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By H. H. Podgurski, F. N. Davis

In silver alloys containing less than 0.2 wt pet Cu. the reaction 9 + 1/2 0, = CuO(s) was found to proceed to equilibrium between 700o and 808oC. From measurements of the equilibrium dissociation pressures of the CuO at several temperatures, the differential heat of solution and the activity coeflicients for copper in silver were calculated. These values were found to be in reasonable agreement with those calculated from data appearing in the literature. A metastable "copper oxide" with an atom ratio of oxygen to copper as high as 1.7 was formed by internal oxidation at 300°C of these same dilute Ag-Cu alloys. No anomalous behavior was noted in the temperature dependence of oxygen solubility in silver. The solubility minima between 300" and 800°C reported several years ago can be accounted for, at least in part, by reactions with trace impurities, such as copper. Cold-worked siloer exhibits an enhanced permeability to oxygen. THIS investigation was undertaken because of our interest in interactions between solute and lattice defects in metals. The reason for the choice of the O-Ag system for study is the anomaly in the solubility of oxygen in silver reported by Steacie and Johnson1 in 1926, specifically that isobars between 100 and 800 Torr show solubility minima at 400°C. It was also claimed that the copper impurity in the silver was not responsible for the minima. Recently, Eichenauer and Müller2 proposed that surface adsorption might have been responsible for this solubility anomaly, but no adsorption isotherms are available to check the pressure and temperature dependence observed at the low temperatures. Surface-tension measurements on silver made by Buttner, Funk, and udin3 suggest that a considerable fraction of a monolayer of oxygen exists on silver at 922°C and at an oxygen pressure of 150 Torr. To account for the pressure sensitivity reported by Steacie and Johnson1 at 300°C, the oxygen bound to the surface at 922°C cannot be considered relevant; the existence of a surface layer at 300°C characterized by a lower energy of binding would be required to explain the effect. All of our attempts to detect an interaction of this type with surface sites have failed. In this investigation we have not been able to associate the dissolution of oxygen in silver with a dislocation interaction. Evidently, severely cold-worked silver does not contain a sufficient number of trapping -sites for oxygen. Indeed, our work shows that oxidation of trace impurities in the silver was probably responsible for Steacie and Johnson's results. In addition, we have been able to establish the nature of the reaction with copper impurity in silver by thermodynamic considerations. EXPERIMENTAL PROCEDURE Measurements of both the internal oxidation rates and the solubility were made volumetric ally in a system equipped with a gas burette, a mercury manometer, a McLeod Gage, and a mass spectrometer. The silver and the silver-alloy samples were protected from contamination by mercury vapor from our pressure gages by suitably placed refrigerated (-78°C) traps. Silica reaction vessels were employed for experiments performed above 500°C. Spectroscopically pure gases were used in this investigation. The highest-purity silver used in the solubility measurements was 99.999 pet. By chemical analysis 2 ppm of Cu were found in this silver. The two Ag-Cu alloys used in this research were made up to 0.14 and 0.15 wt pet Cu starting with 99.999 pet Ag. An unexpected source of error was discovered in the course of the work. At temperatures near 800°C silver distilled from the hot silica reaction tubes into cooler regions of our system. Although the weight loss of silver from the sample was not important in itself, oxygen was being consumed by the silver distilled into the cooler part of the system to form a stable oxide phase from which the oxygen was not recovered. In a separate experiment conducted to determine the necessary correction, losses between 0.2 and 0.3 cu cm (stp) of 0, in 24 hr were measured at 810°C. On the assumption that the flux of silver from the vessel to form Ag2O de-

Jan 1, 1964

By S. Shapiro, G. Krauss

RECENT investigations1 3 of the products of marten-sitic transformation in Fe-Ni and Fe-Ni-C alloys have made use of light microscopy to describe mar-tensitic fine structure. The application of conventional metallographic techniques to this problem was possible because of the similarity of distributions of parallel striations developed by etching polished surfaces to distributions of transformation twins which are positively identified in thin films by transmission electron microscopy. The surface striations frequently are not well-defined, and could also be due to, for example, rows of etch pits which are not resolved by the light microscope. This note describes the etching effects revealed by examination of surface replicas of mar-tensite in the electron microscope. The application of a replica technique both extends the observations of fine structure made with the light microscope and allows the results of conventional metallography to be used with more confidence. Samples of an Fe-33 wt pct Ni alloy were used for this study because of the detailed knowledge of the fine structure of martensite which has been developed'-4 for alloys of about this composition. Samples transformed to martensite at -120°C, and transformed samples heated to 340°C to effect a small amount of reversal of martensite to austenite, were examined. Surfaces were first prepared for replication by elec-tropolishing in a chromium oxide-acetic acid electrolyte at a current density of 0.1 amp per sq cm and a temperature of 15°C or a perchloric acid-acetic acid electrolyte at a current density of approximately 2 amps per sq cm and a temperature of 15°C. The polished surfaces were then etched for 4 to 7 sec by immersion in a solution of equal parts HC1, HNO,, and H20. Application of the etchant for this period of time produced discrete attack of certain features without loss of resolution due to overlapping of areas most susceptible to etching. The etched surfaces were replicated by 1) preshadowing with Pt-Pd alloy at an angle of 20 to 30 deg, 2) depositing a thin carbon film, and 3) stripping the film and shadowing material by immersion in a 5 pct nital solution. Two types of etching effects were observed by examination of the surface replicas in the electron microscope: l) continuous striations centered at the bottom of long grooves or the tops of pyramidal elevations on the sample surface, and 2) high densities of fine etch pits. Examples of both types of features are shown in Figs. 1 to 4. The striations are in each case continuous and have the same characteristic configurations as do transformation twins in martensite. Fig. 1 shows that the density of grooves decreases toward the edge of a martensite plate and Fig. 2 shows a region where the striations are of varying length. Similar examples of transformation twin arrangements determined by transmission electron microscopy of thinned foils of martensite have been shown in the literature,'~ and, based on these similarities, the striations and their associated grooves or mounds are considered to be evidence for the presence of transformation twins. The transf~rmation twins in martensite are on the order of l00 A thick, much too fine for resolution by the light microscope. It appears that orientation-dependent etching of the matrix martensite about the twins results in grooves or surface elevations which

