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By H. R. Gardner

The heat treatmmt of plutonium was studied using the Jominy end-quenching technique commonly used for determining the hardenability of steel. Plutonium specimens were end-guenched from temperatures in each of the ß, y, d, d') and E phases. One series of specimens with a low-iron content, 165 pprn Fe, and another gvoup with a high-iron content, 678 pprn Fe, were used in order to study the effect of a Pu-Pu,Fe eutectic network on the hardness and micro-structure. Hardness traverses indicated no significant variations in hardness with either cooling rate or quench temperature. Metallographic studies indicated major effects on microstructure. Grain size was found to vary markedly with quenching temperature and cooling rate. It was determined that the Pu-PueFe eutectic network could be modified extensively by heat treatment, including spheroi -dization in the y phase and 6 phase below 413°C. An unidentified spheroidal inclusion was observed to go into solution in the delta and higher temperature phases. 1 HE element plutonium is unique among metals in that it has six allotropic forms in the solid state.' These have been designated' as the a, ß, y, d, d', and phases. The respective phase transformations occur at approximate temperatures of 122", 210°, 319°, 450°, and 480°C with a melting point at 640°C. With this number of phase transformations it becomes pertinent to consider the effect of heat treatment and cooling rate in the various phases on the microstructure and hardness of plutonium. To determine; the effect of a wide range of cooling rates, the Jominy end-quenching technique was applied to cylindrical plutonium specimens. In addition, since the presence of iron in amounts greater than 500 pprn is common in plutonium and results in a network of the Pu-Pu6Fe eutectic, it was decided to study heat treatment effects on two bomb reduced plutonium buttons with different iron contents. A low iron button containing 165 ppm Fe and a high iron button containing 678 ppm Fe were selected for this comparison. EXPERIMENTAL PROCEDURE Experimental Material. The cylindrical bars for Jominy quenching were cast from button stock in vacuo in MgO coated graphite molds. Metal pouring temperature was approximately 950°C and the molds were preheated to 300°C. The castings were machined to 0.5 in. diam. by 2.5 in. long cylinders. Chemical analysis and density data for the two groups of Jominy specimens containing different iron contents are presented in Table I. Except for iron, heats 19-12-1 and 20-2-1 are comparable within the limits of analytical accuracy. Representative specimens from the low-iron and high-iron bars were taken for metallographic examination. The low iron specimen was found to have extensive microcracking, Fig. 1. In addition, numerous unidentified spheroidal inclusions were present, Fig. 17. The average grain size of the low-iron plutonium is 0.068 mm, Fig. 4. In the high-iron plutonium, a Pu-Pu6Fe eutectic network is prominent, Fig. 7. The average size of the network is 0.100 mm. Unidentified spheroidal inclusions were also common in the high-iron plutonium. The average grain size of the high-iron plutonium is 0.036 mm. Experimental Technique. A Jominy end-quenching fixture was fabricated for glove box use. A 2.5 in. water height was used with an orifice of 0.250 in. ID. The orifice to specimen distance was maintained at 0.5 in. Annealing temperatures of 160°, 265°, 400°, 465°, and 535°c were chosen for the study of the effect of quenching from ß, y, d, d', and e phases on microstructure and hardness. During quenching, cooling curves were obtained from the Jominy specimens at distances from the quenched end of 1/16, 1/8, 3/8, 3/4, 1-1/4, and 2 in. Cooling rate calculations were made from the cooling curves for temperature intervals of 100° to 110° 160" to 170°, 330" to 340°, 420° to 430°, and 490° to 500°c. These temperature intervals were chosen

Jan 1, 1962

By M. Weinstein, J. F. Elliott

IN conjunction with a study on the solubility of hydrogen in liquid pure iron and iron alloys, new and

