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By C. G. Dunn, J. L. Walter

A study has been made of the nature of the slow growth or nucleation stage of secondary recrystallization to the cube texture in sheets of high-purity 3 pct SiFe. Cube-oriented nuclei were identified and their growth observed, using surface markings together with micrographic and X-ray techniques to provide information on grain boundary interactions and the driving forces for growth. FACTORS that promote growth of certain grains during the early stages of secondary recrystallization have been considered theoretically1 but have been little explored in a direct experimental way. In certain cases,2'3 it has been reported that the primary recrystallization grains (nuclei), which eventually become secondaries, were found to be larger than the other grains into which they grew-Factors such as grain boundary "mobility" and differences in strain energy may contribute to the

Jan 1, 1961

By T. A. Read, M. S. Wechsler, D. S. Lieberman

IN the formation of martensite in steel, it has been observed that the habit plane does not change continuously as the alloy content is varied. Instead, it appears that discrete habits correspond to certain ranges of composition. Greninger and Troiano' found that in low-, medium-, and high-carbon steels, the habits are approximately (1l1), (225), and (259), respectively.* The work of Mehl and Van Winkle2 indicated that the change from the (225) to the (259) habit is fundamentally a consequence of the lower transformation temperature rather than the higher carbon content. Also, Otte and Read3 observed that the habit plane orientation for a chrome-carbon steel scattered within a cone of semivertex angle of 5 deg, which was outside of the experimental error in the determination of the habit plane. These observations suggest the importance of investigating what factors in the crystallography of the formation of martensite account for the several types of habit and the inherent scatter in the precise orientation of the habit plane. A theoretical treatment of the austenite-martensite transformation has been given,4 which considers the total transformation distortion to be composed

Jan 1, 1961

By Mathews K. E, Willstead T. V C

Initial glory holing was followed by sublevel stoping, with a small proportion of total production mined by shrink and cut-and-fill methods.The sublevel stoping method was successfully modified to cater for altering ground conditions encountered at increasing depths. At present, 94 per cent of production comes from sublevel stopes. The evolution of this mining method and current techniques and practices is outlined. A combined shrink and,sublevel benching method was also developed to increase the mining rate of narrow orebodies over the standard stoping lift of 380 ft. Pillar recovery and stope filling operations have been continuously modified to suit the relIuirements of a rapidly developing mine.INTRODUCTIONOre production commenced at Mount Isa Mines in June 1931. Since then production has increased from approximately 2,500 tons of lead ores per mine day to the current 11,000 tons of sulphide ores per mine day comprising 3,100 tons of lead ore and 7,900 tons of copper ore. The early planners selected sublevel stoping with ring drilling for ore breaking as the most efficient and economical for Mount Isa conditions: This method satisfied requirements for:1. a low cost mining method for the comparatively low grade ores,2. a stoping sequence allowing development, stope preparation, breaking and drawing of ore to proceed concurrently,3. a method of extraction in which broken ore in the stopes would be kept to a minimum because of adverse effects of oxidation on mill metallurgy and...

