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By Thomas C. Wilder

The concentration and activity of oxygen in liquid copper has been measured by the reversible galvanic cell: at 1100°and 1200°C for the concentration range of oxygen of 3 to 5600 ppm Measurements for approximately thirly alloys at each temperature indicate that the activity of oxygen roughly follows Henry's law, the activity coefficients of oxygen being 0.12 and 0.205 at 1100° and 1200°C, respectively. These results compare javorably with the results of seven other electrochemical and gaseous equilibrium studies on this system, the free energy of the solution reaction 1/2 O2 = O (7 at. pct in Cu, liq) being -18.10 * 0.30 kcal per gfw at 1200°C. Estimates of the standard molar free energy of formation of CupO(S) are also made. Praclicul consideration of this cell as an oxygen sensor for liquid metals is discussed briefly. SOLID mixed-oxide electrolytes which have a defect structure in the anion sublattice have recently become a very popular means by which the chemical potential of oxygen is measured at high temperatures. Since the pioneering work of Kiukkola and Wagner1 such electrolytes have been used in numerous cell studies for determining the thermodynamic properties of metallic oxides and oxy compounds, the partial pressure of oxygen in vacuum systems and other atmospheres, and the properties of oxygen dissolved in metals and alloys. The use of a solid electrolyte in a cell for a fast reliable method of oxygen determination in liquid metals would be a very important tool to the process metallurgist. In copper, for example, the oxygen content of the molten metal in the cathode furnace is a prime factor in determining the "set" or solidification profile of cast wire bars. In this investigation the activity of oxygen in liquid copper was measured by an electrochemical cell employing the electrolyte ZrO2 + 7 1/2 wt pct CaO. The cell used at 1100° and 1200°C was

Jan 1, 1967

By J. Tarwater

The torsional testing of cylindrical medium-carbon steel specimens, heat treated to a high strength level, revealed a stress-strain relationship that was dependent on the direction of torsional plastic pre-strain. This Bauschinger effect was observed in prestrained specimens both with and without subsequent elevated-temperature strain aging. Yield stresses in strain-aged specimens exceeded those of simply prestrained specimens and the difference in stress was greater when the prestrain direction opposed the test direction. This behavior is discussed in terms of the classical dislocation pile-up using Cottrell's equation, A plastically prestrained strain-hardenable member, loaded in a direction opposite to the direction of prestrain, produces a stress-strain relationship differing appreciably from the curve representing reloading in the prestrain direction. This phenomenon, referred to as the Bauschinger effect, will be discussed in terms of the stress differences ob- served at a specified strain. The effect, dating back to the 1880's, was first attributed to grain boundary stresses. When later work revealed that the effect was also present in single crystals, revised theories attributed the diminished applied reverse stress to assistance from internal long-range stresses. These stresses have been associated with dislocation pile-ups or with dislocation arrays having analogous stress patterns. The stress patterns are subject to alteration by interaction with interstitial solute atoms and acceleration of the interaction may be accomplished with elevated-temperature strain aging. As discussed herein, the interaction showed a directional effect with regard to the applied stresses necessary for small plastic strains. Aside from the rigorous Bauschinger stress-strai relationship, which compares prestrained members, it is interesting to compare the stress-strain curve of a member being prestrained with that of a prestrained member being reverse loaded. For small strains which are a fraction of the prestrain deformation, the applied stresses of the reverse reloaded member are smaller. However, as the reverse strain approaches the prestrain value, the stresses approach equivalence. It has been reported1 that the stress required to return a prestrained specimen to its initial "zero" position generally exceeds the prestrain stress because of the work hardening occurring on potential slip systems during prestrain.

Jan 1, 1963

By William D. Manly, John Towers, Paul A. Beck

RECENT work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium' showed that the isothermal increase of the average grain diameter D with time follows the equation [D = K(to + A)-Eq I] Here [to] is that portion of the total annealing time [t], which is available for grain growth, i.e. the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to [D-K-tnEq2] For high purity aluminum the exponent n increases in the ratio of about 1 to 5 in the temperature range of 350° to 600°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isothermal grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker3 Fig I shows a log D vs. log t plot of French's data, together with the 500, 600 and 100°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 700°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French's data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.1 Walker's specimens were 0.125 in., i.e. 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker's data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation [D-D. =K• t,Eq3] Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the