Jan 1, 1963

By G. S. Hume

Activity in geological exploration and drilling continued in Canada in 1945 at about the same rate as in the previous year, but with disappointing results as far as new production is .concerned. Both in the foothills and on the Plains of Alberta, however, there are wildcat wells that have either given encouraging shows or some production, which are very important in relation to future developments. The normal decline of Turner Valley, the largest producing field in Canada, has continued, and this decrease has not been offset by new discoveries. In addition, the closing of the Canol pipe line on March 31, 1945, isolated the Norman Wells field in the Mackenzie River valley, and the outlet at present. is confined to supplying the relatively small local requirements. This

Jan 1, 1946

By Stanley Herold

A FEW notes on the occurrence and significance of mud volcanoes in Colombia may be of interest at the present time, owing to the renewed activity in geological exploration of, the coastal regions bordering the Caribbean Sea. The best-known volcanoes are found a few miles from the seacoast. One is situated to the south of Puerto Colombia; the second, to the east: of Cartagena near the village of Turbaco; and the third, near the village of Puerto Escondido south of the Sinu River. Others. are reported in more inaccessible localities. Usually they stand 2 1/2 or 3 ft. (0.762 or 0.914 m.) above the surrounding ground at the crater, though several craters from 10 to 20 ft. (3.04 to 6.09 m.,) apart will often build up an extensive mound at low gradient. The shallow mound may cover 1/2 or 3/4 acre (0.2 to 0.3 ha.) with an elevation of 12 or 15 ft. (3.65 or 4.57 m.) at the center. The craters are formed of hardened blue clay; the inside diameters vary from 14 to 24 in. (35.56 to 60.96 cm.). The rim is continuous, except on one side where there is usually a cut 3 or 4 in. deep, thus allowing an overflow. The craters are filled to the rim-cut- with a thick mixture of blue clay mud and water, which is kept in agitation by escaping gas. Fig. 1 shows the bubble in the act of bursting and Fig. 2 the appearance of the surface of the viscous fluid a second or so later. The frequency of the explosions is determined by the weight of the column of fluid in the neck of the volcano, consequently, such explosions are not synchronous in a group of craters. Ordinarily, there are two or three explosions in about 3' minutes. The supply of gas is small but steady and sufficient pressure must accumulate before the bubble can enter the column of fluid. The water is derived from the surface and enters the sedimentary strata not` far distant from the volcano. During long dry seasons, as the supply of water fails the volcano dries and geyser action ceases.

Jan 7, 1919

By H. C. Casey, M. B. Panish

The roles of the phase diagram and the diffusion and solubility analyses in the selection of sources for the diffusion of zinc into GaAs are discussed. Isothermal sections of- the phase diagram are described at 1000°, 775°, 744°, and 700°. Below 744° the three solid phases, Zn3As2, GaAs, and ZnAsz, may be in equilibrium. In the composition regions where the three solid phases are in equilibrium, the partial pressures of the components do not vary with composition and there is no liquid phase. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected to yield reproducible diffusion profiles without surface damage. The 5/50/45 ternary source Provides a significant improvement in the reproducibility and planarity of- the zinc diffusion as compared with other zinc diffusion sources that result from starting with elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. Several experimental diffision profiles for the 5/50/45 diffusion source have been determined. The profiles are very steep in the region of the junction and produce devices that exhibit step junction behavior. The junction depth varies as the square root of time. Diffusion at 700°C for 4 hr gives a 5-µ junction depth and a surface concentration of 2.4 x1020 cm-3. The surface concentration is enhanced by a factor of three and the junction depth decreased by a factor of ten as compared with diffusion with a starting source 01- elemental zinc. The differences in dijyusion behavior with these two sources are due primarily to the approximately 10' greater equilibrium As4 partial pressure for the 5/50/45 source. ThE most common technique for the preparation of GaAs p-n junctions for diverse applications ranging from switching diodes to injection lasers has been to diffuse zinc into the solid from the vapor phase. The zinc impurity has generally been provided by introducing into a diffusion ampoule elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. For the purpose of eliminating surface deterioration, zinc has been diffused into GaAs through SiO2 films1 and from zinc-doped SiO2 films.2 During a study of the injection and recombination mechanisms in GaAs junctions, we found that these diffusion techniques either resulted in nonreproducible diffusion profiles and nonplanar junction interfaces or were extremely inconvenient to use. An unpublished report by Allen and pearson3 emphasized that an understanding of diffusion requires relating the diffusion conditions and system compositions to the ternary phase diagram. Recent studies have made it possible to relate the effect of starting source composition on the GaAs sample surface and diffusion profile reproducibility and, in addition, to estimate the expected surface concentration and zinc diffusivity. These studies include the Ga-As-Zn phase diagram,415 the determination of the incorporation reaction for zinc as a substitutional impurity,6 and the analysis of the concentration dependence of the diffusion coefficient.' In this paper the role of the phase diagram in the selection of the starting diffusion source composition is illustrated, and an application of the diffusion and solubility analyses is used to demonstrate their utility in the estimation of surface concentration and diffusivity for various starting source compositions. Consideration of the isothermal sections of the ternary phase diagram shows that below about 744° C a composition region exists where the three solid phases Zn3As2, GaAs, and ZnAs2 are in equilibrium without a liquid phase. In this region the partial pressures of the components do not vary with composition, and thus the surface concentration and diffusivity depend only on temperature. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected. As will be described in detail, this diffusion source yields reproducible diffusion profiles without surface damage, planar junction interfaces, and steep profiles that result in devices with step junction behavior. Only closed diffusion systems are considered. Open or flowing vapor systems require the maintaining of constant vapor pressures in the flowing gas and represent control problems outside the scope of this discussion.