Jan 1, 1961

By Leo F. Reinartz

The history of steelmaking in the United States is a fascinating story of determination, sudden tragedy, exploitation, and inventive genius rolled into one gigantic plot. Mr. Reinartz' flowing interpretation of the progress made in the last one hundred years is being presented in a series of four articles. THIS is the Age of Steel. We live in a mechanized era. Our everyday lives--everything we see or do-are organized and influenced by this versatile metal. Our industries, our farms, our homes, and our transportation-yes, our vocations and avocations, or luxuries and necessities-all are dependent upon smelting iron and making steel. Take away iron and steel and soon our vaunted civilization would revert to a primitive existence. These metals, often in crude forms, have been known for thousands of years. Down through the ages, until about one hundred years ago, steel was made laboriously, and at high est, in small batches. During those years, methods of manufacture did not change very much. Over long periods of time only warriors, royalty, and wealthy people could afford to use articles made of iron or steel. History has recorded that the nations which were expert in iron and steel manufacture, and had access to rich iron-ore deposits, were the leaders in war or in peaceful pursuits. At the end of the 18th century, thirteen struggling American colonies had broken not only the political shackles that bound them to Great Britain, but also many of the economic bonds. They had showed their skill, Yankee ingenuity, and energy by making iron and steel articles for their own use. After the Revolutionary War, more and more hardy American pioneers pushed westward through the Allegheny Mountain passes and down the rivers into the fertile Ohio River and Kentucky country. Demands for articles made of iron increased. The iron industry on the east coast grew and prospered. As this trend continued, iron industrialists moved their plants westward to be near the large deposits of high-grade coal in western Pennsylvania, eastern Ohio, and nothern West Virginia. They also desired to use the local iron ores and water resources of those areas. Blast furnaces and ironworks were built in the Pittsburgh, Youngstown, southern Ohio, and northern West Virginia districts. In 1810, the United States produced 53,908 gross tons of cast iron and 917 tons of steel. Iron ore discovery A white man first discovered large deposits of iron ore in the northern Michigan and Lake Superior country in 1844. One year later, the Sault

Jan 1, 1961

By S. E. Haszko

Fused alumina or silica crucibles were used as the containing vessel. X-ray powder photographs were taken with CrKa radiation and the use of Straumanis type Norelco cameras of 114.6 mm diam. Crystallographic data for these compounds are shown in Table I. These results are in agreement with others of this series reported previousiy by Wernick and Geller.l The abnormally large atomic volume of Eu and Yb metal3 is manifested in EuA12 and YbAl2, when one compares them with the compounds reported in Ref. 1. However, the behavior of Yb in the Ni compound is the same as that observed in Ni5Yb having the Cu5Ca structure.4 Thus, it appears that Yb has a valence closer to 3 only in the Ni compounds; i.e.. the 2s and Id electrons are lost to the conduction band. 1,4 Europium in EuAl2, appears to have a valence closer to 2. In previous work.' X-ray patterns of ingots of NdCo2 indicated a multiphase material with faint indication of the presence of a phase having the MgCu2 structure. It was thought that NdCo2 formed peri-tectically from the melt, resulting in a multiphase system when cooled under nonequilibrium conditions. An X-ray pattern of a sample from a melt cooled more slowly than in past work showed that the major phase was NdCo2. The lattice constant, Table 1, is in excellent agreement with the value one can predict from the data of Ref 1. One of the other phases was identified as Co,Nd. The author wishes to thank J. H. Wernick for his guidance in this work, and D. Dorsi for the preparation of these compounds. 'J. H. Wernick and S. Geller: AIME Trans., in press. 'J. H. Wernick and S. E. Haszko: to be published. 'F. H. Spedding and A. II. Daane: Progress in Nuclear Energy, Series 5, Eds.: H. M. Finniston and J. P. Howe, McGraw-Hill Book Co., 1956. 'S. E. Haszko: to be published. 'J. H. Wernick and S. Geller: unpublished work. 6J. 11. Wernick and S. Geller: Acla Cryst., 1959, vol. 12, p. '162. The Influence of Hydrogen on the Lattice Parameters of Ti-Sn Alloys A. Coucoulas and H. Margolin A reinvestigation of the lattice parameters of Ti-Sn alloys by the present authors has revealed consistently higher c and a values than those obtained by Worrier. The difference is most pronounced in the c-parameters which are, therefore, used as a basis of comparison. This discrepancy was not due to air contamination, since precautions were taken to exclude this possibility. Specimens for Debye-Scherrer photograms were prepared by arc-melting 15-g buttons of Bureau of Mines titanium and 99.99 pct Sn, with compositions of 6, 8, 10, and 12 at. pct Sn. These buttons were forged under an oxygen-acetylene torch to 1/8-in. sq rods to produce relatively fine grained material. Scale and some surface were ground off, and the rods, after wrapping in molybdenum and titanium sheet, were vacuum annealed 15 min at 800 °C to remove hydrogen. Heat treatment of one of the samples at 875°C to produce ß and reveal a at the surface showed no surface contamination. Following the vacuum treatment, the specimens were wrapped in molybdenum and annealed for 1week at 800°C under two atmospheres of argon. After water-quenching, the rods were ground so that the thickness tapered to 0.1 mm at the tips. The ground specimens were then recapsuled as previously and reannealed 1 hr at 800°C to remove cold work. The