Jan 1, 1948

By Burton Atkinson, David Johnston

Evaluation of Ellenburger reservoirs in West Texas has been an uncertain matker at best because of the lack of cores and suitable core-analysis method. Large amounts of oil arc produced from sections from which sample cuttings are obtained that contain litile porosity and no oil saturation. It has long been realized that the formation in some areas contained numerous fractures and solulion cavities that probably contained the major part of the oil present but the magnitude of the porous system conltaining oil has been unknown. Diamond coring cquipmene, used in the mining industry lor many years, has been developed for oil-field use to obtain high core recovery in fractured dolomite that is not possible with conventional coring equipment. A 36ft section of the core recovered from a fractured Ellenburger reseivoir waS analyzed by a unique but simple method to obtain the first defmite evaluation of one section of the producing formation. The cores and the method of analysis used are described and the results arc discussed in some detail. Discussion The first successful known analyses of cores recovered from the Ellenburger formation in the Permian Basin area were made on cores recovered with the use of diamond core heads. Conventionul coring methods previously used have had lour core recovery and standard methods of analysis have proved to be inadequate for evaluation of those cores that were recovered. Core Descriplion The Ellenburger formation to be dis cussed was cored using diamond core heads and oil-base drilling fluid. Of the total 103 ft cored to a depth of 8893 ft in the Ellenburger, 99 ft or 96 pct was recovered. The dolomite cores were described as gray to white, crystalline to coarscIy crystalline, with chert and calcite inclusions. Occasional shale partings ? to ¼ in. in width were noted. A small amount of green clay was found in some of the coarsely crystalline material. So intergranular porosity was found by inspection in any of the cores. The core urns highly fractured over most of its length with not more than two continuous feet that failed to contain fractures. The fractures Were nearly vertical and varied in width from those harely visible to as much as one millimeter. Scattered solution voids, or vugs, as large as 3 cm in diameter occurred in association with same •a

Jan 1, 1949

By N. W. Ratliff, P. J. Closmann

Production of oil by expansion from a cylindrical reservoir composed of two concentric regions of different properties has been determined as a function of time for a reservoir producing at constant terminal pressure. The parameters involved are permeability, porosity, compressibility and oil viscosity. Results agree with those of a generally accepted method for uniform reservoirs when all parameters are taken as uniform. Cumulative production at any given time is reduced below that of the uniform reservoir when a region of considerably lower permeability adjoins the well; cumulative production increases when a high-permeability region adjoins the well. Curves are presented illustrating quantitative effects of these variations. INTRODUCTION Most petroleum reservoirs can be exploited by release of pressure and consequent expansion of underground fluid. During part of the production history of certain reservoirs by this mechanism, fluid compressibility can be considered small and constant. Cumulative fluid produced by this means as a function of time was calculated for a uniform reservoir by van Everdingen and Hurst.l For certain cases where a production well has been damaged or where an acid treatment has been used, a zone of properties different from those of the reservoir may be created around the production well. In such a case, expansion of the reservoir fluid takes place in a system composed of two concentric cylindrica1 regions of different reservoir properties. Such composite systems were studied in connection with heat flow by Jaeger2 who presented a solution for temperature distribution in a radial system with an infinitely large outer radius. Similar heat flow problems have been studied by other authors Oil production from composite reservoirs was studied for constant production rate by Hurst,4 Loucks and Guerrero,5 and Carter.6 THEORY This work considers constant terminal pressure. Cumulative flow is calculated for a composite bounded system in which no flow takes place across the outer boundary (Fig. 1). Since the flow is considered to be purely radial, the problem involves only one space dimension and time. It is convenient to define the following dimen-sionless pressure drops (Fig. 1).