Jan 1, 1969

By B. Mueller

Altered concepts regarding the raw material used in conventional blast furnace plants as well as new technologies for the reduction of iron ores make it necessary to reconsider the design of pelletizing plants. The incorporation of a pelletizing plant within a conventional integrated steel mill involves considerations of the problems of using in-plant fines. A modern pelletizing plant in Mexico serves as an example of the technical solution. In recent times, pelletizing plants are also being integrated within steel mills based upon direct reduction processes. The design of such pelletizing plants must take into account special product quality requirements.

Jan 1, 1977

By Forbes K. Wilson

"For his vision, determination, dedication, and leadership in the conquest of the remote and rugged Ertsberg and the technical and human barriers to its development and for his lecture ..." It is a great honor for me to be included among the Jackling Award recipients, many of whom have been close friends and associates. My subject is the development of the Ertsberg, a copper mine located 4' south of the equator, 70 miles (113 km) from the south coast of Irian Jaya---the easternmost province of the republic of Indonesia at an elevation of 12,000 ft (3658 m) in an area which was inhabited by a few "stone age" people when I first arrived there in 1960. Persistence, tenacity, immagination and innovation were all required to bring the Ertsberg into production. The technical, financial and political problems that have been faced over the past 16 years were unique in many respects. I hope that my paper will give some encouragement and help to future developers of mines in difficult and inhospitable surroundings.

Jan 1, 1978

By Strathmore R. B. Cooke, Iwao Iwasaki

RECENTLY spectrophotometry has been reported to provide a convenient technique for the rapid and reproducible determination of xanthate concentration in pulp solution 1,2 and for a kinetic study of xanthate decomposition in acid solutions." Since the application of this analytical technique is feasible for those compounds showing pronounced light absorption maxima in the near ultraviolet region, it was deemed advisable to investigate the absorption spectra of some of the organic compounds that are used in flotation. It is known empirically that certain groups of atoms in an organic compound cause characteristic light absorption in the ultraviolet and near ultraviolet range, and the wavelengths and intensities of the corresponding absorption maxima are relatively independent of the nature of the remainder of the compound. The characteristic values of such groups, which are known as chromophores, are given in the literature. 4,5 According to this information, many of the sulphydryl compounds are expected to show absorption maxima in the near or long wavelength ultraviolet region, whereas the saturated fatty acids and the saturated alkylamines do not.

