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By L. S. Deitz

This part of the symposium deals with the problems encountered by the consumer of nonferrous scrap, that is, the smelter and refiner who melts the selected scrap items and produces foundry ingots of specified compositions or billets for rolling or extrusion in nonferrous mills. The fundamental problems are quite similar for all secondary' nonferrous metals. However, these remarks will be confined to the copper-base alloys since in the sorting, melting and refining of these alloys probably all the usual types of problems are encountered; in addition, papers are being presented later on secondary lead, zinc and aluminum. While metallurgical

Jan 1, 1943

By E. T. Cox

The peninsula of Florida is remarkable for the uniform character and simplicity of its geological structure. Major Henry Whiting, of the U. S. Army, was one of the first to give an account of the physical features and rocks of Florida, in an article published in 1839, in the American Journal of Science (vol. xxxv., p. 47). He says: " The rocks found in situ are all calcareous, though siliceous boulders are occasionally seen, and nodules of hornstone are here and there mingled with the limestone, which elicit sparks and are sometimes used by the Indians for flints."

Jan 1, 1896

By John C. Smock

While I was engaged in the preparation of a catalogue or list of mineral localities of the United States, east of the one hundredth meridian, for the U. S. Geological Survey, the thought occurred to me that an arrangement or classification of the iron-ore districts of the eastern part of our country according to their geological horizons would be an interesting topic for a paper, and would furnish a basis upon which to arrange many facts brought out by the constant development of our iron-mining districts. Our text-books of mineralogy, geology, and ore-deposits describe the iron-ores and the

Jan 1, 1884

By Joseph A. Gill, Ernest A. Curth

The Government and Leeco concluded a cost-sharing agreement in 1976 to demonstrate longwall mining of a thin coalbed, 1 m or less, in a mine near Hyden, Ky. A premining investigation laid the groundwork for mine design and equipment specifications. Four- legged shields, a face conveyor, a stage loader and an in-web shearer were selected to operate on a 183 m face. Lengwall mining began in 1979 and initially was slowed by low mining height and equipment problems. A rock mechanics program provides early warning capability and criteria for future mine design. Monitoring of surface effects is included.

Jan 1, 1981

By Wayne L. Dowdey

With proud humility and keen anticipation, I accepted the office of President of the Institute one year ago, and it is with a great deal of pride in you-our membership that I make this report. You are the reason for a productive and prosperous year for AIME. Superior, good or satisfactory results were experienced in 1978 from almost everything we did as a leading engineering technical society. I recognize and pay tribute to the WAAIME organization. Their work is vital to our efforts, and their programs have proven effective. WAAIME can depend upon our continuing support.

Jan 6, 1979

By Robert Keeney

AT the beginning of the use of the electric furnace, for the manufacture of calcium carbide and ferro-alloys, experimental work was conducted in it upon the production of steel from iron ore. Stassano performed two series of experiments in Italy, the first1 during the years 1898 to 1902, and the second2 in 1908. For many years steel and wrought iron have been produced directly from ore on a small scale in the forge, crucible, and reverberatory furnaces; but the difficulties attending the operation of these combustion processes have prevented their adoption to any great extent. The combustion

Jan 2, 1914

By David K. Hylbert

This study investigated roof falls in room-and-pillar drift coal mines in eastern Kentucky and utilized geologic methods for predicting roof conditions in advance of mining. In the Highsplint mine, the roof was classified in four categories or conditions: Condition A and B (Laminated Shale); Condition C (Rolling Sandstone with Shale in Pockets); and Condition D (Zone of Major Sandstone Roll(s)). Structure contour and isopach maps of the Darby coal bed and associated immediate roof rocks were wed to project axial trends of the sandstone roof. Trend mapping in the mine and on outcrop provided more detailed control for roof projections.

Jan 12, 1978

By David K. Hylbert

This study investigated roof falls in room-and-pillar drift coal mines in eastern Kentucky and utilized geologic methods for Predicting roof conditions in advance of mining. In the Highsplint mine, the roof was classified in four categories or conditions: Condition A and B (Laminated Shale); Condition C (Rolling Sandstone with Shale in Pockets); and Condition D (Zone of Major Sandstone Roll(s)). Structure contour and isopach maps of the Darby coal bed and associated immediate roof rocks were used to project axial trends of the sandstone roof. Trend mapping in the mine and on outcrop provided more detailed control for roof projections.