Jan 1, 1961

By H. W. Fleming

In 1955, the results of a regional, geological interpretation of the northern portion of New Brunswick were used as a basis for selecting, for intensive exploration, three areas in which structural and stratigraphic conditions were believed to be favourable. Airborne electromagnetic work, in one of these areas, provided the justification for acquiring the Murray group. Even though the initial results were discouraging, this geological interpretation, combined with the fortuitous discovery of cop• per-bearing float, was sufficient reason for carrying out further work using geochemical methods. This work finally resulted in the discovery of the Murray massive-sulphide deposit, after about eighteen months of coordinated exploration on the property. While this deposit is a typical New Brunswick-type base-metal occurrence, extensive leaching has produced a fossil gossan that rendered it an elusive target for exploration techniques of limited penetration Full credit for localizing the target area is given to the geochemical techniques, but geophysical surveys were needed to provide the necessary

Jan 1, 1961

By R M. Ennis, J. C. Botham

This paper is one of a series pre-pared to study the role of fuels and reductants in metallurgical processes, especially from the viewpoint of Canadian requirements. The object of these studies is to provide a reason-ably authoritative interpretation on the interrelation of fuels in light of the considerable changes that have taken place in the Canadian energy field during the past few years. Previous papers in this group have dealt with the problem generally, and specifically in terms of the development of the iron and steel industry of Western Canada. These latter papers, presented at the Symposium on Iron and Steel in Western Canada held in Edmonton, Alberta, on September 8-9, 1959, surveyed the ferrous processes of interest for use in Wes tern Canada, especially with regard to solid fuel requirements. At that time it was evident that there was a need for a similar study of the fuels aspect of the non-ferrous metals industry.

Jan 1, 1961

By R. C. Neavel

One of the most important requirements to be met by any coal producer is delivery of size consists tailored to specific applications. Generally these specifications include a minimum as well as a maximum size limit. The customers of a major Indiana coal producer noticed that some shipments of sized coal contained a large proportion of undersize pieces. Also, in these shipments, the pieces which remained within the specified limits were cracked and, when handled, crumbled readily. The producer, certain that these shipments had been properly sized at the tipple, suspected that degradation had occurred in transit. The Indiana Geological Survey was requested to examine the coal from one of these shipments to attempt to determine the cause of breakage. Two basic facts about coal and coal seams led to the employment of petrographic techniques in this investigation. First, all coal seams consist of accumulations of diverse organic and inorganic constituents; and second, most coal breakage, either desirable or undesirable, can be attributed to the inherent weakness of some of these constituents or to poor adhesion between certain constituents. Analyses of degraded coal Sampling: Samples were secured from 2 stock piles of 2-by 4-inch coal in a dealer's yard. The coal in both piles had received the same treatment from mining to storage, although it had been mined and shipped on two different days. The size consist of one pile, however, appeared smaller than that of the other. The sample from the degraded pile is referred to as the slack sample, and the other is called the unslack sample. Size analyses: In order to determine the actual size consist, the samples were screened, with a minimum of rough handling, on square 2-inch, 1-inch, 1/2-inch, and 12-mesh screens. It is assumed that 100 percent of the 2-by 4-inch coal is retained on a 2-inch round screen at the tipple. Analyses of several loads at the tipple indicate that approximately 26 percent of the 2- by 4-inch coal, 100 percent of which was assumed held on a 2-inch round screen, passed through a 2-inch square screen. Twenty-six percent may be taken as the normal difference between round and square screens. Results of the analyses of stockpile coal are shown in Table 1. Cumulative percent versus size are plotted on a Rosin-Rammler chart as Figure 1. Both samples approximately follow normal size distribution; this indicates that breakage is not size preferential and also that the samples are representative of the stockpiles. Although both samples exhibit the same general size distribution, the median size of the slack sample is considerably smaller than that of the unslack sample. Fifty-five percent of the unslack sample was undersize (29 percent greater than the normal 26 percent difference), and 83 percent of the slack sample was undersize (57 percent greater than the normal 26 percent difference). Both piles contained a greater percentage than normal of undersize coal; this indicates that they were both affected by degradation, but to a different degree. Bedding-plane analyses: Coal, because of its laminated nature, will break preferentially along bedding planes, especially where adjacent constituents are poorly cemented to each other. Subsequent breakage perpendicular to the