Jan 1, 1967

By J. D. Rice, P. L. Wearden, W. L. Hensou

Solutions to the unsteady-state partial water-drive reservoir performance problem can be obtained through the use of analogue computers or high-speed electronic digital computers. The solutions that have previously been resolved for use on digital computers, however, demand a knowledge of the aquifer parameters. Generally, the analogue computers now in use do not require this knowledge. A solution is presented herein where the aquifer performance, expressed in terms of difference equations, is related to the reservoir performance as expressed by the modified Scbiltbuis material-balance equation. A numerical procedure for a medium-sized digital computer also is presented in which a solution to the set of equations defining the aquifer and reservoir performance is obtained and the aquifer parameters (permeability and sand thickness) are automatically optimized while simultaneously matching the known pressure behavior. Predicted pressure behavior can be calculated using rates from any assumed future production practice. The procedure provides an output format which presents the cumulative, incremental and average rate of natural water influx, the per cent gas-cap expansion, the calculated reservoir pressure, the measured reservoir pressure, and the difference between the measured and calculated pressures. Results of a test problem are presented in comparison with results obtained by the Bruce Analyzer, Ohio Oil Co. 's Pace General Purpose Analogue Computer, and Sun Oil Co.'s Single-Pool Electronic Reservoir Analyzer. These results indicate that unsteady-state reservoir perlormance for a single-pool system can be adequately simulated by a numerical method employing a digital computer and that the special-purpose analogue computer can be supplanted by this method. INTRODUCTION The numerical approach to the unsteady-state partial water-drive reservoir performance problem heretofore has been limited in that solutions have been resolved only for certain fixed parameters. Also, prior to the advent of high-speed electronic digital computers in the last few years, calculations were so tedious and time-consuming that they ordinarily were neglected, or some other means of obtaining the solutions were used. The analogue approach had been used for obtaining solutions to the transmission-of-heat problem and, consequently, means were developed for applying the electrical analogue to the unsteady-state reservoir performance problem. Bruce submitted a paper for AIME publication in Sept. 1942, in which he described an electronic device (now called the Bruce Analyzer) for analyzing the water-drive performance of any reservoir, based on either steady or unsteady-state flow characteristics. 1 Sun Oil Co. adopted the analogue approach in 1949 and now has two special-purpose high-speed electronic reservoir analyzers in use.2,3 Two main features of Sun's analyzers are (1) the high repetitive rate of reproducing the entire history of reservoir performance cyclically a number of times per second, and (2) the elimination of the necessity of knowing the properties of the associated aquifer. Since the advent of larger and faster digital computers, the possibility of incorporating this second feature into a numerical approach appeared feasible. Previous work has been done and material published covering the application of numerical methods to the behavior of the pressure with respect to time at any point in an associated aquifer? However, the aquifer parameters must be known from some source. The material presented in Ref. 4 has been used to a great degree in developing the numerical method described herein. DIFFERENTIAL EQUATION AND BOUNDARY CONDITIONS The problem of simulating the performance of a reservoir and the associated aquifer is to determine the characteristics of the aquifer such that the

By Samuel L. Hoyt

This paper gives a brief description of an investigation made several years ago on the diffusion of zinc into copper. The material for that study was furnished in the form of thin copper strips coated with zinc. The result was required rather quickly and at not too great an expense, and especially information was desired as to the rate at which zinc would diffuse from the zinc coating into the copper and the temperature at which the operation should be carried out. A study of the requirements of this problem indicated that the solution might be secured by means of six determinations. This is the smallest number that will give the information desired and, at the same time, furnish checks on the accuracy of the determinations which justify an abbreviated experimental program. This does not count a preliminary test which was designed to give some idea of the correct temperature to use. The minimum number of temperatures that can be used is two. Knowing the rates of diffusion of zinc into copper at two properly chosen temperatures, it is possible to calculate the rate for any other temperature, and also to check the accuracy of the determination by means of the heat of diffusion, which is calculated from the effect of temperature on the rate of diffusion. The minimum number of determinations at any one temperature is three. The amount of diffusion which occurs at a fixed temperature is definitely related to the time of diffusion, so that by determining the amount of diffusion for three different time intervals, this relationship may be established and possibly a check on the accuracy may be secured. This accounts for the six determinations or experiments, and suggests the logical plan of the work. The check used here is not generally applicable to diffusion phenomena, but it seems to hold closely enough for the limited amount of diffusion in this investigation to justify its use. The samples used were 5 to 6 mils thick and about 1 in. square. They were placed between iron blocks and set in the hot zone of a nichrome furnace which had been brought to the desired temperature Time was taken from the moment the samples reached the furnace

Jan 1, 1929

By Samuel L. Hoyt

This paper gives a brief description of an investigation made several years ago on the diffusion of zinc into copper. The material for that study was furnished in the form of thin copper strips coated with zinc. The result was required rather quickly and at not too great an expense, and especially information was desired as to the rate at which zinc would diffuse from the zinc coating into the copper and the temperature at which the operation should be carried out. A study of the requirements of this problem indicated that the solution might be secured by means of six determinations. This is the smallest number that will give the information desired and, at the same time, furnish checks on the accuracy of the determinations which justify an abbreviated experimental program. This does not count a preliminary test which was designed to give some idea of the correct temperature to use. The minimum number of temperatures that can be used is two. Knowing the rates of diffusion of zinc into copper at two properly chosen temperatures, it is possible to calculate the rate for any other temperature, and also to check the accuracy of the determination by means of the heat of diffusion, which is calculated from the effect of temperature on the rate of diffusion. The minimum number of determinations at any one temperature is three. The amount of diffusion which occurs at a fixed temperature is definitely related to the time of diffusion, so that by determining the amount of diffusion for three different time intervals, this relationship may be established and possibly a check on the accuracy may be secured. This accounts for the six determinations or experiments, and suggests the logical plan of the work. The check used here is not generally applicable to diffusion phenomena, but it seems to hold closely enough for the limited amount of diffusion in this investigation to justify its use. The samples used were 5 to 6 mils thick and about 1 in. square. They were placed between iron blocks and set in the hot zone of a nichrome furnace which had been brought to the desired temperature Time was taken from the moment the samples reached the furnace