By D. U. Deere, F. D. Patton

Introduction A close relationship exists between the geologic investigation and the stability analysis of the slopes of an open pit mine. One significant result of this relationship is that the stability analysis is no better than the assessment of pertinent geologic factors that enter into the analysis. In some slope stability problems the engineering solution becomes obvious once the geologic framework is established. In other cases, establishing the geologic framework is only the first stage in the process of analysis. However, even in these cases the geology should not be neglected once the analysis is made. The geology should be periodically reviewed when new slopes are excavated. This will help ensure that the basic assumptions for the analysis have not changed and will permit changes when new conditions are encountered. In recent years improved methods of stability analysis have been accompanied by advances in laboratory testing techniques and new knowledge of the shear strength of rock discontinuities. At the same time there have been improvements in field geological descriptions. As more experience is gained in analyzing and predicting the stability of rock slopes, the importance of certain geologic factors has become more apparent. Some of these factors were described in a paper given at the Open Pit Mining Symposium in Johannesburg, South Africa in September 1970 (I). This paper includes many of the points covered at that meeting but with additional emphasis on the significance of the major geologic structures. Other papers given at the South African symposium also considered geological and hydrogeological factors in slope stability analysis (2) (3) (4) (5) (6). This paper first describes the approach to a slope stability problem including assessment of the relative roles of field geology studies, laboratory testing, stability analyses, and continued slope monitoring studies. Next, is described a framework which has been found useful for classifying or separating the several types of slope stability problems encountered in open pit mines. The principal geologic factors in slope stability problems in rock are discussed and brief comments are made on how these factors distinguish stability problems in rock slopes from those normally encountered in soil slopes. The over-riding control of major geologic structures, especially faults, in most slope stability problems is emphasized. In this regard the relative importance of statistical studies is contrasted with knowledge of the positions of key structural

Jan 1, 1971

By Karl Fetters

IN the process of making steel in the open-hearth furnace the refining of the metal during the working period of the heat is largely accomplished through the agency of the slag. From the birth of the process until the present day steelmakers have recognized the importance of the slag in determining the composition of the metal and the quality of the product. The general relationships between slag composition and metal analysis have long been known, at least in a qualitative or approximate fashion. For examples, the iron oxide content of the slag is higher on lower carbon heats; the more basic slags are higher in iron oxide for a given carbon content; certain amounts of iron oxide and lime are required for phos-phorus removal and a high lime-silica ratio is needed if the sulphur content of the metal is to be diminished. In recent years a number of quantita-tive relationships involving these and other variables have been developed through plant and laboratory studies by numerous investigators in this country and abroad. The direct comparison of laboratory and open-hearth data involves the question of the degree to which each approaches the conditions of chemical equilibrium, a question which, from the open-hearth standpoint, we are scarcely yet in position to answer. And, although a considerable body of dependable equilibrium data has been obtained in the laboratory, this work has not yet been extended to cover the ranges of slag composi-tion encountered in basic open-hearth practice. In the present study we shall not attempt to draw comparisons between data from the two sources; nor do we attempt to draw conclusions as to the approach to chemical equilibrium in the open-hearth furnace. Many of the operating variables that are likely to be erratic or unrecorded during the earlier stages of the heat become more consistent and are more readily subject to observation and control during later stages. For example, undigested lime or ore gradually goes into solution, the rate of carbon drop levels off, and the temperature of the metal is brought under control. For these and other reasons a greater degree of self-consistency is likely to be found among data obtained during the

Jan 1, 1940

By R. I. Jaffee, R. W. Wood, H. R. Ogden, D. N. Williams

D. W. Morgan, D. H. Polonis,and R Taggart (Uuivevsity of Washington)—Dispersion hardening in titanium-copper alloys is of particular interest to us in view of our current research activities in phase transformations in this system. We should like to raise questions concerning several points in the paper. The flow sheet for fabrication and heat treatment (Authors' Fig. 2) indicates that 0.045 in sheet is treated in air for a period of 30 min at 1625' F. Were any surface coatings used to reduce oxygen contamination at this stage? One might ask the same question about the 8-hr annealing at 1400F. Contamination during fabrication and heat treatment of such thin sections could be considerable without some protection. Although the authors state that no analyses were made, they note that contamination masks the distinction between base strengths of the different alloys. In this connection, what fabrication and heat-treatment procedures were used in obtaining the comparison specimens of unalloyed titanium? It would seem that oxygen contamination must cast doubt on the reliability of the proposed strength-mean free path relationship deduced from the data (Authors' Fig. 5). It is usual to evaluate dispersion hardening on the basis of yield strength rather than ultimate tensile strength, and accordingly we have replotted the authors' Fig. 1 to include yield strength. The yield strength data do not justify a discontinuity of 3 p at either 70" or 1000 OF. Can the authors substantiate their conclusion 1) with additional evidence? Otherwise it seems that they have succeeded only in pointing out the possibility of a linear relationship between yield strength (or Uts) and the logarithm of the nleall free path, comparable with that demonstrated for iron-carbon alloys (Authors' Ref. 2). Work in our own laboratories has shown that the hardness of the phase Ti,Cu is 235 Vpn, and that of a 1.5 pct (at.) (2 pct wt) supersaturated solid solution of copper in titanium is 190 Vpn. This small difference in hardness would suggest that Ti2Cu should not be a very effective dispersion-hardening phase. D. N. Williams, R. W. Wood, H. R Ogden, RI. L Jaffee (authors' reply)— This discussion brings out some interesting points with respect to the interpretation of our results, and also raises some questions regarding the experimental technique. We shall consider the latter questions first. Contamination during heat treatment was prevented by performing all heat treatments in argon-filled Vycor capsules. Fabrication was done in air, with the usually observed scaling. Scale was removed