Jan 1, 1961

By Marvin L. Whisman

Several parameters controlling the reproducibility of tritium determina¬tion in organic compounds by liquid scintillation counting were evaluated by the Federal Bureau of Mines. These included optimum volume of scintillator solution for maximum counting efficiency, reproducibility of counting a sealed commercial standard and comparison with duplicate counts on laboratory-prepared samples. The error introduced by using microliter pipets, optical differences in counting vials, reproducibility of counting organic samples where quenching is a factor, reproducibility of counting laboratory-prepared samples with an added internal standard, optimum ratio of internal standard activity to sample activity, effect of sample volume upon counting efficiency, count rate at which coincidence losses become apparent, and reproducibility of organic compound radioassay by the standard addition technique are outlined. From the evaluation of these parameters, a technique that can be applied routinely to organic compounds containing tritium has been established, and details are included in this report.

Jan 1, 1961

C. G. Dunn (Generai! Electric Research Laboratory)— The author is to be commended on his attempt to calculate the residual strain energy from information on the dislocation density within the subgrains and a surface energy associated with the subgrains. However, much closer agreement between a calculated critical size of a nucleus and the observed size of grains that did not continue growing can be obtained if a reasonable correction is made in obtaining the energy of the surfaces of the subgrains. For example, since the sample is a single crystal with a cold-rolling reduction of 70 pct in thickness, one needs either an average disorientation for this or an average subgrain boundary energy rather than the 2.5 deg disorientation of a bent crystal, which was used by the author. From either the Laue photographs of the author or the pole density plot of Koh and Dunn 16 for a (113) [332] cold-rolled crystal the

Jan 1, 1961

[NORTH AMERICA UNITED STATES Alabama BIRMINGHAM BURROWS, WILLIAM C. CORD, RICHARD H. COSTON, OTIS D. JR. FAIRHOPE RUFFLES, WILLIAM R. HUNTSVILLE WAGGONER, JERRY B. MOBILE PETROUTSON, PETER C. SELMA JONES, JAMES J. JR. UNIVERSITY CUDWORTH, JAMES R. JONES, WALTER B. RICHARDS, EDWARD F.]