Jan 1, 1929

By W. A. Backofen, B. C. Wonsiewicz

The Plasticity transition in magnesium was studied by plane-strain compression of single crystals and polycrystalline material at temperatures from about 20" to 307°C. Reduction of single crystals along the c axis was accommodated by twinning on {1011) and retwinning on (10 12}, followed by basal shear in the doubly twinned volume. Deformation in that mode can result in sufficient independent shears for arbitrary shape change. Fracture in c axis compression, below about 100°C, has been related to excessive shear caused by unloading from the stress for {1011} twinning (-50 ksi at 20°C) to that for slip within the twin (-3 ksi); ductility follows from heating because the stress difference is lowered and the twin volume, in which elastic strain energy is dissipated on unloading, is increased. The stress for (1011) twinning is strongly temperature-dependent but not given by a critical resolved shear stress law. The latter is attributed to the influence of stress concentration from prior intersecting shear on nonbasal planes, the former to the temperature dependence of the preliminary slip. THE basic symmetry of hcp crystals has the effect of limiting the number of independent slip systems and making twinning an important deformation mechanism. The general result in wrought polycrystalline aggregates is a more or less sharply developed texture (or preferred orientation) which underlies a strong anisotropy in mechanical behavior. Knowing how the one influences the other is essential background for the use of such materials. Magnesium was of interest in this work because of the unexplained plasticity transition that it undergoes somewhere in the neighborhood of 200°c.''~ At lower temperatures plastic deformation before fracture in polycrystalline material is limited, while at higher temperatures extensive deformation is possible. The transition temperature commonly determines the lower limit of the range in which magnesium is worked. The limited ductility can be traced to a lack of independent crystallographic shears. A minimum of five are required for arbitrary shape change.' Around room temperature, however, slip on all known systems provides only four.' In each case, the slip direction is in the (0001) basal plane so that slip does not allow strain along the c axis. With increasing temperature, more slip occurs on the ( 1011) pyramidal plane and the ( 1010) prism plane but without change in direction.'?' Thus, that development alone cannot explain the transition temperature.

Jan 1, 1968

By S. F. Radtke, J. A. Snyder, R. M. Scriver

An automatic, continuous casting arc furnace employing a nonconsum-able electrode and a direct current arc has been constructed and operated successfully for titanium. A comparison of the properties of arc and induction-melted titanium indicates that where high ductility, formability, and toughness are required, arc-melted metal is preferable. BECAUSE of the reactivity of titanium metal with all known refractories and the common atmospheric gases, melting of the metal presents numerous problems. It is necessary to provide an inert atmosphere in the furnace as well as a crucible material that will not react with the molten metal, if a ductile ingot is to be produced. Two special furnaces have been developed that meet the requirements and one, the induction heated graphite furnace, has been described in some detail.' Little information is available for sizable units wherein power is applied to the melt through an arc, and the dearth of technical information on such a furnace prompted this report. It has been demonstrated clearly that arc melting produces titanium metal with superior toughness, ductility, and formability. To produce titanium ingots with these properties, an automatic, continuous casting arc furnace has been developed and is described herein. The history of arc melting may be traced to 1800, when Sir Humphrey Davy2 first experimented with Volta's electric battery and found that light could be produced and an arc formed between two carbon points attached to the cell. The discovery of the arc was followed by the design and construction of an arc furnace by Napier," in 1845, for the reduction of metal oxides. In 1853, Pichou' described a similar furnace, although it was not until the discovery of the dynamo in 1867 that the arc furnace could achieve commercial significance. In 1878, Siemens- esigned the first arc furnace intended for the melting of metals and by 1882 had melted steel and platinum successfully. . This was followed by Moissan's" classical work with the arc furnace in 1892. W. von Bolton,' in 1905, found that the arc furnace was suited admirably for melting refractory metals. In his work with tantalum, no suitable refractories for retaining the molten metal were found to exist. Together with Otto Simpson, he developed an arc furnace with a water-cooled copper crucible in which tantalum could be melted without contamination. This technique proved eminently successful. In his paper on the preparation of ductile titanium, Krolle first described an application of the von Bolton furnace to the melting of this metal. The

Jan 1, 1952

By D. K. Crampton, H. l. Burghoff, J. T. Stacy

THE effect of cold-working upon electrical conductivity of copper and of copper alloys appears not to be generally known in detail Although several papers on the subject have been presented, showing variable effects according to alloy composition, it is often assumed that the 2 to 3 per cent lowering of the conductivity of ordinary tough-pitch copper by severe cold-working is typical for copper alloys Because of this situation it was decided to carry out the present work upon several types of copper, copper-zinc alloys over the commercial range of brasses, other binary alloys, and numerous age-hardening alloys in the quenched, and quenched and aged conditions The large number of alloys investigated made it impossible to study every one in the detail it may have merited Inasmuch as several interesting points that could not be satisfactorily explained came to light, further work is contemplated by the authors It is usually considered that the normal effect of cold-work on ductile metals and unordered alloys is to decrease conductivity slightly In alloys that are in the ordered state, as annealed or otherwise heat-treated, cold-working tends to disorder the structure, resulting in very marked lowering of conductivity The random state of atomic arrangement produces lower conductivity than the ordered state for the same composition 1 PREVIOUS WORK previous work in the authors' laboratory has shown the electrical conductivity of several copper alloys to be decreased by greater amounts than might have been expected, in view of the general knowledge on the subject, when cold-worked Guillet and Ballay2 investigated the influence of cold-work upon the resistivity of several metals and alloys, including copper and some copper alloys The increase of resistivity due to severe working was less than 4 per cent for all pure metals tested, while the increases for the alloys were generally higher In the copper-zinc alloys, they found that the increase of resistance due to drawing increased with zinc content, and reported a 21 7 per cent increase of resistance for an alloy containing 67 9 per cent Cu as severely worked Masima and Sachs3 studied the change in electrical resistance of three brass crystals when stretched in the tensile test, obtaining increases in resistance of the order of 3 per cent for 30 to 40 per cent reduction of area of the specimens The resistance decreased again when the cold-worked crystals were subsequently annealed Bardenheuer and Schmidt4 found that the conductivity of copper was decreased by 3 to 4 per cent when reduced 50 per cent by working The conductivity of 72-28