Jan 1, 1979

H. H. Kellogg (Columbia University)—The accurate measurements of the equilibrium gas ratios for the reaction: Pb(1) + H2S = PbS(c) + H2 [I] reported in this paper are a distinct contribution to the literature, and the authors are to be congratulated. I wish to comment, however, on the correlation of the data which is presented. The authors show a straight line correlation of log H2S/H2 vs 1/T, Fig. 1, and are satisfied with this for calculation of ?Fo even when extrapolated to low temperature (427 °C). Heat capacity data for the constituents of this reaction are available (at least to 900°K), however, and ACP for reaction [I] is finite and positive in the temperature range studied. Simplification of the heat capacity equations yields: ?CP= 2.71 + 1.65 x 10-3T (298°-900°K) This positive value of ?CP should result in a small but noticeable curvature of a plot of log K vs 1/T. That the experimental data fail to show such a curvature may be traced to another oversimplification of the author's treatment of their data. They assume that the activity of liquid lead is unity for all temperatures, so that

Jan 1, 1961

By Charles Willard Hayes

Shortly after the discovery of black phosphate on Swan creek, in Hickman county, Tennessee, prospectors familiar with the Florida phosphate came to the region and began the search for rock similar to that found in Florida. Among these was Mr. E. Slattery, who located at Linden, in Perry county. He gave a piece of the Florida rock to Mr. C. C. Sutton, and the latter discovered on Tom's creek a deposit which bore a strong

Jan 1, 1896

By Henry F. Hebley

INTRODUCTION How often has the thoughtful observer pondered the apparent contradictions experienced in the weather? One can take records of two days, one in the winter and one in the summer. The "degree days" indicate that space heating and domestic load were present in one case and not in the other. The Business Index may be about the same, indicating that the industrial activity of the area and its concomitant use of fuel were about the same. Thus the volume of the products of combustion released to the atmosphere varied only as related to the space heating demand. Yet on one day in winter the atmosphere may be clear and bracing, while on a summer's day the air is thick and murky and the visibility sharply reduced. The situation may be reversed. What are some of the factors that contribute to the creation of these conditions? These few notes have been prepared to indicate some of the influences that are exerted on the problem. THE SOURCES OF ATMOSPHERIC POLLUTION The industrial area of Pittsburgh, Pa., has been a dominant center for the production of iron and steel for over one hundred years. In fact, with the growth of the numerous auxiliary processes Allegheny County which contains Pittsburgh is probably the most industrialized county in the world. In addition, the type of manufacture carried out in this area is predominant dependent on thermal energy (heat). That energy is supplied from coke and coal produced in the vicinity of Pittsburgh. Indicative of the stupendous quantities of fuel that are employed in this industrial area's economy, the following (Table No. taken from the U. S. Census (1940) may I of interest. An influence that has never been fully appreciated by many individuals is the fact that no matter what adventures the gases of combustion experience as they pass through the various processes, ulti¬mately the spent gases are discharged through chimneys to the atmosphere.