Jan 1, 1961

By J. R. Lucas, R. L. Frantz

Mine sealing programs for the alleviation of acid mine drainage were begun by the Federal Government in the '30's. As part of an acid mine research project to The Ohio State University, a field test was undertaken to determine the effectiveness of mine seals for reducing mine acid. Details of the tests made at the McDaniels mine show the feasibility of air-sealing and flooding an acid-producing drift coal mine. Work by the University continues. The Federal Government undertook in the early thirties an extensive mine sealing program for the alleviation of acid mine drainage. In the states of West Virginia, Ohio, and Pennsylvania many general summaries have been made on this program but no critical evaluation with supporting data has been found on the effectiveness of mine seals for reducing mine acid. Because of this it was decided to undertake a field testing program as part of an acid mine research project of the Engineering Experiment Station, The Ohio State University. The objective of this phase of the project was to develop and install a field research laboratory for acid mine drainage studies. Specifications for such a mine laboratory were developed and resulted from the following considerations: 1) Size and preservation—the test mine shou1d be of limited size to permit frequent and detailed examinations; it should be in a reasonably sound condition to permit safe entry. 2) Isolation—the mine should be physically separated from all other mines. 3) Openings—a minimum number would be desirable to reduce the sealing problem. 4) Structure—the mine especially near the openings should be structurally sound. 5) Acid production—the mine should be producing significant quantities of acid. After considerable searching, the McDaniels mine was selected in the Hocking coal field in Vinton County just above Lake Hope State Park in southeastern Ohio. The small drift mine in the middle Kittaning coal consisted of two small rooms with one mine opening about 6 ft above a seasonal stream bed. Before it was finally decided to seal the mine, a short study was made of the acid drainage over several months. Fig. 1 shows a plot of acidity (milligrams per liter), flow (gallons per minute), and acid production (pounds per day) vs time over the sampling period. Because the coal was overlain with a porous sandstone, the mine drainage was consistent the year around even though the mine was

Jan 1, 1961

By F. H. Buchella, J. F. Buchanan

The San Manuel copper deposit is located about 45 miles northeast of Tucson. The concentrator, smelter, administration building, and other plant facilities are located about seven miles southeast of the ,nine area at the new town of Sari Manuel as shown on Figure 1 (Sketch).

Jan 1, 1961

By W. C. Thurber, C. J. McHargue

THE deformation textures of metals have been extensively studied because of both the practical implications in metal fabrication and the fundamental insight into the behavior of the metal during deformation. Most studies have been concerned with pure metals or solid-solution alloys and relatively little attention has been directed toward more complex alloy systems. Barrett' and Brick2 have summarized work on multiphase systems in terms of the relative ease of deformation of the phases. Thus, if the phases are deformed about equally, each develops its usual texture for the particular fabrication process. This behavior has been reported for Ag-Cu and Cd-Zn alloys3 and 62-38 brass.4 A dispersion of hard particles in a softer matrix interferes with the normal reorientation of the matrix lattice during deformation, thus distorting the texture or in some cases preventing its development. Increasing the amount of carbon in steel has been observed to increase the randomness of the ferrite5 and almost random textures have been reported for A1-12 pct Si eutectic alloy wires.6 It has also been noted that if the second phase is platelike, deformation causes the platelets to line up in a common direction. The present work concerns a quantitative study of the deformation textures in aluminum-uranium alloys containing 5 or 13 wt pct U. Alloys in this composition range are characterized by a pure aluminum matrix in which the intermetallic compound UA14, is dispersed. From a fundamental standpoint, this system affords the opportunity for studying the effects of a dispersed phase on texture development in an essentially pure metal matrix. Further, these alloys are commonly used as fuels for nuclear research and testing reactors, and a knowledge of the preferred orientation may be useful in evaluating physical and mechanical properties as well as response to fabrication. The deformation textures in sheets of aluminum (99.996 pct), Al-5 pct U alloy, and Al-13 pct U alloy were determined for reductions in thickness of 90 pct by cold rolling. The texture in an alloy rod of the latter composition which had been extruded at 455°C was also determined. It can be readily ascertained from the aluminum-uranium phase diagram that the 5 pct U alloy is hypoeutectic and contains 7.3 wt pct (3.4 vol. pct) UAl4. The 13 pct U alloy has the eutectic composition and contains 18.9 wt pct (9.4 vol. pct) UAl,; however, because of nonequilibrium solidification conditions, the typical eutectic microstructure was not developed. The alloys were prepared by open-air melting in graphite crucibles. The slab castings were cropped and cold reduced 90 pct in thickness on a two-high mill. The slabs were reversed after each pass. Although the uranium-bearing alloys exhibited edge cracking, they could be cold rolled to the desired thickness. Small coupons 1.5 by 0.75 by 0.1 in. thick were sheared from the center of the rolled plate with a major axis parallel to the rolling direction. To obtain a specimen of sufficient thickness for machining of the X-ray diffraction specimen, three coupons were laminated into a single three-ply sandwich with a suitable adhesive. Adhesives which could be cured at room temperatures were selected in order to prevent recrystallization during bonding. Bondmaster M-648 (Rubber and Asbestos Corp.) was used for the pure aluminum laminate and Armstrong A-6 (Armstrong Products Co.) was used for the alloys. The alloy for extrusion was cast in a cylindrical graphite mold! cropped and machined into a 3-in. diam by 4-in. long billet. This billet was preheated to 455°C, upset to 3.125 in. diam, and extruded on a 700-ton hydraulic press at a speed of 6 fpm through a flat-face, 1-in. diam die. The rod was quenched with a water spray as it emerged from the die. Pole-distribution data were obtained using the diffractometric method described by Jetter and Borie.7 A spherical X-ray diffraction specimen of