Jan 1, 1941

By I. Fatt

Laboratory relative permeability data on reservoir rock are obtained on samples which are not subjected to overburden pressure during the permeability measurements. These data are then used for calculating the performance characteristics of reservoirs in which the rock is under the pressure of the overburden. Recent observations have shown that the permeability and porosity of reservoir sandstones are decreased by application of overburden pressure. These observations led us to a study of the effect of overburden pressure on the relative permeability characteristics of sandstones. A previous note from this laboratory1 showed that overburden pressure, simulated by applying hydraulic pressure to the outside of a plastic mounted core. caused a reduction in permeability of the core by as much as 50 per cent at 10,000 psig. In a multiphase fluid flow system, the relative permeability at a given saturation will change if the permeability or the effective permeability changes but not if both permeability and effective permeability change by the same ratio. The tests described in this note were made to determine the effect of overburden pressure on permeability and effective gas permeability in the gas-oil system. The gas-oil system was chosen because the available equipment was best suited for studying this system. The resultant data can be applied to other systems of interest because the gas permeability in the gas-oil system is the permeability of the nonwetting phase and, as such, is equivalent to the gas permeability in the gas-oil-water system and to the oil permeability in the oil-water system. EXPERIMENTAL METHOD Cylindrical test plugs, one in. in diameter and one in. long, were cut from sandstone core samples from three different reservoirs. After extraction in toluene, the plugs were mounted in Lucite by conventional core mounting methods.3 The core properties are given in the legend in Fig. 1. The mounted cores were machined to fit the apparatus shown in Fig 4. Air permeabilities as a function of overburden pressure were measured by connecting lines (1) and (2) to a conventional air permeameter. To measure porosity changes as a function of overburden pressure, the lines leading to (1) and (2) and the core were saturated with kerosene; line (1) was capped and a small bore precision calibrated pipet was connected to (2). Changes in pore volume of the core as overburden pressure was applied were noted by reading the amount of kerosene produced into the pipet. To correct for the change in volume of the lines inside the hydraulic cell as a function of pressure, a pressure-vs-volume run was made with a solid Lucite cylinder substituted for the core. The change in volume of the lines was about 10 per cent of the change in pore volume of the core. No correction was needed for the permeability measurements because there was no measurable pressure drop in the lines at the maximum overburden pressure. Relative gas permeabilities were measured by the stationary liquid method described by Osoba, et al.' Gas saturations were obtained by allowing the kerosene from a kerosene saturated core to evaporate out. This procedure was followed

Jan 1, 1953

By J. J. Bodmer

The substances or materials employed in this manufacture, are the same as those used in the preparation of mortar and concrete, viz., the different kinds of lime and sand. Instead of, or in conjunction with, sand there may be used calcined clay, blast-furnace slag, clinkers or ashes from furnaces, natural puzzolana, powdered chippings from stone quarries, etc. Of the different kinds of sand, pitsand—siliceous sand, as it commonly occurs mixed with gravel—and the sand found on the seashore, where the salt has been washed out by long exposure, whilst out of reach of the tide, may be used. The purer the above-named materials are from admixtures of clay, earth, or organic substances, the more complete will be their combination with the lime, the quicker will the manufactured brick or block set, and the more satisfactory will be the quality which it ultimately attains. For this reason, subdivided blast-furnace slag is preferable in most cases to sand, and the only sand which, in reference to setting capacity, is analogous to blast-furnace slag, is the volcanic sand occurring in different localities in North and South Wales, as an almost pure calcined silica. The lime used for the manufacture may be either slaked or unslaked. In the first case, (slaked), in order. to obtain satisfactory results, the lime must be strongly hydraulic. The use of unslaked lime, however, is by far preferable. A process for using fresh or unslaked lime has been patented in England by Major-General Scott. Lime thus prepared is called " selenitic lime," and consists of a mixture of fresh (unslaked) lime with sulphate of lime, or plaster of Paris. The graystone lime, for instance, found by the Medway, is mixed with from 5 to 7 per cent. of plaster, which has the effect of keeping the lime from slaking when water is added. This mixture also partakes of the nature of cement, and when used for mortar, or concrete, attains in a shorter time a greater degree of hardness than the same lime would ever have obtained after being slaked. Bodmer's process for the manufacture of artificial stone bricks consists chiefly in the use of automatic measuring, forwarding, and mixing apparatus, by means of which the materials are supplied and unite in a continuous stream, and are accurately measured. They

By J. J. Bodmer

THE substances or materials employed in this manufacture, are the same as those used in the preparation of mortar and concrete, viz., the different kinds of lime and sand. Instead of, or in conjunction with, sand there may be used calcined clay, blast-furnace slag, clinkers or ashes from furnaces, natural puzzolana, powdered chippings from stone quarries, etc. Of the different kinds of sand, pit-sand-siliceous sand, as it commonly occurs mixed with gravel-and the sand found on the seashore, where the salt has been washed out by long exposure, whilst out of reach of the tide, may be used. The purer the above-named materials are from admixtures of clay, earth, or organic substances, the more complete will be their combination with the lime, the quicker will the manufactured brick or block set, and the more satisfactory will be the quality which it ultimately attains. For this reason, subdivided blast-furnace slag is preferable in most cases to sand, and the only sand which, in reference to setting capacity, is analogous to blast-furnace slag, is the volcanic sand occurring in different localities in North and South Wales, as an almost pure calcined silica. The lime used for the manufacture may be either slaked or unslaked. In the first case, (slaked), in order to obtain satisfactory results, the lime must be strongly hydraulic. The use of unslaked lime, however, is by far preferable. A process for using fresh or unslaked lime has been patented in England by Major-General Scott. Lime thus prepared is called " selenitic lime," and consists of a mixture of fresh (un¬slaked) lime with sulphate of lime, or plaster of Paris. The gray-stone lime, for instance, found by the Medway, is mixed with from 5 to 7 per cent. of plaster, which has the effect of keeping the lime from slaking when water is added. This mixture also partakes of the nature of cement, and when used for mortar, or concrete, attains in a shorter time a greater degree of hardness than the same lime would ever have obtained after being slaked. Bodmer's process for the manufacture of artificial stone bricks consists chiefly in the use of automatic measuring, forwarding, and mixing apparatus, by means of which the materials are supplied and unite in a continuous stream, and are accurately measured. They