Jan 11, 1957

At the meeting of the Board of Directors held Tuesday, Feb. 18, 1919, there were present nineteen Directors and the Secretary of the Institute. The following officers were elected for the year: A. R. Ledoux, first vice-president; George D. Barron, treasurer; Bradley Stoughton, secretary; and the following committees: Executive Committee, Finance Committee, Library Committee, Committee on Papers and Publications, Committe on Membership. The personnel of these committees will be published in the Year Book. A vote of thanks was passed to each officer and member of the several committees that arranged the New York Meeting of the Institute. The meeting dates for the Board were arranged for the year. The report of the Treasurer was presented, also the report of the Auditing

Jan 4, 1919

By Floyd Kelley

THE literature of the last decade is rich with information relating to the cause and means of control of grain growth in pure metals, but is deficient concerning the role diffusion plays in grain growth, although during this period many new products that depend on diffusion for their properties and success have been developed. Among these are cementation products, produced by calorizing, chromizing, and carbonizing, or by mixing, pressing, and sintering powdered metals such as Syke's iron-molybdenum die material, Genelite, and Elcon Metal (copper, tungsten) etc. This is a fertile field for new developments, but before it can be util-ized to the fullest extent there must be a thorough investigation of the processes by which diffusion and grain growth take place. Grain growth plays no small part in the process and certainly the physical properties of these products depend largely on the grain size and state of equilibrium produced. The field of investigation does not end here, but may be extended to the effect of diffusion on impurities, segregations and dendrites in the broad field of ferrous and non-ferrous metallurgy. A number of years ago the author investigated several of these cases and noted, with striking regularity, the pronounced effect of diffusion in promoting recrystallization and grain growth. An example of this phenomenon is given in his paper on chromizing1 which contained photomicrographs of large radial or columnar crystals produced by diffusion of chromium in the solid state. Another manifestation of this effect was discussed by Austen,2 who showed the part hydrogen plays in the decarburization of steel and the effect of diffusion upon the grain structure.

Jan 1, 1928

By W. G. Woolnough

Production of oil in Australia is negligible at present. A very small quantity of crude is being recovered from lean pumpers in Victoria, and a little activity is evidenced in Queensland, where two new wells were sunk during 1934. One of these, at Warooby Creek near Roma, obtained a noteworthy gas flow, but no oil production has been recorded. Geological investigation is going on in Western Australia, but no drilling activity is apparent. The "boom" in oil prospecting came to an end when the wave of depression swept over the country, and the investing public turned its attention actively towards gold. There is great activity in gold prospecting at present. I still maintain as strongly as ever that the prospects of obtaining flow oil in Queensland, Western Australia and Victoria are good, and that really scientific methods must ultimately succeed. Active and excellent geological work is being carried out in the Mandated Territory of New Guinea, and it is reported that drilling is likely to be undertaken next year. Matters in Papua are at a standstill. The question of extraction of oil from the oil shales of New South Wales and Tasmania is perennially active, and attempts to exploit this source commercially are renewed from time to time. Hydrogenation of coal is also receiving a good deal of attention.

Jan 1, 1935

By Frank R. Milliken

SCOPE THIS paper is a running commentary on metallurgical problems and developments, stressing ilmenite flotation, since the start of operations five years ago, at the mill of National Lead Company, Titanium Division, Maclntyre Development, Tahawus, New York. [ ] GENERAL In early 1941, when, world conditions threatened to cut off the supply of ilmenite (obtained largely from India) to this country, the National Lead Company started to develop and bring into production their Maclntyre Development. This operation supplied the bulk of the ilmenite used during the war period for the manufacture of the much needed titanium pigments. Maclntyre Development is at Tahawus, New York, on the headwaters of the Hudson River in the center of the scenic Adirondack Mountains. A general description of the operation was given in the Adirondack Issue of Mining and Metallurgy for November 1943. Operating tonnages and production have increased since 1943, however. Nearly 10,000 tons of ore and waste is broken and loaded daily in the open-pit mine. About half of this tonnage is ore, from which is produced nearly 800 tons of ilmenite concentrate and 1600 tons of magnetite concentrate daily. ORE-TYPES From an ore-dressing standpoint, there are five rather distinct ore types and two waste-rock types in the mine. The ore types are shown in Table 1. The anorthosite waste is a coarse-grained white rock, largely labradorite feldspar. The gabbro waste is generally finer grained, and contains, in addition to feldspar, 35 to 75 pct iron silicates such as hornblende, pyroxene, garnet and biotite. A minor mineral mineralogically, but important metallurgically, is apatite. A few calcite