Jan 1, 1948

By A. N. Holden

A DISLOCATION mechanism has been described by Cottrell' by which metals can yield locally, I. form Liiders bands, giving rise to a characteristic stress-strain curve with a sharp yield point and appreciable strain at constant or decreasing stress. It is undoubtedly the best mechanism that has been suggested to date." In its present development, however, the dislocation mechanism provides a more satisfying explanation for the sharp yield point than for the extensive localized flow occurring at the lower yield stress. The primary objective in this paper is to extend the dislocation mechanism to account for localized cataclysmic flow by a dislocation collision process and to give experimental evidence to support such a process. Only the yielding of iron containing carbon -will be discussed, although other metal-solute systems are known to behave similarly. Cottrell Mechanism In brief, Cottrell explains the yield point in the following way: The dislocations in iron which must propagate to produce slip usually lie at the center of local concentrations of carbon atoms, since segregation about these dislocatlons relieves some of the local stress resulting from them. A dislocation surrounded by a "cloud" of carbon atoms is thus anchored, and a higher stress is required to set it in motion than to move a free dislocation. Considering all available dislocatlons to be anchored in this fashion, the iron exhibits a yield point when the first dialocations break free and move through the lattice causing slip. This first breaking away of a dislocation enables other dislocations to break loose by "interaction" and the process becomes a cataclysm producing local deformation or Luders bands. The yield point in the stress-strain diagram for iron is absent in freshly deformed material, but returns gradually with time; the phenomenon is one aspect of what is called strain aging. The rate at which the yield point returns following straining depends on the temperature of aging. According to Cottrell the rate of return of the yield point in strained iron is limited by the rate of diffusion of carbon at the aging temperature, the mechanism is onr: of reforming the solute atmospheres around carbon-free dislocations that had stopped moving coincident with the removal of stress. If the specimen is retested immediately after straining and unloading, carbon will not have had time to diffuse to, and re-anchor, dislocations and the yield point will not occur. The carbon diffusion limitation for the rate of strain aging apparently applies if the criterion for strain aging is either the change in hardness" or the change in electrical resistance" of the strained speci- men with aging time. The possibility exists, however, that the yield point actually returns to strained iron at some rate other than that deduced from hardness or electrical resistance data. Therefore, as a preliminary experiment, the rate of yield point return in a rimmed sheet steel strained 6 pct in tension was measured at 27°, 77°, and 100°C. A plot of yield-point elongation for each of these temperatures against aging time appears in Fig. 1. The aging process is described by curves which rise to a plateau value of elongation that seems independent of temperature, but at a rate that depends on temperature. Very long times lead to a further rise in the yield-point elongation above the plateau value. However, if the later increase in yield-point elongation is ignored and the log of the time to reach half the plateau value of elongation is plotted against 1/T, a straight line results for which an activation energy of about 25 kcal pel- mol may be assigned. Within the accuracy of this sort of experiment this is approximately the activation energy for the diffusion of carbon in iron (20 kcal per mol), and the carbon diffusion limitation suggested for the yield-point return on strain aging is valid. The Cottrell mechanism thus explains in a qualitative manner the occurrence of a yield point in iron and its return with strain aging. It fails, however, to explain some of the other experimental observations that have been made of the yielding behavior of iron. For example, it is known that the yield point in iron becomes less pronounced with increasing grain size. Annealed single crystals of iron have very small yield-point elongations .if indeed they have any,' compared to a polycrystalline steel. If the only requirement for a yield point is that the dislocations in the lattice of the annealed. material be anchored by carbon atoms, the difference in the behavior of single crystals and polycrystals is not explained. That a dislocation mechanism may be entirely consistent with little or no yield point in an annealed single crystal will become apparent later when dislocation interaction is discussed. Strain aging produces a definite yield point even in single crystals. This accentuation of the yield-point phenomenon in single crystals after strain

Jan 1, 1953

By C. F. Riisness, E. R. Parker

THAT grain size has a great effect on the mechanical properties of metals has been recognized for a long time. Bassett and Davis1 in 1919 did excellent work in [ ] determining the effect of grain size on the hardness of brass. About the same time Jeffries2 and Sykes3 ascertained the effect of grain size on the strength and ductility of several metals at temperatures ranging from 80°K. to their melting points. When creep was recognized as an important property of metals, those engaged in the study of this property tried to determine the effect of grain size 4-9 on creep rates. Unfortunately, most of the investigations were conducted on only two grain sizes, often designated simply as "fine" and "coarse." It is well known that at high temperatures coarse-grained test bars creep less than fine-grained bars. The relation between grain size and size of test bar, [ ] however, has been frequently overlooked. In his early work, Jeffries2 showed that the number of grains in the cross section has a more important influence on the properties of the material than the actual grain size. More recently Hanson and Sandford10 and Pell-Walpole,11 in their measurements of the creep and tensile properties of tin, tested a wide range of grain sizes and correlated the grain size with the strength. Hanson9 later established the relation between the number of grains in the cross section and the. creep rate: At high temperatures, generally a coarse-grained structure is considered superior in creep to a fine-grained structure, but it is evident that for a given bar size continuously increasing the grain size will