Jan 1, 1874

By C. Y. Ang, C. Wert

Quench aging of supersaturated solid solutions of nitrogen in columbium takes place in reasonable times in the temperature range 300&apos; to 500°C. Changes in internal friction, hardness, and electrical resistivity are found to accompany this change. THERE is practically no detailed information in the literature concerning interstitial solid solutions in either columbium or tantalum. The fact that both of these metals are used extensively commercially in both pure and alloyed states makes studies of their properties of value. While the plan is to study both these metals and their alloys extensively, so far only a small number of measurements have been made. This paper presents data obtained in the initial investigations of columbium. The principal interstitial impurities of columbium are likely to be hydrogen, carbon, oxygen, and nitrogen. The first of these, hydrogen, is outside the scope of internal friction measurements at present and nothing quantitative is known about the initial hydrogen content of the specimens. However, it is believed that it is completely absent after the preliminary heat treatments are carried out. The carbon content of the original samples is low and can be reduced still further during sample preparation. Oxygen is normally present to some extent in columbium and can also be added or removed easily. Nitrogen is also normally present in small amounts and can also be controlled within limits. Since it is not possible yet to remove all the nitrogen from columbium and since it is possible to remove essentially all the oxygen and carbon, initial measurements were made on the alloy system nitrogen in columbium. In this sense then, the alloys are true binary alloys. Little is known about the effects of nitrogen on the physical and metallurgical properties of columbium, so it was necessary to perform some rather elementary measurements on the specimens. These measurements are described briefly in the next section and are discussed in detail in later sections. Scope of the Work That internal friction is associated with diffusion of nitrogen in columbium has been known for some time. It is similar in nature to that for carbon and nitrogen in a-iron. In these latter cases, the information obtained from internal friction has been useful metallurgically.&apos; and it is not too much to expect useful information from similar studies on columbium containing nitrogen. The technique of internal friction measurements is adequately described by Ke2 At a frequency of 1 cps the internal friction peak for nitrogen in columbium occurs at 300°C and that for oxygen at 160°C." So that all the measurements will be meaningful metallurgically, the internal friction has been calibrated by making a measurement of the damping at the two peaks and a measurement of oxygen and nitrogen content by chemical analysis. A comparison of the two gives the following calibration factor: To go from damping capacity expressed in terms of 1/Q to weight percent of oxygen and nitrogen in solid solution in columbium, multiply the peak values of internal friction by about 4 and 3 respectively." Data from which these factors were calculated are presented in Table I. The increase of electrical resistance of columbium caused by the addition of oxygen and nitrogen as interstitial impurities has been quantitatively determined. At room temperature the percentage increase is small for small additions of impurities (<0.1 wt pct); as the temperature is lowered it becomes an increasingly larger factor of the total resistance. An empirical relation has been established to express the resistivity at — 195°C in terms of weight percent of oxygen and nitrogen in solid solution. It is easy to make supersaturated solid solutions of nitrogen in columbium and to observe aging phenomena. The optimum aging temperature, as in the case for carbon and nitrogen in a-iron, occurs at the temperature for which the time necessary for a single place-change in diffusion is about 1 to 10 millisec. This means for nitrogen in columbium that significant property changes should take place for this alloy at about 400" to 500°C in reasonable time intervals. Results of such aging experiments are

Jan 1, 1954

By J. H. Swisher

In measuvements of the solubility of nitrogen in fer-rilic Fe-P alloys, tile nitrogen solubility is found to be Less in pIrospliorus-bearing alloys than in pure iron. The reduction in solubility is about 20 pct in a 1.0 wt pct P alloy at 1300°C and about 30 pct in a 0.23 wt pct P alloy at 440°C. Diffusion coefficient measurements at 1150 and 585°C show that phosphorus also decreases the nitrogen diffusivity in iron. In previous work on the Fe-P-N system, phosphorus was found to reduce the nitrogen solubility in liquid iron slightly.&apos; Indirect evidence for similar behavior in a Fe at low temperature was obtained by Dickenscheid and Brauner.&apos; These authors found that phosphorus reduces the height of the internal-friction peak due to dissolved nitrogen. The results of Dickenscheid and Brauner were confirmed by J. C. Swartz of this Laboratory in a single internal-friction experiment using the same specimen stock as in the solubility measurements described below. In the present investigation, the solubility of nitrogen in a fer rite-stabilized Fe-1.0 wt pct P alloy was measured in the temperature range from 800" to 1300°C. Additional experiments were performed in the temperature range from 440° to 585°C, using an Fe-0.23 wt pct P alloy and NH3-H2 gas mixtures. EXPERIMENTAL The experiments were performed in a vertical tube furnace wound with platinum wire. For experimental temperatures of 800°C and above, a mixture of 5 pct Hz in N2 was used as the reacting gas. The gas mixture was prepurified from oxygen by passage over platinized asbestos at 450°C, and subsequently over anhydrone to remove water. Flow rates of the gases were measured with capillary flow meters. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. The specimens used for the high-temperature solubility measurements were in the form of rectangular plates, 0.534 by 1.6 by 3.8 cm. The specimens were cleaned in trichloroethylene and annealed for 2 hr in hydrogen at the beginning of each experiment. In measuring the nitrogen solubility, the specimens were held in the reacting gas until equilibrated, then cooled in a water-cooled copper block at the bottom of the furnace. The time needed for equilibration at 1150°C was determined by measuring the average nitrogen content of the 1.0 pct P alloy as a function of reaction time. As will be described, the nitrogen diffusivity in the alloy at 1150°C is only slightly less than its calculated diffusivity in pure iron. At temperatures other than 1150°C, the reaction time used in measuring the nitrogen solubility was about twice the calculated equilibration time for pure iron at the same temperature. With a few exceptions, the procedure for the low-temperature solubility measurements was the same as that described above. The compositions of the NH3-H2 gas mixtures were determined by collecting gas samples from the gas train and analyzing them for NH3 by titration with HC1. The specimen thicknesses were less than those used for the high-temperature experiments, eg., 0.124 and 0.051 cm for measurements at 585° and 440°C, respectively. Nitrogen concentrations were obtained by chemical analysis, using the Kjeldahl method. The Fe-P alloys were made by adding ferrophos-phorus to electrolytic Plastiron (Type 104 A). Commercial ferrophosphorus, containing 3 pct Mn and 0.35 pct Si as the major impurities, was first purified by melting under an FeO slag. In a separate heat, the electrolytic iron was melted and vacuum-carbon-deoxidized prior to making the ferrophosphorus addition. The principal impurities and their concentrations in weight percent in the 1.0 pct P alloy are as follows: Mn, 0.01; Si, <0.01; C, 0.01; 0, 0.003; and N, 0.0012. The impurity levels in the 0.23 pct P alloy are con-