Jan 1, 1961

By A. Boltax

Precipitation processes occurring during both furnace cooling and aging of copper-iron albys were studied by means of electrical and magnetic measurements. On furnace cooling, two distinct stages in the precipitation process were detected; one occurring above and the other below 850° C. The kinetics of precipitation from quenched alloys were studied between 200° and 700°C. The reaction appears to be consistent with the concept of tmcleation of precipitate particles at dislocation loops formed by the clustering of quenched-in vacancies. A study Of in copper-iron alloys is particularly interesting because the combination of magnetic and electrical properties in these allovs provides a quantitative means of following the course of the precipitation reaction. (The details of precip-

Jan 1, 1961

By D. R. Cook

This paper is a case history of an exploration venture for base metals, begun by the Rocky Mountain District of Bear Creek Mining Company in 1952 and completed in 1954. The project was based on the idea of W. S. Burbank, U. S. Geological Survey, that commercial deposits of base metals might occur in Paleozoic sediments beneath hydrothermally altered volcanic rocks in the Southern Bonanza mining district, Colorado. Here, an area of andesitic rocks, four square miles in extent, has been argillized, pyritized, chloritized and silicified. Geological, geophysical and geochemical studies were followed by the diamond drilling of three holes totalling 6,220 feet. Further alteration ang geochemical studies were made on the cores from these holes. A brief review of the alteration and geologic mapping, colored aerial photograph interpretation, geochemical soil and rock sampling, magnetic, gravity and radio-metric surveys are presented together with some conclusions regarding this work. This paper is a case history of an exploration venture for base metals, begun by the Rocky Mountain District of Bear Creek Mining Company in 1952 and completed in 1954. Important contributions were made to the project by personnel of the Rocky Mountain District and the Geophysics Division. Individual acknowledgements to these people are made at the end of the paper. BASIS FOR THE PROJECT The project was based on the idea of W. S. Burbank (1947, p. 444) that commercial deposits of base metals might occur in Paleozoic sediments beneath hydrothermally altered volcanic rocks in the Southern Bonanza mining district, Colorado. Paleozoic sedimentary rocks, including the favorable Leadville limestone, are exposed three miles south of the altered area, and reason exists to believe that they might underlie it within a reasonable depth. Alteration of pre-mineral volcanic rocks has been used successfully as a guide to concealed orebodies in the Main Tintic and East Tin tic mining districts, Utah (Bill-ingsley, 1933, p. 120-122; Lovering et al, 1949; Howd, 1957, p. 124-134; Cook, 1957, p. 73) and could be a useful guide here. GENERAL GEOLOGY AND STRUCTURE The Northern and Southern Bonanza mining districts are northwest of the San Luis Valley in southern Colorado, just within the northeastern edge of the San Juan volcanic province. The districts are1ocated on the southern extension of the Sawatch uplift, a prorninent northwest-trending structural high. The highly productive mining camp. of Leadville, Gilman and Aspen are on the northeastern and northwestern flanks of this uplift where Paleozoic limestones have