Jan 1, 1947

By Guy Ruggles

IN this paper the authors aim to chronicle the experience and salient points brought out in changing flotation reagents at a concentrator which had probably been using a minimum amount of oil at a minimum cost per ton, to a more complicated system requiring a partial chemical control. The original oils were coal tar and pine oil. The new reagents are line, xanthate and pine oil. It was found that there were no insur-mountable difficulties and eventually the cost of the new reagents per ton of ore proved to be very little more than that of the old. LIME PLANT When the question of handling lime came up there were two propositions open: (1) to handle the lime dry; (2) to handle it wet in the form of an emulsion. Granting that a dry lime feeder would function properly, delivering lime uniformly, the chief objection was the dust that would be raised when these feeders were being charged or operated, as the only possible location was on a gallery beneath which men were working. With this objection the handling of lime as an emulsion seemed to he the better scheme. The lime plant which was first installed was for experimental work on one section. This was gradually changed and developed until it was of sufficient size to accommodate 20 sections. The various changes will not be discussed and the following description deals only with the fully developed plant. Crude as it is, and perhaps somewhat expensive to operate, the lime-handling plant has been quite successful. Much has been learned which will pave the way for a better installation in the future.

Jan 1, 1927

By Jan Wolski

Today's rapidly shrinking world requires a common language of measurements, a consistent system which could be used by everyone. The S.I. system of units is generally accepted as such and is already in use by a great majority of nations in the world. The change to S.I. units is also slowly taking place in U.S. engineering practice. The transition period is difficult and long because it takes time to get familiar with the new system, to start "feeling" values in new units. Instruments, formulas, computer programs, survey grids, etc. have to be converted or exchanged. The transition period should be used not only for substitution of units, but also for rationalization of presently used calculation methods. This paper examines the major parameters of mine ventilation from the above point of view and discusses a system which is much simpler and more consistent than the American Unit System still in use in the United States. In October 1979, the Society of Mining Engineers of AIME decided to introduce the S.I. unit system in all its publications including the periodical "Mining Engineering", and since February 1980 the system has been used consistently, not only in SME publications but in all conferences and meetings organized by this Society. The authors have no intention of explaining the details of the S.I. system in general. Any reader can find this information in many available publications and conversion tables, and in particular in the ASTM Standard for Metric Practice, E380-79. A comparison is made between various units used in mine ventilation from the past and those presently in use. This will allow an easy translation from one system to another, important when reading publications from abroad. S.I. and customary U.S. formulae are shown side by side for easier visualization of similarities and differences. Recommendations for the necessary steps in order to switch from American to S.I. units conclude the paper.

Jan 1, 1982

By Frank R. Milliken

This paper is a running commentary on metallurgical problems and developments, stressing ilmenite flotation, since the start of operations five years ago, at the mill of National Lead Company, Titanium Division, MacIntyre Development, Tahawus, New York. In early 1941, when world conditions threatened to cut off the supply of ilmenite (obtained largely from India) to this country, the National Lead Company started to develop and bring into production their MacIntyre Development. This operation supplied the bulk of the ilmenite used during the war period for the manufacture of the much needed titanium pigments. MacIntyre Development is at Tahawus, New York, on the headwaters of the Hud- son River in the center of the scenic Adirondack Mountains. A general description of the operation was given in the Adirondack Issue of Mining and Metallurgy for November 1943. Operating tonnages and production have increased since 1943, however. Nearly 10,000 tons of.ore and waste is broken and loaded daily in the open-pit mine. About half of this tonnage is ore, from which is produced nearly 800 tons of ilmenite concentrate and 1600 tons of magnetite concentrate daily. Ore—types From an ore-dressing standpoint, there are five rather distinct ore types and two waste-rock types in the mine. The ore types are shown in Table I. The anorthosite waste is a coarse-grained white rock, largely labradorite feldspar. The gabbro waste is generally finer grained, and contains, in addition to feldspar, 35 to 75 pct iron silicates such as hornblende, in garnet and biotite. A minor mineral mineralogically, but important metallurgically, is apatite. A few calcite