Jan 1, 1968

By AIME AIME

ALBERT PORTEVIN, distinguished French physical metallurgist .and savant, has been added to the Institute&apos;s list of Honorary Members. Professor Portevin&apos;s work in collaboration .with A. M. Garvin represents one of the greatest steps ever made in understanding the heat-treatment of steel and the function of steel-alloying elements. In addition, he has published the results of important work, on the castability of ternary alloys, on the determination of oxygen and-oxides in steel, and on high-temperature oxidationn and scaling of steel. Notable also are his studies on methods of testing metals, on the constitu¬tion and structure of alloys, on founding and welding, and on alloys of aluminum, magnesium, and copper. Professor Portevin was horn in Paris in 1880, entering

Jan 1, 1938

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

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

Jan 1, 1970

THE translators wish to record their appreciation of the help given by many individuals with whom they have discussed various details of the work. They are particularly indebted to Mrs. Anne Noble McKeachie, who initiated their collaboration; to Miss Cora Adamson, who spent many hours in making an accurate copy of a much-mutilated &st draft of the translation; and to the Yale University Library which gave access to its excellent collection of books on all aspects of the history of the sciences. The reader will share with the translators their obvious indebtedness to Mr. Carl P. Rollins, Mr. James W. Boyden, and the staff of the Printing-Office of the Yale University Press. The publication of this translation by the American Institute of Mining and Metallurgical Engineers has been made possible by a grant from the Seeley W. Mudd Memorial Fund, administered by a committee composed of Harvey S. Mudd, H. DeWitt Smith, and George Otis Smith. The translators are gratified that their work has been judged to fall within the scope of this Fund, which was established for the advancement of the sciences of mining and metallurgy by the encouragement of research and the dissemination of knowledge, and especially for the furtherance of such activities as might benefit the younger members of the profession. While Biringuccio&apos;s book would scarcely serve as a dependable text for the young mining student or metallurgist, it can give him a sense of his membership in a long-standing and honorable profession and enable him better to see his own work in true perspective. It is hoped that this English edition of a sixteenth-century Italian work will be read by the practicing metallurgist as well as by those who have already found pleasure in exploring the past of their profession. A man always feels more at home in a foreign country with men of his own craft than in his birthplace with those of different interests: As in space, so in time, and the modem metallurgist who may be unmoved by the literary and artistic Renaissance will quickly appreciate the spirit of that exciting period as he talks shop with Biringuccio on a visit to mine, smelter, forge, and foundry; as he sees in different forms the very furnaces and machines whose operation and response he knows so well; and as he discusses with this engineer of four centuries ago such topics as the best kinds of fuel or refractory for a given operation, and the importance of adequate supplies of power and material.