Jan 1, 1944

THE foundation established by the partners of the late Robert W. Hunt provides for both a medal and a prize. The latter has not been given before this year, and the first award is to C. H. Herty, Jr., for his several papers on the physical chemistry of the open-hearth process.. He is the son of the well known chemist of the same name. He was born at Athens, Ga., on Oct. G 1896, graduated from the University of North Carolina in 1918, and went into war service as foreman of U. S. Chemical Plant No. 4, at Saltsville, Va. In 1919 he went to Massachusetts Institute of Technology, where he was successively instructor, research assistant, and research associate in the School of Chemical En-gineering practice receiving his master's degree in 1921 and his Ph.D. in 1924. He continued his brilliant work on the physical chemistry of the open-hearth process, much of it being done in cooperation with the Bethlehem Steel Co. at its Lackawanna plant, and dealing with the elimination of sulfur. In 1926 he joined the staff of the U. S. Bureau of Mines, in charge of its ferrous metallur-gical work at Pittsburgh, and continues to be active in research work on the physical chemistry and metallurgy of the open-hearth process. His Institute publications are: Some Factors Affecting the Elimination of Sulfur in the Basic Open-hearth Process," "Chemical Equilibrium of Manganese, Carbon and Phosphorus in the Basic Open-hearth Process" and "Desulfurizing Action of Manganese and Iron," and he will present a paper on ?Effect of Temperature on the Solubility of Iron Oxide in Iron" at the annual meeting.

Jan 2, 1928

By Luther W. Lennox

During the last few years, one of the great problems in the milling of all ores has been that of grinding. This subject involves not merely the cost of the operation, but also the selection of the proper degree and character of grinding to yield the best metallurgical results on the given ore. Considering the diversity of machinery, one is led to wonder at the variety of grinding methods employed, even when realizing that metallurgy demands varying products. In an attempt to investigate the relative grinding resistances of a number of ores now being milled in this country and Alaska, the manage-mxitofthe Portland mills requested Samples of average mill-run of ore from various companies. The request met with a ready response, indicating the desire of all operators to gain information on the subject. The difficulties involved in this investigation were numerous, lack of time for outside problems during this strenuous period being a serious one. Also, we were unable, in the time, to obtain a correct 150-mesh screen; in the screen analyses tabulated and plotted herewith, the 150-mesh screen was used merely to protect the 200-mesh screen, not to ascertain points on the curves. The experimental grinder was a small iron tube-mill, 8 by 121/2 in., in which was placed a definite number (74) and weight (3450 gm.) of 3/4-in. steel balls, 1 Ib. water and 1 Ib. ore. To obtain uniform conditions, each ore was first crushed and screened, and from the sized products a "standard feed" was artificially prepared, the same standard being adopted for all tests in that particular series. The prepared feed was

Jan 1, 1920

By R. C. Hirschfeld, H. H. Einstein, R. W. Bruhn, R. A. Nelson

The objective of the model studies described in this paper is to determine the effect of planar discontinuities on the strength and deformability of a rock mass. A model material was used because it satisfied concurrently three requirements that available natural-rock samples did not: (1) low strength, which was desirable for minimizing the loads that had to be applied in the laboratory; (2) ease of producing test specimens with geometrically regular joint patterns; and (3) uniformity of the test specimens. The model tests were performed on specimens made from a single modeling material and tested under triaxial stress conditions with [u,=u,]. Results are presented in this paper for tests on specimens that had (1) a single joint set inclined at several angles to the major principal direction, including 0º and 90°, and (2) two joint sets that were mutually perpendicular, one set perpendicular to and one set parallel to the major principal direction. Several different joint spacings were used in each series. Future tests will include a series with two sets of joints that make oblique angles with each other and with the major principal direction. The results of model tests and tests on cores of jointed rock by several investigators (e.g., Müller and Pacher,l Moore,2 Krsmanovic and Milic,3 Hayashi,4 Rosenblad,5 Jaeger,6 and Lane and Heck 7, have contributed significantly to the design of these experiments, which are believed to be the first in which a comprehensive study has been made of the combined effects under triaxial loading of joint spacing and joint orientation (Fig. 1).

