavy oil was obtained from three different sands. So far as the author knows, no work has been done in that locality since 1902. There are thus four distinct fields in the north end of the Peruvian coasta1 plain. The remaining productive locality of Peru is the Pirin or Pusi field, at the northwest end of Lake Titicaca, Department of Puno, in southern Peru. The first prospecting near Pusi was done by Brown Brothers, of Los Angeles, Calif., who obtained modest production about 1906; according to reports, activities ceased about 1914 or 1915. The maximum annual production was obtained about 1908, estimated at 76,000 barrels. Peru possesses two distinct geographic provinces in which we may look for the development of a larger oil industry; namely, the coastal plain province, and the inter-Andean plains. Coastal Plain Province The coastal province is most prominently developed in the Province. of Tumbes and the Departments of Piura, and Lambayeque.l It 1 For details concerning the geology of this part of Peru, see Bol. No. 50, Cuerpo de Ingenirros de Minas "Informe preliminar sobre In Zona Petrolifera del Norte del Peru," par V. 1". Marsters.

Jan 1, 1923

By V. F. Marsters

Peru has produced petroleum since the early seventies, the first work being in the Zorritos field, in the Province of Tumbes, adjoining Ecuador. In the early nineties, the Negritos field, in the Department of Piura, came into prominence, and by 1905 had attained an annual production of 335,160 bbl. The early development of the field was under the general direction of the London & Pacific Petroleum Co., but it is now handled by the International Petroleum Co. In 1900 and 1901, the Lobitos field became the seene of marked activity. In 1905, its total production amounted to 75,000 bbl.; it has continued to increase, as has Negritos. From 1897 to 1902, there was prospecting in the region of La Brieta (or Fernandex), on the Mancora River, about 25 to 30 km. from the coast. Small production of a heavy oil was obtained from three different sands. So far as the author knows, no work has been done in that locality since 1902. There are thus four distinct fields in the north end of the Peruvian coasta1 plain. The remaining productive locality of Peru is the Pirin or Pusi field, at the northwest end of Lake Titicaca, Department of Puno, in southern Peru. The first prospecting near Pusi was done by Brown Brothers, of Los Angeles, Calif., who obtained modest production about 1906; according to reports, activities ceased about 1914 or 1915. The maximum annual production was obtained about 1908, estimated at 76,000 barrels. Peru possesses two distinct geographic provinces in which we may look for the development of a larger oil industry; namely, the coastal plain province, and the inter-Andean plains. Coastal Plain Province The coastal province is most prominently developed in the Province. of Tumbes and the Departments of Piura, and Lambayeque.l It 1 For details concerning the geology of this part of Peru, see Bol. No. 50, Cuerpo de Ingenirros de Minas "Informe preliminar sobre In Zona Petrolifera del Norte del Peru," par V. 1". Marsters.

Jan 1, 1923