Jan 1, 1949

By Elwood Haynes

As in organic nature certain animal and vegetable forms have undergone modifications, and thus, as it were, fitted themselves to live in a new environment, so it has been found possible in certain instances to form new metallic combinations which are practically immune to the natural conditions that exist on the earth at the present time. A few of the metals, such as gold, silver, and the metals of the platinum group, are found native, but the commoner heavy metals are nearly always found in the form of oxides or sulphides. For a number of years I have made experiments with a view to finding certain metallic combinations or alloys which would not only resist oxidation and other harmful influences, but would also possess valuable physical properties, which would render them fit for special service. The first decisive step made in this direction was the discovery of an alloy of nickel and chromium in 1898. The properties of this alloy have already been described in a previous paper.' Immediately following the discovery of the nickel-chromium alloy, I produced an alloy of cobalt and chromium, which has likewise been described in the reference given, but the range of proportion between the cobalt and chromium is so great, and the combination is modified to such a marked degree by the introduction of other substances, that I have felt justified in reading another paper on this subject, describing more fully my researches in this particular direction. As early as 1907 and 1908,I made alloys or combinations of cobalt, chromium, and tungsten; cobalt, chromium, and molyb-

Jan 1, 1913

By C. F. Hardy, D. R. Mitchell

Bolts held up roofs as mining machines went on to set new records, but rising labor costs still plagued operators.

Jan 2, 1951

By J. A. Capp

For certain classes of electric railways a steel conductor is preferable to the oldcr atld more commonly used overhead trolley-wire. The third-rail presents a rather better appearance, because of the absence of an overhead structure; it is easily installed, cheaply maintai~ied, presents s large area for conducting and collecting the current, and is therefore particularly suitable for high speed and heavy service. With costs calculated on the basis of equal coilductirity in rail aud trollej-wire, the third-rail constrrictiol~ is cl~caper than thc overhead trolley. But the average interurban road will lise a trolley-wire of considerably less conductivity than would be obtained with the smallest size steel rail (about 60 lb. per pard) that mould ordinarily be used, and here the first clost of trolley construction would generally be less thau that of the third-rail. While no third-rail installation has jet bee11 in operation long enough to give figurcs of value, it ~vould appear that the cost of maintenance of the thirdrail construction should be less than that of the overhead trolley. This consideration, together with that of sightliness and adaptability (particularly in the case of terminals, yards and very heavy or high-speed service), will frequently off'set the higher cost of the third-rail construction and make it the preferable means of' conducting the current from thc generator to the car-motor. For the first third-rail installations, old track rails were used when obtainable, and these old rails were supple~rlented with new rails of standard T-section and composition. With the coming of the very heavy, high-speed service during the past few years, the resistance of these old and new standard T-rails was found to be so high that they mould not carry the high currents necessary without too great a drop in the line-potential. The rails would, therefore, have to be suppleme~~ted with addi-

Jan 1, 1904

The National Mine Health and Safety Academy near Beckley, W. Va., is dedicated to reducing accidents and improving health conditions in the mining industry through education and training. Though this basic mission remains unchanged, the Academy now serves a much broader mining community than it did when established in the late 1960s. From its original emphasis on training federal coal, metal, and nonmetal mine safety inspectors, the Academy has expanded its programs to reach mining industry and labor representatives, state agency employees, and university students taking mining-related courses. The Academy's resident programs, short courses, seminars, and continuing education courses cover a wide range of subjects and various experience levels, but all have been developed with one idea in mind - to reduce accidents and health hazards through education and training of the widest possible audience.

Jan 11, 1979

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

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

Jan 1, 1969