Jan 1, 1962

By L. S. Darken, H. A. Wriedt

THE constitution diagram of the iron-copper system derived by Daniloff' exhibits, at the iron-rich end, phase fields similar to those of the iron-carbon diagram. At 1484° 1094°, and 850°C there are, respectively, a 6-y-L peritectic, a y-E-Lperitectic, and a a-y-E eutectoid. The phase designated E is copper-rich, containing 4 pct Fe or less according to the temperature. The composition of copper-saturated ferrite (a-solid solution) has been determined previously only twice as a function of temperature. By electrical conductivity measurements, Buchholtz and Köster2 found 3.4 pct Cu in ferrite at a eutectoid temperature of 810°C. They represented the composition of saturated ferrite by the equation, log (%Cu) = 4.32-4125 (1/T) Gregg and Daniloff3 reported that Köster later modified his opinion, raising the indicated eutectoid temperature to 833 °C and the copper content of eutectoid ferrite to 3.7 pct. The literature contains several indications4-7 that the work of Köster and his co-workers is not reliable. Norton,8 using an X-ray method, found that 1.4 pct Cu dissolved in ferrite at the approximate eutectoid temperature of 850°C and that the solubility decreased to about 0.3 pct at 700°C. Below 700°C his experimental data show almost no change in solubility. These findings, although inconsistent with the work of Ruer and Goerens4 and of Smith and Palmer,7 have been used generally since their publication. In investigations involving the observation of arrests in temperature during continuous heating or cooling the precise location of the eutectoid temperature has been obscured by a large hysteresis. The more reliable work 579 where the results are not effected by this hysteresis indicates a eutectoid temperature between 840° and 850°C. The foregoing discrepancies, along with a few observations in this Laboratory relating to the precipitation of copper from ferrite, prompted us to rein-vestigate the lower temperature portion of the Fe-Cu system. In this investigation the solubility of copper in ferrite was obtained by the chemical analysis of high-purity iron equilibrated with copper-silver alloys. This method eliminated the necessity for retaining by a quench the physical state of the specimen existing at the equilibration temperature. EXPERIMENTAL The reaction of the iron with the copper alloy was

Jan 1, 1961

By Waldemar Lindgren

The following pages present data accepted by many geochemists and geologists regarding the succession of minerals and the temperatures of formation in ore deposits affiliated with igneous rocks. They also present the individual views of the author on the composition of the solutions that were active and on the mode of deposition. He does not regard these views as speculations or hypotheses but as forming a well motivated and consistent theory. It is not certain, however, that all investigators will subscribe to them. Introduction The mining engineer may not always be interested in the field of stability and temperature of origin in the mineralogy of ore deposits, but he certainly is interested in the succession of minerals because this has a definite bearing on the understanding of the ores and on the best processes of extraction. It is proposed, therefore, to summarize in plain language the principal features of succession as shown in metallic ores. Chemical analyses of ores are always important, but the real knowledge of succession—sometimes called paragenesis-—of ores has been gained only in the last 20 years, by the study of polished sections. The study of hand specimens threw much light on the subject—as shown, for instance, by Breithaupt, whose "Paragenesis," written a hundred years ago, is still useful—but the results have been modified by our slowly gained understanding of the processes of replacement. Indications of Temperature Melting Points.—In the first place, a distinction must be made as to whether the ore is a product of magmatic consolidation, of pegmatitiza-tion or of hydrothermal activity. Most of the ores fall in the latter class. In any case, the melting points, although of importance, are not definite indications. In a magma the oxides and sulfides are likely to be among the earliest crystalline products (magnetite, ilmenite, zircon, corundum,