Jan 1, 1961

Recent literature is reviewed with emphasis on the design and scale up of mixers. Most important aspects of mixing have resulted from the study of Newtonian fluids and only a minor attempt has been made to extend the work to non-Newtonian materials.The rheology of non-Newtonian materials is outlined and the typical behaviour of mineral slurries is indicated.The importance of flow velocity, flow pattern, and fluid turbulence is discussed with relation to suspension of solids and rate of reaction.Data on experimental leaching of ore from Mary Kathleen, Queensland, show the effect of different mixing impellers.In conclusion, factors involved in the selection of a mixer are presented with emphasis on economic appraisal after pilot experimentation.INTRODUCTIONThe subject of mixing has attracted considerable attention during recent years, but relatively little work has been undertaken for the study of non-Newtonian materials. Most work has been restricted to Newtonian fluids because there are less inconsistencies in such study.Mixing, by definition, implies blending or combining, and ranges from gentle mixing which blends the contents of a large tank in 24 hours to violent mixing which completely homogenises the contents of a tank within seconds. Metzner and Otto (1957) have pointed out the present lack of knowledge on the degree (or quality) of mixing. Apart from this fact the design of mixers for Newtonian materials would seem to be reasonably certain.Both capital and operating costs rise rapidly with increasing mixer size. Therefore the design, or selection, of a mixer is a matter for economic consideration in the overall aspect of plant design and operation.

Jan 1, 1961

By J. C. Humbert, J. F. Elliott

The solubility of nitrogen in liquid pure Fe, Cr, and Ni, in liquid Fe-Ni, Fe-Cr, and Ni-Cr alloys and Fe-Cr-Ni alloys, has been measured by the Sieverts' type apparatus between 1500° and 1800°C. Tabulations and graphs of the solubility data and activity coefficients are shown. Heats of solution are reported. Interaction coefficients of the several elements in Fe. Cr, and Ni ave also reported. THE solubility of a gas in a liquid metal is usually measured by either the quenching technique or the so-called Sieverts' method. In the quenching method, 1-3 the melt is equilibrated at the desired temperature and pressure with the gas phase having a known fugacity of the gas being studied. The melt is sampled and the sample is quenched and analyzed chemically for its gas content. In Sieverts' method the melt is contained in a closed chamber. The apparent volume of this chamber, i.e. the "hot volume," is usually determined by introducing a known quantity of an inert gas having very closely the same physical characteristics as does the experimental gas. Alternatively, the experimental gas is used with an inert specimen having the same general physical characteristics as does the experimental melt. Subsequently, the experimental melt is equilibrated with the experimental gas by introducing a known quantity of the gas into the calibrated chamber. The solubility of the gas is obtained from P-V-T relationships. The quenching method suffers from' the limitation that some gas may be gained (as in the case of Cr-Fe alloys) or lost (as in the case of Fe-Ni alloys) during solidification and cooling of the sample. With Sieverts' method sampling and analysis are unnecessary. However, errors can result from the difficulty of determining accurately the "hot volume,"

Jan 1, 1961

By E. G. King

In continuation of the study of thermodynamic properties of the common interoxidic compounds of ferroalloy elements, this report gives the results of low-termperature heat-capacity measurements and entropy evaluations of the monotungstates of sodium, magnesium, and calcium. Previous reports4 5/ of this laboratory dealt with low-temperature heat capacities, entropies, and heats of formation of the sodium vanadates. Heat-capacity measurements of the monotungstates of sodium, magnesium, and calcium (Na2W04, MgW04, and CaW04) were conducted throughout the temperature range 51° to 298° K. The entropies at 298° K. were evaluated and then combined with entropy data for the elements and oxides to obtain entropies of formation. This information is an essential part of the data needed for thermodynamic appraisals of chemical reactions of these substances. No similar data for any tungstate are to be found in the literature.