Jan 1, 1970

By Samuel Storchheim

IT was noted that variations existed in the magnetic properties, namely, coercive force, He, and rema-nence, Br, of 18/8 stainless steel wires of the same analysis when these wires were given the same percentage of reductiori of area at different rates of reduction. In order to determine the extent of these variations, a program was initiated whereby commercial 302 and 304 stainless steels were drawn with a wide variation of speeds. Ultimate tensile strengths and specific resistances, as well as the Hc-BT measurements, were determined. If variations of considerable magnitude were found, it was thought that the knowledge accrued from the investigation could probably aid in determining the particular drawing speed required to obtain desired properties for a given specification for a particular analysis of wire. Drawing Procedure Two specimens (set I, No. 302 and No. 304), the chemical analyses of which are given in Table I, were drawn at different speeds, namely, 45 to 3900 ft per min, directly from 0.016 in. diam wire to 0.004 in. diam wire, a 93.7 pct reduction of area. To obtain this high percentage of reduction, the wire at 0.016 in. was softened by annealing at 1150°C. It was then strung in a No. 16CF variable speed Vaughn drawing unit and passed through 13 B.&S. gage dies of successively smaller diameter, as shown in the accompanying table. Following this step, several hundred feet of the wire was drawn, at a particular speed, through the dies and wound upon a spool. Once the sample of wire was drawn at the desired speed, the spool with the finished sample was removed, tagged for later identification, and an empty spool was placed in the machine. Another wire sample was drawn at a different speed, after making the necessary adjustments upon the Vaughn unit. At the greater speeds, several thousand feet of sample were drawn to insure that the wire to be used for testing would be uniform. This was done because the desired speed was not reached instantly; the wire taking a short while to attain the required drawing rate. All speed measurements were made by placing a tachometer against one of the machine's pulleys during the actual drawing of the specimens. 84.4 pct reduction of area. The 0.072 in. diameter wire was also annealed at 1150°C. The process of obtaining samples was the same as described above. The only difference between the two was that the rates involved were not as extensive, set II covering a range of 625 to 1150 ft per min. Tensile tests were carried out for the 0.004 in. diam wires on a horizontal Scott Tensile Tester, while tensile tests for the 0.028 in. diam wires were made on a vertical Scott Tensile Tester. Each value listed in the tables represented the average of five samples with a maximum deviation of approximately 3 pct among the samples. Resistance per foot of the wires was determined by use of standard bridges accurate to the nearest hundreth of an ohm for the 0.004 in. wire, and to the nearest thousandth of an ohm for the 0.028 in. wire. The resistances per foot were then converted to resistivities by use of the following equation: P = RxCM where R is the resistance per ft in ohms per ft; CM, the area in circular mils; and P, the resistivity in ohms—CM. The values listed in the tables likewise

Jan 1, 1952

By R. C. Hall

The magnetic anisotropy and magnetostriction of single crystals of alloys between 25 and 59 wt pct Co in Fe have been determined in the disordered and ordered states. The magrzetostriction is large and positive for all alloys in both states of order (up to 150 x 10-6 for A,, and 40 x 10-6 for 111). The magnetic anisotropy becomes zero rzear 41 pct Co for the disordered state. Ordering shifts the zero-anisotropy composition to about 50 pct Co. COBALT-iron alloys have for many years been of interest as magnetic materials because they have unusually high magnetic saturation values.' This interest was increased recently by the development of Supermendur.' Supermendur is an alloy of 49 pct Co-49 pct Fe-2 pct V* which was found by suitable purification and heat treatments, including a magnetic anneal, to possess excellent magnetic properties. These included a square hysteresis loop with a low coercive force and a high magnetization, and a low total loss. Two factors which are important in determining the magnetic hysteresis properties are the basic magnetic properties of magnetostriction and anisotropy. Alloys having zero anisotropy and zero magnetostriction show improved hysteresis properties.3 Since very meager data4-' are available in the literature on the single-crystal anisotropy and magnetostriction of the cobalt-iron alloys, the present program was undertaken to determine these two properties in the disordered and ordered states. EXPERIMENTAL TECHNIQUES Ingots of the cobalt-iron alloys containing from 25 pct to 59 pct Co in iron were vacuum melted from electrolytic iron and cobalt of 99.9 pct purity. The ingots were cooled at a rate of about 1°C per hr through the transformation temperature (950" to 980°C dependent on the alloy content) for the growth of large grains. From these grains, single-crystal disks were fabricated with either the (110) or (100) plane parallel to the faces of the disk. The crystals were given two heat treatments to produce either the ordered state (cooling rate of 20°C per hr from 850 "C) or the disordered state (water quench from 850 °C). Since the iron-cobalt alloys order very rapidly, the water quench may not have produced complete disorder in all cases. Due to the method of growth, the crystals were not perfect. Most of the samples had low-angle boundaries and a few had some small included grains. These imperfections could and probably did affect the accuracy of both the magnetic anisotropy and magnetostriction measurements. Much of the scatter in the data may be attributed to the crystal imperfections. The methods of determining the spontaneous saturation magnetostriction and the anisotropy have been previously described.419110 MAGNETOSTRICTION The magnetostriction in the [loo] and [Ill] directions (hO0 and ?111 respectively) is illustrated in Fig. 1 for the disordered state. Both ?100 and ?111i became large positive values as cobalt was added to iron. The state of order did not have a large effect on the magnetostriction. The effect of order did not appear too consistent in these data. Tentative curves are shown in Fig. 1 for the ordered magnetostriction near the FeCo composition; here ?100 appeared to be lowered and ?111 raised as the degree of order was increased. These results agree qualitatively with the