Jan 1, 1937

By William Fink

ZINC is one of the effective elements introduced to enhance the strength of aluminum. This strengthening is principally attributable to the high solid solubility of zinc in aluminum and the pronounced variation of solubility with temperature. Consequently an accurate determination of the solid solubility curve is desirable. The solid solubility relations have been studied by numerous investigators. Shepherd' first established the existence of a solid solution region at the aluminum end of the diagram (y phase) by specific volume and microscopic determinations. Bauer and Vogel2 published a constitutional diagram which showed the limits of solid solubility as determined by thermal and microscopic methods. Hanson and Gayler3 presented the aluminum-zinc diagram which is now most generally accepted (Fig. 1). Chill-cast samples were given thermal treatments designed to obtain equilibrium conditions, quenched, and microscopically examined.. The solubility was placed between 15 to 20 per cent at 600 C., 20 to 22 per cent at 140° C. and 36 to 38 per cent at 270° C. Sander and Meissner4 decidedly modified the limits of they phase field of Hanson and Gayler's diagram by using similar methods on chill-cast specimens annealed for a shorter period of time. Tanabe,5 utilizing dynamic hardness, electrical conductivity and dilatometric measurements of specimens at temperature, obtained values comparable to Hanson and Gayler's at room temperature, but appreciably lower at higher temperatures. Nishimura6 concluded from age-hardening results of aluminum-zinc alloy chill castings, which had been quenched from 400° to 500° C., that the solubility of zinc in aluminum at room temperature is less than 5

Jan 1, 1932

By H. B. Bell, P. C. Lidster

A study has been made of the use of ThO2-Y2O3 solid electrolytes to determine activity of chromium in Fe-Cr and Ni-Cr alloys in the temperature range 1300° to 1700°K. This method has been shown to give results which agree with the best vapor pressure measurements. SEVERAL investigations1"5 have been made of chromium activities in Fe-Cr alloys. Most of these have been made by vapor pressure measurements using knudsen cell techniques while one has been made using gas equilibration with H2/H2O gas mixtures. In the present investigation electromotive force measurements have been made on this system using a thoria yttria solid electrolyte. This system was -chosen to establish the technique of measurement at low oxygen potentials, before extending it to Fe-Ni-Cr alloys. The cell used was Pt Cr • Cr2O3 ilThO2 • Y2O3 llalloy • Cr2O3 IPt Since the oxygen pressure of the chromium-chromic oxide mixture lay in the range 10"19 to 1027 atm in the temperature range investigated, thoria yttria electrolytes were used. It was soon found during the investigation that considerable care was required to prepare satisfactory electrolytes and a study was made to find the best method of preparing pellets of TI1O2-Y2O3 solid solution of as near theoretical density as possible. Various compositions in the range 2 to 15 mole pct Y2O3 were studied but the experimental measurements were made with electrolytes containing 4 to 5 pct Y2O3. The method of preparation finally adopted was to use thorium oxalate and yttria as raw materials. The thorium oxalate was decomposed at 900°C for 6 hr to give a reactive powder. This powder was then mixed with the appropriate amount of yttria and ground in an agate mortar for about 4 hr. The powder was moistened with absolute alcohol as a lubricant and pressed in a metal die at a pressure of 7 tons per sq in. The pellets were then heated at 1100°C for 24 hr followed by 24 hr at 1250°C. After this firing cycle the material was reground and repelleted and again fired at 1100° and 1250°C followed by heating for 7 days at 1600°C. It was found in later experiments that a further firing of 4 hr at 2000°C improved the density further and gave pellets of only 2 pct porosity. After firing, the pellets were polished on emery paper and finally with the 2 µ diamond paste. The polishing was followed by a final firing of 24 hr at 1500°C. Investigation showed that this final treatment minimized reaction between the electrolytes and chromium oxide. It was believed that this was because of a lowering of the surface energy of the electrolyte surface. Two types of investigation were carried out to check that the pellets were satisfactory oxygen ion elec-