Jan 1, 1961

By R. E. Hudrlik, G. W. Preckshot

The diffusion coefficients of silver from solid silver in molten lead were measured to within ± 0.8 pet in a columnar type diffusion cell ower, the temperature range of 326° to 530°C. Fick's law describes the process up to 530°C where the laminar mechanism appareltly breaks down. These is negligible resistance at the interface as shown by mathematical analyses. The diffusion coefficients are found concentration independent. IT would seem that diffusion in liquid metals would be free of such effects as molecular structure, dissociation. polarization. and compound formation. This view was taken by Gorman and preckshot in their study of diffusion of copper from solid copper into molten lead. They reported diffusion coefficients which were independent of the concentration over the range of 478° to 750°C. They found that the Stokes-Einstein equation with constant radius of the diffusing specie represented the diffusion data better than Eyring's rate theory equation and Sheibel's correlation. The radius of diffusion was found to be that of the doubly charged copper. There appeared to be no resistance across the solid-liquid boundary. In the present work the diffusion coefficients for silver in liquid lead were measured over a range of temperatures of 350° to 505°C. The solubility of silver in lead over the range of 303° to 630°C was also obtained. These results are compared with calculated or correlated values or with data in the literature. EXPERIMENTAL Procedure—The experimental equipment techniques and procedures were those reported in detail by Gorman and preckshot9 and will not be repeated here. Measured values of WT, Co, A. L were obtained for various diffusion times and the diffusion coefficient was computed for the case of no resistance at the interface9, 11 by: WT/CoAL = 1- 8/p2 n=1 1/(2n - 1)2 exp[-(2n - 1)2p2 Dt/4L2] [1] or where there was resistance at the interface by: WT = 1- ?n=1 2h2/ap2L [sxp [-Dan2t]/[(h2 + an2) L + h] The roots an are those of the transcendental equation3 tan (an L) = Iz/cun. The diffusion coefficient is that defined by Hartley and Crank.7 The total silver in the lead cylinder and equilibrium slug was determined by a cupellation technique' with proper correction for losses. Analysis of known samples showed that this method is surprisingly accurate. The amount of silver in the lead adhering to the silver cylinder was obtained in the same fashion as shown by Gorman and preckshot.9 The small errors involved in this determination are not critical since the silver in this adhering lead layer is only 3 to 15 pet of the total diffused. Materials—Electrolytic silver containing 99.9+ pet Ag obtained from General Refineries of Minneapolis, Minn. was used for all but runs 7 and 8. For the balance of the runs this silver was reduced with hydrogen at 1100°C and its oxygen content was found to be about 0.017 pet. For the runs. 7 and 8, phosphorous-reduced silver of the same purity was obtained from Handy and Harman Co. of Chicago, Ill. The densities of the phosphorus-reduced silver and the hydrogen-reduced electrolytic silver were 10.484 and 10.487 g per cm3, respectively. These values agree with those reported for pure silver. Silver which was reduced at 900 C had an average density of 9.998 g per cm3, indicating porosity. This silver was used for a number of runs which were not tabulated in Table I. These are indicated by crosses on Fig. 2. The 99.999 pet Pb was obtained from the National Lead Co. Research Laboratory of Brooklyn, New York. DISCUSSION OF RESULTS The diffusion and solubility results are reported in Table I for eleven runs using either phosphorus-reduced electrolytic silver or hydrogen-reduced silver at 1100° C. The solubility data shown in Fig. 1 show the excellent agreement with that reported by Heycock and Neville.8 The data of Friedrichs5 apparently are in error. The experimental solubility data of this work are reported to 0.3 pet. The experimental diffusion coefficients computed from Eq. [1] are reported within 1.2 pet of the mean and are plotted in Fig. 2. These are expressed within +0.8 pet of the experimental values over the entire temperature range by: D= 8.26 x 10 -5 e-1925/RT . [3] There appears to be little difference due to the

Jan 1, 1961