Jan 1, 1942

By R. F. Dickerson, D. A. Vaughan, A. F. Gerds

ALTHOUGH the metallurgy of uranium has been under intensive study since the early 1940&apos;s, no systematic effort has been made to identify the non-metallic inclusions in uranium. Uranium carbide (UC), which is probably the most common inclusion found in graphite-melted metal, has been tentatively identified by previous investigators, but the other nonmetallic inclusions have received little attention. Since metallography is a valuable tool in metallurgical studies, the metallographic identification of the nonmetallic inclusions in uranium is important. Such an investigation has been completed and the identification of slag-type inclusions and of uranium monocarbide, uranium hydride, uranium dioxide, uranium monoxide, and uranium mononitride is described. Metallographic Preporation It is often possible to prepare specimens for metal-lographic examination equally well by several methods. The specimens which were examined in this work were prepared by one of two acceptable methods. For the convenience of the reader, both methods will be discussed in detail and will be referred to simply as Method I or Method II in the subsequent sections. For both Methods I and 11, specimens for microscopic examination usually were mounted either in bakelite or in Paraplex room temperature mounting plastic. Method I—Specimens were ground in a spray of water on a revolving disk covered successively with 120-, 240-, and 600-grit silicon carbide papers. It was necessary to perform the final grinding operation carefully on worn 600-grit paper to keep the scratches as fine as possible. After washing and drying, the specimens were polished for 3 to 4 min on a slow speed wheel (250 rpm) covered with a medium nap cloth. Diamet Hyprez Blue diamond polishing paste, Grade 00, 0 to 2 µ, was used as abrasive with kerosene as lubricant on the wheel. Specimens were washed thoroughly in alcohol and final polished electrolytically in an electrolyte composed of 1 part stock solution (118 g CrO, dissolved in 100 cm3 H2O) with 4 parts of glacial acetic acid. A stainless steel cathode was used. At an open circuit potential of 40 v dc, a polishing time of 2 sec retained inclusions well with the bath at room temperature. If additional etching was required to sharpen the interface between the metal and the inclusions, an electrolyte composed of 1 part stock solution (100 g CrO3 and 100 cm8 H20) and 18 parts glacial acetic acid was used at room temperature. Best results were obtained by etching for from 10 to 15 sec at 20 v dc in the open circuit. Surfaces obtained by this method are suitable for microscopic examination. However, if desired, they may be etched further with other chemicals. Method 11—Rough grinding was done on a wet 180- or 240-grit continuous grinding belt. The specimen was then ground by hand successively on 240-, 400-, and 600-grit silicon carbide papers in a stream of water. Final polishing was accomplished on a 4 in. high speed wheel (3400 rpm) covered with Forstmann&apos;s cloth. Linde B levigated alumina, suspended in a 1 volume pet chromic acid solution, was the abrasive. Specimens usually were polished in 5 min or less by this technique. Often the inclusions present in the metal were identified in the mechanically polished condition. When etching was required to outline inclusions more sharply, one of the two following methods was used. In the first method, the specimen is etched lightly while electropolishing in the chromic-acetic acid solution described above (1 part of stock solution to 4 parts of acetic acid). The electrolyte was refrigerated in a dry ice-ethyl alcohol bath and specimens were etched at 60 v dc on the open circuit for 2 or 3 cycles of 3 to 4 sec each. The second technique utilizes electrolytical etching at about 10 v dc (open circuit) in a 10 pet citric acid solution at room temperature. X-Ray Diffraction Technique The major problem in the identification of inclusions in metals by X-ray diffraction techniques is the extraction of a sufficient amount of each type of inclusion to obtain an X-ray diffraction pattern. In the present study, X-ray diffraction patterns were obtained from individual inclusions of the order of 10 µ diam. The polished and etched samples shown in the micrographs were examined at a magnification of X54 or XI00 with a binocular microscope. This allowed sufficient working distance to extract the inclusions with a needle probe for powder X-ray diffraction analysis. Friable inclusions such as MgF2, CaF2, UO2, and UH3 could be freed from the metal by probing the as-polished and etched surface. The fine particles then were picked up on the end of a Vistanex-coated glass rod (0.002 in. diam) which was held in a brass adapter made to fit the powder X-ray diffraction camera. The end of the glass rod was centered in the path of the X-ray beam. In the case of the UC, UO, and UN inclusions which are smaller in size, more metallic in appearance, and less friable than the other inclusions, it was necessary to etch the inclusion in relief before extraction. UN inclusions etched sufficiently in relief in the electrolytic polishing solution described in Methods I and II by increasing the polishing time. UN inclusions were relief etched by extending the

Jan 1, 1957

By R. Webeler

In order to study the role of work hardening in the fatigue process, use was made of the great sensitivty of the resistivity of AuCu to cold work. A change of the resistivity of AuCu of the order of 1 to 2 pct at the temperature of liquid nitrogen was found to occur as a consequence of severe fatigue. ACCORDING to Orowan&apos;s theory,&apos; the process of fatigue In metals 1s associated with the production of a number of small regions which have undergone strain hardening. This phenomenon is supposed to occilr even if the stress applied during fatiguing is always smaller than the yield stress. In an attempt to verity the existence of such regions, Welber and Webeler&apos; undertook to detect the stored energy associated with severe fatigue in copper. Previous experiments" had shown that the energy stored in a sample of copper which has been cold worked by torsion is released in the temperature range between 150" and 250°C when the sample is heated from room temperature and that no more energy is released (or absorbed) between 250" and 450°C. In particular the stored energy amounted to 0.41 cal per g for a case in which the mechanical energy expended in twisting the sample was 11.9 cal per g. In the case of fatigued copper, however, no release of stored energy could be detected between 150" and 250°C, so that the experimental error of &0.02 cal per g represents an upper limit for the amount of energy stored in strain hardening., It seemed desirable to attack the problem in a new fashion. For this purpose, it was decided to make use of the fact that, if an alloy capable of undergoing the order-disorder transition is ordered and then cold worked, the resistivity, p, increases very greatly above the value for the ordered state even if the deformation is very small. Some insight into the nature of the fatigue process may be obtained then by measuring the resistivity of an ordered sample before and after subjecting it to fatigue. For reasons which will become apparent from the following remarks, considerably more can be learned by carrying out the resistivity measurements at two different temperatures. In the case of a material containing impurities, vacancies, dislocations, or other imperfections of essentially atomic dimensions, the resistivity, p, according to Matthiessen&apos;s rule, can be represented as a sum of two terms p = p, + p, where p, is the (temperature dependent) resistivity of the pure metal, and p, is the temperature independent contribution of the imperfections. Briefly, the physical basis for this rule is the following: The main contribution of the impurities in question to the resistivity results from the fact that they interrupt the periodicity of the lattice and thus scatter the conduction electrons with a probability which is almost independent of temperature. In order that this be the case, it is necessary that the&apos; extension of the impurities be small enough—roughly less than one electron mean free path—so that their main effect on the resistivity occurs for the foregoing reason. If an alloy like AuCu is partly or completely disordered by quenching from an appropriate temperature, Matthiessen&apos;s rule also applies to a very good approximation* with p, representing in this case the resistivity po of the ordered sample and p, the additional (temperature independent) resistivity due to the disorder. In general, the disorder can be represented in terms of atoms which are displaced from their "proper" positions in the superlattice and which thus qualitatively represent the imperfections in the superlattice responsible for the term p,. Since the misplaced atoms are distributed at random throughout the super-lattice, their contribution to the resistivity still can be considered in terms of the scattering of conduction electrons by lattice defects. The situation is somewhat more complex in the case of an alloy disordered by cold work because the process of disordering here does not involve a random redistribution of the atoms; however, Matthiessen&apos;s rule also holds in this case. Whenever Matthiessen&apos;s rule does apply, the values of the quantity /3 = (p? — /(T, — T,), where p, and p, are the values of the resistivity at two fixed temperatures, T, and T,, respectively, is constant (independent of p,) for a given alloy or metal. In particular, if a sample of AuCu is subjected to ordinary cold work, the value of /3 remains equal to Po, the value for the ordered material. According to Orowan&apos;s theory,&apos; as remarked before, a fatigued sample contains a large number of isolated severely cold-worked regions, which make up only a small proportion of the metal. Thus, if a sample of AuCu initially in the ordered state is fatigued, more or less disordered regions will be produced within the ordered material. If these regions are small enough so that Matthiessen&apos;s rule applies, then it follows from the previous discussion that /3 again will remain equal to Po. If the effect of fatigue is to produce cold-worked regions which are macroscopic—of the order of at least several electron mean free paths—the effective resistivity, p, has to be computed by use of the ordinary laws of large-scale electrodynamics. For the sake of simplicity, it will be assumed here that the cold-worked regions are completely disordered and have a resistivity, p,. For a given proportion A of disordered regions the effective resistivity, p, for the current in a given direction depends on the geometrical configuration of these regions. In any case, the value of p for such