Jan 1, 1970

By J. Chipman, T. P. Floridis

The equilibrium of gaseous H2O-H2, mixtures with liquid iron is used to establish the activity coefficient of dissolved oxygen as log f o = — 0.20 [%O]. Discrepancies in earlier work are explained or eliminated. Additions of cobalt, molybdenum, tungsten, and platinum increase the activity coefficient of oxygen whereas copper and gold decrease it. THE importance of dissolved oxygen as a refining agent in liquid steel has led to a number of studies of its thermodynamic properties. It is the purpose of this paper to examine the effects of a number of alloying elements on the activity of oxygen in the steel bath. As a preliminary to the study of the effects of alloying elements, it seemed desirable to examine certain minor discrepancies in the published data on the properties of oxygen in simple iron-oxygen solutions. The activity and free energy of oxygen in liquid iron were studied by chipman1 in 1933 by means of the reaction h2(g)+-o = H2O (g);K; = PH2O/PH2[% O] [1] The data were in fairly good agreement with calculations from results on the similar reaction CO (g) + O- = CO2 (g); K2 =P CO2/P CO [% O] [2] which had been obtained by Vacher and Hamilton2 as an incidental part of their study of the reaction of carbon with oxygen dissolved in the melt. It was found that the equilibrium ratio k1 was not a true constant but varied with the oxygen concentration in the manner shown in Fig. 1, which is copied from the original paper. This early observation has been refuted in subsequent work but is confirmed in the present paper, and an explanation of the discrepancy can now be presented. In Fig. 1, the two points on the extreme right were disregarded in drawing the

Jan 1, 1959

By C. E. Reinhard

A useful accelerated weathering test should be capable of placing any series of metals quantitatively in the same order of endurance as that noted under a particular set of actual exposure conditions. The development of such a test must necessarily depend to a considerable extent upon data obtained from a wide variety of exposures. This paper offers preliminary data from exposure tests on nine metals placed in 11 locations in the Lehigh Valley, within a radius of 20 miles from Palmerton. The exposure conditions vary from a severe industrial atmosphere to a pure rural atmosphere. The data are offered as evidence of the necessity for the identification and evaluation of the variables of corrosion and as illustration of some of the variations to be considered in the development of a useful accelerated test. It is quite clear, from this evidence, that a useful accelerated test must be versatile to the extent of showing the probable variations of corrosion resulting from differences in atmosphere as well as from differences in the metals. The paper is presented solely with the object of pointing out the wide variations in relative merits of several common metals in resisting corrosion and without any thought of initiating controversy regarding the merits of particular metals. For this reason the metals are designated only by symbols in the tables and no key is given to these symbols. Test Procedure Specimens, 4 by 6 in., were cut to accurate dimensions from each of the following metals or alloys: aluminum, ascoloy, copper, copper steel, galvanized iron, and zinc. Additional grades of these metals bring the total to nine types. Since it was impossible to obtain the required number of copper-steel specimens having equal surface conditions of rust and scale, it was thought advisable to pickle these specimens in a hot solution of 10 per cent. sulfuric acid. All other specimens were carefully cleaned in ether and alcohol and weighed just prior to exposure. Four specimens of each type of metal were mounted on a test rack by means of porcelain insulators. The racks were so constructed that

Jan 1, 1929

By C. E. Reinhard

A useful accelerated weathering test should be capable of placing any series of metals quantitatively in the same order of endurance as that noted under a particular set of actual exposure conditions. The development of such a test must necessarily depend to a considerable extent upon data obtained from a wide variety of exposures. This paper offers preliminary data from exposure tests on nine metals placed in 11 locations in the Lehigh Valley, within a radius of 20 miles from Palmerton. The exposure conditions vary from a severe industrial atmosphere to a pure rural atmosphere. The data are offered as evidence of the necessity for the identification and evaluation of the variables of corrosion and as illustration of some of the variations to be considered in the development of a useful accelerated test. It is quite clear, from this evidence, that a useful accelerated test must be versatile to the extent of showing the probable variations of corrosion resulting from differences in atmosphere as well as from differences in the metals. The paper is presented solely with the object of pointing out the wide variations in relative merits of several common metals in resisting corrosion and without any thought of initiating controversy regarding the merits of particular metals. For this reason the metals are designated only by symbols in the tables and no key is given to these symbols. Test Procedure Specimens, 4 by 6 in., were cut to accurate dimensions from each of the following metals or alloys: aluminum, ascoloy, copper, copper steel, galvanized iron, and zinc. Additional grades of these metals bring the total to nine types. Since it was impossible to obtain the required number of copper-steel specimens having equal surface conditions of rust and scale, it was thought advisable to pickle these specimens in a hot solution of 10 per cent. sulfuric acid. All other specimens were carefully cleaned in ether and alcohol and weighed just prior to exposure. Four specimens of each type of metal were mounted on a test rack by means of porcelain insulators. The racks were so constructed that