Jan 1, 1961

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 P. Chiotti, E. R. Stevens

The electromotive force between pure magnesium and Mg-Zn alloys in a fused KC1-LiCl-MgC12 cell was measured over the temperature range 360° to 730°C and for alloy compositions of 0.052 to 0.635 atom fraction magnesium. The calculated activity coefficients of magnesium in the liquid alloys may he represented by the relation These data and the phase diagram were employed in calculating the standard free energy of formation for the compounds MgZn, MgZn2, and MgZn2, In the temperature range from 25° to 590°C the relation ZINC-rich magnesium alloys have been shown to be very effective in reducing various solute chlorides or oxides from fused salts such as KC1-LiC1 eutectic. Such reactions are of interest in the developinent of pyrometallurgical methods for reprocessing nuclear reactor fuels.' As the conceniration of the magnesium is increased beyond 5 to 10 wt pct the extent to which solutes, such as yttrium, lanthanum, cerium, and other rare earths, can be reduced or removed from the salt decreases. This effect is due to the resulting change in the activity of the solutes in the Zn-Mg alloy as well as the change in the activity of both the zinc and mag- nesium. The purpose of the present investigation was to determine the thermodynamic properties of the Zn-Mg system which, in addition to yielding information on the alloying behavior of these two elements, would permit a more quantitative understanding of the above reactions. Since this investigation was initiated several publications have appeared in the literature giving results on the thermodynamic properties for the liquid alloys of this system. 2-4 Kozuka, Moriyama, and Kushima3 measured the vapor pressure of zinc over four different alloy compositions by a carrier-gas technique. Eremenko and Tukashenko2 and Terpilowski4 measured the electromotive force between pure magnesium and various alloys in a fused salt cell. Earlier work has been summarized by Hultgren, Orr, Anderson, and Kelley.5 In the present investigation electromotive-force measurements were made on a cell of the type The temperature range covered for the lower-melting alloys was roughly 375° to 730°C. These data were employed in calculating the thermodynamic properties for the liquid alloys and in conjunction with the phase diagram,' reproduced in Fig. 1, were used in calculating the standard free energy of formation of the compounds MgZn, MgZn2, and Mg2 Zn11. The results obtained are compared with available data from the literature. MATERIALS AND EXPERIMENTAL PROCEDURES Materials employed were: Bunker Hill slab zinc, 99.99 pct pure; Ames Laboratory magnesium containing 13 ppm N, 195 ppm C, and trace amounts of calcium, copper, nickel, and silicon; reagent grade KC1, LiC1; and high-purity MgC12 obtained from Dow Chemical Co. The electrolyte consisting of KC1-LiCl eutectic (44.4 wt pct LiC1) to which was added 15 wt pct MgCl2, was dried in a quartz tube by heating to 340° C under vacuum for a period of 4 to 5 hr, and then passing HC1 through the salt as the temperature was slowly raised to above the melting point of the salt. After about 3 hr the HC1 was shut off and the system flushed with argon and then vacuum applied for 1 hr. The salt was finally siphoned through a sintered glass filter and cast into a Pyrex container which was sealed and

Jan 1, 1965