Jan 1, 1956

By O. D. Gonzalez

ThIS communication presents the results of a determination of the permeabilities of hydrogen and deuterium in a iron from 360° to 560°C. Recently Heu-mann and primas&apos; have given values of the diffusivity and solubility in a iron of the two isotopes from which the permeability can be calculated. The work reported in the present communication, however, is a direct measurement of the rate of permeation of the isotopes through an identical iron specimen under the same conditions, so that systematic errors can be minimized in the calculation of the ratio of the permeabilities—the value which is usually of main importance in establishing limits for isotopic differences in diffusive processes. Experimentally the procedure used was the usual one: a steady-state flow of gas produced by a pressure difference across an iron membrane was observed as the pressure rise with time in a previously evacuated, calibrated volume connected to the outlet side of the membrane, while a constant pressure of gas was maintained on the opposite inlet side. The membrane was a cylindrical tube 9.38 cm long, 0.730 cm inside diam, 0.187 cm wall thickness, fabricated of 99.95 pct vacuum-melted National Research Corp. iron (less than 0.003 pct C). One end was sealed by a heliarc-welded iron (99.95 pctj lid of 0.147 cm thickness; the other end of the tube was welded to a 304 stainless-steel tube (0.318 cm ID and 0.318 cm wall) which connects to a vacuum system and to the calibrated volume including a dibutylphthalate manometer. The temperature of the iron membrane was maintained constant to ±0.l°C and was measured with an iron-constantan thermocouple which was calibrated against a standard Pt/Pt-Rh thermocouple: the temperature variation along the length of the membrane did not exceed ±0.5°C. Hydrogen was allowed to pass through the membrane assembly for 72 hr at 615°C before permeability measurements were begun. The system was tested at temperature before and after the experiments by a substitution of helium for hydrogen in the inlet side; under these conditions the pressure rise observed in the outlet side was negligible at all times. The gases used for the permeability measurements were 99.95 pct Matheson prepurified H2 and 99.7 pct D2 (0.3 pct HD) from the Isomet Corp. The gases were dried with liquid N2 before use. In Fig. 1 the logarithms of observed flows, jt, for a pressure difference of 73.4 cm Hg are plotted against T-1 Each point in Fig. 1 represents the slope determined by a least-square evaluation of a plot of the pressure in the outlet side of the membrane against time, including at least two separate sets of observations. Each point in the figure has an uncertainty of ±0.6 pct arising from the experimental uncertainty in the pressure and time measurements. The standard deviation of the observed pressures from the straight lines in all cases is less than the experimental precision of the measurements. The observed flow, jt, includes a small but not negligible flow through the stainless-steel connection.

Jan 1, 1968

By R. G. Hudson, L. Yang

In electrochemical separation of metals, it is necessary to control the potential applied between the electrodes so that only the desired electrode reactions can occur. A knowledge of the minimum potential needed for a given electrode reaction to take place continuously is therefore pertinent to the success of the process. In molten chloride systems at high temperatures, activation polarization is believed to be small,1,2 so the minimum potential needed for the electrolytic decomposition of a molten metal chloride MC1n (n = valence of the metal ion) is therefore essentially the equilibrium electrode potential E of the metal-chlorine galvanic cell in the solution. If the decomposition products are pure M and chlorine at a pressure of p atm, E*Eo-rt/nf in [i] Since EO (the standard electrode potential of MCln) is a constant at a given temperature and R (the gas constant), and F (the Faraday&apos;s constant) are all constants, the variation of E with the electrolytic bath conditions is largely determined by the effect of the latter on the activity of the metal chloride amcln (standard state = pure MC1,). Measurement of E and study of how amCin varies with temperature and concentration, the nature of the solvent, and that of the coexisting solutes are therefore pertinent in the selection of optimum operating conditions for the electrochemical separation of metals. Because of its low melting point, high decomposition potentials of its components, and the low solubility of heavier metals in it, the LiC1-KC1 eutectic melt is a useful solvent and has been used in the electrodeposition of Mo,3Ce,4 and u5 metals. Senderoff and Brenner3 measured the potentials of Zn/Zn++, Fe/Fe++, Cu/Cu+, Mo/Mo+++, and Ag/Ag+ against an Ag/AgCl (pure) reference electrode at 600°C and a concentration of 4.1 mole pct of each chloride and came to the conclusion that complex ion formation occurred in some of the melts. Laitinen and LiUe gave an electromotive force series at 450°C for a number of {Metal/Metal ions (unit activity)) electrodes in LiC1-KC1 eutectic melt, the {pt/pt++ (unit activity)) electrode being chosen as the reference. Walker and Danly7 studied the ther-modynamic properties of NiC12 in LiC1-KC1 eutectic melt over a wide range of temperatures and concentrations by measuring the electrode potential between a nickel electrode and a chlorine electrode in the melt. Since potential measurements made by using the chlorine reference electrode are of more direct significance both in the study of electrochemical separation and in the evaluation of the thermodynamic properties of the melt, it is therefore decided to measure the electrode potentials of cells of the type {M/MCin (mole fraction = N) in LiC1-KC1 eutectic melt/Cl2 over a range of N values and temperature for a number of metal chlorides. The results should indicate the order by which the various metals plate out on the cathode and how this order is affected by temperature and the concentration of the metal chloride in the solu-

Jan 1, 1960