Jan 1, 1929

By R. M. Brick

AN increased demand for information in regard to the effect of gaseous elements in steel has accompanied the recognition of the importance of grain size. Attempts to correlate grain-size characteristics with gas con-tent, particularly oxygen in solution or in the form of included metallic oxides, have not been universally successful. Certain definite effects of dissolved gases are recognized; specifically, the role of hydrogen in causing internal cracks or "flakes" and that of nitrogen in preventing excessive grain growth of ferritic chromium steels. When irregular behavior or properties are found in a well-known steel and no definite cause for the abnormality may be assigned on the basis of chemical and metallographic tests, dissolved gases are frequently blamed as the culprits. The solubilities of hydrogen1 and nitrogen2 in pure liquid iron are known but of the ternary systems, iron-alloying element-gas, only the Fe-Si-N3 and Fe-Cr-N systems have received attention and here the study was confined to liquid alloys. Krivobok4 published a curve show-ing the solubility of nitrogen in liquid Fe-Cr alloys but gave no informa-tion on the experimental procedure employed. The considerable experimental work reported on the Cr-N binary alloys has been reviewed by Hansen.5 It is generally agreed that the nitride CrN is a stable phase although the existence of nitrides within limited temperature ranges of stability, viz., Cr3N2 and Cr2N, has been disputed, Adcock6 and others7 have reported a eutectic between Cr and CrN at 1580°C., although the supporting evidence is not complete.

Jan 1, 1940

By Walter Showak

The published phase diagrams for the copper-zirconium system1,2 indicate that the solid solubility of zirconium in copper is not accurately known. Studies made on relatively impure alloys by Pogodin, Shumova, and Kugucheva3 yielded a maximum solubility value of 1 wt pct Zr at the eutectic temperature. Allibone and sykes5 reported that an as-cast 0.2 wt pct Zr alloy is single phase at room temperature. Limited results obtained by Raub and Enge14 indicated that zirconium solubility in copper is less than 0.13 wt pct Zr at 940°C. Tn 1960, on the basis of a microstructural examination of several copper-rich Cu-Zr alloys, saarivirta6 placed the maximum solubility of zirconium in copper at 0.15 wt pct at the eutectic temperature, 980°C. The present note describes results obtained during a re-investigation of the Cu-Zr system for the purpose of accurately establishing the solidus and solvus curves and the eutectic temperature in copper-rich alloys. High-purity copper (99.99 pet) and zirconium (99.64 pet) consolidated reactor grade sponge were used to prepare several alloys, containing up to 2 wt pct Zr, by induction melting in graphite crucibles in vacuum and chill casting into a split steel mold. The melting procedure consisted of first melting the copper charge and then adding the bulk zirconium wrapped in pure copper foil. Chemical analyses were made of both the cold-rolled alloy ingots after homogenization at 925°C for 450 hr in evacuated quartz capsules and of small specimens which had been used in the phase diagram studies. 'The carbon content of each alloy was also determined and was found to be less than 0.001 wt pct in every case. Metallographic and electrical resistivity measurements were used as the primary methods for this investigation, although some thermal analysis studies were also performed. Heat treatments of all the alloys were carried out with the specimens wrapped in molybdenum or alloy foil (of the same composition as the specimen) and sealed in quartz tubes either in vacuum or under a purified helium atmosphere. Following high-temperature anneals for long periods of time, slight depletion of zirconium from the specimen surface was observed. Therefore, careful preparation of samples for microscopic examination and chemical analysis of the samples themselves was necessary to check the composition of samples used in determining phase boundaries. Points on the solvus curve were determined on quenched specimens by both isothermal reaction after solution heat treatment at 950°C for 8 hr and by isothermal annealing of alloy specimens at successively higher temperatures for times ranging from 24 to 500 hr. Liquation studies for positioning of the solidus and eutectic temperatures were performed by holding a pre-

Jan 1, 1962

By M. G. Corson

Information regarding the use of ixanganese alloys has hitherto been incomplete and available only from widely scattered sources. This paper attempts a systematic description of properties and uses of alloys other than manganese bronze, manganin and duralumin, which are probably the only non-ferrous alloys associated with manganese in the minds of most metallurgists. Properties of Manganese Manganese can react either acid or basic; it is hard to obtain in the pure state; it has two different crystalline lattice structures, both of the cubic system, one stable above 850" C. and the other below 650" C., both coexisting in the intermediate range. Although the commercial product is hard and brittle, the pure metal seems to be ductile. In fact Zhemchuzhny, in Russia, was able to obtain ductile manganese and draw it to fine wires by the simple expedient of adding about 3 per cent. copper to the alumino-thermic product. Copper most probably brings the sili-cides, aluminides, nitrides and carbides present in the commercial product into a much less harmful form of distribution. One industrial use that can be foreseen for wrought manganese articles is as anodes for electrolytic processes in sulfate and nitrate solutions, particularly with high voltages. A practically insoluble skin of manganese peroxide is likely to form in such cases and an insoluble and strong anode material will be available. Manganese as a Scavengek Because of its activity manganese might become the most efficient scavenger and refiner of copper, were it not for the fact that 0.01 per cent.

By Lawrence Wright

THE occurrence of gold, gold-silver, silver-lead-zinc ores in the post-Cambrian sediments in the Black Hills of South Dakota, and their genetic relationship to the Tertiary intrusives, is well known and accepted, but the occurrence of gold in the pre-Cambrian rocks at the Homestake mine, which underlie this Tertiary gold mineralization, has given rise to differ-ences of opinion as to the period of major gold introduction into the older rocks. Fig. 1 illustrates. the distribution of mineralization along the axis of the Tertiary uplift in both pre-Cambrian and post-Cambrian rocks. The following possibilities have been presented: 1. The Homestake gold deposit was formed in pre-Cambrian time and the deposits in the overlying Cambrian sediments formed during Ter-tiary time. 2. The Homestake lode existed at the beginning of Cambrian time, but was enriched by the passage of Tertiary auriferous solutions. 3. The Homestake lode was represented by pre-Cambrian quartz-chlorite sulfide mineralization, very low in gold content and the gold superimposed on the older nearly barren mineralization during the Ter-tiary metallogenic epoch. 4. The sulfides and sulfarsenides as well as gold were deposited in both pre-Cambrian and post-Cambrian rocks during the Tertiary period. Those favoring the first proposition feel that the question is pretty well settled, while the proponents of the second theory are more flexible in their view, feeling that the amount of gold introduced in either period is still an open question. The third and fourth theories, with some modifi-cations, are supported by the proponents of the Tertiary theory, who feel that the evidence strongly favors that period. The following pages are intended to present the evidence and to give the reaction of various observers with my own comments and conclu-sions; also, the accumulated facts of observation gathered over a period of close association with the area under discussion, beginning in 1919.

Jan 1, 1936

By A. G. Taylor, H. P. Ehrlinger, U. C. Tainton

FOR the last 15 years lead has been the standard material for anodes in electrolytic zinc production and it has been generally accepted that this lead should be as free as possible from impurities. Laistl says, "Next in importance to the purity of solution is the purity of the electrodes and tank lining material. The purest lead obtainable should be used for anodes." The same conclusion is expressed by Ingalls2 and by two German investigators who say that experiments have demonstrated that the purer the lead, the greater is its resistance to corrosion during electrolysis.3 Pure lead, however, while the best material hitherto available for anodes, is not entirely free from objection. The plain lead anode gradually disintegrates under electrolysis, so that the life of an anode, say 1/4 in. thick, is frequently not more than two years. Part of the lead from the anode finds its way to the cathode, lowering the purity of the deposited zinc and decreasing the hydrogen overvoltage. The rest of the lead that comes from the disintegration of the anode goes into the manganese dioxide which is precipitated in the cells, rendering unsaleable what might otherwise be a valuable by-product. Yet a further disadvantage of plain lead anodes comes from their tendency to bend or buckle during electrolysis, as a result of intercrystalline oxidation. This makes it necessary to use a fairly aide spacing between anode and cathode to avoid short circuits, and thus leads to a higher power consurnption than would otherwise be necessary. The power consumption is also affected by the high decomposition voltage at a lead peroxide surface.

Jan 1, 1929